Combination container with liquid, container set, and manufacturing method of container with liquid

Abstract

To suppress deterioration by oxygen of a liquid.SOLUTION: A combination container with liquid includes: a first container which stores a liquid and which has oxygen permeability; and a second container which stores the first container and which has an oxygen barrier property. The second container includes a laminate. The laminate includes: an inner surface facing a storage space; and an outer surface on the opposite side from the inner surface. The laminate includes a sealant layer, a first barrier layer, a resin layer and a second barrier layer in order from the inner surface toward the outer surface.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a combination liquid-filled container, a container set, and a method for manufacturing a liquid-filled container. [Background technology]

[0002] Containers for storing liquids are known (for example, Patent Document 1). Depending on the type of liquid, the liquid may be decomposed by oxygen inside the container. To address this problem, it is conceivable to use containers with oxygen barrier properties.

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2011-212366 DISCLOSURE OF THE INVENTION

[0004] However, oxygen can dissolve in the liquid during production. Containers with oxygen barrier properties cannot address deterioration of the liquid caused by dissolved oxygen in the liquid. In other words, conventional technologies have not been able to adequately suppress oxygen-induced deterioration of the liquid contained in the container. The present disclosure aims to suppress deterioration of the liquid caused by oxygen.

[0005] A first liquid-containing combination container according to one embodiment of the present disclosure includes: a first container that contains a liquid and has oxygen permeability; a second container that houses the first container and has oxygen barrier properties; the second container includes a laminate; The laminate includes an inner surface facing the storage space of the second container and an outer surface opposite to the inner surface, The laminate includes, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

[0006] A second liquid-containing combination container according to one embodiment of the present disclosure includes: a first container that contains a liquid and has oxygen permeability; a second container that houses the first container and has oxygen barrier properties; an oxygen absorbing member housed in the second container, the oxygen absorbing member includes an oxygen absorber that absorbs oxygen in the second container, the second container includes a first film and a second film that accommodates the first container between the first film and the second film; the first film and the second film are joined at a seal portion in a peelable manner, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, In the direction in which the first seal portion and the first container face each other, the first container is located between the first seal portion and the oxygen absorbing member.

[0007] A third liquid-containing combination container according to one embodiment of the present disclosure includes: a first container that contains a liquid and has oxygen permeability; a second container that houses the first container and has oxygen barrier properties; the second container includes a first film and a second film that accommodates the first container between the first film and the second film; the first film and the second film are joined at a seal portion in a peelable manner, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, The sealing portion further includes a first side sealing portion connected to one end of the first sealing portion, a second side sealing portion connected to the other end of the first sealing portion, and an additional sealing portion positioned between at least one of the first side sealing portion and the second side sealing portion and the first container.

[0008] A method for manufacturing a liquid-filled container according to one embodiment of the present disclosure includes: A method for manufacturing a liquid-filled container using a liquid-filled combination container according to one embodiment of the present disclosure, comprising: closing the second container containing the first container; and adjusting the oxygen concentration by absorbing oxygen in the second container with an oxygen scavenger, In the step of adjusting the oxygen concentration, oxygen in the first container permeates the first container, moves to the outside of the first container, and is absorbed by the oxygen absorber in the second container.

[0009] A first container set according to one embodiment of the present disclosure includes: a first container for containing a liquid; a second container that accommodates the first container, the first container is oxygen permeable; the second container has oxygen barrier properties, the second container includes a laminate; The laminate includes an inner surface facing the storage space of the second container and an outer surface opposite to the inner surface, The laminate includes, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

[0010] A second container set according to one embodiment of the present disclosure includes: a first container for containing a liquid; a second container that accommodates the first container; an oxygen absorbing member accommodated in the second container, the first container is oxygen permeable; the second container has oxygen barrier properties, the oxygen absorbing member includes an oxygen absorber that absorbs oxygen in the second container, the second container includes a first film and a second film that accommodates the first container between the first film and the second film; the first film and the second film are joined at a seal portion in a peelable manner, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, In the direction in which the first seal portion and the first container face each other, the first container is located between the first seal portion and the oxygen absorbing member.

[0011] A third container set according to one embodiment of the present disclosure includes: a first container for containing a liquid; a second container that accommodates the first container, the first container is oxygen permeable; the second container has oxygen barrier properties, the second container includes a first film and a second film that accommodates the first container between the first film and the second film; the first film and the second film are joined at a seal portion in a peelable manner, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, The sealing portion further includes a first side sealing portion connected to one end of the first sealing portion, a second side sealing portion connected to the other end of the first sealing portion, and an additional sealing portion positioned between at least one of the first side sealing portion and the second side sealing portion and the first container.

[0012] A container according to one embodiment of the present disclosure comprises: A laminate is provided, The laminate includes, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

[0013] A laminate according to one embodiment of the present disclosure includes: A laminate used in a container, The insulating film includes, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

[0014] According to the present disclosure, deterioration of liquid due to oxygen can be suppressed. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a diagram for explaining an embodiment of the present disclosure, and is a perspective view showing an example of a combination container containing liquids. [Figure 2A] 2A is a longitudinal cross-sectional view showing a first container filled with liquid that can be included in the combination container filled with liquid of FIG. 1. FIG. [Figure 2B] FIG. 2B is a vertical cross-sectional view showing a method for measuring the oxygen transmission rate through the closure of the first container shown in FIG. 2A. [Figure 3] FIG. 3 is a diagram showing an example of a method for manufacturing the combination container filled with liquid of FIG. 1 and the first container filled with liquid of FIG. [Figure 4] FIG. 4 is a diagram showing an example of a method for manufacturing the combination container filled with liquid of FIG. 1 and the first container filled with liquid of FIG. [Figure 5] FIG. 5 is a diagram showing an example of a method for manufacturing the combination container filled with liquid of FIG. 1 and the first container filled with liquid of FIG. [Figure 6] FIG. 6 is a perspective view showing how to use the first container filled with liquid shown in FIG. [Figure 7A] FIG. 7A is a perspective view showing another example of the second container. [Figure 7B] FIG. 7B is a perspective view showing still another example of the second container. [Figure 7C] FIG. 7C is a perspective view showing still another example of the second container. [Figure 7D] FIG. 7D is a perspective view showing still another example of the second container. [Figure 8] FIG. 8 is a perspective view showing a modified example of the second container. [Figure 9A] FIG. 9A is a cross-sectional view showing an example of an oxygen absorbing member containing an oxygen absorber. [Figure 9B] FIG. 9B is a cross-sectional view showing another example of an oxygen absorbing member containing an oxygen absorber. [Figure 9C]FIG. 9C is a cross-sectional view showing an example of an oxygen-absorbing film containing an oxygen absorbing agent. [Figure 10] FIG. 10 is a diagram for explaining a specific example of the second container, and is a front view showing a combination container containing liquids. [Figure 11] 11 is a side cross-sectional view of the liquid-filled combination container shown in FIG. [Figure 12] FIG. 12 is a front view illustrating a method for manufacturing the combination liquid container shown in FIG. [Figure 13] FIG. 13 is a front view illustrating a method for manufacturing the combination liquid container shown in FIG. [Figure 14] FIG. 14 is a front view illustrating a method for manufacturing the combination liquid container shown in FIG. [Figure 15A] 15A is a front view showing a modified example of the first seal portion of the second container shown in FIG. [Figure 15B] FIG. 15B is a front view showing another modified example of the first seal portion shown in FIG. [Figure 15C] 15C is a front view showing yet another modified example of the first seal portion shown in FIG. [Figure 15D] FIG. 15D is a front view showing yet another modified example of the first seal portion shown in FIG. [Figure 16] FIG. 16 is a front view showing a modified example of the auxiliary seal portion of the second container shown in FIG. [Figure 17] FIG. 17 is a side cross-sectional view showing a modification of the liquid-containing combination container shown in FIG. [Figure 18] FIG. 18 is a perspective view showing a method for manufacturing the liquid-filled combination container shown in FIG. [Figure 19] FIG. 19 is a front view showing a modification of the seal portion of the second container shown in FIG. 10, in which a notch is provided. [Figure 20] FIG. 20 is a front view showing a modification of the second container shown in FIG. 10, in which an additional seal portion is provided. [Figure 21] FIG. 21 is a diagram illustrating a method for opening the second container shown in FIG. [Figure 22] FIG. 22 is a front view showing a modified example of the additional seal portion shown in FIG. [Figure 23] FIG. 23 is a front view showing another modified example of the additional seal portion shown in FIG. [Figure 24] FIG. 24 is a front view showing yet another modified example of the additional seal portion shown in FIG. [Figure 25] FIG. 25 is a front view showing another modified example of the liquid-containing combination container shown in FIG. [Figure 26A] FIG. 26A is a diagram showing an example of a layer structure of a laminate that can be used for a second container as a film container. [Figure 26B] FIG. 26B is a diagram showing another example of the layer structure of a laminate that can be used for the second container as a film container. [Figure 26C] FIG. 26C is a diagram showing yet another example of the layer structure of a laminate that can be used for the second container as a film container. [Figure 26D] FIG. 26D is a diagram showing still another example of the layer structure of a laminate that can be used for the second container as a film container. [Figure 26E] FIG. 26E is a diagram showing still another example of the layer structure of a laminate that can be used for the second container as a film container. [Figure 26F] FIG. 26F is a diagram showing yet another example of the layer structure of a laminate that can be used for the second container as a film container. DETAILED DESCRIPTION OF THE INVENTION

[0016] An embodiment of the present disclosure relates to the following [1] to

[42] .

[0017] [1] A first container that contains a liquid and has oxygen permeability; a second container that houses the first container and has oxygen barrier properties; the second container includes a laminate; The laminate includes an inner surface facing the storage space of the second container and an outer surface opposite to the inner surface, The laminated body includes, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

[0018] [2] The liquid-filled combination container according to [1], wherein the resin layer contains a thermoplastic resin.

[0019] [3] The liquid-filled combination container according to [1] or [2], wherein the resin layer is a stretched film.

[0020] [4] The liquid-filled combination container according to any one of [1] to [3], wherein the resin layer has a thickness of 5 μm or more.

[0021] [5] The laminate further includes a first adhesive layer located between the first barrier layer and the resin layer, and a second adhesive layer located between the resin layer and the second barrier layer; The liquid-filled combination container according to any one of [1] to [4], wherein the first adhesive layer and the second adhesive layer contain a cured product of a curable resin composition.

[0022] [6] The liquid-filled combination container according to [5], wherein the first adhesive layer is in contact with the resin layer.

[0023] [7] The liquid-filled combination container according to [5], wherein the first adhesive layer is in contact with the first barrier layer and the resin layer.

[0024] [8] The laminate further includes a first barrier substrate in contact with the first barrier layer; The liquid-filled combination container of [6] or [7], wherein the first barrier layer is located between the first adhesive layer and the first barrier substrate.

[0025] [9] The liquid-filled combination container according to any one of [5] to [8], wherein the second adhesive layer is in contact with the resin layer.

[0026]

[10] The liquid-filled combination container according to any one of [5] to [8], wherein the second adhesive layer is in contact with the second barrier layer and the resin layer.

[0027]

[11] The laminate further includes a second barrier substrate in contact with the second barrier layer; The liquid-filled combination container according to

[10] , wherein the second barrier layer is positioned between the second adhesive layer and the second barrier substrate.

[0028]

[12] The liquid-filled combination container according to any one of [1] to

[11] , wherein the first barrier layer is a transparent vapor-deposited film, and the second barrier layer is a transparent vapor-deposited film.

[0029]

[13] The liquid-filled combination container according to any one of [1] to

[12] , wherein the resin layer contains polyamide.

[0030]

[14] The laminate further includes a second resin layer and a third barrier layer, The liquid-filled combination container according to any one of [1] to

[13] , wherein the second barrier layer, the second resin layer, and the third barrier layer are arranged in this order from the inner surface toward the outer surface.

[0031]

[15] The oxygen permeability of the laminate is 0.20 mL / (m 2 A liquid-containing combination container of any of [1] to

[14] , which has a temperature of 100°C (320°F) or less (×day×atm).

[0032]

[16] The liquid-filled combination container according to any one of [1] to

[15] , further comprising an oxygen absorber that absorbs oxygen in the second container.

[0033]

[17] The liquid-filled combination container according to any one of [1] to

[16] , further comprising an oxygen detector for detecting the oxygen state in the second container.

[0034]

[18] A first container that contains a liquid and is oxygen permeable; a second container that houses the first container and has oxygen barrier properties; an oxygen absorbing member housed in the second container, the oxygen absorbing member includes an oxygen absorber that absorbs oxygen in the second container, the second container includes a first film and a second film that accommodates the first container between the first film and the second film; the first film and the second film are joined at a seal portion in a peelable manner, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, A liquid-filled combination container, wherein the first container is positioned between the first seal portion and the oxygen absorbing member in a direction in which the first seal portion and the first container face each other.

[0035]

[19] The first container includes a container body including an opening and a plug that closes the opening, the plug is oxygen permeable; The liquid-filled combination container of

[18] , wherein the container body faces the first seal portion and the stopper faces the oxygen absorbing member.

[0036]

[20] The first container includes a container body including an opening and a plug that closes the opening, the plug is oxygen permeable; The liquid-filled combination container of

[18] , wherein the stopper faces the first seal portion and the container body faces the oxygen absorbing member.

[0037]

[21] The seal portion includes a first side seal portion connected to one end of the first seal portion and a second side seal portion connected to the other end of the first seal portion, a space for accommodating the first container is formed between the first side seal portion and the second side seal portion; a notch is provided in at least one of the first side seal portion and the second side seal portion; The combination liquid-filled container according to any one of

[18] to

[20] , wherein the second container can be opened by cutting the first film and the second film starting from the notch.

[0038]

[22] The first film and the second film have a planned opening portion that is planned to be cut starting from the notch, The liquid-containing combination container

[21] , wherein the intended opening portion is located between the oxygen absorbing member and the first container.

[0039]

[23] The first film and the second film each include a main portion that forms a space for accommodating the first container, and an extension portion that is connected to the main portion; A liquid-filled combination container according to any one of

[18] to

[22] , wherein the sealing portion includes a main sealing portion that partitions the space that accommodates the first container, and an auxiliary sealing portion that joins the first film and the second film in the extension portion.

[0040]

[24] The main seal portion includes the first seal portion, a first side seal portion connected to one end of the first seal portion, and a second side seal portion connected to the other end of the first seal portion, The liquid-filled combination container of

[23] , wherein the auxiliary seal portion includes a first auxiliary seal portion connected to the first side seal portion and a second auxiliary seal portion connected to the second side seal portion.

[0041]

[25] The liquid-filled combination container according to

[23] , wherein the auxiliary seal portion is spaced apart from the main seal portion.

[0042]

[26] The main seal portion includes the first seal portion, a first side seal portion connected to one end of the first seal portion, and a second side seal portion connected to the other end of the first seal portion,

[25] A liquid-filled combination container, wherein the auxiliary seal portion includes a first auxiliary seal portion located on an extension line of the first side seal portion and a second auxiliary seal portion located on an extension line of the second side seal portion.

[0043]

[27] A liquid-filled combination container according to any one of

[18] to

[26] , wherein the sealing portion includes a first side sealing portion connected to one end of the first sealing portion, a second side sealing portion connected to the other end of the first sealing portion, and an additional sealing portion positioned between at least one of the first side sealing portion and the second side sealing portion and the first container.

[0044]

[28] The liquid-filled combination container of

[27] , wherein the additional seal portion includes a first additional side seal portion positioned between the first side seal portion and the first container, and a second additional side seal portion positioned between the second side seal portion and the first container.

[0045]

[29] The liquid-filled combination container of

[27] , wherein the additional seal portion is connected to at least one of the first side seal portion and the second side seal portion.

[0046]

[30] A liquid-filled combination container according to any one of

[27] to

[29] , wherein, in the direction in which the first seal portion and the first container face each other, the end of the first container on the side of the first seal portion is located at the same position as the end of the additional seal portion on the side of the first seal portion, or at a position closer to the first seal portion than the end of the additional seal portion on the side of the first seal portion.

[0047]

[31] A liquid-filled combination container according to any one of

[27] to

[30] , wherein the inner edge of the additional seal portion facing the first container moves away from at least one of the first side seal portion and the second side seal portion as it approaches the first seal portion in the direction in which the first seal portion and the first container face each other.

[0048]

[32] The second container is bent with the second film on the inside, and a first portion of the second container accommodating the first container and a second portion of the second container overlap each other, the second portion is located on one side of the first portion in a direction in which the first seal portion and the first container face each other when the second container is in an unfolded state before being bent; The combination liquid container of any one of

[18] to

[31] , wherein the oxygen absorbing member is bent together with the second container so that the middle portion of the oxygen absorbing member is positioned on the top of the bent portion of the second film.

[0049]

[33] The liquid-filled combination container according to

[32] , further comprising an oxygen detector positioned between the oxygen absorbing member and the first film.

[0050]

[34] The second container is further bent with the second film on the inside, and the first portion and the third portion of the second container overlap each other. the third portion is located on the other side of the first portion in a direction in which the first seal portion and the first container face each other when the second container is in an unfolded state before being bent; The liquid-containing combination container of

[32] or

[33] , wherein the first part, the third part, and the second part are stacked in this order.

[0051]

[35] Further comprising an outer box for housing the second container; the first container includes a container body including an opening and a plug that closes the opening, the plug is oxygen permeable; the second container accommodates the first container and the oxygen absorbing member such that one of the stopper and the container body is adjacent to the first seal portion and the other of the stopper and the container body is adjacent to the oxygen absorbing member; The second container is bent with the second film on the inside, and a first portion of the second container that accommodates the first container and a second portion of the second container overlap with each other. The second container is further bent with the second film on the inside, and the first portion and the third portion of the second container overlap each other. the second portion is located on one side of the first portion in a direction in which the first seal portion and the first container face each other when the second container is in an unfolded state before being bent; the third portion is located on the other side of the first portion in a direction in which the first seal portion and the first container face each other when the second container is in an unfolded state before being bent; The outer box includes a bottom portion, a top portion facing the bottom portion, and a side wall portion located between the bottom portion, A liquid-filled combination container according to any one of

[18] to

[34] , wherein a second container is contained in the outer box, the second container being folded so that the first part, the second part, and the third part overlap, with the container body of the first container facing the bottom of the outer box and the stopper of the first container facing the top of the outer box.

[0052]

[36] A first container containing a liquid and having oxygen permeability; a second container that houses the first container and has oxygen barrier properties; the second container includes a first film and a second film that accommodates the first container between the first film and the second film; the first film and the second film are joined at a seal portion in a peelable manner, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, The sealing portion further includes a first side sealing portion connected to one end of the first sealing portion, a second side sealing portion connected to the other end of the first sealing portion, and an additional sealing portion positioned between at least one of the first side sealing portion and the second side sealing portion and the first container.

[0053]

[37] A method for manufacturing a liquid-filled container using any one of the liquid-filled combination containers [1] to

[36] , closing the second container containing the first container; and adjusting the oxygen concentration by absorbing oxygen in the second container with an oxygen scavenger, A method for manufacturing a liquid-filled container, wherein, in the step of adjusting the oxygen concentration, oxygen in the first container passes through the first container, moves out of the first container, and is absorbed by the oxygen absorber in the second container.

[0054]

[38] a first container for containing a liquid; a second container that accommodates the first container, the first container is oxygen permeable; the second container has oxygen barrier properties, the second container includes a laminate; The laminate includes an inner surface facing the storage space of the second container and an outer surface opposite to the inner surface, The container set, wherein the laminate includes, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

[0055]

[39] a first container for containing a liquid; a second container that accommodates the first container; an oxygen absorbing member accommodated in the second container, the first container is oxygen permeable; the second container has oxygen barrier properties, the oxygen absorbing member includes an oxygen absorber that absorbs oxygen in the second container, the second container includes a first film and a second film that accommodates the first container between the first film and the second film; the first film and the second film are joined at a seal portion in a peelable manner, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, A container set, wherein the first container is positioned between the first seal portion and the oxygen absorbing member in a direction in which the first seal portion and the first container face each other.

[0056]

[40] a first container for containing a liquid; a second container that accommodates the first container, the first container is oxygen permeable; the second container has oxygen barrier properties, the second container includes a first film and a second film that accommodates the first container between the first film and the second film; the first film and the second film are joined at a seal portion in a peelable manner, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, The container set, wherein the sealing portion further includes a first side sealing portion connected to one end of the first sealing portion, a second side sealing portion connected to the other end of the first sealing portion, and an additional sealing portion positioned between at least one of the first side sealing portion and the second side sealing portion and the first container.

[0057]

[41] A laminated body is provided. The container, wherein the laminate includes, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

[0058]

[42] A laminate for use in a container, A laminate comprising, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

[0059] An embodiment of the present invention will be described below with reference to the drawings. In the drawings accompanying this specification, the scale and aspect ratios have been appropriately changed and exaggerated from those of the actual objects for the sake of ease of illustration and understanding. Configurations shown in some drawings may be omitted in other drawings.

[0060] In this specification, terms that specify shapes, geometric conditions, and their degrees, such as "parallel," "orthogonal," and "identical," as well as values of lengths and angles, are not limited to their strict meanings, but are interpreted to include a range within which similar functions can be expected.

[0061] "Restraint" means to restrain something from happening or occurring, or to prevent something from happening or occurring. "Restraint" does not only mean to completely prevent something from happening or occurring, but also to reduce the possibility of something happening or occurring, or to make something less likely to happen or occur.

[0062] In this specification, when multiple upper limit candidates and multiple lower limit candidate values are listed for a certain parameter, the numerical range of the parameter may be constructed by combining any one upper limit candidate with any one lower limit candidate. As an example, consider the following statement: "Parameter B may be greater than or equal to A1, greater than or equal to A2, or greater than or equal to A3. Parameter B may be less than or equal to A4, less than or equal to A5, or less than or equal to A6." In this example, the numerical range of parameter B may be greater than or equal to A1 and less than or equal to A4, greater than or equal to A1 and less than or equal to A5, greater than or equal to A1 and less than or equal to A6, greater than or equal to A2 and less than or equal to A4, greater than or equal to A2 and less than or equal to A5, greater than or equal to A2 and less than or equal to A6, greater than or equal to A3 and less than or equal to A4, greater than or equal to A3 and less than or equal to A5, or greater than or equal to A3 and less than or equal to A6.

[0063] 1 to 26F are diagrams illustrating one embodiment of the present disclosure. A container set 20 includes a first container 30 and a second container 40. A liquid-filled first container 30L includes a first container 30 and a liquid L contained in the first container 30. The liquid-filled first container 30L is also referred to as a liquid-filled container. The first container 30 has oxygen permeability. The first container 30 includes at least a partial oxygen-permeable portion. The second container 40 has oxygen barrier properties. The second container 40 is capable of containing the liquid-filled first container 30L. A liquid-filled combination container 10L includes a liquid-filled first container 30L and a second container 40, and the liquid-filled first container 30L is contained in the second container 40. With this liquid-filled combination container 10L, by adjusting the oxygen concentration in the second container 40, not only the oxygen concentration in the first container 30 but also the amount of dissolved oxygen in the liquid L can be adjusted. The oxygen-permeable first container 30 is an airtight container.

[0064] An airtight container is one that does not detect any gas leakage using the liquid immersion method specified in JIS Z 2330:2012. More specifically, a container that prevents the leakage of air bubbles when immersed in water is considered airtight. Furthermore, an airtight container is considered to be in an airtight state if no air bubbles are detected when immersed in water. In the liquid immersion test, the container to be tested 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 for 10 minutes.

[0065] Each component of the liquid-containing combination container 10L will be described in more detail with reference to the illustrated specific example. First, the liquid-containing first container 30L will be described.

[0066] As described above, the liquid-filled first container 30L includes the first container 30 and the liquid L contained in the first container 30. The first container 30 is oxygen permeable. On the other hand, the first container 30 can seal the liquid L. In other words, the first container 30 is permeable to oxygen but impermeable to the liquid L.

[0067] The liquid L contained in the first container 30 is not particularly limited. The liquid 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. The liquid is not limited to a liquid in the strict sense. The liquid may be a suspension in which solid particles are dispersed. The liquid L as food may be tea, coffee, black tea, soup, broth, stock, or a concentrated liquid obtained by concentrating one or more of these. The liquid as medicine may be an oral medicine, an external medicine, or an injection. The liquid L may be something other than a food or medicine. The liquid L may be blood or a bodily fluid.

[0068] The interior of the first container 30 may be sterile. The liquid L may be a liquid that must be maintained in a sterile state. Examples of liquids L that must be maintained in a sterile state include highly sensitive liquids such as foods and pharmaceuticals. Highly sensitive liquids L are susceptible to deterioration due to post-sterilization (also known as terminal sterilization) performed after production. Post-sterilization is not applicable to highly sensitive liquids. Examples of post-sterilization include high-pressure steam, dry heat, radiation, ethylene oxide gas, and hydrogen peroxide gas plasma. In this specification, a highly sensitive liquid L refers to a liquid in which post-sterilization of the liquid L results in decomposition of 5% or more by weight of all active ingredients contained in the liquid, and in which post-sterilization of one or more active ingredients contained in the liquid results in decomposition of 1% or more by weight. A highly sensitive liquid L to which post-sterilization is not applicable can be produced using a production line arranged in a sterile environment. That is, a highly sensitive liquid L can be produced using an aseptic procedure. Examples of highly sensitive liquids L include anticancer drugs, antiviral drugs, vaccines, and antipsychotics.

[0069] To adjust the amount of oxygen in the liquid L produced by aseptic processing, the entire space in which the liquid L production line is located can be purged with an inert gas. However, filling the entire space in which the liquid L production line is located with an inert gas atmosphere requires a huge capital investment and may also raise safety concerns for workers. Due to the above background, adjustment of the amount of oxygen in the liquid L has generally been achieved by substituting the atmosphere in the first container 30 containing the liquid L with an inert gas, bubbling the liquid L with an inert gas, or the like.

[0070] In contrast, according to the invention of the present inventors described below, by storing the liquid-filled first container 30L inside the second container 40, 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. The effects resulting from the invention of the present inventors are remarkable and exceed the range predicted from the state of the art.

[0071] In addition, the product (liquid L) labeled as "sterilized" or "sterile" and the inside of the container containing said product, as well as the product (liquid L) such as pharmaceuticals for which "sterility" is a condition for commercialization and the inside of the container containing said product, fall under the category of "sterile state" as used in this specification. -6 The product (liquid L) that fills the container and the inside of the container that holds the product also fall under the "sterile state" as used in this specification. A product that does not grow bacteria when stored at room temperature (e.g., 20°C) or higher for four weeks and the inside of a container that holds the product also fall under the "sterile state" as used in this specification. A product that does not grow bacteria when stored in a refrigerated state (e.g., 8°C or lower) for eight weeks or more and the inside of a container that holds the product also fall under the "sterile state" as used in this specification. A drug that does not grow bacteria when stored at a temperature between 28°C and 32°C for two weeks and the inside of a container that holds the drug also fall under the "sterile state" as used in this specification.

[0072] The following describes the first container 30 that contains the liquid L. As described above, the first container 30 can seal the liquid L. That is, the first container 30 can hold the liquid L without leakage.

[0073] The first container 30 has oxygen permeability. The term "oxygen permeable" means that oxygen can permeate the container at a predetermined oxygen permeation rate or more in an atmosphere at a temperature of 23°C and a humidity of 40% RH, and move between the inside and outside of the container. The predetermined oxygen permeation rate is 1×10 -1The predetermined oxygen permeation rate may be 1 (mL / (day×atm)) or more, 1.2 (mL / (day×atm)) or more, or 3 (mL / (day×atm)) or more. With an oxygen-permeable first container 30, the amount of oxygen in the first container 30 can be adjusted by oxygen permeation through the first container 30.

[0074] An upper limit may be set for the amount of oxygen that permeates the first container 30. Setting an upper limit can prevent water vapor and the like from leaking from the first container 30. Setting an upper limit can prevent the liquid L in the first container 30 from being affected by a high gas permeation rate after the second container 40 is opened. The amount of oxygen that permeates the first container 30 may be 100 (mL / (day×atm)) or less, 50 (mL / (day×atm)) or less, or 10 (mL / (day×atm)) or less.

[0075] Any of the above-mentioned lower limits of oxygen transmission rate may be combined with any of the above-mentioned upper limits of oxygen transmission rate to define a range of oxygen transmission rates.

[0076] All gases may be permeable through the first container 30. Alternatively, only some gases including oxygen, for example, only oxygen, may be permeable through the first container 30.

[0077] The first container 30 may have oxygen permeability by being permeable to oxygen throughout the entire first container 30. The first container 30 may have oxygen permeability by being permeable to oxygen only through a portion of the first container 30.

[0078] The oxygen permeability coefficient of the material constituting the oxygen-permeable portion of the first container 30 is 1×10 -12 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or more is acceptable, and 5×10 -12 (cm 3 (STP)·cm / (cm 2 sec Pa)) or more, and 1 × 10 -11 (cm 3(STP)·cm / (cm 2 ·sec·Pa) or more. By setting a lower limit for the oxygen permeability coefficient, oxygen permeation through the first container 30 is promoted, and the oxygen concentration in the head space HS of the first container 30 can be quickly adjusted. When the oxygen-permeable part includes multiple layers, the material constituting at least one layer may have the above oxygen permeability coefficient, or the materials constituting all layers may have the above oxygen permeability coefficient. The oxygen permeability coefficient of the material constituting the oxygen-permeable part of the first container 30 is 1×10 -9 (cm 3 (STP)·cm / (cm 2 ·sec·Pa) or less may also be acceptable.

[0079] The oxygen concentration (%) in the headspace HS of the first container 30 is also simply referred to as the oxygen concentration (%) in the first container 30.

[0080] When the object to be measured does not contain rubber and is not a molded container, the oxygen permeability coefficient is a value measured in accordance with JIS K7126-2:2006 using an OXTRAN 2 / 21 permeability measuring device manufactured by MOCON, USA, at a temperature of 23°C and a humidity of 50%RH. When the object to be measured falls under at least one of the following conditions: containing rubber or being a molded container, the oxygen permeability coefficient is a value measured in accordance with ASTM D3985. In this case, the oxygen permeability coefficient is a value measured in an environment of 23°C and a humidity of 50%RH using an OXTRAN 2 / 61 permeability measuring device manufactured by MOCON, USA.

[0081] The area of the oxygen permeable portion of the first container 30 is 1 mm 2 More than 10mm is fine. 2 More than 30mm is fine. 2 Similarly, the thickness of the oxygen-permeable portion of the first container 30 may be 3 mm or less, 1 mm or less, or even a few tenths of a mm or less. This promotes oxygen permeation through the first container 30, and allows the amount of oxygen in the first container 30 to be adjusted quickly.

[0082] The illustrated first container 30 includes a container body 32 with an opening 33 and a stopper 34 held in the opening 33 of the container body 32. The stopper 34 prevents leakage of the liquid L from the opening 33. In this example, the stopper 34 may be oxygen permeable. From the viewpoint of promoting the transfer of oxygen from inside the first container 30 to outside the first container 30, it is preferable that the oxygen-permeable portion of the first container 30 is not in contact with the liquid L. In a container including the container body 32 and the stopper 34, the stopper 34 is usually separated from the liquid L contained in the container body 32. In other words, oxygen permeation through the stopper 34 of the first container 30 can be promoted during normal storage of the first container 30. In this regard, imparting oxygen permeability to the stopper 34 allows the amount of oxygen in the first container 30 to be quickly adjusted.

[0083] The oxygen-permeable plug 34 has the above-mentioned oxygen permeability coefficient (cm 3 (STP)·cm / (cm 2 The stopper 34 may be formed of a material having a permeability of 0.1 mbar (MPa) or less (MPa). The oxygen permeability coefficient of the material forming the stopper 34 may be greater than the oxygen permeability coefficient of the material forming the container body 32. A portion of the stopper 34 may be oxygen permeable. A portion of the stopper 34 may be made of a material having oxygen permeability throughout its entire thickness. For example, the stopper 34 may have oxygen permeability throughout its entire thickness in a central portion spaced from the periphery, and have oxygen barrier properties in a peripheral portion surrounding the central portion.

[0084] For example, the configuration of the oxygen-permeable portion of the first container may be determined so that storing a first container 30 containing a liquid with an oxygen dissolution rate of 8 mg / L in the second container 40 for four weeks can reduce the oxygen concentration (%) in the first container 30 by 5% or more.

[0085] In the illustrated example, the area of the opening 33, i.e., the opening area of the container body 32, is 1 mm 2 More than 10mm is fine. 2 More than 30mm is fine. 2The thickness of the stopper 34 may be 3 mm or less, or 1 mm or less. This promotes oxygen permeation through the first container 30, allowing the oxygen concentration inside the first container 30 to be adjusted quickly. The stopper 34 can be pierced with a syringe needle. Furthermore, from the viewpoint of being able to be pierced with a straw, the thickness of the stopper, for example, the thickness of a film-like stopper, may be a few tenths of a millimeter or less.

[0086] From the viewpoint of suppressing the leakage of water vapor and the like, and from the viewpoint of suppressing the influence on the liquid in the first container 30 due to the high gas permeation rate after the second container 40 is opened, an upper limit may be set on the area of the opening 33. Specifically, the area of the opening 33 may be set to 5000 mm 2 From the viewpoint of ensuring strength, the thickness of the stopper, for example, the thickness of a rubber stopper, may be 0.01 mm or more.

[0087] The oxygen-permeable plug 34 is not particularly limited and may have various configurations. In the illustrated example, the plug 34 is inserted into the opening 33 of the container body 32 to close the opening 33. The plug 34 shown in FIG. 2A includes a plate-shaped plate portion 34a and an insertion protrusion 34b extending from the plate portion 34a. The insertion protrusion 34b is, for example, cylindrical. Multiple insertion protrusions 34b may be provided circumferentially. The insertion protrusion 34b is inserted into the opening 33. The plate portion 34a includes a flange portion extending radially outward from the insertion protrusion 34b. The flange portion of the plate portion 34a is placed on the head 32d of the container body 32. The plug 34 may include an external spiral or an internal spiral. The plug 34 may be attached to the container body 32 by interlocking spirals.

[0088] The stopper 34 may contain silicone. The stopper 34 may be formed only from silicone. A portion of the stopper 34 may be formed from silicone. The silicone contained in the stopper 34 is solid in the environment in which the first container 30 is intended to be used. The silicone contained in the stopper 34 does not need to contain silicone that becomes liquid at room temperature, such as silicone oil. Silicone is a substance whose main chain is a siloxane bond. The stopper 34 may be formed from a silicone elastomer. The stopper 34 may be formed from silicone rubber.

[0089] Silicone rubber refers to a rubber-like material made of silicone. Silicone rubber is a synthetic resin whose main component is silicone, and is a rubber-like substance. Silicone rubber is a rubber-like substance whose main chain is a siloxane bond. Silicone rubber may be a thermosetting compound containing a siloxane bond. Examples of silicone rubber include methyl silicone rubber, vinyl-methyl silicone rubber, phenyl-methyl silicone rubber, dimethyl silicone rubber, and fluorosilicone rubber.

[0090] The oxygen permeability coefficient of silicone and silicone rubber is 1 x 10 -12 (cm 3 (STP)·cm / (cm 2 sec Pa)) or more, and 1 × 10 -11 (cm 3 (STP)·cm / (cm 2 ·sec·Pa) or more. The oxygen permeability coefficient of silicone and the oxygen permeability coefficient of silicone rubber are 1×10 -9 (cm 3 (STP)·cm / (cm 2 ·sec·Pa) or less. Compared to natural rubber, silicone and silicone rubber have a hydrogen permeability coefficient that is about 10 times higher, an oxygen permeability coefficient that is about 20 times higher, and a nitrogen permeability coefficient that is about 30 times higher. Compared to butyl rubber, silicone and silicone rubber have a hydrogen permeability coefficient that is 70 times higher, an oxygen permeability coefficient that is 40 times higher, and a nitrogen permeability coefficient that is 650 times higher.

[0091] At least a portion of the plug 34 may be made of silicone. That is, the entirety or a portion of the plug 34 may be made of silicone or silicone rubber. For example, a portion of the plug 34 may be made of silicone or silicone rubber over its entire thickness. The portion may be the central portion of the plug 34, or a part or all of the peripheral portion surrounding the central portion.

[0092] As shown in Fig. 2A, the container body 32 may include a bottom 32a, a body 32b, a neck 32c, and a head 32d, in this order. As shown in Fig. 2A, the bottom 32a and the body 32b mainly form a storage space for the liquid L. 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 has a narrower width, particularly a narrower diameter, than the body 32b and the head 32d.

[0093] The container body 32 may include a transparent portion so that the contained liquid L can be observed from the outside. "Transparent" means that the transmission haze of the target portion is 80.0 or less.

[0094] A light source that mimics the spectrum of D65 standard light (hereafter referred to as the D65 standard light source) is used to measure transmission haze. Before measuring transmission haze, the D65 standard light source is turned on for 15 minutes to stabilize the output of the D65 standard light source. When measuring transmission haze, the angle of incidence on the sample is set to 0°. The test environment for measuring transmission haze is a temperature of 23°C ± 2°C and a relative humidity of 50% ± 5%. The sample is placed in the test environment for 16 hours before starting the test. Other measurement conditions for measuring transmission haze are in accordance with JIS K7136:2000. Transmission haze is the arithmetic mean of five measured values. The five measured values are measured at five measurement positions on the measurement sample to be evaluated.

[0095] The illustrated first container 30 further includes 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 FIGS. 1 and 2A, 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 toward the head 32d. This prevents the stopper 34 from coming off the container body 32 while leaving a portion of the stopper 34 exposed. In addition, the fastener 36 can maintain a liquid-tight and airtight relationship between the stopper 34 and the container body 32. The fastener 36 keeps the first container 30 airtight. The fastener 36 may be a sheet metal fixed to the head 32d. The fastener 36 may be a cap screwed onto the head 32d. The metal fastener 36 has oxygen barrier properties.

[0096] In the illustrated example, the oxygen permeability coefficient of the material constituting the container body 32 may be smaller than the oxygen permeability coefficient of the material constituting the stopper 34. The container body 32 may have oxygen barrier properties. That is, the first container 30 may have oxygen permeability only in a portion thereof. The oxygen permeability coefficient of the material constituting the portion having oxygen barrier properties is 1×10 -13 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or less is also acceptable, and 1×10 -17 (cm 3 (STP)·cm / (cm 2 ·sec·Pa) or less may also be acceptable.

[0097] Examples of the container body 32 having oxygen barrier properties include a can made of metal, a container body including a metal layer formed by vapor deposition or transfer, and a glass bottle. Oxygen barrier properties can also be imparted to a container body 32 made using a resin sheet or resin plate. In this example, the resin sheet or resin plate may include a layer having oxygen barrier properties, such as an ethylene-vinyl alcohol copolymer (EVOH) or polyvinyl alcohol (PVA). The container body 32 may also include a laminate including a metal vapor deposition film or a metal oxide vapor deposition film. A container body 32 made of a laminate or glass can be imparted with transparency as well as oxygen barrier properties. When the first container 30 or the container body 32 is transparent, the liquid L contained therein can be confirmed from the outside of the first container 30.

[0098] A portion of a container having oxygen permeability means that oxygen can pass through the portion of the container at a predetermined oxygen permeation rate or more in an atmosphere at a temperature of 23°C and a humidity of 40%RH, and move between the inside and outside of the container. The predetermined oxygen permeation rate is 1×10 -1 The predetermined oxygen transmission rate may be 1 (mL / (day×atm)) or more, 1.2 (mL / (day×atm)) or more, or 3 (mL / (day×atm)) or more. The amount of oxygen in the first container 30 can also be adjusted by making a portion of the first container 30 oxygen permeable.

[0099] The predetermined oxygen transmission rate 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 transmission rate, it is possible to suppress leakage of water vapor and the like, and to suppress the effect on the liquid in the first container 30 after the second container 40 is opened due to a high oxygen transmission rate. The range of the oxygen transmission rate may be determined by combining any of the above-mentioned lower limits of the oxygen transmission rate with any of the above-mentioned upper limits of the oxygen transmission rate.

[0100] The oxygen permeation rate (mL / (day×atm)) through a portion of a container is measured using a test container 70 that includes the portion, as shown in FIG. 2B. The test container 70 includes a partition wall 71. The test container 70 includes an internal space defined 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 permeation rate through the portion of the container is specified as the oxygen permeation rate (mL / (day×atm)) of the test container 70.

[0101] The oxygen concentration in the test vessel 70 is maintained at 0.05% or less. The test vessel 70 is connected to a first flow path 76 and a second flow path 77. The second flow path 77 is connected to an oxygen measuring device 79 that measures the amount of oxygen. The oxygen measuring device 79 can measure the amount of oxygen (mL) flowing through the second flow path 77. The oxygen measuring device 79 is an oxygen measuring device used in OXTRAN (2 / 61) manufactured by MOCON, USA. The first flow path 76 supplies gas into the test vessel 70. The first flow path 76 supplies oxygen-free gas. The first flow path 76 supplies nitrogen. The second flow path 77 exhausts gas from the test vessel 70. The first flow path 76 and the second flow path 77 have oxygen barrier properties. The first flow path 76 and the second flow path 77 maintain a state in which the test vessel 70 is substantially free of oxygen.

[0102] 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 of the atmosphere in which the test container 70 is placed is higher than the oxygen concentration inside the test container 70. The test atmosphere is an air atmosphere. The oxygen concentration of the 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 passing through a portion 30X of the container. The gas inside the test container 70 is discharged through the second flow path 77. By measuring the amount of oxygen flowing through the second flow path 77 with the oxygen measuring device 79, the daily oxygen transmission rate (mL / (day×atm)) that passes through the portion 30X in an atmosphere with a temperature of 23°C and a humidity of 40% RH can be measured.

[0103] In the illustrated example, the test container 70 is placed in a test chamber 78. The atmosphere in the test chamber 78 is maintained at a temperature of 23°C and a humidity of 40% RH. Air is supplied to the test chamber 78 through a supply line 78A. The gas in the test chamber 78 is discharged through a discharge line 78B. The air is circulated through the supply line 78A and the discharge line 78B, and the oxygen concentration in the test chamber 78 is maintained at 20.95%.

[0104] In the example shown in Fig. 2B, a pump for circulating air may be provided in one of the supply line 78A and the discharge line 78B. As long as the oxygen concentration in the test chamber 78 can be maintained constant, the supply line 78A and the discharge line 78B shown in Fig. 2B may be open to an air atmosphere under atmospheric pressure.

[0105] FIG. 2B illustrates a method for measuring oxygen transmission rate using an oxygen-permeable portion 30X of the first container 30 as an example. In the example shown in FIG. 2B, a partition wall 71 is composed of the oxygen-permeable portion 30X of the first 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 first container 30 and a main wall 72 connected to a peripheral portion 30Y of the portion 30X. The main wall 72 has a through-hole 72A. The portion 30X is exposed to the through-hole 72A. In other words, the through-hole 72A is closed by the portion 30X. The area surrounding the through-hole 72A and the portion 30Y adjacent to the portion 30X are hermetically joined. In the illustrated example, the portion 30Y adjacent to the portion 30X is airtightly joined to the surrounding portion of the through-hole 72A of the main wall portion 72 via a flash-free bonding material 73 having oxygen barrier properties. In the example shown in Fig. 2B, the portion near the stopper 34 of the container set 20 shown in Fig. 2A is cut. In this example, the stopper 34 constitutes the oxygen-permeable portion 30X. The portions 32c and 32d forming the opening 33 of the container body 32 and the fastener 36 are airtightly connected to the main wall portion 72 via the barrier bonding material 73 as the portion 30Y adjacent to the oxygen-permeable portion 30X.

[0106] In the example shown in FIG. 2B , 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. A fastener 36 creates an airtight seal between the container body 32 and the stopper 34. The fastener 36, which is made of oxygen barrier material such as aluminum, partially covers the stopper 34. The container body 32 and the fastener 36, which also have oxygen barrier properties, 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 first container 30 is closed during actual use, such as being compressed within the opening 33 and being fastened by the fastener 36. Therefore, the oxygen transmission rate through the stopper 34 can be measured under conditions similar to those during actual use.

[0107] The method for measuring the oxygen permeation rate (mL / (day×atm)) through a portion of a container has been described above. The oxygen permeation rate (mL / (day×atm)) through the entire container can be determined by dividing the container into two or more portions and adding together the oxygen permeation rates measured for each portion. For example, the oxygen permeation rate of the first container 30 shown in FIG. 2A can be determined by measuring the oxygen permeation rate of the container body 32 and adding together the oxygen permeation rate of the container body 32 and the oxygen permeation rate of the portion 30X measured by the method shown in FIG. 2B. The oxygen permeation rate (mL / (day×atm)) of the container body 32 can be measured using a test container 70 prepared by combining the container body 32 with a main wall portion 72.

[0108] The volume of the first 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.

[0109] In the illustrated example, the container body 32 is a colorless or colored glass bottle. The container body 32 is formed, for example, from borosilicate glass. The first container 30 may also be a vial. A vial is a container that includes a container body, a stopper inserted into the opening of the container body, and a seal as a fastener 36 for fixing the stopper. 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 first container 30, which is a vial, may be 1 mL or more, or 3 mL or more. The volume of the first container 30, which is a vial, may be 500 mL or less, or 200 mL or less.

[0110] When the first container 30 is a vial, the oxygen permeability coefficient of the material making up the stopper 34 may be greater than the oxygen permeability coefficient of the glass making up the container body 32. By separating the oxygen-permeable portion of the first container 30 from the liquid L, the movement of oxygen from inside the first container 30 to outside the first container 30 can be promoted. The first container 30, which is a vial, can be stably placed on a mounting surface by bringing the bottom 32a of the container body 32 into contact with the mounting surface. At this time, the stopper 34 is separated from the liquid L. The stopper 34 does not come into contact with the liquid L. Therefore, oxygen permeation through the stopper 34 of the first container 30 can be promoted when the first container 30 is normally stored.

[0111] The illustrated first container 30 can maintain a negative internal pressure under atmospheric pressure. The first container 30 can contain a gas while maintaining the gas at a negative pressure under atmospheric pressure. The first container 30 may also be able to contain a gas while maintaining the gas at a positive pressure under atmospheric pressure. In these examples, the first container 30 may have sufficient rigidity to maintain its shape. However, the first container 30 may deform somewhat under atmospheric pressure when maintaining a negative or positive internal pressure. Examples of first containers 30 that can maintain a negative or positive internal pressure include the above-mentioned vials and cans made of metal.

[0112] Being able to store a gas at a negative pressure under atmospheric pressure means being able to store the gas without breaking even when the internal pressure is maintained at a negative pressure of 0.80 atm or more. A container capable of storing a gas at a negative pressure under atmospheric pressure may be airtight when the internal pressure is 0.80 atm. A container capable of storing a gas at a negative pressure under atmospheric pressure may be able to maintain a volume at an internal pressure of 0.80 atm that is 95% or more of the volume at an internal pressure of 1.0 atm. Being able to store a gas at a positive pressure under atmospheric pressure means being able to store the gas without breaking even when the internal pressure is a positive pressure of 1.2 atm or less. A container capable of storing a gas at a positive pressure under atmospheric pressure may be airtight when the internal pressure is 1.20 atm. A container capable of storing a gas at a positive pressure under atmospheric pressure may be able to maintain a volume at an internal pressure of 1.2 atm that is 105% or less of the volume at an internal pressure of 1.0 atm.

[0113] The first container 30 is intended to be housed within a second container 40 that has oxygen barrier properties. The first container 30 housed within the second container 40 may be able to house gas without breaking when the difference in internal pressure between the first container 30 and the second container 40 is 0.2 atm or less. The first container 30 housed within the second container 40 may be airtight when the difference in internal pressure between the first container 30 and the second container 40 is 0.2 atm or less. When the difference in internal pressure between the first container 30 and the second container 40 is 0.2 atm or less, the first container 30 housed within the second container 40 may have a volume that is 95% to 105% of the volume of the first container 30 when the internal pressure of the first container 30 is the same as the internal pressure of the second container 40. In these states where the first container 30 is housed in the second container 40, the internal pressure of the first container 30 may be lower than the internal pressure of the second container 40, or the internal pressure of the first container 30 may be higher than the internal pressure of the second container 40.

[0114] The second container 40 has a volume sufficient to accommodate the first container 30. The second container 40 can be sealed by welding, such as heat sealing or ultrasonic bonding, or by bonding using a bonding material, such as an adhesive or glue. The second container 40 may be an airtight container. The volume of the second container 40 may be, for example, 5 mL or more and 1200 mL or less. When the first 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 second container may be 1.5 mL or more and 500 mL or less.

[0115] The second container 40 has oxygen barrier properties. The second container 40 has oxygen barrier properties when the oxygen permeability (mL / (m 2 × day × atm) is 1 or less. 2 The oxygen permeability (day × day × atm) may be 0.5 or less, or 0.1 or less. When the object to be measured does not contain rubber and is not a molded container, the oxygen permeability is a value measured in accordance with JIS K7126-2:2006 using an OXTRAN 2 / 21 permeability measuring device manufactured by MOCON, USA, at a temperature of 23°C and a humidity of 50%RH. When the object to be measured falls under at least one of the following conditions: containing rubber or being a molded container, the oxygen permeability is a value measured in accordance with ASTM D3985. In this case, the oxygen permeability is a value measured in an environment of 23°C and a humidity of 50%RH using an OXTRAN 2 / 61 permeability measuring device manufactured by MOCON, USA.

[0116] The oxygen permeability coefficient of the material constituting the second container 40 having oxygen barrier properties is 1×10 -13 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or less is also acceptable, and 1×10 -17 (cm 3 (STP)·cm / (cm 2 ·sec·Pa) or less may also be acceptable.

[0117] Examples of the second container 40 having oxygen barrier properties include a can made of metal, a container having a metal layer formed by vapor deposition or transfer, and a glass bottle. The second container 40 may include a laminate including a layer having oxygen barrier properties. The laminate may include a resin layer having oxygen barrier properties, such as ethylene-vinyl alcohol copolymer (EVOH) or polyvinyl alcohol (PVA), or a metal vapor deposition film. The second container 40 may include a transparent portion. A portion of the second container 40 may be transparent. The entire second container 40 may be transparent. A second container 40 using a laminate, or a second container 40 using glass or resin, can be imparted with transparency in addition to oxygen barrier properties. By imparting transparency to the second container 40, the liquid-filled first container 30L contained therein can be confirmed from the outside of the second container 40.

[0118] In the example shown in FIG. 1, the second container 40 is made of a resin film with oxygen barrier properties. The second container 40 is a so-called pouch. The second container 40 shown in FIG. 1 is a so-called gusset bag. The second container 40 includes a first film 41a (first main film), a second film (second main film) 41b, a first gusset film 41c, and a second gusset film 41d. The first film 41a and the second film 41b face each other. The first gusset film 41c is folded and positioned between the first film 41a and the second film 41b. The first gusset film 41c connects one side edge of the first film 41a and one side edge of the second film 41b. The second gusset film 41d is folded and positioned between the first film 41a and the second film 41b. The second gusset film 41d connects the other side edge of the first film 41a and the other side edge of the second film 41b. The first and second films 41a, 41b and the first and second gusset films 41c, 41d are also joined to each other at their upper and lower edges. The films 41a to 41d are airtightly joined, for example, by welding such as heat sealing or ultrasonic bonding, or by joining using a joining material such as an adhesive or bonding material.

[0119] In the second container 40 shown in FIG. 1, instead of joining separate films, a single folded film may form two or more adjacently arranged films 41a-41d. That is, two or more films including films 41a-41d may be formed from a single seamless film material. As shown in FIG. 1, a gusset bag can form a rectangular bottom surface of the second container 40. By placing the first container 30 on the bottom surface, the first container 30 can be stably stored in the second container 40. However, as shown in FIG. 7A, the second container 40 may include a bottom film 41e in addition to the first film 41a and the second film 41b instead of a gusset bag. This pouch is also called a standing pouch. This pouch can also form the bottom surface, allowing the first container 30 to be stably stored in the second container 40.

[0120] As shown in Figures 7B to 7D, a second container 40 that can be developed into a flat surface may be used. All of the second containers 40 shown in Figures 7B to 7D can be produced by joining resin films at a seal portion 49. The second container 40 shown in Figure 7B can be produced by joining a first film 41a and a second film 41b at a seal portion 49 provided around the periphery thereof.

[0121] The second container 40 shown in Fig. 7C has a film 41 folded at a fold 41x. The second container 40 can be produced by joining the facing portions of the folded film 41 at a seal 49. In the second container 40 shown in Fig. 7C, a storage space is formed in the area surrounded by the fold 41x and the three-sided seal 49. In the example shown in Fig. 7C, the first film 41a and the second film 41b, which form a space for storing the first container 30 between them, are made of a single film material. There is no seam between the first film 41a and the second film 41b.

[0122] The second container 40 shown in Fig. 7D is also called a pillow-shaped container. The film 41 is formed into a cylindrical shape by joining both ends of a single film 41 together as a seal 49, and the two ends of the cylindrical shape are then further joined as a seal 49 to obtain the second container 40. In the example shown in Fig. 7D, the first film 41a and the second film 41b, which form a space between the first film 41a and the second film 41b for accommodating the first container 30, are made of a single film material. There is no seam between the first film 41a and the second film 41b.

[0123] In the various examples described above, the film forming the second container 40 may be transparent.

[0124] FIG. 8 shows another example of the second container 40. As shown in FIG. 8, the second container 40 may include a container body 42 and a lid 44. The container body 42 includes a storage portion 42a and a flange portion 42b. The storage portion 42a may form a rectangular parallelepiped storage space. The first container 30 is stored in this storage space. The storage portion 42a may have a rectangular parallelepiped outer shape with one side open. The flange portion 42b is provided on the periphery of the opening of the storage portion 42a. The lid 44 is flat. The periphery of the lid 44 can be airtightly joined to the flange portion 42b of the container body 42. The container body 42 and the lid 44 may be formed of a resin plate having oxygen barrier properties. The lid 44 and the container body 42 may be transparent. The thickness of the resin plate having oxygen barrier properties may be 0.05 mm to 2 mm or 0.1 mm to 1.5 mm.

[0125] The second container 40 shown in FIG. 8 can maintain a negative internal pressure under atmospheric pressure. The second container 40 can contain a gas while maintaining the gas at a negative pressure under atmospheric pressure. The second container 40 may also be capable of containing a gas while maintaining the gas at a positive pressure under atmospheric pressure. In these examples, the second container 40 may have sufficient rigidity to maintain its shape. However, the second container 40 may deform somewhat under atmospheric pressure when maintaining a negative or positive internal pressure. An example of the second container 40 capable of maintaining a negative or positive internal pressure is a can made of metal.

[0126] By at least partially separating the oxygen-permeable portion of the first container 30 from the second container 40, which has oxygen barrier properties, the transfer of oxygen from the first container 30 to the second container 40 can be promoted. In the example shown in FIG. 1 , a gap G is formed between the stopper 34 of the first container 30 housed in the second container 40 and the second container 40. The gap G can be ensured by making the housing space of the second container 40 larger than the outer shape of the first container 30. If the second container 40 is made of a flexible material such as a resin film, the gap G between the stopper 34 and the second container 40 can be formed by adjusting the shape of the second container 40.

[0127] The first container 30 and the second container 40 described above constitute the container set 20 and the combination container 10. The first container 30L containing liquid and the second container 40 form the combination container 10L containing liquid.

[0128] Next, a method for manufacturing the liquid-containing combination container 10L will be described. By manufacturing the liquid-containing combination container 10L, a liquid-containing first container 30L with an adjusted oxygen concentration can be obtained.

[0129] First, a first container 30L filled with liquid and a second container 40 before closing are prepared. The first container 30L filled with liquid is produced by filling the first container 30 with liquid L. For example, the liquid L, such as food or medicine, is produced using a production line installed in a sterile environment maintained at positive pressure. The sterile environment is maintained at positive pressure to prevent the intrusion of foreign matter such as bacteria. As a result, the internal pressure of the obtained first container 30L filled with liquid becomes positive, similar to the production environment.

[0130] As shown in Fig. 3, an opening 40a for accommodating a first container 30L containing liquid remains in the second container 40 before it is closed. In the second container 40 shown in Fig. 1, for example, the upper edges of the films 41a to 41d are not joined to each other to form the opening 40a. In the second container 40 shown in Fig. 8, a container body 42 is prepared without a lid 44 attached. Then, as shown in Fig. 3, the first container 30L containing liquid is accommodated in the second container 40 through the opening 40a.

[0131] Thereafter, the second container 40 is filled with an inert gas, for example, nitrogen. In the example shown in FIG. 4, the inert gas is supplied from the supply pipe 15. The supply pipe 15 passes through an opening 40a and enters the second container 40. The outlet 15a of the supply pipe 15 is located inside the second container 40. By supplying the inert gas from the supply pipe 15, the inside of the second container 40 is replaced with the inert gas. In other words, the liquid-filled first container 30L is placed in an inert gas atmosphere. The inert gas is a stable gas with low reactivity. Examples of the inert gas include rare gases such as helium, neon, and argon, and nitrogen.

[0132] It should be noted that either the filling of the second container 40 with the inert gas or the placement of the first container 30L containing the liquid in the second container 40 may be carried out first, or both may be carried out in parallel.

[0133] Next, as shown in FIG. 5, the second container 40 is closed while containing the liquid-containing first container 30L and filled with inert gas. In the second container 40 shown in FIG. 1, the second container 40 is closed by joining the upper edges of the films 41a to 41d together to close the opening 40a. In the second container 40 shown in FIG. 8, the second container 40 is closed by joining the peripheral edge of the lid 44 to the flange portion 42b of the container body 42. Joining may be performed using a joining material such as an adhesive or bonding material, or may be performed by welding using heat sealing, ultrasonic bonding, or the like. The second container 40 is now in an airtight state.

[0134] It is to be noted that the second container 40 containing the liquid-containing first container 30L may be closed under an inert gas atmosphere instead of supplying the inert gas from the supply pipe 15. This method also allows the liquid-containing first container 30L to be sealed in the second container 40 together with the inert gas.

[0135] Furthermore, the steps up to closing the second container 40 may be performed in a sterile environment. That is, the liquid-filled first container 30L, which has been manufactured in a sterile environment, and the second container 40, which has been sterilized or manufactured in a sterile environment, are brought into a sterile environment, such as a sterile chamber. If this chamber is partitioned from the air atmosphere and contains an inert gas atmosphere, the supply of inert gas through the supply pipe 15 can be omitted. Then, the second container 40 containing the liquid-filled first container 30L is closed in a sterile environment. Therefore, the inside of the second container 40 containing the liquid-filled first container 30L is also sterile. That is, the liquid-filled first container 30L can be stored in the second container 40 in a sterile environment.

[0136] The liquid-filled first container 30L is then stored in the second container 40. As described above, the second container 40 has oxygen barrier properties. Oxygen permeation through the second container 40 is effectively inhibited. The first container 30 is oxygen permeable in at least a portion. Furthermore, the second container 40 is filled with an inert gas, and the oxygen concentration in the second container 40 is very low. In this liquid-filled combination container 10L, oxygen in the first container 30 permeates the first container 30 and moves into the second container 40. As oxygen moves from the first container 30 to the second container 40, the oxygen concentration in the second container 40 increases and decreases. At a final equilibrium state where oxygen permeation through the first container 30 is balanced, the oxygen concentration in the first container 30 can match the oxygen concentration in the second container 40.

[0137] In addition, when the oxygen concentration in the first container 30 decreases, the oxygen partial pressure in the first container 30 decreases. When the oxygen partial pressure in the first container 30 decreases, the saturated solubility (mg / L) of oxygen in the liquid L in the first container 30 also decreases. As a result, the amount of oxygen dissolved in the liquid L (mg / L) decreases.

[0138] As described above, by storing the liquid-containing first container 30L in the second container 40, it is possible to reduce the oxygen concentration (%) of the gas stored together with the liquid in the first container 30. In addition, it is possible to reduce the amount of oxygen (mg / L) dissolved in the liquid L in the first container 30. For example, by storing the liquid-containing first container 30L in the second container 40 before use, it is possible to reduce the amount of oxygen (mg / L) dissolved in the liquid L in the first container 30.

[0139] Highly sensitive liquids L, such as food and medicines, can be decomposed by oxygen. For example, solutes in an aqueous solution of medicine can be decomposed by oxygen. Solutes in a liquid as a medicine or an aqueous solution of medicine can be decomposed by oxygen. Particles dispersed in a liquid suspension of medicine or food can be decomposed by oxygen. On the other hand, by storing the liquid L in the first container 30 placed inside the second container 40, decomposition of the liquid L by oxygen can be suppressed. In other words, this embodiment, in which the oxygen concentration in the first container 30 can be adjusted after the liquid L is sealed, is suitable for highly sensitive liquids L, such as food and medicines.

[0140] Instead of or in addition to filling the second container 40 with an inert gas when the second container 40 is closed, an oxygen absorber 21 may be provided to absorb oxygen in the second container 40. The oxygen absorber 21 absorbs oxygen, thereby reducing the oxygen concentration in the second container 40 and transferring oxygen from the first container 30 to the second container 40. By using the oxygen absorber 21, the oxygen concentrations in the second container 40 and the first container 30 can be more effectively reduced. The present inventors have confirmed that by using a sufficient amount of oxygen absorber 21, the oxygen concentrations in the second container 40 and the first container 30 can be maintained low, for example, below 0.3%, 0.1% or less, 0.05% or less, less than 0.03%, or even 0%. Furthermore, the reduction in the oxygen concentration in the first container 30 also reduces the amount of oxygen dissolved in the liquid L contained in the first container 30. The present inventors 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 can be maintained at, for example, less than 0.15 mg / L, 0.04 mg / L or less, 0.03 mg / L or less, 0.02 mg / L or less, less than 0.015 mg / L, or even 0 mg / L.

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

[0142] The oxygen absorber 21 is not particularly limited as long as it is a composition capable of absorbing oxygen. Iron-based or non-iron-based oxygen absorbers can be used as the oxygen absorber 21. For example, oxygen absorber compositions containing 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 as the main components of the oxygen absorption reaction may be used as the oxygen absorber. As shown in FIGS. 1 and 8, the combination container 10 may include an oxygen absorbing member 22 housed in a second container 40 together with a liquid-containing first container 30L. As shown in FIG. 9A, the oxygen absorbing member 22 may include an oxygen-permeable packaging body 22a and an oxygen absorber 21 housed in the packaging body 22a. The deoxidizing member 22 containing the deoxidizing agent 21 may be an iron-based moisture-dependent FX type, an iron-based self-reacting S type, SPE type, ZP type, ZI-PT type, ZJ-PK type, or E type, all of which are available from Mitsubishi Gas Chemical Company, Inc. The deoxidizing member 22 containing the deoxidizing agent 21 may be an organic self-reacting GLS type, GL-M type, or GE type, all of which are available from Mitsubishi Gas Chemical Company, Inc. The deoxidizing member 22 containing the deoxidizing agent 21 may be a pharmaceutical-grade ZH type, Z-PK-Ya, Z-PR, Z-PKR, or ZM type, all of which are available from Mitsubishi Gas Chemical Company, Inc.

[0143] 9B, in order to promote oxygen absorption by the oxygen absorber 21, the oxygen absorbing member 22 may contain a water retention agent 22b that retains water. Examples of the water retention agent 22b include one or more selected from the group consisting of diatomaceous earth, silica, and activated carbon. The water retention agent 22b may be used as a support that supports the oxygen absorber 21.

[0144] In an example where the liquid L contains a non-aqueous solvent such as alcohol or oil, the moisture-retaining agent 22b that retains moisture is effective in ensuring the oxygen absorption function of the oxygen absorber 21. A non-aqueous solvent refers to a solvent in which the main component with the largest volumetric percentage is other than water. A non-aqueous solvent may be substantially free of water. The volumetric percentage of water in a non-aqueous solvent may be 2% or less, 1% or less, or 0.5% or less. A non-aqueous solvent may not contain water.

[0145] When the liquid L is an aqueous solution, the oxygen absorbing member 22 does not need to contain the water retention agent 22b. The first container 30, which is oxygen permeable, often has water vapor permeability. In this example, moisture can be supplied to the oxygen absorber 21 without using the water retention agent 22b. Rather, moisture absorption by the water retention agent 22b may be suppressed. For example, the water absorption capacity of the water retention agent 22b used in the oxygen absorbing member 22 may be 5% or less of the volume (mL) of the liquid L contained in the first container 30. Storage conditions for liquids such as pharmaceuticals may be set so that the volume loss is 5% or less over the shelf life of the pharmaceutical (e.g., 3 years). The loss of the liquid L in the first container 30 can be regulated. This storage condition can be met by setting the water absorption capacity of the water retention agent 22b to 5% or less of the initial volume (mL) of the liquid L.

[0146] When activating the oxygen absorber 21 using water vapor that has permeated the first container 30 and migrated into the second container 40, a portion or all of the oxygen absorber 21 and a portion or all of the oxygen absorbing member 22 may be disposed vertically above the oxygen-permeable portion of the first container 30. For example, if the container body 32 has oxygen barrier properties and the stopper 34 has oxygen permeability, a portion or all of the oxygen absorber 21 may be disposed above the stopper 34. If the container body 32 has oxygen barrier properties and the stopper 34 has oxygen permeability, a portion or all of the oxygen absorbing member 22 may be disposed above the stopper 34. Water vapor is lighter than nitrogen, oxygen, and many inert gases. Therefore, water vapor that has permeated the first container 30 can be efficiently used to activate the oxygen absorber 21.

[0147] The oxygen absorbing agent 21 may be contained in the oxygen absorbing film 23. FIG. 9C shows an example of a laminate 46 including the oxygen absorbing film 23. The laminate 46 including the oxygen absorbing film 23 may form the films 41a to 41e of the second container 40 shown in FIG. 1 and FIGS. 7A to 7C. The laminate 46 including the oxygen absorbing film 23 may form the container body 42 or the lid 44 of the second container 40 shown in FIG. 8. The laminate 46 including the oxygen absorbing film 23 may form the films 41a and 41b of the second container 40 shown in FIGS. 10 to 25 (described later). The laminate 46 shown in FIG. 9C includes a first layer 46a, a second layer 46b, and a third layer 46c. The first layer 46a may be an outermost layer made of polyethylene terephthalate, polyamide, or the like. The second layer 46b may be an oxygen barrier layer made of aluminum foil, a metal oxide vapor deposition film, a metal vapor deposition film, or the like. The third layer 46c may be an innermost layer forming a heat-seal layer. The illustrated third layer 46c includes a matrix 23a made of a thermoplastic resin and an oxygen absorber 21 dispersed in the matrix 23a. As shown in FIG. 9C, the second container 40 may include an oxygen absorbing film 23 containing the oxygen absorber 21 as part of the laminate 46. The oxygen absorber 21 is not limited to being included in the heat-seal layer or the innermost layer 46c, but may also be included in an intermediate layer of the laminate, such as an adhesive layer.

[0148] As another example, the first container 30 may include an oxygen absorbing film 23 containing the oxygen absorber 21. The oxygen absorber 21 may be provided separately from the first container 30 or the second container 40 as in the examples shown in Fig. 1 or 8, or may be provided as a part of the first container 30 or the second container 40 as shown in Fig. 9C.

[0149] The oxygen concentration (%) in the first container 30 and the oxygen concentration (%) in the second container 40 are determined by a single measuring device suitable for measuring these oxygen concentrations. Known measuring devices for measuring oxygen concentrations include headspace oxygen measuring devices, fluorescent contact oxygen measuring devices, and fluorescent non-contact oxygen measuring devices. The dissolved oxygen amount (mg / L) of the liquid contained in the first container 30 is determined by a single measuring device suitable for measuring the dissolved oxygen amount of the liquid. Known measuring devices for measuring dissolved oxygen amount include fluorescent contact oxygen measuring devices and fluorescent non-contact oxygen measuring devices. An appropriate measuring device is selected for measuring the oxygen concentration and dissolved oxygen amount, taking into consideration the measurement limit, measurement stability in the oxygen concentration range to be measured, the measurement environment, measurement conditions, etc.

[0150] The headspace oxygen measurement device used in the headspace method is the Lighthouse FMS760 headspace analyzer. In measurements using this measurement device, a container containing the oxygen to be measured is irradiated from the outside with light of a frequency absorbable by oxygen, and the light that passes through the headspace HS of the container and exits the container is received. The change in light intensity before and after transmission is measured, and the oxygen concentration (%) within the container can be determined based on this change in light intensity. Therefore, if the first container 30 is transparent to light from the measurement device, the oxygen concentration within the first container 30 can be determined without opening the first container 30. If the second container 40 is transparent to light from the measurement device, the oxygen concentration within the first container 30 can also be measured by irradiating light from the outside of the second container 40 without opening the second container 40. The oxygen concentration (%) within the second container 40 can also be measured using the Lighthouse FMS760 headspace analyzer. The saturated solubility of oxygen in liquid L can be determined from the measured oxygen concentration (%) and temperature of the headspace HS. Based on the determined saturated solubility, the amount of oxygen dissolved in liquid L (mg / L) can be determined. In this way, the headspace analyzer FMS760 can measure the oxygen concentration inside a container from outside the container. However, the lower limit of the oxygen concentration measurable by the headspace analyzer FMS760 is higher than the lower limit of the oxygen concentration measurable by other measurement devices.

[0151] The Microx4 oxygen measuring device, manufactured by PreSens, Germany, is used as a fluorescent contact-type oxygen measuring device. The Microx4 oxygen measuring device is a needle-type device. The Microx4 oxygen measuring device can measure the oxygen concentration and dissolved oxygen amount inside a container by inserting a needle into the container, and although it depends on the configuration of the part of the container where the needle is inserted, it has excellent measurement stability. By preparing multiple combination containers or containers made under the same conditions and measuring the oxygen amount inside each container at different times with the needle-type oxygen measuring device, it is possible to evaluate changes in oxygen amount over time.

[0152] By placing an oxygen sensor in the container in advance, the oxygen concentration and dissolved oxygen amount in the first container 30 and the second container 40 can be measured using a fluorescent non-contact oxygen measurement device. The Fibox3 oxygen measurement device manufactured by PreSens, a German company, is used as the fluorescent non-contact oxygen measurement device. The oxygen sensor emits fluorescence when it receives light in a specific wavelength range. The amount of fluorescence signal from the oxygen sensor fluctuates as the amount of oxygen around the sensor increases. The fluorescent non-contact oxygen measurement device can emit light of a specific wavelength at which the oxygen sensor emits fluorescence, and can measure the oxygen concentration (%) and dissolved oxygen amount (mg / L) by measuring the amount of fluorescence signal from the oxygen sensor. When the first container 30 is placed in the second container 40, the amount of dissolved oxygen in the liquid L can be measured by irradiating light from outside the second container 40 without opening the second container 40.

[0153] As shown in FIGS. 1 and 8 , the container set 20 and the combination container 10 may be provided with a dehydrating agent 24 that absorbs moisture in the second container 40. The dehydrating agent 24 is a substance or a composition containing such a substance that has the ability to absorb moisture such as water vapor or water. Examples of the dehydrating agent 24 include calcium chloride, soda lime, and silica gel. The dehydrating agent 24 may be housed in the second container 40 together with the first container 30, and the second container 40 may then be closed. In the example shown in FIG. 1 , the dehydrating agent 24 is disposed in the second container 40 as a dehydrating member housed in a package. Similar to the oxygen absorber described above, a film-like dehydrating film containing a dehydrating material may be included as part of the first container 30 or the second container 40. In this example, the oxygen barrier layer constituting the second container 40 and the dehydrating film containing the dehydrating agent 24 may be laminated and integrated. When a non-aqueous solvent such as glycerin or alcohol is contained in the first container 30, the dehydrating agent 24 contained in the second container can remove moisture such as water vapor and water from the first container 30. The inventors of the present invention have confirmed that by containing a dehydrating agent in the second container 40, the moisture content in the first container 30 can be reduced to 100 μg or less, 50 μg or less, or 10 μg or less.

[0154] When the dehydrating agent 24 is used, the moisture content, such as water vapor and water, in the first container 30 is measured using the Karl Fischer method. Specifically, the moisture content in the first container 30 is determined by coulometric titration using a Karl Fischer moisture meter MKC-610 manufactured by Kyoto Electronics Manufacturing Co., Ltd. If the Karl Fischer moisture meter MKC-610 cannot be used, the moisture content in the first container 30 is determined using a Karl Fischer moisture meter MKC-710M manufactured by Kyoto Electronics Manufacturing Co., Ltd.

[0155] The container set 20 and the combination container 10 may include an oxygen detector 25 that detects the oxygen state in the second container 40. The oxygen detector 25 may display information about the detected oxygen state. The oxygen detector 25 may include a display unit 26 that displays information about the oxygen state. The oxygen detector 25 may detect the oxygen concentration. The oxygen detector 25 may display the detected oxygen concentration value. The oxygen detector 25 may display the detected oxygen concentration value by color. The oxygen detector 25 may display the oxygen concentration range to which the detected oxygen concentration value belongs by color.

[0156] The oxygen detector 25 may contain a variable organic dye whose color changes reversibly upon oxidation and reduction. For example, the oxygen reducer 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 reducer may also contain an oxygen indicator ink composition. The oxygen indicator ink composition may contain a resin solution, a thiazine dye, reducing sugars, and an alkaline substance. The thiazine dye, reducing sugars, and alkaline substance may be dissolved or dispersed in the resin solution. The substance contained in the oxygen detector 25 may reversibly change upon oxidation and reduction. By using an oxygen detector 25 containing a reversible substance, the oxygen detector 25 placed in a container changes color as oxygen is removed from the container before deoxidation is complete. By observing the display on the oxygen detector 25, the oxygen-related conditions within the container can be ascertained. In addition, the oxygen detector 25 contained in the container can change its display color to indicate an increase in oxygen concentration after deoxidation is complete, for example, if a pinhole or the like forms in the container during distribution, allowing oxygen to enter the container.

[0157] The oxygen detector 25 may be a commercially available tablet-type oxygen detector. The oxygen detector 25 may be an oxygen detector available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "Ageless Eye." The oxygen detector 25 may also be an oxygen detector coated with an ink composition having oxygen detection functionality, such as an oxygen detector available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "Paper Eye." "Ageless Eye" and "Paper Eye" are functional products that can easily indicate by a color change that an oxygen-free state, where the oxygen concentration inside a transparent container is less than 0.1% by volume, exists. The oxygen detector 25 may also be used in conjunction with an oxygen absorber, such as an oxygen absorber available from Mitsubishi Gas Chemical Co., Ltd. under the trade name "Ageless," to maintain the freshness of food and the quality of medical drugs.

[0158] As shown in FIG. 1 , the oxygen detector 25 may be arranged so that the display unit 26 can be observed from the outside of the transparent second container 40. In the example shown in FIG. 1 , the oxygen detector 25 is housed in the second container 40, along with the oxygen absorber 21 and the oxygen absorbing member 22. The oxygen detector 25 may be joined to the inner surface of the second container 40 or the outer surface of the first container 30 via welding or a bonding material. The oxygen detector 25 may be arranged so that the display unit 26 is not obscured by the oxygen absorbing member 22 or the dehydrating agent 24. Furthermore, if a label is affixed to the first container 30, the oxygen absorbing member 22, the dehydrating agent 24, and the oxygen detector 25 are preferably arranged so as not to cover the label.

[0159] Furthermore, the oxygen detector 25 may detect the oxygen state within the first container 30. That is, the container set 20 and the combination container 10 may include an oxygen detector 25 that detects the oxygen state within the first container 30. This oxygen detector 25 may be housed within the first container 30. The oxygen detector 25 may display information regarding the detected oxygen state within the first container 30. The oxygen detector 25 may include a display unit 26 that displays information regarding the oxygen state within the first container 30. The oxygen detector 25 may detect the oxygen concentration within the first container 30. The oxygen detector 25 may display the detected oxygen concentration value within the first container 30. The oxygen detector 25 may display the detected oxygen concentration value within the first container 30 using a color. The oxygen detector 25 may display the oxygen concentration range to which the detected oxygen concentration value within the first container 30 belongs using a color.

[0160] The oxygen concentration in the space not occupied by the liquid L in the first container 30, known as the headspace HS, can be reduced to approximately 1.5% or less by, for example, replacing the headspace HS with an inert gas or bubbling the liquid L with an inert gas before attaching the stopper 34 to the container body 32. It is also believed that the amount of oxygen dissolved in the liquid contained in the container can be reduced by producing 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 production line in an atmosphere replaced with an inert gas requires extensive renovation of the manufacturing equipment and a huge capital investment. In addition, in the field of expensive chemicals, the chemicals are often freeze-dried and stored in powder form to ensure stability against temperature, oxygen, moisture, light, etc. However, converting liquid chemicals into powder form for storage and then converting the powdered chemicals back into liquid form for use have significant disadvantages in terms of effort, time, and cost.

[0161] In contrast, according to this embodiment, a first container filled with a liquid can be manufactured in the conventional manner using existing equipment, etc. Therefore, equipment modifications and capital investments can be avoided. In particular, when applied to liquids such as chemicals, this is useful in that it eliminates the need for approval applications to public institutions regarding changes to manufacturing equipment or manufacturing processes. It also eliminates the need for the labor of freeze-drying the liquid L or reconstituting a powder into a liquid. Furthermore, there are no special restrictions on the first container 30. Therefore, materials that are widely used as containers for foods, chemicals, etc. because of their low elution amounts, such as glass and resins such as polyethylene and polypropylene, can be used as materials for the first container.

[0162] Additionally, in the above-described specific example, the first container 30 has a container body 32 and a stopper 34. This first container 30 may be a vial. However, conventionally, vials containing liquid, particularly vials containing liquid in a sterile state, are made of butyl rubber or fluororubber, which have low oxygen permeability and even oxygen barrier properties. In contrast, in the above-described specific example, the stopper 34 has oxygen permeability. That is, oxygen can pass through the stopper 34. For example, if the oxygen permeability coefficient (cm 3 (STP)·cm / (cm 2 The oxygen permeability coefficient (kJ / cm 2 ·sec·Pa) is set to be large. The stopper 34 may be made of silicone or silicone rubber. Furthermore, the oxygen permeability coefficient of the silicone or silicone rubber making up the stopper 34 may be larger than the oxygen permeability coefficient of the material making up the container body 32. In this specific example, oxygen passes through the stopper 34 and moves out of the first container 30. Therefore, by using an oxygen-permeable stopper 34, oxygen permeability can be easily imparted to existing containers such as vials that have been used conventionally.

[0163] In this specific example, the time required to reach equilibrium depends on the oxygen permeability of the stopper 34. Therefore, by adjusting the area of the opening 33 of the container body 32 and the thickness of the stopper 34 as described above, it is possible to shorten the time required for oxygen permeation through the first container 30 to reach equilibrium after the first container 30 is placed inside the second container 40. This makes it possible to suppress decomposition of the liquid L due to oxygen.

[0164] Furthermore, the partial volume of the first container 30 (volume of the headspace HS), obtained by subtracting the volume of the liquid L from the volume of the first container 30, may be 50 mL or less, 30 mL or less, 10 mL or less, or 5 mL or less. By setting an upper limit on the partial volume of the first container 30 (volume of the headspace HS), the amount of oxygen in that volume can be reduced. Therefore, with this liquid-filled combination container 10L, the time required for oxygen permeation through the first container 30 to reach equilibrium after the second container 40 containing the first container 30 is closed can be shortened. This makes it possible to suppress decomposition of the liquid L due to oxygen.

[0165] Similarly, the volume of the liquid L contained in the first container 30 may be 20 mL or less, or may be 10 mL or less. With such a liquid-containing combination container 10L, it is possible to shorten the time it takes for oxygen permeation through the first container 30 to reach equilibrium after the second container 40 containing the first container 30 is closed. This makes it possible to suppress decomposition of the liquid L due to oxygen.

[0166] Furthermore, upper and lower limits may be set for the ratio (%) of the partial volume (mL) of the first container 30 (the volume of the headspace HS) obtained by subtracting the volume of the liquid L from the volume of the first container 30 to the partial volume (mL) of the second container 40 obtained by subtracting the volume occupied by the first container 30 from the volume of the second container 40. This ratio may be set to 50% or less, or 20% or less. By setting such an upper limit, the oxygen concentration in the first container 30 can be sufficiently reduced. Furthermore, a storage space for the first container 30 can be secured within the second container 40, making it easy to store the first container 30 within the second container 40. Furthermore, the time required for oxygen permeation through the first container 30 to reach equilibrium after the second container 40 containing the first container 30 is closed can be shortened. This reduces decomposition of the liquid L due to oxygen. This ratio may be set to 5% or more, or 10% or more. By setting the lower limit in this manner, the second container 40 does not become too large relative to the first container 30, and deterioration in the handleability of the combination container 10 can be suppressed.

[0167] Whether oxygen permeation through the first container 30 is in equilibrium is determined based on the oxygen concentration inside the first container 30. This determination is made when the difference between the oxygen concentration value (%) inside the first container 30 at a certain point in time and the oxygen concentration value (%) inside the first container 30 24 hours before that point in time is within ±5% of the oxygen concentration value (%) inside the first container 30 at that point in time.

[0168] In this manner, a liquid-filled first container 30L and a liquid-filled combination container 10L with adjusted oxygen concentration and dissolved oxygen amount can be obtained. In conventional techniques, reducing the oxygen concentration (%) in the headspace HS in the first container 30 by inert gas replacement or bubbling alone is often difficult due to the presence of liquid L in the first container 30. As a result, it is difficult to reduce the dissolved oxygen present in the liquid L. In contrast, according to one specific example of the above-described embodiment, the liquid-filled first container 30L and gas are contained in the second container 40, eliminating the need to contain the liquid L directly. Therefore, the oxygen concentration in the second container 40 can be sufficiently reduced. By adjusting the volume of the second container 40, the oxygen concentration in the first container 30 at equilibrium can be kept below 1%. This effect is suitable when the liquid L is a highly sensitive drug or food.

[0169] In particular, when oxygen absorber 21 that absorbs oxygen in second container 40 is used, the oxygen concentration in first container 30 can be reduced to less than 0.3%, 0.1% or less, 0.05% or less, less than 0.03%, or even 0%, and the oxygen concentration in second container 40 can be reduced to less than 0.3%, 0.1% or less, 0.05% or less, less than 0.03%, or even 0%. Furthermore, when oxygen absorber 21 that absorbs oxygen in second container 40 is used, the amount of dissolved oxygen in liquid L in first container 30 can be reduced to less than 0.15 mg / L, 0.04 mg / L or less, 0.03 mg / L or less, even less than 0.015 mg / L, or even 0 mg / L. In addition, by disposing oxygen absorber 21 outside first container 30, oxygen absorber 21 does not impair the sterilized state inside first container 30.

[0170] If it takes a long time for the oxygen concentration or dissolved oxygen amount to decrease, deterioration of the liquid L due to oxygen will progress. The period or time from closing the second container 40 until oxygen permeation through the first container 30 reaches equilibrium is preferably within four weeks. If equilibrium is reached within four weeks, for example, if the oxygen concentration in the second container 40 becomes less than 1%, deterioration of the liquid L as a pharmaceutical can be effectively suppressed. For highly sensitive liquid L, the period until equilibrium is reached is preferably within 20 days, more preferably within one week, and even more preferably within three days. On the other hand, it takes a certain period of time for the liquid L to reach equilibrium, which reduces the dissolved oxygen amount to a certain extent. The period or time from closing the second container 40 until oxygen permeation through the first container 30 reaches equilibrium may be one hour or more.

[0171] The adjustment of the amount of oxygen in the first container 30 in the second container 40 may be carried out until the permeation of oxygen through the first container 30 reaches equilibrium. The adjustment of the amount of oxygen in the first container 30 in the second container 40 may be carried out until the oxygen concentration in the second container 40 increases to a predetermined value. The adjustment of the amount of oxygen in the first container 30 in the second container 40 may be carried out until the oxygen concentration in the first container 30 decreases to a predetermined value. The adjustment of the amount of oxygen in the first container 30 in the second container 40 may be carried out until the amount of oxygen dissolved in the liquid L in the first container 30 decreases to a predetermined value. The adjustment of the amount of oxygen in the first container 30 in the second container 40 may be carried out until the liquid L in the combination container 10 is used. Furthermore, while the first container 30 is housed in the second container 40 and the amount of oxygen is being adjusted, the liquid-filled combination container 10L may be circulated.

[0172] The method of using the liquid-containing combination container 10L will now be explained.

[0173] To use the liquid L contained in the combination container 10, first, the second container 40 is opened. Next, the first container 30L containing the liquid is removed from the opened second container 40. Thereafter, the liquid L can be removed from the first container 30L containing the liquid, and the liquid L can be used. For the illustrated first container 30, the first container 30 can be opened by removing the fastener 36 from the container body 32 and then removing the stopper 34 from the container body 32. This allows the liquid L in the first container 30 to be used.

[0174] As shown in FIG. 6 , the liquid L may be a medicine to be injected into the syringe 60. The liquid L may be a liquid contained in a first container 30, which is a vial. The liquid L may be an injectable medicine. Examples of injectable medicines include anticancer drugs, antiviral drugs, vaccines, and antipsychotics. The syringe 60 may include a cylinder 62 and a piston 66. The cylinder 62 may include a cylinder body 63 and a needle 64 protruding from the cylinder body 63. The cylindrical needle 64 allows access to the space in the cylinder body 63 for containing the liquid L. The piston 66 may include a piston body 67 and a gasket 68 held by 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 to define a space for containing the liquid L within the cylinder body 63. The liquid L injected into the syringe 60 may be transferred from the syringe 60 to another syringe, container, or the like before being administered to a patient or the like. In this example, it may be administered to the patient from a separate syringe, container, etc.

[0175] It is preferable that the pressure inside the liquid-containing first container 30L be adjusted. As an example, it is preferable that the pressure inside the liquid-containing first container 30L be maintained low, particularly at a negative pressure. This example effectively prevents unintended leakage of the liquid L during storage of the liquid-containing first container 30L and splashing of the liquid L when the first container 30L is opened. The problems of leakage and splashing are more serious for toxic liquids, such as highly pharmacologically active drugs. Furthermore, in the example shown in FIG. 6, if the liquid-containing first container 30L is under positive pressure, the liquid L automatically flows into the syringe 60. In this case, it becomes difficult to precisely inject the desired amount of liquid L into the syringe 60.

[0176] On the other hand, highly sensitive liquids that are susceptible to degradation by post-production sterilization treatments, such as gas, heat, or gamma rays, such as foods and pharmaceuticals, specifically anticancer drugs, antivirals, vaccines, and antipsychotics, are manufactured and packaged in a sterile environment. In other words, liquids that cannot be sterilized are manufactured using aseptic procedures. This sterile environment is typically maintained at a predetermined positive pressure to prevent the intrusion of bacteria. Therefore, the pressure inside the container is a predetermined positive pressure corresponding to the sterile environment, making it difficult to adjust the internal pressure of the container after it is closed.

[0177] According to the present embodiment, such a problem can be addressed. As described above, the first container 30L containing the liquid is stored in the second container 40. During this storage, the oxygen concentration in the second container 40 decreases due to the oxygen absorber 21 or due to replacement with an inert gas, causing oxygen in the first container 30 to permeate the first container 30 and move into the second container 40. This allows the pressure in the first container 30 to be reduced. In other words, the pressure in the first container 30 containing the liquid L can be adjusted after the first container 30 is closed and the liquid L is sealed inside.

[0178] From the viewpoint of adjusting the internal pressure of the first container 30, a second container 40 capable of storing a gas under a negative pressure at atmospheric pressure may be used. For example, the second container 40 shown in FIG. 8 may be used, and the second container 40 containing the first container 30 may be closed under an inert gas atmosphere maintained at a negative pressure. The pressure inside the closed second container 40 becomes less than atmospheric pressure. In this case, oxygen permeation from the first container 30 to the second container 40 is promoted. In particular, the pressure inside the first container 30 can be significantly adjusted by ensuring a large volume of the second container 40 or by significantly reducing the initial pressure of the second container 40. As a result, the pressure inside the first container 30, which is initially positive, can be adjusted to atmospheric pressure (1 atm) or below, or even to a negative pressure, by storing the first container 30 inside the second container 40. This allows the production of a pressure-adjusted liquid-filled first container 30L without depending on the method for producing the liquid L or the method for sealing the liquid L into the first container 30.

[0179] Closing the second container 40 under negative pressure promotes oxygen permeation through the first container 30. Therefore, the time required for oxygen permeation through the first container 30 to reach equilibrium after the second container 40 containing the liquid-containing first container 30L is closed can be shortened.

[0180] Negative pressure refers to pressure below atmospheric pressure, i.e., pressure below 1 atm. Positive pressure refers to pressure above atmospheric pressure, i.e., 1 atm. Whether or not a container is under negative pressure is determined using a pressure gauge if the container is equipped with one. If the container is not equipped with a pressure gauge, it is determined using a syringe. Specifically, when a syringe needle is inserted into a target container, it is determined whether or not the liquid or gas contained in the syringe flows into the container when 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 is under negative pressure. Similarly, whether or not a container is under positive pressure is determined using a pressure gauge if the container is not equipped with a pressure gauge, it is determined using a syringe. Specifically, when a syringe needle is inserted into a target container, it is determined whether or not the liquid or gas contained in the container flows into the syringe when 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 there was positive pressure inside the container.

[0181] In the embodiment described above, the container set 20 includes a first container 30 having oxygen permeability in at least a portion thereof and a second container 40 capable of containing the first container 30 and having oxygen barrier properties. The liquid-filled combination container 10L includes a first container 30 containing a liquid L and having oxygen permeability in at least a portion thereof, and a second container 40 containing the first container 30 and having oxygen barrier properties. When oxygen permeation through the first container 30 is in equilibrium, the oxygen concentration in the first container 30 may be less than 1%. Furthermore, a method for manufacturing the liquid-filled first container 30L includes the steps of closing the second container 40 containing the liquid-filled first container 30L and adjusting the amount of oxygen in the liquid-filled first container 30L contained within the second container 40. In the oxygen amount adjustment step, oxygen in the first container 30 permeates the first container 30, thereby reducing the oxygen concentration in the first container 30 and potentially reducing the amount of oxygen dissolved in the liquid L.

[0182] 1, a gap G may be formed between the oxygen-permeable plug 34 of the first container 30 housed in the second container 40 and the second container 40. According to this example, it is possible to prevent the second container 40, which has oxygen barrier properties, from covering the oxygen-permeable plug 34. This prevents the second container 40 from interfering with oxygen transmission through the first container 30. Therefore, by providing the gap G, it is possible to promote a reduction in the amount of oxygen in the first container 30.

[0183] According to this embodiment, oxygen in the first container 30 can pass through the first container 30 and move into the second container 40. By replacing the atmosphere in the second container 40 with an inert gas, the oxygen concentration (%) in the second container 40 can be increased, and the oxygen concentration (%) in the first container 30 can be decreased. As the oxygen concentration (%) in the first container 30 decreases, the amount of oxygen dissolved in the liquid L (mg / L) also decreases. Therefore, the amount of oxygen dissolved in the liquid L can be reduced, and decomposition of the liquid L by oxygen can be suppressed.

[0184] Instead of or in addition to replacing the second container 40 with an inert gas, using an oxygen absorbing agent 21 in the second container 40 to absorb oxygen can further reduce the oxygen concentration in the first container 30 and the amount of oxygen dissolved in the liquid L in the first container 30. By using the oxygen scavenger 21, the oxygen concentration in the first container 30 can be reduced to less than 0.3%, 0.1% or less, 0.05% or less, less than 0.03%, or even 0%, and the oxygen concentration in the second container 40 can be reduced to less than 0.3%, 0.1% or less, 0.05% or less, less than 0.03%, or even 0%. By using the oxygen scavenger 21, the amount of oxygen dissolved in the liquid L in the first container 30 can be reduced to less than 0.15 mg / L, 0.04 mg / L or less, 0.03 mg / L or less, even less than 0.015 mg / L, or even 0 mg / L. Since the oxygen absorber 21 can be disposed outside the first container 30, the oxygen absorber 21 does not impair the sterility of the inside of the first container 30.

[0185] In this combination container 10, the second container 40 is responsible for reducing the amount of oxygen and for providing oxygen barrier properties. The liquid-filled first container 30L may be responsible for ensuring the sterility of the interior and the contained liquid L. In this way, the storage environment required for the liquid L is efficiently realized by the combination of the first container 30 and the second container 40. With the combination container 10 and container set 20, the storage environment required for the liquid L can be realized inexpensively and easily with a high degree of freedom.

[0186] In a specific example of the above-described embodiment, the first container 30 has a container body 32 having an opening 33 and a plug 34 that closes the opening 33. The plug 34 may be oxygen permeable. The plug 34 may contain silicone. The oxygen permeability coefficient of the material that makes up the plug 34 is 1×10 -12 (cm 3 (STP)·cm / (cm 2 The oxygen permeability coefficient (cm sec Pa) of the material constituting the plug 34 may be equal to or greater than the oxygen permeability coefficient (cm sec Pa). 3 (STP)·cm / (cm 2 ·sec·Pa) is the oxygen permeability coefficient (cm 3 (STP)·cm / (cm 2 sec·Pa). According to this specific example, oxygen permeates the stopper 34 and moves out of the first container 30. Therefore, oxygen permeability can be imparted to the area of the first container 30 exposed to the liquid L, such as the so-called headspace HS. This allows oxygen permeation through the first container 30 to proceed smoothly, and the time required for oxygen permeation through the first container 30 to reach equilibrium after the first container 30 is placed in the second container 40 can be shortened.

[0187] In a specific example of the above-described embodiment, the container body 32 may have oxygen barrier properties. Oxygen that has permeated the first container 30 enters a region separated from the liquid L, such as the headspace HS, within the first container 30. Therefore, dissolution of oxygen that has permeated the first container 30 into the liquid L can be suppressed.

[0188] In one specific example of the above-described embodiment, the area of the opening 33 of the container body 32 is 10 mm 2Over 500mm 2 The thickness of the stopper 34 may be 0.1 mm or more and 5 mm or less. With this type of liquid-filled combination container 10L, it is possible to shorten the time it takes for oxygen permeation through the first container 30 to reach equilibrium after the first container 30 is placed inside the second container 40. This makes it possible to suppress decomposition of the liquid L due to oxygen.

[0189] Here, the results of the experiments carried out by the present inventors will be explained.

[0190] Example 1 A vial with a capacity of approximately 9.2 mL was prepared as the first container. The first container had the configuration shown in Figure 1. The vial, which constituted the first container, included a glass container body. The container body had oxygen barrier properties. The first container was capable of maintaining a negative gas pressure under atmospheric pressure. Approximately 4 mL of water for injection (aqueous solution) was placed in the first container as liquid L. The opening of the container body containing the water for injection was closed with a rubber stopper. The rubber stopper was made of silicone rubber and had oxygen permeability. An aluminum seal was fixed to the top of the container body using hand clippers to prepare a liquid-filled first container. The aluminum seal functioned as the fixing device shown in Figure 2. In other words, the aluminum seal prevented the rubber stopper from coming off the container body. After sealing using the aluminum seal, the space between the container body and the rubber stopper was airtight. A headspace of approximately 4.2 mL, not filled with water for injection, remained in the first container. The first container was closed in air. Therefore, the headspace of the first container 30 contained air. The oxygen concentration in the headspace of the first container 30 was 21.0%. The amount of dissolved oxygen in the water for injection contained in the first container was 8.84 mg / L. The oxygen transmission rate of the stopper of the first container was measured using the method shown in FIG. 2B and was found to be 3 (mL / (day×atm)), demonstrating that the first container of Example 1 was oxygen permeable.

[0191] Next, a second container made of a transparent oxygen-barrier packaging material was prepared. The second container had the structure shown in Figure 1. The second container was a so-called pouch. The first container containing the liquid and an oxygen absorbing member containing an oxygen absorber were placed inside the second container, and the second container was sealed by heat sealing. The closed second container contained approximately 100 mL of air. The oxygen absorbing member contained an oxygen absorber capable of absorbing 200 mL of oxygen.

[0192] All materials and components used in the first container in Example 1 were sterilized. The process of placing the water for injection in the first container, closing the first container, placing the liquid-filled first container and the oxygen absorber in the second container, and closing the second container was carried out in an isolator under sterile conditions. The use of sterilized materials and the operation in the isolator under sterile conditions were also carried out in Comparative Examples 1 and 2 described below.

[0193] <Comparative Example 1> A first container filled with liquid was prepared in the same manner as in Example 1. This first container filled with liquid was designated Comparative Example 1. That is, the second container was omitted in Comparative Example 1. The rubber stopper of the first container was made of silicone rubber, as in Example 1.

[0194] <Comparative Example 2> In Comparative Example 2, the rubber stopper that closes the opening of the container body of the first container was made of butyl rubber. Comparative Example 2 differs from Example 1 in this respect, but was otherwise similar to Example 1. The oxygen permeability of the butyl rubber that made up the rubber stopper in Comparative Example 1 was 80 (cm 3 / (m 2 × 24h × atm), which was so low that it had no oxygen permeability.

[0195] <Evaluation> For Example 1 and Comparative Example 2, the second container was closed, and then the liquid-containing combination container was stored. For Comparative Example 1, the first container was closed, and then the liquid-containing first container was stored. Example 1, Comparative Example 1, and Comparative Example 2 were stored in an air atmosphere at 22°C under atmospheric pressure. Changes over time in the amount of dissolved oxygen (mg / L) in the injection water, the oxygen concentration (%) in the first container, and the oxygen concentration (%) in the second container were confirmed during the storage period. The amount of dissolved oxygen (mg / L) in the injection water, the oxygen concentration (%) in the first container, and the oxygen concentration (%) in the second container were measured using an oxygen measuring device Fibox3 manufactured by PreSens, Germany. Oxygen measuring chips were placed in the first and second containers. By using the oxygen measuring device Fibox3, the amount of dissolved oxygen (mg / L) in the injection water, the oxygen concentration (%) in the first container, and the oxygen concentration (%) in the second container were measured from the outside of the container without destroying the container. The detection limit of the oxygen concentration using the oxygen measuring device Fibox3 was 0.03%. The detection limit of dissolved oxygen using the oxygen measurement device Fibox3 was 0.015 mg / L.

[0196] The measurement results of the oxygen concentration (%) in the second container are shown in Table 1. The measurement results of the oxygen concentration (%) in the first container are shown in Table 2. The measurement results of the oxygen dissolution amount (mg / L) in the injection water are shown in Table 3. In these tables, "0" means that no oxygen was detected.

[0197] [Table 1]

[0198] [Table 2]

[0199] [Table 3]

[0200] As shown in Tables 1 to 3, in Example 1, the oxygen concentration in the second container decreased to 0% one day after the second container was closed. In Example 1, the oxygen concentration in the first container could be decreased to 0%. In Example 1, the amount of dissolved oxygen in the water for injection contained in the first container could be decreased to 0 mg / L.

[0201] Next, a specific example of the liquid-containing combination container 10L will be further described. According to the following specific example, the liquid-containing combination container 10L can be easily handled.

[0202] In the following description and the drawings used in the following description, parts that may be configured similarly to the above-mentioned examples or parts that may be configured similarly among several specific examples described later will be designated by the same reference numerals, and duplicated explanations will be omitted. In the liquid-filled combination container 10L described below, the first container 30, the oxygen absorbing member 22, the oxygen detector 25, etc. may have the same configurations as those described above.

[0203] 10 to 25 are diagrams illustrating a specific example of the second container 40. FIGS. 10 and 11 show a liquid-filled combination container 10L. FIG. 10 is a front view of the liquid-filled combination container 10L. FIG. 11 is a longitudinal cross-sectional view of the liquid-filled combination container 10L. As shown in FIGS. 10 and 11, the liquid-filled combination container 10L includes a liquid-filled first container 30L, a second container 40, and an oxygen absorber 21. In the illustrated example, the liquid-filled combination container 10L includes an oxygen detector 25. The oxygen detector 25 may include a display unit 26.

[0204] The first container 30 may be configured as described above. The illustrated first container 30 includes a container body 32 having an opening 33 and a stopper 34 that closes the opening 33. The stopper 34 is oxygen permeable, meaning that oxygen can pass through the stopper 34.

[0205] The oxygen absorber 21 may be contained in the second container 40 as an oxygen absorbing member 22. The oxygen absorbing member 22 may include an oxygen-permeable packaging body 22a and the oxygen absorber 21 contained in the packaging body 22a. The oxygen absorbing member 22 may further include a water retention agent 22b. The second container 40 or the first container 30 may include an oxygen absorbing film 23.

[0206] The second container 40 has oxygen barrier properties. The second container 40 is a container made of film. The second container includes a first film (first main film) 41a and a second film (second main film) 41b. The first film 41a and the second film 41b are arranged facing each other. The first film 41a and the second film 41b may be different films. The first film 41a and the second film 41b may be a single film folded back as described with reference to FIGS. 7C and 7D. The first film 41a and the second film 41b are joined to each other at a linear seal portion 49. The joining at the seal portion 49 may be, for example, welding such as heat sealing or ultrasonic bonding, or joining using an adhesive or bonding material. A storage space S for accommodating the first container 30 is formed between the first film 41a and the second film 41b.

[0207] The first film 41a and the second film 41b are peelable at the seal portion 49. When a user applies force to peel the first film 41a and the second film 41b, the first film 41a and the second film 41b separate from each other at the seal portion 49. The seal portion 49 becomes peelable by adjusting the processing conditions during bonding and the material and thickness of the bonding material (sealant layer). The seal portion 49 may be linear.

[0208] Peelable means that a user of the liquid-filled combination container 10L can grasp the second container 40 by hand and peel the first film 41a and the second film 41b from each other without using any device or auxiliary tool. The heat seal strength of the peelably joined seal portion, measured in accordance with JIS Z 0238, may be 3 N / 15 mm or more and 15 N / 15 mm or less, or 4 N / 15 mm or more and 7 N / 15 mm or less. The heat seal strength is the arithmetic mean of five measured values.

[0209] The seal portion 49 includes a curved first seal portion 49a. The first seal portion 49a may be linear. The first container 30 contained in the second container 40 faces the first seal portion 49a. The first container 30 faces the linear first seal portion 49a in the first direction D1. The first seal portion 49a is curved so as to protrude in the first direction D1 away from the first container 30. The first seal portion 49a is curved so as to protrude outward from the storage space S of the second container 40. The first seal portion 49a is curved so as to protrude in a direction that widens the storage space S of the second container 40.

[0210] In the illustrated example, the seal portion 49 includes a first side seal portion 49b connected to one end of the first seal portion 49a and a second side seal portion 49c connected to the other end of the first seal portion 49a. A storage space S for the second container 40 that stores the first container 30 is formed between the first side seal portion 49b and the second side seal portion 49c. A minimum distance DXa between the first side seal portion 49b and the second side seal portion 49c along the first film 41a may be shorter than a length L30 of the first container 30 along the direction in which the stopper 34 is inserted into the opening 33. A minimum distance DXb between the first side seal portion 49b and the second side seal portion 49c along the second film 41b may be shorter than a length L30 of the first container 30 along the direction in which the stopper 34 is inserted into the opening 33. In the illustrated example, the direction in which the plug 34 is inserted into the opening 33 is the same as the first direction D1 in which the first container 30 and the first seal portion 49a face each other.

[0211] The minimum distance DXa along the first film 41a between the first side seal portion 49b and the second side seal portion 49c is the minimum length of the first film 41a between the first side seal portion 49b and the second side seal portion 49c. The minimum distance DXb along the second film 41b between the first side seal portion 49b and the second side seal portion 49c is the minimum length of the second film 41b between the first side seal portion 49b and the second side seal portion 49c. The length L30 of the first container 30 is the axial length of the first container 30, and is usually the longitudinal length of the first container 30.

[0212] By making the minimum distances DXa, DXb along the films 41a, 41b between the side seal portions 49b, 49c shorter than the length L30 of the first container 30, it is possible to prevent the orientation of the first container 30 from changing significantly within the second container 40. In other words, the orientation of the first container 30 within the second container 40 is stabilized. This allows the stopper 34 of the first container 30 and the oxygen absorbing member 22 containing the oxygen absorber 21 to be stably maintained in a face-to-face state, as will be described later, and promotes oxygen release from the first container 30.

[0213] The sealed portion 49 further includes a second sealed portion 49d that faces the first sealed portion 49a in the first direction D1. In the illustrated example, the sealed portion 49 includes the first sealed portion 49a and the second sealed portion 49d that face the first direction D1, and a first side sealed portion 49b and a second side sealed portion 49c that face the second direction D2. The sealed portion 49 is formed in a circumferential shape by the first sealed portion 49a, the second sealed portion 49d, the first side sealed portion 49b, and the second side sealed portion 49c. The circumferential sealed portion 49 defines the storage space S of the second container 40. Instead of the second sealed portion 49d, a folded portion 41x formed by folding back a single piece of film, as shown in FIG. 7C, may be provided.

[0214] As shown in FIGS. 10 and 11 , the first film 41a and the second film 41b each include a main portion 50a that defines the storage space S and an extension portion 50b connected to the main portion 50a. The main portion 50a includes a first sealed portion 49a, a second sealed portion 49d, a first side sealed portion 49b, and a second side sealed portion 49c, as well as a portion surrounded by these sealed portions 49a, 49d, 49b, and 49c. The extension portion 50b is connected to the main portion 50a at the first sealed portion 49a. The extension portion 50b may be connected to at least the curved top portion of the first sealed portion 49a. The extension portion 50b may be connected to at least the portion of the first sealed portion 49a that protrudes most from the first container 30 in the first direction D1, in which the first container 30 and the first sealed portion 49a face each other. In the extension portion 50b, the space between the first film 41a and the second film 41b is open to the outside. In the extension portion 50b, the space between the first film 41a and the second film 41b is not sealed by a seal portion.

[0215] By grasping the extension 50b, the user can easily apply a peeling force to the first film 41a and the second film 41b. At this time, the peeling force is concentrated at the apex of the bend of the first sealed portion 49a. In the illustrated example, the peeling force is concentrated at the bent portion of the bent first sealed portion 49a. This allows the first film 41a and the second film 41b to be easily and smoothly peeled from the bent first sealed portion 49a as a starting point. In this second container 40, the first sealed portion 49a is the intended opening portion. The intended opening portion is the portion that is intended to be opened when the second container 40 is opened.

[0216] In the illustrated example, the second direction D2 is perpendicular to the first direction D1. The third direction D3 is perpendicular to both the first direction D1 and the second direction D2. The first film 41a and the second film 41b face each other in the third direction D3. The first film 41a and the second film 41b have a rectangular shape when laid out flat. The first film 41a and the second film 41b include a pair of edges extending in the first direction D1. The first film 41a and the second film 41b include a pair of edges extending in the second direction D2. The edges extending in the first direction D1 form the long sides of the rectangular shape. The edges extending in the second direction D2 form the short sides of the rectangular shape.

[0217] To clarify the relationship between directions between drawings, common directions are indicated in several drawings by arrows with common symbols. The tip of the arrow is the first side of each direction. The opposite side of the arrow is the second side of each direction. An arrow pointing into the paper in a direction perpendicular to the paper surface of the drawing is indicated by a symbol with an x in a circle, as shown in Figure 10, for example. An arrow pointing out of the paper in a direction perpendicular to the paper surface of the drawing is indicated by a symbol with a dot in a circle, as shown in Figure 11, for example.

[0218] Next, a method for manufacturing the combination liquid-containing container 10L shown in FIGS. 10 and 11 will be described with reference to FIGS.

[0219] First, as shown in FIG. 12, a liquid-filled first container 30L, an oxygen absorbing member 22, an oxygen detector 25, and a second container 40 are prepared. The second container 40 is not yet closed. In the illustrated example, a first film 41a and a second film 41b are joined at a first seal portion 49a, a first side seal portion 49b, and a second side seal portion 49c. This three-sided seal generally forms a storage space S that accommodates the first container 30, the oxygen absorbing member 22, and the oxygen detector 25. Meanwhile, the first film 41a and the second film 41b are not joined at a second seal portion 49d. That is, the second container 40 has an opening 40a that leads to the storage space S.

[0220] 13, the first container 30 is accommodated in the accommodation space S of the second container 40. In the illustrated example, the first container 30 is accommodated in the accommodation space S of the second container 40 such that the container body 32 of the first container 30 faces the first seal portion 49a. The bottom portion 32a of the container body 32 faces the first seal portion 49a in the first direction D1.

[0221] Next, as shown in Fig. 14, the deoxidizing member 22 and the oxygen detector 25 are accommodated in the accommodation space S of the second container 40. The deoxidizing member 22 is sheet-shaped. The deoxidizing member 22 is accommodated in the accommodation space S of the second container 40 so that one side edge of the sheet-shaped deoxidizing member 22 faces the stopper 34 of the first container 30. The oxygen detector 25 is sheet-shaped. The sheet-shaped oxygen detector 25 is overlapped with the deoxidizing member 22 in the third direction D3.

[0222] Thereafter, the first film 41a and the second film 41b are joined at the second seal portion 49d to close the second container 40. This results in a liquid-filled combination container 10L. Prior to closing the second container 40, the storage space S of the second container 40 may be replaced with an inert gas. The second container 40 may be closed under an inert gas atmosphere. Unlike the first seal portion 49a, the second seal portion 49d may be formed in a linear shape. Unlike the first seal portion 49a, the second seal portion 49d may be joined so that it cannot be peeled apart. Therefore, even when the first container 30, the oxygen absorbing member 22, and the oxygen detector 25 are housed inside, the first film 41a and the second film 41b can be easily and stably joined at the second seal portion 49d.

[0223] In the liquid-filled combination container 10L thus produced, the oxygen absorber 21 of the oxygen absorbing member 22 absorbs oxygen in the second container 40. This reduces the oxygen concentration in the second container 40. As the oxygen concentration in the second container 40 decreases, oxygen passes through the oxygen-permeable stopper 34 and moves from the first container 30 to the second container 40. This reduces the oxygen concentration in the first container 30, and reduces the amount of oxygen dissolved in the liquid L contained in the first container 30. In particular, the stopper 34 faces the oxygen absorbing member 22. This effectively prevents the oxygen transfer path from the first container 30 through the stopper 34 to the oxygen absorbing member 22 from being unintentionally blocked, for example, preventing the pair of films 41a, 41b from adhering to each other.

[0224] The liquid-filled combination container 10L described above includes a first container 30 that contains a liquid L and has oxygen permeability, a second container 40 that contains the first container 30 and has oxygen barrier properties, and an oxygen absorbing member 22 contained in the second container 40. The oxygen absorbing member 22 contains an oxygen absorber 21 that absorbs oxygen in the second container 40. The second container 40 includes a first film 41a and a second film 41b that contains the first container 30 between the first film 41a. The first film 41a and the second film 41b are peelably joined at a seal portion 49. The seal portion 49 includes a first seal portion 49a that faces the first container 30. The first seal portion 49a is bent so as to protrude away from the first container in a direction D1 in which the first seal portion 49a and the first container 30 face each other. In the direction D1 in which the first seal portion 49a and the first container 30 face each other, the first container 30 is located between the first seal portion 49a and the oxygen removing member 22.

[0225] According to this specific example, as already explained, it is possible to reduce the oxygen concentration inside the first container 30 and the amount of oxygen dissolved in the liquid L contained in the first container 30. Furthermore, the second container 40 can be easily opened by peeling off the first film 41a and the second film 41b at the first seal portion 49a, starting from the bent first seal portion 49a.

[0226] Furthermore, when opened, the first container 30 is located in the open portion of the second container 40. In particular, the first container 30 is positioned within the second container 40 by the first seal portion 49a that protrudes away from the first container 30. Therefore, when the second container 40 is opened, the first container 30 can be stably grasped. This allows the first container 30 to be removed from the second container 40. In other words, when using the liquid L contained in the first container 30, the first container 30 can be easily removed from the second container 40.

[0227] Furthermore, no waste such as scraps is generated when the second container 40 is opened. The oxygen absorbing member 22 and the oxygen detector 25 remain contained in the second container 40 even after the first container 30 is removed from the second container 40. Therefore, the second container 40, the oxygen absorbing member 22, and the oxygen detector 25, which are discarded after the second container 40 is opened, are easy to handle.

[0228] As described above, the liquid-containing combination container 10L described above has the advantage of being able to reduce the oxygen concentration in the first container 30 and the amount of oxygen dissolved in the liquid L, as well as the advantage of being easy to handle during use.

[0229] Although the specific example described above illustrates a curved first seal portion 49a, the configuration of the first seal portion 49a is not limited to this example. As shown in FIG. 15A, the first seal portion 49a may be curved. In the example shown in FIG. 15A, the first seal portion 49a is curved so as to protrude toward a second side away from the first container 30 in the first direction. As shown in FIG. 15B, only a portion of the first seal portion 49a may be bent. As shown in FIG. 15C, only a portion of the first seal portion 49a may be curved. As shown in FIGS. 15B and 15C, both end portions of the first seal portion 49a may extend linearly along the second direction D2. These examples also make it easier to peel the first film 41a and the second film 41b from the first seal portion 49a.

[0230] 15D, the portion of the first sealed portion 49a that protrudes most in the first direction D1 away from the first container 30 may be the portion of the first sealed portion 49a that extends most in the third direction D3. That is, in the example shown in Fig. 15D, the angle that the outer edge 49ae of the first sealed portion 49a forms with respect to the first direction D1 in which the first container 30 and the first sealed portion 49a face each other is smallest at the portion of the first sealed portion 49a that protrudes most in the first direction D1 away from the first container 30. According to this example, it is possible to more easily peel the first film 41a and the second film 41b from the first sealed portion 49a.

[0231] As shown in FIG. 10 , the seal 49 may include a main seal 49X that defines the space S for accommodating the first container 30 and an auxiliary seal 49Y that joins the first film 41a and the second film 41b at the extension 50b. In the illustrated example, the main seal 49X includes the first seal 49a, the first side seal 49b, the second side seal 49c, and the second seal 49d. The auxiliary seal 49Y prevents the first film 41a and the second film 41b from curling at the extension 50b. Therefore, the auxiliary seal 49Y makes it easier to grip the extension 50b of the first film 41a and the second film 41b. This further facilitates handling of the liquid-filled combination container 10L. Furthermore, the rigidity of the second container 40 is improved at the extension 50b, allowing the second container 40 to protect the first container 30.

[0232] 10, the auxiliary seal portion 49Y includes a first auxiliary seal portion 49Ya connected to the first side seal portion 49b and a second auxiliary seal portion 49Yb connected to the second side seal portion 49c. The first auxiliary seal portion 49Ya may extend linearly along an extension of the first side seal portion 49b. The second auxiliary seal portion 49Yb may extend linearly along an extension of the second side seal portion 49c. These examples more effectively prevent the first film 41a and the second film 41b from curling at the extension portion 50b. These examples more effectively improve the rigidity of the second container 40 at the extension portion 50b.

[0233] The configuration of the auxiliary seal portion 49Y is not limited to the configuration shown in FIG. 10 and other figures. As shown in FIG. 16, the auxiliary seal portion 49Y may be spaced apart from the main seal portion 49X. In the example shown in FIG. 16, the auxiliary seal portion 49Y includes a first auxiliary seal portion 49Ya located on an extension of the first side seal portion 49b and a second auxiliary seal portion 49Yb located on an extension of the second side seal portion 49c. The first auxiliary seal portion 49Ya and the second auxiliary seal portion 49Yb may be linear, bent, or dotted as shown in FIG. 16. These examples also prevent the first film 41a and the second film 41b from curling at the extension portion 50b. These examples also improve the rigidity of the second container 40 in the area of the extension portion 50b.

[0234] 17, the second container 40 of the liquid-filled combination container 10L may be further folded. In the example shown in FIG. 17, the second container 40 is bent with the second film 41b facing inward. FIG. 10 shows a first folding axis BA1 along which the second container 40 is folded. By bending the second container 40, the second portion 40P2, which was located on one side (first side) of the first portion 40P1 in the first direction D1 from the first portion 40P1 in the unfolded state of the second container 40, faces the first portion 40P1 containing the first container 30 of the second container 40 in the third direction D3. That is, the first portion 40P1 and the second portion 40P2 overlap in the third direction D3. The first portion 40P1 and the second portion 40P2 may be in contact with each other or may be separated from each other. The first portion 40P1 and the second portion 40P2 may be joined together.

[0235] The oxygen absorbing member 22 containing the oxygen absorber 21 is in a sheet shape. The sheet-shaped oxygen absorbing member 22 is bent together with the second container 40. The middle portion of the bent oxygen absorbing member 22 is located on a bent apex (folded apex) 41bx of the second film 41b. As shown in FIG. 17 , the bent apex 41bx is the position of the folded second film 41b that protrudes most toward the first side in the first direction D1. The bent apex 41bx is the position farthest from the first container in the direction in which the stopper 34 is inserted into the container body 32.

[0236] 17, folding the sheet-like deoxidizing member 22 together with the second film 41b makes it easier to ensure a path for oxygen to travel between the first container 30 and the deoxidizing member 22. More specifically, gaps are more likely to be formed between the deoxidizing member 22, the stopper 34 of the first container 30, and the second film 41b. Oxygen can stably travel from the stopper 34 to the deoxidizing member 22 through these gaps, so that the oxygen concentration in the first container 30 and the amount of oxygen dissolved in the liquid L contained in the first container 30 can be stably reduced.

[0237] 17, the oxygen detector 25 is positioned between the oxygen absorber 22 and the first film 41a. The display portion 26 of the oxygen detector 25 positioned in this manner can be easily observed through the transparent first film 41a. Therefore, by observing the display portion 26 of the oxygen detector 25, information about the oxygen concentration in the second container 40 can be stably obtained.

[0238] In the example shown in FIG. 17, the second container 40 is bent twice with the second film 41b facing inward. In addition to the first folding axis BA1, FIG. 10 also shows a second folding axis BA2 along which the second container 40 is folded. By folding the second container 40 about the second folding axis BA2, the third portion 40P3, which was located on the other side (second side) in the first direction D1 from the first portion 40P1 of the second container 40 containing the first container 30 when the second container is unfolded, faces the third direction D3. That is, the first portion 40P1 and the third portion 40P3 overlap in the third direction D3. The first portion 40P1 and the third portion 40P3 may be in contact with each other or may be separated from each other. The first portion 40P1 and the third portion 40P3 may also be joined together. The second container 40 is folded around the second folding axis BA2 so that the second film 41b faces inward. By folding the second container 40 twice, the liquid-containing combination container 10L can be made smaller.

[0239] By folding twice, the second portion 40P2 and the third portion 40P3 are located on the same side of the first portion 40P1. The first film 41a in the first portion 40P1 is not covered by the second portion 40P2 or the third portion 40P3. Therefore, the first container 30 can be clearly observed through the first film 41a of the second container 40. This makes it easy to observe the state of the first container 30 and the state of the liquid L contained in the first container 30. In addition, the label attached to the first container 30 can also be easily observed. Information about the liquid L may be written on this label.

[0240] In the illustrated example, the first portion 40P1, the third portion 40P3, and the second portion 40P2 are stacked in this order. The second portion P2 and the third portion 40P3 may be in contact with each other or may be separated from each other. The second portion P1 and the third portion 40P3 may be joined together. This example allows the radius of curvature of the second portion 40P2 relative to the first portion 40P1 to be increased. Therefore, a more stable oxygen transfer path between the first container 30 and the deoxidizing member 22 can be ensured. This allows oxygen to stably transfer from the stopper 34 to the deoxidizing member 22, thereby stably reducing the oxygen concentration in the first container 30 and the amount of oxygen dissolved in the liquid L contained in the first container 30.

[0241] As shown in FIG. 18 , the liquid-filled combination container 10L may further include an outer box 55 that houses the second container 40. The outer box 55 includes a bottom 56, a top 57 facing the bottom 56, and a sidewall 58 located between the bottom 56 and the top 57. As shown in FIG. 17 , the second container 40 is folded so that the first portion 40P1, the second portion 40P2, and the third portion 40P3 overlap. As shown by the two-dot chain line in FIG. 17 , the second container housing the first container 30 may be housed in the outer box 55 such that the bottom 32a of the container body 32 of the first container 30 faces the bottom 56 of the outer box 55 and the stopper 34 of the first container 30 faces the top 57 of the outer box 55. In this example, the liquid-filled combination container 10L can be stored with the bottom 56 positioned on a support surface such as a desk or shelf. At this time, the oxygen-permeable stopper 34 separates from the liquid L and comes into contact with the gas in the headspace HS in the first container 30. Storing the liquid-filled combination container 10L in this state promotes oxygen permeation through the stopper 34, and the oxygen concentration in the first container 30 and the amount of oxygen dissolved in the liquid L can be reduced in a short time after the first container 30 is placed in the second container 40.

[0242] As described above, the second container 40 has a storage section S between the first side seal portion 49b and the second side seal portion 49c. As shown in FIG. 19 , the second container 40 may include a notch 51 in one or both of the first side seal portion 49b and the second side seal portion 49c. The notch 51 may be a slit or a cut. The second container 40 may be openable by cutting the first film 41a and the second film 41b starting from the notch 51. The illustrated second container 40 can be easily opened starting from the first seal portion 49a. However, depending on the situation, the second container 40 may be opened more easily and reliably by cutting the first film 41a and the second film 41b starting from the notch 51 rather than peeling the first film 41a and the second film 41b at the first seal portion 49a. Therefore, by forming notches 51, which serve as starting points for cutting the first film 41a and the second film 41b, on the outer edges 49ae, 49be of the side seal portions 49b, 49c, the combination liquid container 10L can be handled even more easily.

[0243] As shown by dotted lines in FIG. 19 , the second container 40 may include a planned opening portion 52. The planned opening portion 52 is a portion where the films 41a and 41b are planned to be cut when the second container 40 is opened. The planned opening portion 52 may be a portion connected to the notch 51. The planned opening portion 52 may have a configuration that enables more reliable cutting at the planned opening portion 52. The planned opening portion 52 may be formed by the material of the first film 41a and the second film 41b or by processing the first film 41a and the second film 41b. Specifically, the planned opening portion 52 may be formed by imparting anisotropy to the material of the first film 41a and the second film 41b by stretching or the like. The planned opening portion 52 may be formed by processing the first film 41a and the second film 41b by half-cutting or laser processing, or by straight-cutting, which cuts an intermediate film.

[0244] The first container 30 may be located on one side of the first film 41a and the second film 41b cut along the notch 51, and the oxygen absorbing member 22 may be located on the other side of the first film 41a and the second film 41b cut along the notch 51. That is, when the second container 40 is cut along the notch 51, the first container 30 may be placed on one side of the second container 40 along the cutting line, and the oxygen absorbing member 22 and the oxygen detector 25 may be located on the other side of the second container 40. According to this example, the first container 30 can be easily removed from the second container 40 when the second container 40 is opened. This allows for easy handling of the liquid-filled combination container 10L. In the example shown in FIG. 19 , the notch 51 is located between the first container 30 and the oxygen absorbing member 22 in the first direction D1, in which the first container 30 and the oxygen absorbing member 22 face each other. In the first direction D1 in which the first container 30 and the deoxidizing member 22 face each other, the intended opening portion 52 is located between the first container 30 and the deoxidizing member 22.

[0245] As shown in FIG. 20 , the seal portion 49 may include a main seal portion 49X that defines the storage space S of the second container 40, and an additional seal portion 49Z located between the main seal portion 49X and the first container 30. The seal portion 49 includes a first side seal portion 49b and a second side seal portion 49c. The first container 30 is located between the first side seal portion 49b and the second side seal portion 49c in the second direction D2. The additional seal portion 49Z may be located between the first container 30 and at least one of the first side seal portion 49b and the second side seal portion 49c. In the example shown in FIG. 20 , the additional seal portion 49Z includes a first additional seal portion 49Za located between the first side seal portion 49b and the first container 30 in the second direction D2, and a second additional seal portion 49Zb located between the second side seal portion 49c and the first container 30 in the second direction D2. The additional seal portion 49Z is located away from the first seal portion 49a in the direction in which the first container 30 and the first seal portion 49a face each other.

[0246] When opening the second container 40, first, the first film 41a and the second film 41b are peeled off at the first seal portion 49a. Next, as shown in Fig. 21, the first film 41a and the second film 41b are peeled off at the first side seal portion 49b and the second side seal portion 49c. The films 41a and 41b are peeled off at the side seal portions 49b and 49c from the end connected to the first seal portion 49a toward the end connected to the second seal portion 49d. In other words, the films 41a and 41b are peeled off at the side seal portions 49b and 49c in the second direction D2, which is the longitudinal direction of the side seal portions 49b and 49c.

[0247] When peeling the first film 41a and the second film 41b, at least one of the first film 41a and the second film 41b is folded back away from the other. In the example shown in FIG. 21, only the first film 41a is folded back away from the second film 41b. As the films 41a and 41b are peeled back at the side seals 49b and 49c, the folded edge E41 of the film reaches the additional seal 49Z. At this time, the bonding force between the first film 41a and the second film 41b increases rapidly. In other words, the force required to peel the first film 41a and the second film 41b increases rapidly. Therefore, the additional seal 49Z prevents the first film 41a and the second film 41b from being unintentionally peeled back too far. This prevents the first film 41a and the second film 41b from peeling off all at once, which could cause the first container 30 to fall out of the second container 40.

[0248] 20 , the arrangement area of the additional seal portion 49Z may at least overlap the arrangement area of the first container 30 in the first direction D1 in which the first seal portion 49a and the first container 30 face each other. This example effectively prevents the first container 30 from falling out of the second container 40 when the first film 41a and the second film 41b are peeled away to open the second container 40. Furthermore, it is possible to prevent the orientation of the first container 30 from changing in the storage space S of the second container 40. Therefore, it is possible to maintain the positioning of the first container 30 and the oxygen absorbing member 22 in the storage space S of the second container 40. This allows the oxygen concentration in the first container 30 and the amount of oxygen dissolved in the liquid L to be stably reduced.

[0249] In the first direction D1, in which the first sealed portion 49a and the first container 30 face each other, the end of the first container 30 facing the first sealed portion 49a may be located at the same position as the end of the additional sealed portion 49Z facing the first sealed portion 49a. As shown in FIG. 20 , in the first direction D1, the end of the first container 30 facing the first sealed portion 49a may be located closer to the first sealed portion 49a than the end of the additional sealed portion 49Z facing the first sealed portion 49a. According to these examples, when the folded edge E41 of the film comes into contact with the additional sealed portion 49Z, the first container 30 positioned between the first film 41a and the second film 41b can be easily gripped. This makes it easier to handle the liquid-filled combination container 10L.

[0250] As shown in Fig. 21, the film folded edge E41 formed when the first film 41a and the second film 41b are peeled away is inclined with respect to the second direction D2 so as to be closer to the second sealed portion 49d inward in the second direction D2 than in the first direction D1. Therefore, as shown in Fig. 20, the additional sealed portion 49Z may be spaced apart from the side sealed portions 49d and 49c in the second direction D2. That is, the additional sealed portion 49Z may not be connected to the side sealed portions 49d and 49c. Note that "inward in the second direction D2" refers to the side closer to the center of the second container 40 in the second direction D2. "Outward in the second direction D2" refers to the side farther from the center of the second container 40 in the second direction D2.

[0251] As shown in Figures 22 to 24, the additional seal 49Z may be connected to the side seals 49d and 49c. In the example shown in Figures 22 to 24, the first additional seal 49Za is connected to the first side seal 49b. The second additional seal 49Zb is connected to the second side seal 49c. By connecting the additional seal 49Z to the side seals 49d and 49c, it is possible to more effectively prevent the first film 41a and the second film 41b from being unintentionally peeled off too far.

[0252] The shape of the additional sealed portion 49Z in a plan view can also be modified in various ways. The additional sealed portion 49Z only needs to have a configuration that allows the film folded edge E41 to be reached when the first film 41a and the second film 41b are peeled off. In the example shown in FIG. 22, the additional sealed portions 49Za and 49Zb have a semicircular shape when the second container 40 is laid out flat. In the example shown in FIG. 23, the additional sealed portions 49Za and 49Zb have a triangular shape or a triangle with curved corners when the second container 40 is laid out flat. In the example shown in FIG. 24, the additional sealed portions 49Za and 49Zb have a trapezoidal shape or a trapezoid with curved corners when the second container 40 is laid out flat.

[0253] 23 and 24, an inner edge 49Ze of the additional seal portion 49Z facing the first container 30 may be spaced apart from the corresponding side seal portion 49b, 49c as it approaches the first seal portion 49a in a first direction D1 in which the first seal portion 49a and the first container 30 face each other. In the example shown in FIGS. 23 and 24, the first additional seal portion 49Za includes an inner edge 49Ze that approaches the first container 30 and is spaced apart from the first side seal portion 49b in the second direction D2 toward the second side in the first direction D1. In the example shown in FIGS. 23 and 24, the second additional seal portion 49Zb includes an inner edge 49Ze that approaches the first container 30 and is spaced apart from the second side seal portion 49c in the second direction D2 toward the second side in the first direction D1. 24, this inner edge 49Ze functions as a guide that guides the first container 30 to a predetermined position when the first container 30 is placed into the storage space S of the second container 40 through the opening 40a provided at the position of the second seal portion 49d. With this inner edge 49Ze, the first container 30 can be easily and stably positioned at a predetermined relative position with respect to the deoxidizing member 22 in the storage space S of the second container 40. Therefore, the oxygen concentration in the first container 30 and the amount of oxygen dissolved in the liquid L can be stably reduced.

[0254] The seal strength of the seal portion 49 may be increased on the second seal portion 49d side of the first side seal portion 49b and the second side seal portion 49c. In other words, the bonding strength between the first film 41a and the second film 41b may be increased on the second seal portion 49d side of the first side seal portion 49b and the second side seal portion 49c. The processing temperature when forming the seal portion 49 may be higher on the second seal portion 49d side of the side seal portions 49b and 49c. The number of processing steps when forming the seal portion 49 may be increased on the second seal portion 49d side of the side seal portions 49b and 49c. According to this example, peeling of the first film 41a and the second film 41b, which starts from the first seal portion 49a, can be easily stopped halfway through the side seal portions 49b and 49c. This makes it possible to prevent the first container 30 from unintentionally falling out of the second container 40 when the second container 40 is opened.

[0255] In the above-described example, the first container 30 was placed in the second container 40 with the container body 32 facing the first seal portion 49a and the stopper 34 facing the oxygen absorbing member 22. As shown in FIG. 25 , the first container 30 may be placed in the second container 40 with the stopper 34 facing the first seal portion 49a and the bottom 32a of the container body 32 facing the oxygen absorbing member 22. The liquid-filled combination container 10L shown in FIG. 25 can also be expected to have the following effects. That is, the first film 41a and the second film 41b can be easily peeled at the first seal portion 49a starting from the curved first seal portion 49a, thereby easily opening the second container 40. Furthermore, when the second container 40 is opened, the first container 30 is located in the open portion of the second container 40. In particular, the first container 30 is positioned within the second container 40 by the first seal portion 49a, which protrudes away from the first container 30. Therefore, the first container 30 can be stably grasped when the second container 40 is opened. This allows the first container 30 to be removed from the second container 40. That is, when the liquid L contained in the first container 30 is used, the first container 30 can be easily removed from the second container 40. Furthermore, no waste such as scraps is generated when the second container 40 is opened. The oxygen absorbing member 22 and the oxygen detector 25 remain contained within the second container 40 even after the first container 30 is removed from the second container 40. Therefore, the second container 40, the oxygen absorbing member 22, and the oxygen detector 25, which are discarded after the second container 40 is opened, are easy to handle.

[0256] Next, a further description will be given of specific examples of the laminate 47 that can be used in the second container 40. In the following description and the drawings used in the following description, parts that can be configured similarly to the above-described specific examples or corresponding configurations will be designated by the same reference numerals as those used for corresponding parts in the above-described specific examples, and duplicated descriptions will be omitted.

[0257] By improving the oxygen barrier property of the second container 40, the oxygen concentration (%) in the second container 40, the oxygen concentration (%) in the first container 30, and the amount of oxygen dissolved (mg / L) in the liquid L in the first container 30 can be sufficiently reduced and stably maintained at a reduced state. Furthermore, by improving the water vapor barrier property of the second container 40, when the liquid L in the first container 30 contains a non-aqueous solvent, it is possible to suppress an increase or decrease in the amount of water vapor in the first container 30 and the second container 40. In addition, when the liquid L in the first container 30 contains an aqueous solvent, it is possible to stably maintain the concentration of the liquid L. An aqueous solvent refers to a solvent in which the main component with the largest volumetric proportion is water.

[0258] The laminate, such as films 41a-41d, included in the second container 40 includes a barrier layer having an oxygen barrier function and a water vapor barrier function. The barrier function of the laminate can be strengthened by increasing the thickness of the barrier layer included in the laminate. However, typically, increasing the thickness of a barrier layer formed as a vapor-deposited film reduces the adhesive strength between the barrier layer and adjacent layers. Furthermore, increasing the thickness of a barrier layer formed as a vapor-deposited film makes the barrier layer more susceptible to cracking. For these reasons, the oxygen barrier property and water vapor barrier property of laminates used in conventional containers have been limited. The present inventors have conducted extensive research into this issue, and as a result have created a laminate with excellent barrier properties. The laminate created by the present inventors will be described below.

[0259] The laminate described below can be applied to the combination container 10 and the second container 40 included in the container set 20. More specifically, the laminate described below may constitute the films 41a to 41e of the second container 40 shown in FIG. 1 and FIGS. 7A to 7C. The laminate described below may constitute the container body 42 or the lid 44 of the second container 40 shown in FIG. 8. The laminate described below may constitute the films 41a and 41b of the second container 40 shown in FIGS. 10 to 25. Furthermore, the laminate described below is not limited to the second container 40, but can be applied to containers (packages) used in a wide variety of fields, and can improve the barrier properties of the containers (packages).

[0260] The laminate 47 includes an inner surface 47a facing the storage space S of the container and an outer surface 47b opposite the inner surface 47a. As shown in FIG. 26A , the laminate 47 may include, in order from the inner surface 47a to the outer surface 47b, a sealant layer 48a, a first barrier layer 48c, a resin layer 48f, and a second barrier layer 48h. The laminate 47 includes two barrier layers 48c and 48h that have a barrier function. Therefore, the laminate 47 has high barrier properties even without increasing the thickness of each of the barrier layers 48c and 48h included in the laminate 47. In other words, the laminate 47 can exhibit high barrier function while suppressing deterioration in adhesion and cracking of the barrier layers 48c and 48h.

[0261] Furthermore, even if defects such as pinholes or cracks occur in one of the barrier layers 48c, 48h, the laminate 47 can maintain a certain level of barrier properties due to the other barrier layer 48c, 48h. In particular, the resin layer 48f is disposed between the first barrier layer 48c and the second barrier layer 48h. The resin layer 48f, which functions as the base material of the laminate 47, can prevent defects such as pinholes or cracks from occurring in both the first barrier layer 48c and the second barrier layer 48h.

[0262] When the laminate 47 is applied to the second container 40 of the container set 20 and the combination container 10, the laminate 47 can exhibit high oxygen barrier function and high water vapor barrier function. By improving the oxygen barrier property of the second container 40, the oxygen concentration (%) in the second container 40, the oxygen concentration (%) in the first container 30, and the amount of oxygen dissolved in the liquid L (mg / L) can be sufficiently reduced and stably maintained at a reduced level. By improving the water vapor barrier property of the second container 40, when the liquid L in the first container 30 contains a non-aqueous solvent, an increase or decrease in the amount of water vapor in the first container 30 and the second container 40 can be suppressed. When the liquid L in the first container 30 contains an aqueous solvent, the concentration of the liquid L in the first container 30 can be stably maintained.

[0263] By disposing the resin layer 48f between the two barrier layers 48c, 48h, the generation of bubbles in the laminate 47 can be suppressed. Therefore, when the laminate 47 is applied to the second container 40 of the container set 20 and the combined container 10, the state of the first container 30 can be observed from outside the second container 40. Furthermore, the oxygen concentration in the second container 40 can be measured using a non-contact oxygen measuring device without opening the second container 40. Furthermore, if the container body 32 of the first container 30 is also transparent, the liquid L in the first container 30 can be observed from outside the second container 40. In this case, the oxygen concentration in the first container 30 can be measured using a non-contact oxygen measuring device without opening the first container 30 and the second container 40. Similarly, the amount of oxygen dissolved in the liquid L in the first container 30 can be measured using a non-contact oxygen measuring device without opening the first container 30 and the second container 40.

[0264] The laminate 47 may be transparent. The laminate 47 may include a transparent portion. As described above, transparency means that the transmission haze of the target portion is 80.0% or less so that the inside of the target portion can be observed from the outside. To enable the target portion to be more clearly observed from the outside, the transmission haze of at least a portion of the laminate 47 may be 58.0% or less, 29.0% or less, 14.5% or less, 7.0% or less, 3.5% or less, or 1.0% or less.

[0265] If the laminate 47 is transparent, the state of the first container 30 can be observed from the outside of the second container 40 to which the laminate 47 is applied. Also, the oxygen concentration in the second container 40 can be measured using a non-contact oxygen amount measuring device without opening the second container 40. Furthermore, if the container body 32 of the first container 30 is also transparent, the liquid L in the first container 30 can be observed from the outside of the second container 40. In this case, the oxygen concentration in the first container 30 can be measured using a non-contact oxygen amount measuring device without opening the first container 30 and the second container 40. Similarly, the amount of oxygen dissolved in the liquid L in the first container 30 can be measured using a non-contact oxygen amount measuring device without opening the first container 30 and the second container 40.

[0266] There is no particular lower limit set for the transmission haze in at least a portion of the laminate 47. The transmission haze in at least a portion of the laminate 47 may be 0% or more, or may be greater than 0%.

[0267] The total light transmittance of a part or the whole of the laminate 47 may be 50% or more, 70% or more, 80% or more, or 90% or more. By setting a lower limit for the total light transmittance of the laminate 47, the state of the first container 30 can be clearly observed from outside the second container 40 to which the laminate 47 is applied. No particular lower limit is set for the total light transmittance of the laminate 47. The total light transmittance of the laminate 47 may be 0% or more, or may be greater than 0%.

[0268] The laminate 47 may have a transmission haze within the above-mentioned predetermined range and a total light transmittance within the above-mentioned predetermined range.

[0269] A D65 standard light source is used to measure total luminous transmittance. Before measuring total luminous transmittance, the D65 standard light source is turned on for 15 minutes to stabilize the output of the D65 standard light source. The angle of incidence on the sample when measuring total luminous transmittance is 0°. The test environment when measuring total luminous transmittance is a temperature of 23°C ± 2°C and a relative humidity of 50% ± 5%. The sample is placed in the test environment for 16 hours before starting the test. Other measurement conditions when measuring total luminous transmittance are in accordance with JIS K7361-1:1997. The total luminous transmittance is the arithmetic mean of five measured values. The five measured values are measured at five measurement positions on the measurement sample to be evaluated.

[0270] The yellowness index (YI value) of the laminate 47, in part or in its entirety, may be 20 or less, 15 or less, 13 or less, or 10 or less. A value of 20 or less makes it easier to see the color of the interior of the package, improving the discernibility of color-based indicators such as Ageless Eye. The yellowness index is an index showing the degree of yellowing of the laminate 47. The laminate 47 exhibits high barrier properties due to the two barrier layers. Compared to using one thick barrier layer, using two barrier layers can reduce the yellowness index of the laminate 47 to the above upper limit or less.

[0271] Setting the upper limit on the yellowness index (YI value) as described above makes it possible to limit yellowish coloration of the laminate 47. Setting the upper limit on the yellowness index (YI value) as described above makes it possible to clearly observe the state of the first container 30 from outside the second container 40 to which the laminate 47 is applied.

[0272] There is no particular lower limit set for the yellowness index (YI value) of the laminate 47. The yellowness index (YI value) of the laminate 47 may be 0 or greater, or may be greater than 0.

[0273] Yellowness is measured using transmitted light. Using spectrophotometric colorimetry, auxiliary illuminant C and a 2-degree visual field, transmittance is measured at 0.5 nm intervals in the range of 300 nm to 780 nm, and the tristimulus values X, Y, and Z in the XYZ color system are calculated based on this. The yellowness (YI value) is determined from the calculated X, Y, and Z values using the following formula: YI=100(1.2769X-1.0592Z) / Y The geometrical optics condition e of JIS Z 8722:2009 is used as the geometrical optics condition when measuring yellowness. To eliminate the influence of scattered light from the edge of the test piece, the diameter of the incident light beam on the test piece is made smaller than the diameter of the opening. Before measuring yellowness, the light source of the measuring device is turned on for 15 minutes to stabilize the output of the D65 standard light source. The incident surface when measuring yellowness is the inner surface 47a of the laminate 47. The test environment for measuring yellowness is a temperature of 23°C ± 2°C and a relative humidity of 50% ± 5%. The sample is placed in the test environment for 16 hours before starting the test.

[0274] The yellowness index (YI value) is the arithmetic mean of five measured values. The five measured values are measured at five measurement positions on the optical sheet to be evaluated. The five measurement positions are located at least 10 mm apart from each other. Other measurement conditions for measuring the yellowness index (YI value) are in accordance with JIS K7373-1:2006.

[0275] The laminate 47 may have one or more of the transmission haze and the total light transmittance in the above-mentioned predetermined range, and the yellowness index in the above-mentioned predetermined range.

[0276] The oxygen permeability of the laminate 47 is 0.20 (mL / (m 2 × day × atm)), and may be less than 0.15 (mL / (m 2 × day × atm)) or less, and 0.14 (mL / (m 2 ×day×atm) or less. With an oxygen permeability having such an upper limit, an extremely high oxygen barrier property can be imparted to the second container 40, and the oxygen concentration (%) in the first container 30 and the amount of oxygen dissolved in the liquid L (mg / L) can be effectively reduced sufficiently and the reduced state can be stably maintained. There is no particular lower limit set for the oxygen permeability of the laminate 47. The oxygen permeability of the laminate 47 is 0 (mL / (m 2 × day × atm)) or more, and 0 (mL / (m 2 ×day×atm)).

[0277] The oxygen permeability of the laminate 47 is 0 (mL / (m 2 ×day×atm)) or more and less than 0.20 (mL / (m 2 × day × atm)) or less, and 0 (mL / (m 2 ×day×atm)) or more 0.15(mL / (m) 2 × day × atm)) or less, and 0 (mL / (m 2 ×day×atm)) or more 0.14(mL / (m) 2 The oxygen permeability of the laminate 47 may be 0 (mL / (m 2 ×day×atm)) but less than 0.20 (mL / (m 2× day × atm)) or less, and 0 (mL / (m 2 × day × atm)) and greater than 0.15 (mL / (m 2 × day × atm)) or less, and 0 (mL / (m 2 × day × atm)) and greater than 0.14 (mL / (m 2 ×day×atm) or less is also acceptable.

[0278] The water vapor permeability of the laminate 47 is 0.50 (g / (m 2 × day)) or less, and 0.30 (g / (m 2 × day)) or less, and 0.20 (g / (m 2 × day)) or less. A water vapor permeability with such an upper limit can impart extremely high water vapor barrier properties to the second container 40. By suppressing the permeation of water vapor in the second container 40 to the outside, the amount of evaporation of the liquid L can be suppressed, thereby suppressing changes in concentration. There is no particular lower limit set for the water vapor permeability of the laminate 47. The water vapor permeability of the laminate 47 is 0 (mL / (m 2 × day × atm)) or more, and 0 (mL / (m 2 ×day×atm)).

[0279] The water vapor permeability of the laminate 47 is 0 (mL / (m 2 ×day×atm)) or more 0.50(g / (m) 2 × day)) or less, and 0 (mL / (m 2 ×day×atm)) or more 0.30(g / (m) 2 × day)) or less, and 0 (mL / (m 2 ×day×atm)) or more 0.20(g / (m) 2 The water vapor permeability of the laminate 47 may be 0 (mL / (m 2 ×day×atm)) and greater than 0.50(g / (m 2 × day)) or less, and 0 (mL / (m 2 ×day×atm)) and greater than 0.30(g / (m 2 × day)) or less, and 0 (mL / (m 2 ×day×atm)) and greater than 0.20(g / (m2 ×day)) or less is also acceptable.

[0280] The water vapor permeability is measured in accordance with JIS K 7129-2:2019. The water vapor permeability is measured under an environment of a temperature of 40°C and a humidity of 90% RH using a permeability measuring device, PERMATRAN (3 / 33), manufactured by MOCON, USA.

[0281] The resin layer 48f functions as a resin base material for the entire laminate 47. The resin layer 48f may be a stretched film. The resin layer 48f may contain a thermoplastic resin as a main component. The main component refers to the component that has the largest mass percentage. A lower limit may be set for the thickness of the resin layer 48f. The thickness of the resin layers 48f, 48j may be 5 μm or more and 60 μm or less, or 7 μm or more and 30 μm or less. These resin layers 48f can function as a resin base material for the entire laminate 47.

[0282] The resin layer 48f may be a substrate that supports at least one of the first barrier layer 48c and the first barrier substrate layer 48d.

[0283] The resin layer 48f, which functions as a resin substrate, imparts mechanical properties, such as strength, hardness, Young's modulus, and bending rigidity, required for the laminate 47. The material of the resin layer 48f, which functions as a resin substrate, may be polyamide, polypropylene, or polyethylene terephthalate.

[0284] As a specific example, the resin layer 48f may be made of oriented polyamide or oriented polyester. The oriented polyamide may be uniaxially oriented polyamide or biaxially oriented polyamide. The oriented polyamide may be uniaxially oriented nylon or biaxially oriented nylon. The oriented polyester may be uniaxially oriented polyester or biaxially oriented polyester, or uniaxially oriented polyethylene terephthalate or biaxially oriented polyethylene terephthalate.

[0285] Stretched polyamide and stretched nylon have excellent puncture resistance, abrasion resistance, and flex resistance. Therefore, using stretched polyamide or stretched nylon for the resin layer 48f can reduce defects such as pinholes and cracks in the laminate 47. Using stretched polyamide or stretched nylon for the resin layer 48f can reduce the thickness of the laminate 47 while maintaining the strength of the laminate 47. Furthermore, if the resin layer 48f contains stretched polyamide or stretched nylon, even if a defect such as a pinhole or crack occurs in one of the barrier layers 48c, 48h, it can prevent the other barrier layer 48c, 48h from also developing a defect. In this respect, stretched polyamide and stretched nylon are extremely suitable for the resin layer 48f disposed between the two barrier layers 48c, 48h.

[0286] 26B, the laminate 47 may include an inner adhesive layer 48b positioned between the sealant layer 48a and the first barrier layer 48c. The inner adhesive layer 48b may be adjacent to the sealant layer 48a and the first barrier layer 48c. The inner adhesive layer 48b may be bonded to the sealant layer 48a and the first barrier layer 48c. Alternatively, only a water vapor impermeable layer, for example, a polyethylene terephthalate (PET) layer having a thickness of 9 μm or more and 16 μm or less, may be positioned between the inner adhesive layer 48b and the first barrier layer 48c. This example sufficiently suppresses fluctuations in the water vapor concentration inside the container.

[0287] As shown in FIGS. 26C and 26D, the laminate 47 may further include a first adhesive layer 48e positioned between the first barrier layer 48c and the resin layer 48f, and a second adhesive layer 48g positioned between the resin layer 48f and the second barrier layer 48h. The first adhesive layer 48e may include a cured product of a curable resin composition. The second adhesive layer 48g may include a cured product of a curable resin composition. FIG. 26C shows a laminate in which the adhesive layers 48e and 48g are added to the laminate shown in FIG. 26A. FIG. 26D shows a laminate in which the adhesive layers 48e and 48g are added to the laminate shown in FIG. 26B.

[0288] During the curing process of the curable resin composition, bubbles may be generated, albeit slightly. The bubbles may contain, for example, carbon dioxide or water vapor. The generated bubbles cannot pass through the barrier layers 48c and 48h.

[0289] On the other hand, the resin layer 48f is made of, for example, polyamide such as nylon, polypropylene, or polyethylene terephthalate, and is gas permeable. Bubbles generated from the first adhesive layer 48e pass through one main surface (the main surface on the inner surface 47a side) of the resin layer 48f, travel through the resin layer 48f, and can be released from the side end surface of the resin layer 48f to the outside of the container. Bubbles generated from the second adhesive layer 48g pass through the other main surface (the main surface on the outer surface 47b side) of the resin layer 48f, travel through the resin layer 48f, and can be released from the side end surface of the resin layer 48f to the outside of the container. In other words, the resin layer 48f forms a permeation path for releasing bubbles generated during the curing process of the adhesive layers 48e and 48g.

[0290] Furthermore, the resin layer 48f is positioned between the first barrier layer 48c and the second barrier layer 48h. Therefore, one of the first barrier layer 48c and the second barrier layer 48h can be bonded to the resin layer 48f with an adhesive layer, and then the other of the first barrier layer 48c and the second barrier layer 48h can be bonded to the resin layer 48f with an adhesive layer. The resin layer 48f, which is bonded to one barrier layer on one side using an adhesive layer, can have the other side exposed. Therefore, air bubbles generated in the adhesive layer can pass through the resin layer 48f, allowing the air bubbles to be quickly removed. In this case, aging under appropriate conditions can further promote the removal of air bubbles.

[0291] These features prevent air bubbles from being trapped in the high-barrier laminate 47, which includes two barrier layers. They also prevent the high-barrier laminate 47, which includes two barrier layers, from becoming cloudy. Furthermore, the visible light transmittance of the laminate 47 is maintained at a high level, allowing the first container 30 and the liquid L to be clearly observed from outside the second container 40. Furthermore, the oxygen concentration in the second container 40, the oxygen concentration in the first container 30, and the amount of oxygen dissolved in the liquid L in the first container 30 can be measured with high accuracy from outside the second container 40.

[0292] From the viewpoint of suppressing the generation of bubbles in the laminate 47, the resin layer 48f may contain a polyester such as polyethylene terephthalate. The resin layer 48f may contain a polyester such as polyethylene terephthalate as a main component. The main component means the component that has the largest mass percentage. The resin layer 48f may contain a polyester film such as polyethylene terephthalate. The polyester film may be a uniaxially oriented polyester film, a biaxially oriented polyester film, or a stretched polyester film. It may also be a uniaxially oriented nylon film or a biaxially oriented nylon film.

[0293] Furthermore, from the viewpoint of increasing the puncture resistance of the laminate 47, the resin layer 48f may contain a polyamide such as nylon. The resin layer 48f may contain a polyamide such as nylon as a main component. The main component means the component that has the largest mass percentage. The resin layer 48f may contain a polyamide film such as nylon. The polyamide film may be a uniaxially oriented polyamide film, a biaxially oriented polyamide film, or a stretched polyamide film. It may be a uniaxially oriented nylon film or a biaxially oriented nylon film.

[0294] 26E, the laminate 47 may include a first barrier substrate layer 48d adjacent to the first barrier layer 48c. The laminate 47 may include a second barrier substrate layer 48i adjacent to the second barrier layer 48h. The first barrier substrate layer 48d may be a resin substrate that supports the first barrier layer 48c. The second barrier substrate layer 48i may be a resin substrate that supports the second barrier layer 48h.

[0295] In the illustrated example, the first barrier substrate layer 48d is positioned between the first barrier layer 48c and the inner adhesive layer 48b. This arrangement prevents the first barrier 48c from coming into direct contact with the sealant layer 48a, which is prone to dimensional changes and deformation. The presence of the first barrier substrate layer 48d reduces the impact of dimensional changes and deformation of the sealant layer 48a on the first barrier layer 48c. This reduces the occurrence of defects such as cracks and pinholes in the first barrier layer 48c.

[0296] In the illustrated example, the second barrier layer 48h is located between the resin layer 48f and the second barrier substrate layer 48i. The second barrier layer 48h is located between the second adhesive layer 48g and the second barrier substrate layer 48i. That is, the second barrier substrate layer 48i may be closer to the outer surface 47b than the second barrier layer 48h, or may constitute the outer surface 47b. With this arrangement, the second barrier substrate layer 48i is subjected to external forces or shocks due to contact with the outside before the second barrier layer 48h. The external forces or shocks applied to the second barrier layer 48h are weakened by the second barrier substrate layer 48i. This can prevent defects such as cracks or pinholes from occurring in the twelfth barrier layer 48h.

[0297] As shown in FIG. 26F, the laminate 47 may include three or more barrier layers. In the example shown in FIG. 26F, the laminate 47 further includes a second resin layer 48j and a third barrier layer 48k. A laminate including three or more barrier layers can further improve the oxygen barrier property and water vapor barrier property of the laminate 47. FIG. 26F adds a second resin layer 48j and a third barrier layer 48k to the laminate shown in FIG. 26E. The laminate 47 shown in FIG. 26F further includes a third barrier substrate layer 48l. The third barrier substrate layer 48l forms the outer surface 47b. The third barrier substrate layer 48l may be a resin substrate that supports the third barrier layer 48k.

[0298] A third adhesive layer may be provided between the second resin layer 48j and the second barrier substrate layer 48i. A fourth adhesive layer may be provided between the second resin layer 48j and the third barrier layer 48k. These third and fourth adhesive layers may be configured similarly to the adhesive layers 48e and 48g.

[0299] 26F, for the reasons described above, the first barrier substrate layer 48d may be located between the first barrier layer 48c and the inner adhesive layer 48b. Also in the example shown in Fig. 26F, for the reasons described above, the second barrier layer 48h may be located between the resin layer 48f and the second barrier substrate layer 48i, or between the second adhesive layer 48g and the second barrier substrate layer 48i.

[0300] In the example shown in FIG. 26F, the third barrier layer 48k may be located between the second resin layer 48j and the third barrier substrate layer 48l. The third barrier layer 48k may be located between the fourth adhesive layer and the third barrier substrate layer 48l. That is, the third barrier substrate layer 48l may be closer to the outer surface 47b than the third barrier layer 48k, or may constitute the outer surface 47b. With this arrangement, the third barrier substrate layer 48l receives external force or impact due to contact with the outside before the third barrier layer 48k. Therefore, the external force or impact received by the third barrier layer 48k is weakened by the third barrier substrate layer 48l. This can prevent defects such as cracks and pinholes from occurring in the third barrier layer 48k.

[0301] Each layer that may be included in stack 47 will now be described in more detail.

[0302] The barrier layers 48c, 48h, and 48k may contain a metal or an inorganic oxide. The barrier layer may be formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD). The barrier layer may be a vapor-deposited film. The barrier layer may include a vapor-deposited film. A vapor-deposited film is a layer formed by vapor deposition. A vapor-deposited film may include a metal or an inorganic oxide. A vapor-deposited film provides a thin barrier layer with excellent barrier properties. The barrier layer may be a transparent vapor-deposited film. The barrier layer may include a transparent vapor-deposited film. A transparent vapor-deposited film is a transparent layer formed by vapor deposition. The barrier layers 48c, 48h, and 48k as transparent vapor-deposited films can make the laminate 47, including the thin barrier layer with high barrier properties, transparent along with the other layers. Using a transparent laminate 47 for the second container 40 allows the first container 30 to be observed from outside the second container 40.

[0303] The metal contained in the barrier layers 48c, 48h, and 48k is not particularly limited. Examples of the metal include aluminum, tin, chromium, zinc, gold, silver, platinum, and nickel. Each of the barrier layers 48c, 48h, and 48k may contain two or more of these metals.

[0304] The inorganic oxide contained in the barrier layers 48c, 48h, and 48k is not particularly limited. Examples of inorganic oxides include oxides of silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium. Each of the barrier layers 48c, 48h, and 48k may contain two or more of these inorganic oxides. Specifically, the inorganic oxide contained in the barrier layers 48c, 48h, and 48k may be aluminum oxide or silicon oxide. Inorganic oxides are expressed as MOX, such as AlOX and SiOX. In the above formula, "M" represents an inorganic element. From the viewpoint of transparency and gas barrier properties, when M is aluminum (Al), the value of X may be 0.5 or more and 2.0 or less. When M is silicon (Si), the value of X may be 1 or more and 2 or less.

[0305] The thickness of the barrier layers 48c, 48h, and 48k may be 1 nm or more and 1.0 μm or less, 3 nm or more and 100 nm or less, 5 nm or more and 80 nm or less, or 8 nm or more and 50 nm or less.

[0306] The barrier layers 48c, 48h, and 48k may include multiple layers. The multiple layers may include a base barrier layer formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD). The base barrier layer may include a metal or an inorganic oxide. The base barrier layer may be a vapor-deposited film. The base barrier layer may be a transparent vapor-deposited film, i.e., a transparent vapor-deposited film. A vapor-deposited film is a layer formed by vapor deposition. The vapor-deposited film may include a metal or an inorganic oxide.

[0307] The barrier layers 48c, 48h, and 48k may include, in order from the barrier substrate layers 48d, 48i, and 48l, a base barrier layer and an over layer. The barrier layers 48c, 48h, and 48k may include, in order from the barrier substrate layers 48d, 48i, and 48l, a first base barrier layer, an over layer, and a second base barrier layer. The barrier layers 48c, 48h, and 48k may include, in order from the barrier substrate layers 48d, 48i, and 48l, a first base barrier layer, a first over layer, a second base barrier layer, and a second over layer.

[0308] The base barrier layer and the first base barrier layer may be formed directly on one surface of the barrier substrate layer 48d, 48i, 48l by chemical vapor deposition (CVD) or physical vapor deposition (PVD), etc. The base barrier layer and the first base barrier layer may contact the barrier substrate layer 48d, 48i, 48l. The second base barrier layer may be formed directly on the first over layer. The second base barrier layer may contact the first over layer.

[0309] The over layer, first over layer, and second over layer cover and protect any of the barrier layers. The over layer, first over layer, and second over layer may cover the entire barrier layer to be protected. The over layer and first over layer may be formed directly on the first base barrier layer. The over layer and first over layer may contact the first base barrier layer. The second over layer may be formed directly on the second base barrier layer. The second over layer may contact the second base barrier layer.

[0310] The over layer, the first over layer, and the second over layer may be a coating film (coat layer). The over layer, the first over layer, and the second over layer may be a coating film of a resin composition. The over layer, the first over layer, and the second over layer may be prepared by solidifying or curing a coating film applied on the barrier layer to be protected.

[0311] The over layer, the first over layer, and the second over layer may contain a cured product of a curable resin composition. The curable resin composition may be a two-component curable resin composition, a thermosetting resin composition, or an ionizing radiation curable resin composition. The ionizing radiation curable resin composition may be an electron beam curable resin composition or an ultraviolet ray curable resin composition. The over layer, the first over layer, and the second over layer may contain the same resin material as the resin material constituting the adhesive layers 48e and 48g.

[0312] The over layer, the first over layer, and the second over layer may contain the same resin material as the resin layers 48f and 48j, or the same resin material (described later) as the resin materials that constitute the barrier substrate layers 48d, 48i, and 48l.

[0313] The materials constituting the over layer, the first over layer, and the second over layer may contain an alkoxide. As the alkoxide represented by nM(OR2)m, at least one of a partial hydrolyzate of an alkoxide and a hydrolysis condensate of an alkoxide can be used. The partial hydrolyzate of an alkoxide is not limited to one in which all alkoxy groups are hydrolyzed, but may be one in which one or more alkoxy groups are hydrolyzed, or a mixture thereof. Furthermore, as the hydrolysis condensate, a dimer or higher of a partially hydrolyzed alkoxide, specifically a dimer to hexamer, may be used.

[0314] The over layer, the first over layer, and the second over layer may be formed using a coating agent containing a polyvinyl alcohol resin and a silane compound. The coating agent may contain an acid catalyst, an alkali catalyst, a photopolymerization initiator, etc., as needed.

[0315] The thickness of the barrier layers 48c, 48h, and 48k including multiple layers may be 20 nm to 20 μm, 10 nm to 10 μm, 50 nm to 5.0 μm, or 100 nm to 1.0 μm.

[0316] The thickness of the base barrier layer, first base barrier layer, and second base barrier layer may be 1 nm to 1000 nm, 3 nm to 500 nm, 5 nm to 500 nm, 5 nm to 300 nm, 8 nm to 100 nm, or 8 nm to 50 nm. The thickness of the over layer, first over layer, and second over layer may be 10 nm to 10 μm, 50 nm to 5.0 μm, 100 nm to 1.0 μm, or 100 nm to less than 1.0 μm.

[0317] The first barrier layer 48c, the second barrier layer 48h, and the third barrier layer 48k may have the same composition. The first barrier layer 48c, the second barrier layer 48h, and the third barrier layer 48k may have different compositions. The first barrier layer 48c, the second barrier layer 48h, and the third barrier layer 48k may have different materials. The first barrier layer 48c, the second barrier layer 48h, and the third barrier layer 48k may be formed by different deposition methods. The first barrier layer 48c, the second barrier layer 48h, and the third barrier layer 48k may have different thicknesses.

[0318] The barrier substrate layers 48d, 48i, and 48l serve as substrates when forming the barrier layers 48c, 48h, and 48k as vapor-deposited films. The barrier substrate layers 48d, 48i, and 48l are not particularly limited. The barrier substrate layers 48d, 48i, and 48l may be resin films. Examples of resin materials constituting the barrier substrate layers 48d, 48i, and 48l as resin films include polyolefins such as polyethylene and polypropylene, cyclic polyolefins, polystyrene, acrylonitrile-styrene copolymers (AS), acrylonitrile-butadiene-styrene copolymers (ABS), (meth)acrylic resins, polycarbonates, polyvinyl alcohols, saponified ethylene-vinyl ester copolymers, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides such as nylon, polyurethanes, acetal resins, and cellulose resins. The barrier substrate layers 48d, 48i, and 48l may also be laminated films using two or more films of these resin materials. "(Meth)acrylic" encompasses both "acrylic" and "methacrylic."

[0319] The barrier substrate layers 48d, 48i, and 48l preferably have high water vapor barrier properties, high gas barrier properties, and high oxygen barrier properties. The material of the barrier substrate layers 48d, 48i, and 48l preferably has a small amount of deformation, such as shrinkage, during vapor deposition. From these viewpoints, the barrier substrate layers 48d, 48i, and 48l may contain polyethylene terephthalate, may contain polyethylene terephthalate as a main component, or may be a polyethylene terephthalate film.

[0320] The barrier substrate layers 48d, 48i, and 48l may be unstretched films, uniaxially stretched films, or biaxially stretched films. The term "unstretched films" includes not only films that are not stretched at all, but also films that are slightly stretched due to tension applied during film formation.

[0321] The thickness of the barrier substrate layers 48d, 48i, 48l may be 6 μm or more and 2000 μm or less, or 9 μm or more and 100 μm or less.

[0322] The first barrier substrate layer 48d, the second barrier substrate layer 48i, and the third barrier substrate layer 48l may have the same composition. The first barrier substrate layer 48d, the second barrier substrate layer 48i, and the third barrier substrate layer 48l may have different compositions. The first barrier substrate layer 48d, the second barrier substrate layer 48i, and the third barrier substrate layer 48l may have different materials. The first barrier substrate layer 48d, the second barrier substrate layer 48i, and the third barrier substrate layer 48l may have different thicknesses.

[0323] The resin layers 48f and 48j function to hold the layers included in the laminate 47 together. The resin layers 48f and 48j are located between the two barrier layers 48c, 48h, and 48k. By being located between the two barrier layers 48c, 48h, and 48k, the resin layers 48f and 48j can effectively prevent the two barrier layers 48c, 48h, and 48k from bending at a small radius of curvature. This can prevent defects such as cracks from occurring in the two barrier layers 48c, 48h, and 48k. Furthermore, the resin layers 48f and 48j allow for easy adjustment of the flexibility and stiffness of the laminate 47. Furthermore, as described above, the resin layers 48f and 48j can prevent the laminate 47 from becoming cloudy due to bubbles generated during curing of the adhesive layers.

[0324] The resin layers 48f, 48j are not particularly limited. The resin layers 48f, 48j may be resin films. Examples of resin materials constituting the resin layers 48f, 48j as resin films include polyesters (chemically recycled polyesters, mechanically recycled polyesters, fossil fuel polyesters, and biomass polyesters), (meth)acrylic resins, polyolefins such as polyethylene, polypropylene, and polymethylpentene, vinyl resins, cellulose resins, ionomer resins, and polyamides such as nylon 6, nylon 6,6, and polymetaxylylene adipamide (MXD6). The resin layers 48f, 48j may be laminated films using two or more films of these resin materials.

[0325] The resin layers 48f, 48j may be unstretched films or stretched films. The resin layers 48f, 48j may be uniaxially stretched films or biaxially stretched films. The resin layers 48f, 48j, which are stretched films, can impart sufficient mechanical properties to the laminate 47.

[0326] The resin layers 48f, 48j may contain a thermoplastic resin. The resin layers 48f, 48j may contain a thermoplastic resin as a main component. The resin layers 48f, 48j may be thermoplastic resin films. The resin layers 48f, 48j containing a thermoplastic resin can promote the expulsion of air bubbles and provide low transmission haze and high total light transmittance.

[0327] The thickness of the resin layers 48f, 48j may be 5 μm or more and 60 μm or less, or 7 μm or more and 30 μm or less. By setting a lower limit on the thickness of the resin layer 48f, it is possible to impart sufficient mechanical properties to the laminate 47 as a resin base material for the entire laminate 47. By setting an upper limit on the thickness of the resin layer 48f, it is possible to impart appropriate flexibility to the laminate 47 used in the second container 40. By setting an upper limit on the thickness of the resin layer 48f, it is possible to promote the discharge of air bubbles and to impart low transmission haze and high total light transmittance.

[0328] The resin layer 48f and the second resin layer 48j may have the same configuration. The resin layer 48f and the second resin layer 48j may have different configurations. The resin layer 48f and the second resin layer 48j may be made of different materials. The resin layer 48f and the second resin layer 48j may have different thicknesses.

[0329] The adhesive layers 48e, 48g are layers that bond two layers together. The adhesive layers 48e, 48g may contain a cured product of a curable resin composition. The curable resin composition may be a two-component curable resin composition, a thermosetting resin composition, or an ionizing radiation curable resin composition. The ionizing radiation curable resin composition may be an electron beam curable resin composition or an ultraviolet ray curable resin composition. The adhesive used for the adhesive layers 48e, 48g may be a one-component or two-component curing type vinyl-based, (meth)acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, or other laminating adhesive. Specific examples of materials used for the adhesive layers 48e, 48g include a two-component curing type polyurethane-based adhesive or a polyester-based adhesive that uses an isocyanate compound or the like as a curing agent.

[0330] The thickness of adhesive layers 48e, 48g may be 0.1 μm or more and 20 μm or less, 0.1 μm or more and 10 μm or less, 0.1 μm or more and 4.0 μm or less, 0.1 μm or more and 3.0 μm or less, 0.5 μm or more and 3.0 μm or less, 1.0 μm or more and 2.5 μm or less, or 1.0 μm or more and 2.0 μm or less.

[0331] The first adhesive layer 48e, the second adhesive layer 48g, the third adhesive layer, and the fourth adhesive layer may have the same composition. The first adhesive layer 48e, the second adhesive layer 48g, the third adhesive layer, and the fourth adhesive layer may have different compositions. The first adhesive layer 48e, the second adhesive layer 48g, the third adhesive layer, and the fourth adhesive layer may have different materials. The first adhesive layer 48e, the second adhesive layer 48g, the third adhesive layer, and the fourth adhesive layer may have different thicknesses.

[0332] The sealant layer 48a has heat-sealing properties. The sealant layer 48a is not particularly limited, and may be a resin film. The material of the sealant layer 48a may be a thermoplastic resin. The thermoplastic resin constituting the sealant layer 48a may be polyolefin. Examples of thermoplastic resins constituting the sealant layer 48a include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-α-olefin copolymers polymerized using a metallocene catalyst, and ethylene-propylene copolymers such as random or block copolymers of ethylene and propylene.

[0333] The sealant layer 48a may be formed by melt-extruding the resin material described above. The sealant layer 48a may be formed on the first barrier layer 48c. In this example, the inner adhesive layer 48b may be omitted.

[0334] The thickness of the sealant layer 48a may be 10 μm or more and 300 μm or less, or may be 20 μm or more and 100 μm or less.

[0335] The inner adhesive layer 48b bonds the sealant layer 48a and the first barrier layer 48c. The inner adhesive layer 48b may have a configuration similar to that of the above-described adhesive layers 48e and 48g. The inner adhesive layer 48b may include a cured product of a curable resin composition. The inner adhesive layer 48b may be formed between the sealant layer 48a and the first barrier layer 48c by melt-extruding a resin material. The resin material used in the melt-extrusion may be selected from the same range as the material of the sealant layer 48a. The thickness of the inner adhesive layer 48b may be selected from the same range as the thicknesses of the adhesive layers 48e and 48g.

[0336] Here, the results of the experiments carried out by the present inventors will be explained.

[0337] Example A 26E was produced as a laminate according to Example A. This laminate 47 included, in order from the inner surface 47a to the outer surface 47b, a sealant layer 48a, an inner adhesive layer 48b, a first barrier substrate layer 48d, a first barrier layer 48c, a first adhesive layer 48e, a resin layer 48f, a second adhesive layer 48g, a second barrier layer 48h, and a second barrier substrate layer 48i.

[0338] The first barrier layer 48c and the first barrier substrate layer 48d were formed using a barrier film A obtained by forming an inorganic vapor deposition film corresponding to the first barrier layer 48c on a polyethylene terephthalate film corresponding to the first barrier substrate layer 48d. Barrier film A was IB-PET-PBIR available from Dai Nippon Printing Co., Ltd. The thickness of barrier film A was 12 μm. The barrier layer 48 included in IB-PET-PBIR as barrier film A included, in order from the barrier substrate layer side, a first base barrier layer, a first over layer, a second base barrier layer, and a second over layer. The first base barrier layer was a transparent vapor deposition film containing alumina. The second base barrier layer was a transparent vapor deposition film containing alumina.

[0339] The second barrier layer 48h and the second barrier substrate layer 48i were made of the above-mentioned barrier film A, which was obtained by forming an inorganic vapor-deposited film corresponding to the second barrier layer 48h on a polyethylene terephthalate film corresponding to the second barrier substrate layer 48i. That is, the second barrier layer 48h and the second barrier substrate layer 48i were made of the same barrier film A as the first barrier layer 48c and the first barrier substrate layer 48d.

[0340] The resin layer 48f was made of Emblem ONMB-RT available from Unitika Ltd. The resin layer 48f was a biaxially oriented nylon film. The thickness of the resin layer 48f was 15 μm. The first adhesive layer 48e and the second adhesive layer 48g were both made using Rockbond RU77T / H-7, a thermosetting resin available from Rock Paint Co., Ltd. The thickness of the first adhesive layer 48e and the thickness of the second adhesive layer 48g were both 3 μm.

[0341] The sealant layer 48a was made of TPF-4 available from Okamoto Corporation. The thickness of the sealant layer 48a was 30 μm. The inner adhesive layer 48b was made of a thermosetting resin, Rockbond RU77T / H-7 available from Rock Paint Co., Ltd. The thickness of the inner adhesive layer 48b was 3 μm.

[0342] A laminate was produced from the above materials using a dry laminator with a gravure coating unit as follows. First, a resin layer 48f was laminated onto a barrier film A constituting the first barrier layer 48c and the first barrier substrate layer 48d, via a first adhesive layer 48e. A barrier film A constituting the second barrier layer 48h and the second barrier substrate layer 48i was laminated onto the resin layer 48f of the obtained laminate, via a second adhesive layer 48g. A sealant layer 48a was laminated onto the obtained laminate, via an inner adhesive layer 48b. In this way, a laminate according to Example A was obtained.

[0343] Example B As the laminate of Example B, a laminate 47 shown in FIG. 26E was produced in the same manner as the laminate of Example A. The laminate of Example B differed from the laminate of Example A in that a barrier film B was used instead of the barrier film A of Example A. The laminate of Example B was identical to the laminate of Example A in the sealant layer 48a, inner adhesive layer 48b, first adhesive layer 48e, resin layer 48f, and second adhesive layer 48g. The method for producing the laminate of Example B was the same as the method for producing the laminate of Example A, except for the barrier film.

[0344] In the laminate of Example B, the first barrier layer 48c and the first barrier substrate layer 48d were formed using a barrier film B, which was formed by forming an inorganic vapor-deposited film corresponding to the first barrier layer 48c on a polyethylene terephthalate film corresponding to the first barrier substrate layer 48d. Barrier film B was IB-PET-PXB2 available from Dai Nippon Printing Co., Ltd. The thickness of barrier film B was 12 μm. The barrier layers contained in IB-PET-PBIR as barrier film A included, in order from the barrier substrate layer side, a first base barrier layer, a first over layer, a second base barrier layer, and a second over layer. The first base barrier layer was a transparent vapor-deposited film containing alumina. The second base barrier layer was a transparent vapor-deposited film containing alumina.

[0345] In the laminate of Example B, the second barrier layer 48h and the second barrier substrate layer 48i were formed using the above-described barrier film B, which was obtained by forming an inorganic vapor-deposited film corresponding to the second barrier layer 48h on a polyethylene terephthalate film corresponding to the second barrier substrate layer 48i. That is, the second barrier layer 48h and the second barrier substrate layer 48i were made of IB-PET-PXB2, as were the first barrier layer 48c and the first barrier substrate layer 48d.

[0346] Example C 26E was produced as the laminate of Example C, similarly to the laminate of Example A. The laminate of Example C was different from Example A in the resin film used in sealant layer 48a, but was otherwise the same as Example A.

[0347] In the laminate according to Example C, the sealant layer 48a was made of CF7601A available from Toray Advanced Film Co., Ltd. The thickness of the sealant layer 48a was 30 μm.

[0348] The method for producing the laminate of Example C was the same as the method for producing the laminate of Example A, except that the resin film used in the sealant layer was different.

[0349] Example D 26E was produced as the laminate of Example D, similarly to the laminate of Example A. The laminate of Example D was different from Example A in the resin film used for resin layer 48f, but was otherwise the same as Example A.

[0350] In the laminate according to Example D, the resin layer 48f was E5102 available from Toyobo Co., Ltd. The resin layer 48f was a biaxially stretched polyethylene terephthalate film, and the thickness of the resin layer 48f was 16 μm.

[0351] The method for producing the laminate of Example D was the same as the method for producing the laminate of Example A, except that the resin film used in the resin layer was different.

[0352] <Comparative example A> The laminate according to Comparative Example A included, in order from the inner surface 47a to the outer surface 47b, a sealant layer 48a, an inner adhesive layer 48b, a resin layer 48f, a first adhesive layer 48e, a first barrier substrate layer 48d, a first barrier layer 48c, a second adhesive layer 48g, a second barrier layer 48h, and a second barrier substrate layer 48i. In the laminate according to Comparative Example A, the positions of the barrier film A constituting the first barrier layer 48c and the first barrier substrate layer 48d and the resin layer 48f were reversed from those in the laminate according to Example A.

[0353] The laminate according to Comparative Example A was produced as follows. First, the barrier film A constituting the second barrier layer 48h and the second barrier substrate layer 48i was laminated onto the barrier film A constituting the first barrier layer 48c and the first barrier substrate layer 48d, via the second adhesive layer 48g. The resin layer 48f was laminated onto the obtained laminate via the first adhesive layer 48e, and further the sealant layer 48a was laminated onto the obtained laminate via the inner adhesive layer 48b. In this way, the laminate according to Comparative Example A was obtained.

[0354] <Comparative example B> The laminate according to Comparative Example B included, in order from the inner surface 47a to the outer surface 47b, a sealant layer 48a, an inner adhesive layer 48b, a resin layer 48f, a first adhesive layer 48e, a first barrier substrate layer 48d, a first barrier layer 48c, a second adhesive layer 48g, a second barrier layer 48h, and a second barrier substrate layer 48i. In the laminate according to Comparative Example B, the positions of the barrier film A constituting the first barrier layer 48c and the first barrier substrate layer 48d and the resin layer 48f were reversed from those in the laminate according to Example C.

[0355] As a result, the laminate of Comparative Example B differed from Comparative Example A in the resin film used in the sealant layer 48a, but was otherwise identical to Comparative Example A. The sealant layer 48a of the laminate of Comparative Example B was CF7601A available from Toray Advanced Film Co., Ltd. The thickness of the sealant layer 48a was 30 μm.

[0356] The method for producing the laminate according to Comparative Example B was the same as the method for producing the laminate according to Comparative Example A, except that the resin film used in the sealant layer was different.

[0357] <Comparative example C> The laminate of Comparative Example C included, in order from the inner surface 47a to the outer surface 47b, a sealant layer 48a, an inner adhesive layer 48b, a resin layer 48f, a first adhesive layer 48e, a first barrier layer 48c, and a first barrier substrate layer 48d.

[0358] In the laminate of Comparative Example C, the sealant layer 48a, inner adhesive layer 48b, resin layer 48f, first adhesive layer 48e, first barrier layer 48c, and first barrier substrate layer 48d had the same configuration as the laminate of Example A. That is, in the laminate of Comparative Example C, the sealant layer 48a was TPF-4 available from Okamoto Corporation. The thickness of the sealant layer 48a was 30 μm. The inner adhesive layer 48b was a layer using Lockbond RU77T / H-7, a thermosetting resin available from Rock Paint Co., Ltd. The thickness of the inner adhesive layer 48b was 3 μm. The resin layer 48f was Emblem ONMB-RT available from Unitika Ltd. The thickness of the resin layer 48f was 15 μm. The first adhesive layer 48e was made using Lockbond RU77T / H-7, a thermosetting resin available from Rock Paint Co., Ltd. The thickness of the first adhesive layer 48e was 3 μm. The first barrier layer 48c and the first barrier substrate layer 48d were made of a barrier film A obtained by forming an inorganic vapor deposition film corresponding to the first barrier layer 48c on a polyethylene terephthalate film corresponding to the first barrier substrate layer 48d. The barrier film A was IB-PET-PBIR available from Dai Nippon Printing Co., Ltd. The thickness of the barrier film A was 12 μm. The first barrier layer 48c was a vapor deposition film containing alumina.

[0359] The laminate according to Comparative Example C was produced as follows: First, a resin layer 48f was laminated onto the barrier film A constituting the first barrier layer 48c and the first barrier base layer 48d via a first adhesive layer 48e, and then a sealant layer 48a was laminated onto the barrier film A via an inner adhesive layer 48b. In this way, the laminate according to Comparative Example C was obtained.

[0360] <Evaluation 1 (oxygen permeability)> The oxygen permeability (mL / (m) of the laminates according to Examples A to D and Comparative Examples A to C, as well as Examples E, F, and Comparative Example D described below, was 2 The oxygen permeability was measured using an OXTRAN (2 / 21) permeability measuring device manufactured by MOCON, USA, under an environment of 23°C temperature and 40% RH humidity. The results are shown in the "Evaluation 1" column of Tables 4 and 5.

[0361] <Evaluation 2 (water vapor permeability)> The water vapor permeability (g / (m 2 × day) was measured. The water vapor permeability was determined by measuring the weight change of the container containing calcium chloride as described below. First, a test container having a four-sided seal portion as shown in FIG. 7B was produced using the laminates according to Examples A to C and Comparative Examples A to C. The internal space of the test container was a square of 10 cm x 10 cm in plan view when the container was laid out flat. The internal surface area of the test container was 200 cm 2 50 g of calcium chloride was placed inside the test container. Immediately after closing the test container, the test container was stored in a test environment at a temperature of 40°C and a humidity of 90%RH for 14 days. The weight increase of the test container before and after being placed in the test environment was measured using a 200 cm 2 From the measurement results, the hydrogen permeability (g / (m 2 The results are shown in the "Evaluation 2" column of Table 4.

[0362] <Rating 3 (Transmission Haze)> Samples measuring 5 cm x 10 cm were cut out from the laminates of Examples A to D and Comparative Examples A to C. The samples were visually inspected for the absence of any abnormalities such as dust or scratches. The transmission haze of the laminates of each example was measured using the method described above. The incident surface during measurement was the inner surface 47a. A haze meter "HM-150" manufactured by Murakami Color Research Laboratory was used to measure the transmission haze. The measurement results of the transmission haze are shown in Table 4.

[0363] <Evaluation 4 (presence or absence of bubbles)> The laminates according to the examples and comparative examples were checked for the presence or absence of bubbles. The laminates were observed with the naked eye without using a microscope or the like. The evaluation criteria were as follows. The evaluation results are shown in the column "Evaluation 4" in Table 4. A: When observed under a microscope, tiny bubbles were found, but when observed with the naked eye from a distance of 30 cm, no bubbles were found, so the product was deemed to have passed. B: Air bubbles were observed with the naked eye from a distance of 30 cm, and the product was deemed unacceptable.

[0364] [Table 4]

[0365] The appearance was further evaluated as follows.

[0366] Example E 26E, a laminate was prepared by removing the sealant layer 48a and the inner adhesive layer 48b. The laminate included, in order from the inner surface 47a to the outer surface 47b, a first barrier substrate layer 48d, a first barrier layer 48c, a first adhesive layer 48e, a resin layer 48f, a second adhesive layer 48g, a second barrier layer 48h, and a second barrier substrate layer 48i.

[0367] In the laminate of Example E, the first barrier layer 48c and the first barrier substrate layer 48d were formed using a barrier film B obtained by forming an inorganic vapor deposition film corresponding to the first barrier layer 48c on a polyethylene terephthalate film corresponding to the first barrier substrate layer 48d. Barrier film B was IB-PET-PXB2 available from Dai Nippon Printing Co., Ltd. The thickness of barrier film B was 12 μm. The first barrier layer 48c was a transparent vapor deposition film containing alumina.

[0368] In the laminate of Example E, the second barrier layer 48h and the second barrier substrate layer 48i were formed using the above-described barrier film B, which was obtained by forming an inorganic vapor-deposited film corresponding to the second barrier layer 48h on a polyethylene terephthalate film corresponding to the second barrier substrate layer 48i. That is, the second barrier layer 48h and the second barrier substrate layer 48i were made of IB-PET-PXB2, as were the first barrier layer 48c and the first barrier substrate layer 48d.

[0369] The resin layer 48f was made of Emblem ONMB-RT available from Unitika Ltd. The resin layer 48f was a biaxially oriented nylon film. The thickness of the resin layer 48f was 15 μm. The first adhesive layer 48e and the second adhesive layer 48g were both made using Rockbond RU77T / H-7, a thermosetting resin available from Rock Paint Co., Ltd. The thickness of the first adhesive layer 48e and the thickness of the second adhesive layer 48g were both 3 μm.

[0370] A laminate was produced using the above materials as follows. First, a resin layer 48f was laminated on a barrier film A constituting the first barrier layer 48c and the first barrier substrate layer 48d, via a first adhesive layer 48e. A barrier film A constituting the second barrier layer 48h and the second barrier substrate layer 48i was laminated on the resin layer 48f of the obtained laminate, via a second adhesive layer 48g. The adhesive layer was applied using a bar coater. The obtained laminate was adhered to the laminate by applying a pressure of approximately 10 MPa using a press. Thereafter, the laminate was stored in an oven at 40°C for 72 hours to cure the adhesive layer. In this way, a laminate according to Example E was obtained.

[0371] Example F As with the laminate of Example E, a laminate was prepared by removing the sealant layer 48a and inner adhesive layer 48b from the laminate 47 shown in FIG. 26E. The laminate of Example F differed from Example E in the resin film used for the resin layer 48f, but was otherwise identical to Example E. The laminate of Example F used E5102, available from Toyobo Co., Ltd., as the resin layer instead of the Emblem ONMB-RT used as the resin layer in Example E. The resin layer 48f was a biaxially oriented polyethylene terephthalate film. The thickness of the resin layer 48f was 16 μm. The method for preparing the laminate of Example F was the same as the method for preparing the laminate of Example E, except for the resin layer.

[0372] <Comparative example D> The laminate of Comparative Example D included, in order from the inner surface 47a to the outer surface 47b, a first barrier substrate layer 48d, a first barrier layer 48c, a second adhesive layer 48g, a second barrier layer 48h, and a second barrier substrate layer 48i. The laminate of Comparative Example D differed from Examples E and F in that the first adhesive layer 48e and the resin layer 48f were not included between the barrier film B constituting the first barrier layer 48c and the first barrier substrate layer 48d and the barrier film B constituting the second barrier layer 48h and the second barrier substrate layer, but otherwise had the same configuration as Examples E and F.

[0373] The method for producing the laminate according to Comparative Example D was the same as the method for producing the laminate according to Comparative Examples E and F, except that the first adhesive layer 48e and the resin layer 48f were not included.

[0374] <Rating 5 (cloudy)> The laminates according to the examples and comparative examples were checked for the presence or absence of cloudiness. The laminates were observed with the naked eye without using a microscope or the like. The evaluation criteria were as follows. The evaluation results are shown in the column "Evaluation 5" in Table 5. AA: No cloudiness was observed, and the sample passed. A: Cloudiness was observed, but it was minor and therefore passed. B: Cloudiness was observed and the product was rejected.

[0375] <Rating 6 (Piercing Resistance)> Puncture resistance was measured in accordance with the puncture strength test of JIS Z1707:2019. The test piece was fixed in a jig, and a semicircular needle with a diameter of 1.0 mm and a tip radius of 0.5 mm was pierced into the outer surface (the surface made up of the second barrier substrate layer) at a test speed of 50±5 mm / min, and the maximum force (N) until the needle penetrated was measured. Since the target sample did not contain a sealant, puncture resistance from the outer surface 47b was evaluated. The maximum force (N) as the evaluation result was the arithmetic mean value of the measurements at five points. The evaluation results are shown in the column "Evaluation 6" in Table 5.

[0376] [Table 5]

[0377] The evaluation results of Examples E, F, and Comparative Example D revealed that the appearance (cloudiness) was improved by disposing a resin layer between two barrier layers. It is believed that the generation of bubbles was effectively suppressed in Examples B and D due to a phenomenon similar to this evaluation result.

[0378] Example E, in which a biaxially oriented nylon film was used as the resin layer, was excellent in puncture resistance.

[0379] In Example F, which used a biaxially stretched polyethylene terephthalate film as the resin layer, cloudiness could be more effectively suppressed. Since the appearance (cloudiness) of Example F was good, the production speed of Example D could be increased.

[0380] Although one embodiment has been described with reference to specific examples, the above-described specific examples do not limit the present invention. The above-described embodiment can be implemented with various other specific examples, and various omissions, substitutions, changes, additions, etc. can be made without departing from the spirit of the present invention.

[0381] The first container 30 may include a label 37 (see FIG. 10 ). The label 37 may display information about the liquid. The label 37 may be attached to the container body 32. The label 37 does not have to be around the entire circumference to allow for observation of the inside of the container body 32. The label 37 may face the second container 40 to allow for observation of the inscription on the label 37. When the first container 30 is a vial, 10 mm or more, preferably 20 mm or more, of the container body 32 may be exposed between the label 37 and the stopper 34 and fastener 36. The liquid in the first container 30 can be observed through the transparent container body 32. The amount of oxygen in the first container 30 can be measured by irradiating light through the transparent container body 32. In this case, in addition to the neck portion 32c of the container body 32, the body portion 32b may be exposed between the label 37 and the stopper 34 and fastener 36.

[0382] In the above-described specific example, the first container 30 includes a container body 32 and a stopper 34, and the stopper 34 has oxygen permeability. However, at least a portion of the container body 32 may have oxygen permeability, and the stopper 34 may have oxygen barrier properties. Furthermore, the specific configuration of the second container 40 described above is merely an example, and various modifications are possible.

[0383] In order to maintain the relative position between the oxygen absorber 21 or the oxygen absorbing member 22 and the oxygen-permeable portion of the first container 30, the oxygen absorber 21 or the oxygen absorbing member 22 may be fixed to the first container 30 using heat sealing or a bonding material. The oxygen absorber 21 or the oxygen absorbing member 22 may also be fixed to a portion other than the oxygen-permeable portion of the first container 30. With these configurations, an appropriate relative positional relationship between the oxygen absorber 21 or the oxygen absorbing member 22 and the oxygen-permeable portion of the first container 30 is maintained, and the transfer of oxygen from the inside to the outside of the first container 30 can be stably promoted.

[0384] In the example shown in FIGS. 1 and 8 , the container body 32 and the fastener 36 have oxygen barrier properties, and the stopper 34 has oxygen permeability. In the example shown by the two-dot chain lines in FIGS. 1 and 8 , the oxygen absorbing member 22 containing the oxygen absorber 21 is disposed facing the oxygen-permeable stopper 34. The oxygen absorbing member 22 containing the oxygen absorber 21 may contact the oxygen-permeable stopper 34. The oxygen absorbing member 22 containing the oxygen absorber 21 may contact only a portion of the oxygen-permeable stopper 34. The oxygen absorbing member 22 containing the oxygen absorber 21 may be disposed with a gap between it and the oxygen-permeable stopper 34. The oxygen absorbing member 21 and the oxygen absorbing member 22 shown by the two-dot chain lines in FIGS. 1 and 8 can promote the transfer of oxygen from the inside to the outside of the first container 30. Furthermore, the second container 40, which has flexibility and oxygen barrier properties, can be prevented from coming into contact with the oxygen-permeable stopper 34 of the first container 30.

[0385] In order to maintain the relative positions of the deoxidizing member 22 and the stopper 34, the deoxidizing member 22 may be fixed to the first container 30. The deoxidizing member 22 having the deoxidant 21 may be fixed to the stopper 34, the fastener 36, or the first container 30 using heat sealing or a bonding material. When the deoxidizing member 22 is fixed to the stopper 34, it may be fixed to a part of the stopper 34. The deoxidizing member 22 may be fixed to the fastener 36 so that a gap is maintained between the deoxidizing member 22 and the stopper 34. [Explanation of symbols]

[0386] D1: first direction, D2: second direction, D3: third direction, HS: head space, L30: length, S: storage space, E41: folded edge, L: liquid, 10: combination container, 10L: combination container containing liquid, 15: supply pipe, 15a: discharge port, 20: container set, 21: oxygen absorber, 22: oxygen absorber member, 22a: packaging body, 22b: moisture retaining agent, 23: oxygen absorber film, 23a: base material, 24: dehydrating agent, 25: oxygen detector, 26: display unit, 30: first container, 30X: part, 30L: first container containing liquid, 32: container body, 33: opening, 34: stopper, 34a: plate-shaped portion, 34b: insertion protrusion, 36: fastener, 37: label, 40: second container, 40a: opening, 41a: first film, 41b: second film, 41bx: bent top portion, 41c: first gusset, 41d: second gusset, 41x: folded portion, 42: container body, 42a: storage portion, 42b: flange portion, 44: lid, 46: laminate, 47: laminate, 47a: inner surface, 47b: outer surface, 48a: sealant layer, 48b: inner adhesive layer, 48c: first barrier layer, 48d: first barrier substrate layer, 48e: first adhesive layer, 48 f: resin layer, 48g: second adhesive layer, 48h: second barrier layer, 48i: second barrier substrate layer, 48j: second resin layer, 48k: third barrier layer, 48l: third barrier substrate layer, 49: seal portion, 49a: first seal portion, 49ae: outer edge, 49b: first side seal portion, 49be: outer edge, 49c: second side seal portion, 49ce: outer edge, 49d: second seal portion, 49X: main seal portion, 49Y: auxiliary seal portion, 49Ya: first auxiliary seal portion, 49Yb: second auxiliary seal portion, 49Z: additional seal portion, 49Ze: inner edge, 49Za: first additional seal portion, 49Zb: second additional seal portion, 50a: main portion, 50b: extension portion, 51: notch, 52: intended opening portion, 55: outer box, 56: bottom portion, 57: top portion, 58: side wall portion, 60: syringe, 62: cylinder, 63: cylinder body, 64: needle, 66: piston, 67: piston body, 68: gasket, 69: cap, 70: test container, 71: partition wall portion, 72: main wall portion, 72A: through hole, 73: barrier bonding material, 76: first flow path, 77: second flow path, 78: test chamber, 78A: supply path, 78B: discharge path, 79: oxygen measuring device

Claims

1. a first container containing a liquid and having oxygen permeability; a second container that houses the first container and has oxygen barrier properties; the second container includes a laminate; The laminate includes an inner surface facing the storage space of the second container and an outer surface opposite to the inner surface, The laminated body includes, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

2. The liquid-filled combination container according to claim 1 , wherein the resin layer includes a thermoplastic resin.

3. The liquid-filled combination container according to claim 2 , wherein the resin layer is a stretched film.

4. The liquid-filled combination container according to claim 1 , wherein the resin layer has a thickness of 5 μm or more.

5. the laminate further includes a first adhesive layer positioned between the first barrier layer and the resin layer, and a second adhesive layer positioned between the resin layer and the second barrier layer; The liquid-filled combination container according to claim 1 , wherein the first adhesive layer and the second adhesive layer contain a cured product of a curable resin composition.

6. The liquid-filled combination container according to claim 5 , wherein the first adhesive layer is in contact with the resin layer.

7. the laminate further comprises a first barrier substrate in contact with the first barrier layer; 7. The liquid-filled combination container of claim 6, wherein the first barrier layer is located between the first adhesive layer and the first barrier substrate.

8. The liquid-filled combination container according to claim 5 , wherein the second adhesive layer is in contact with the resin layer.

9. the laminate further comprises a second barrier substrate in contact with the second barrier layer; 9. The liquid-filled combination container of claim 8, wherein the second barrier layer is located between the second adhesive layer and the second barrier substrate.

10. 2. The liquid-filled combination container according to claim 1, wherein the first barrier layer is a transparent vapor-deposited film, and the second barrier layer is a transparent vapor-deposited film.

11. The liquid-filled combination container according to claim 5 , wherein the resin layer includes polyamide.

12. the laminate further includes a second resin layer and a third barrier layer; The liquid-filled combination container according to claim 1 , wherein the second barrier layer, the second resin layer, and the third barrier layer are arranged in this order from the inner surface toward the outer surface.

13. The oxygen permeability of the laminate is 0.20 mL / (m ２ 2. The liquid-filled combination container according to claim 1, wherein the liquid-filled combination container has a viscosity of less than 1000 psi (1000 psi x ...).

14. 10. The liquid combination container of claim 1, further comprising an oxygen absorber for absorbing oxygen within the second container.

15. 2. The liquid combination container according to claim 1, further comprising an oxygen detector for detecting an oxygen state in the second container.

16. a first container containing a liquid and having oxygen permeability; a second container that houses the first container and has oxygen barrier properties; an oxygen absorbing member housed in the second container, the oxygen absorbing member includes an oxygen absorber that absorbs oxygen in the second container, the second container includes a first film and a second film that houses the first container between the first film and the second film; The first film and the second film are joined and joined at a seal portion, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, A liquid-filled combination container, wherein the first container is positioned between the first seal portion and the oxygen absorbing member in a direction in which the first seal portion and the first container face each other.

17. The second container is bent with the second film on the inside, so that a first portion of the second container accommodating the first container and a second portion of the second container overlap with each other, the second portion is located on one side of the first portion in a direction in which the first seal portion and the first container face each other when the second container is in an unfolded state before being bent, 17. The combination liquid container according to claim 16, wherein the oxygen absorbing member is bent together with the second container such that a middle portion of the oxygen absorbing member is positioned on the bent apex of the second film.

18. a first container containing a liquid and having oxygen permeability; a second container that houses the first container and has oxygen barrier properties; the second container includes a first film and a second film that houses the first container between the first film and the second film; the first film and the second film are joined at a seal portion, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, The sealing portion further includes a first side sealing portion connected to one end of the first sealing portion, a second side sealing portion connected to the other end of the first sealing portion, and an additional sealing portion positioned between at least one of the first side sealing portion and the second side sealing portion and the first container.

19. A method for manufacturing a liquid-filled container using the liquid-filled combination container according to any one of claims 1 to 18, comprising the steps of: closing the second container containing the first container; and adjusting the oxygen concentration by absorbing oxygen in the second container with an oxygen scavenger, A method for manufacturing a liquid-filled container, wherein in the process of adjusting the oxygen concentration, oxygen in the first container passes through the first container, moves out of the first container, and is absorbed by the oxygen absorber in the second container.

20. a first container for containing a liquid; a second container that accommodates the first container, the first container is oxygen permeable; the second container has oxygen barrier properties, the second container includes a laminate; The laminate includes an inner surface facing the storage space of the second container and an outer surface opposite to the inner surface, The container set, wherein the laminate includes, in order from the inner surface to the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

21. a first container for containing a liquid; a second container that accommodates the first container; an oxygen absorbing member accommodated in the second container, the first container is oxygen permeable; the second container has oxygen barrier properties, the oxygen absorbing member includes an oxygen absorber that absorbs oxygen in the second container, the second container includes a first film and a second film that houses the first container between the first film and the second film; the first film and the second film are joined at a seal portion, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, A container set, wherein the first container is positioned between the first seal portion and the oxygen absorbing member in a direction in which the first seal portion and the first container face each other.

22. a first container for containing a liquid; a second container that accommodates the first container, the first container is oxygen permeable; the second container has oxygen barrier properties, the second container includes a first film and a second film that houses the first container between the first film and the second film; the first film and the second film are joined at a seal portion, the sealing portion includes a first sealing portion positioned facing the first container, the first seal portion is bent so as to protrude away from the first container in a direction in which the first seal portion and the first container face each other, The container set further includes a first side seal portion connected to one end of the first seal portion, a second side seal portion connected to the other end of the first seal portion, and an additional seal portion positioned between at least one of the first side seal portion and the second side seal portion and the first container.

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