Combined container with liquid, container set, and method for manufacturing a container with liquid

The combined container system with a permeable first container and an oxygen-scavenging second container addresses the issue of liquid deterioration by dissolved oxygen, achieving aseptic storage conditions through reduced oxygen levels.

JP7713180B2Active Publication Date: 2025-07-25DAI NIPPON PRINTING CO LTD
View PDF 8 Cites 0 Cited by

Patent Information

Application Number
JP2024527465
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Priority Date
2022-09-28
Filing Date
2023-09-28
Publication Date
2025-07-25
Estimated Expiration
2043-09-28

AI Technical Summary

Technical Problem

Existing containers fail to effectively suppress the deterioration of liquids due to dissolved oxygen, as containers with oxygen barrier properties do not address the issue of oxygen dissolution during liquid storage.

Method used

A combined container system comprising a first container with oxygen permeability and a second container with oxygen barrier properties, where the second container includes a laminate structure with a sealant layer, a first barrier layer, and a resin layer, and may contain an oxygen scavenger to absorb oxygen.

Benefits of technology

The system effectively reduces the dissolved oxygen amount in the liquid to less than 0.015 mg/L, maintaining the liquid in an aseptic state for extended periods without bacterial growth, even at room temperature, thus preventing liquid deterioration.

✦ Generated by Eureka AI based on patent content.

Smart Images

  • Figure 0007713180000006
    Figure 0007713180000006
  • Figure 0007713180000007
    Figure 0007713180000007
  • Figure 0007713180000008
    Figure 0007713180000008
Patent Text Reader

Abstract

This liquid-containing combined container includes a first container that accommodates a liquid and is oxygen-permeable, and a second container that accommodates the first container and has an oxygen barrier property. The second container includes a layered body. The layered body includes an inner surface facing an accommodation space, and an outer surface on the opposite side from the inner surface. The layered body includes, in order from the inner surface toward the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.
Need to check novelty before this filing date? Find Prior Art

Description

Technical Field

[0001] The present disclosure relates to a liquid-containing combined container, a container set, and a method for manufacturing a liquid-containing container.

Background Art

[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 in the container. To address this problem, the use of a container having oxygen barrier properties is considered.

[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 the production of the liquid. A container having oxygen barrier properties cannot address the deterioration of the liquid caused by dissolved oxygen in the liquid. That is, in the prior art, the oxygen deterioration of the liquid stored in the container cannot be sufficiently suppressed. The present disclosure aims to suppress the deterioration of the liquid due to oxygen.

[0005] A first liquid-containing combined container according to an embodiment of the present disclosure includes a first container that stores a liquid and has oxygen permeability, and 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 accommodation space of the second container and an outer surface opposite to the inner surface. The laminate includes, in order from the inner surface toward the outer surface, a sealant layer, a first barrier layer, a resin layer, and a second barrier layer.

[0006] A second liquid-containing combined container according to an embodiment of the present disclosure includes a first container that stores a liquid and has oxygen permeability, and a second container that houses the first container and has oxygen barrier properties. a deoxygenating member housed in the second container. The oxygen removal member contains an oxygen scavenger 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. The first film and the second film are joined in a peelable manner at a seal portion. The seal portion includes a first seal portion that faces the first container. The first seal portion is bent so as to protrude to the side away from the first container in the 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 positioned between the first seal portion and the oxygen removal member.

[0007] A third liquid-containing combined container according to an embodiment of the present disclosure is a first container that contains a liquid and has oxygen permeability, and 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. The first film and the second film are joined in a peelable manner at a seal portion. The seal portion includes a first seal portion that faces the first container. The first seal portion is bent so as to protrude to the side away from the first container in the direction in which the first seal portion and the first container face each other. The seal portion 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.

[0008] A method for manufacturing a liquid-containing container according to an embodiment of the present disclosure is A method for manufacturing a liquid-containing container using a liquid-containing combined container according to an embodiment of the present disclosure, A step of closing the second container that houses the first container; A step of adjusting the oxygen concentration by absorbing oxygen in the second container with an oxygen absorber, and In the step of adjusting the oxygen concentration, oxygen in the first container permeates through the first container and moves outside the first container, and is absorbed by the oxygen absorber in the second container.

[0009] A first container set according to an embodiment of the present disclosure A first container that houses a liquid, and A second container that houses the first container, and The first container has oxygen permeability, The second container has oxygen barrier properties, The second container includes a laminate, The laminate includes an inner surface facing the accommodation space of the second container and an outer surface opposite to the inner surface, The laminate includes a sealant layer, a first barrier layer, a resin layer, and a second barrier layer in this order from the inner surface toward the outer surface.

[0010] A second container set according to an embodiment of the present disclosure A first container that houses a liquid, and A second container that houses the first container, and An oxygen removal member housed in the second container, and The first container has oxygen permeability, The second container has oxygen barrier properties, The oxygen removal 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, The first film and the second film are joined in a peelable manner at a seal portion, The seal portion includes a first seal portion that is located facing the first container, The first seal portion is bent so as to protrude toward the side away from the first container in the 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 positioned between the first seal portion and the deoxidizing member.

[0011] A third container set according to an embodiment of the present disclosure is a first container for storing a liquid, and a second container for storing the first container. The first container has oxygen permeability. The second container has oxygen barrier properties. The second container includes a first film and a second film for storing the first container between the first film. The first film and the second film are detachably joined at a seal portion. The seal portion includes a first seal portion positioned to face the first container. The first seal portion is bent so as to protrude toward the side away from the first container in the direction in which the first seal portion and the first container face each other. The seal portion 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.

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

[0013] A laminate according to an embodiment of the present disclosure is a laminate used for a container, and includes a sealant layer, a first barrier layer, a resin layer, and a second barrier layer in this order from the inner surface to the outer surface.

[0014] According to the present disclosure, deterioration by liquid oxygen can be suppressed.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2A

Figure 2B

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7A

Figure 7B

Figure 7C

Figure 7D

Figure 8

Figure 9A

Figure 9B

Figure 9C

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15A

Figure 15B

Figure 15C

Figure 15D

Figure 16

Figure 17

Figure 18

Figure 19

Figure 20

Figure 21

Figure 22

Figure 23

Figure 24

Figure 25

Figure 26A

Figure 26B

Figure 26C

Figure 26D

Figure 26E

Figure 26F

Mode for Carrying Out the Invention

[0016] One 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 accommodation 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, and is a liquid-containing composite container.

[0018] [2] The resin layer of the liquid-containing composite container according to [1] contains a thermoplastic resin.

[0019] [3] The resin layer of the liquid-containing composite container according to [1] or [2] is a stretched film.

[0020] [4] The thickness of the resin layer of the liquid-containing composite container according to any one of [1] to [3] is 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 first adhesive layer and the second adhesive layer of the liquid-containing composite container according to any one of [1] to [4] contain a cured product of a curable resin composition.

[0022] [6] The first adhesive layer of the liquid-containing composite container according to [5] is in contact with the resin layer.

[0023] [7] The first adhesive layer of the liquid-containing composite container according to [5] 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 first barrier layer of the liquid-containing composite container according to [6] or [7] is located between the first adhesive layer and the first barrier substrate.

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

[0026]

[10] The second adhesive layer of the liquid-containing composite container according to any one of [5] to [8] 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 second barrier layer is a liquid-containing combined container of

[10] , which is located between the second adhesive layer and the second barrier substrate.

[0028]

[12] The first barrier layer is a transparent vapor deposition film, and the second barrier layer is a transparent vapor deposition film, for the liquid-containing combined container according to any one of [1] to

[11] .

[0029]

[13] The resin layer contains polyamide, for the liquid-containing combined container according to any one of [1] to

[12] .

[0030]

[14] The laminate further includes a second resin layer and a third barrier layer. The second barrier layer, the second resin layer, and the third barrier layer are arranged in this order from the inner surface to the outer surface, for the liquid-containing combined container according to any one of [1] to

[13] .

[0031]

[15] The oxygen permeability of the laminate is 0.20 mL / (m 2 ×day×atm) or less, for the liquid-containing combined container according to any one of [1] to

[14] .

[0032]

[16] The liquid-containing combined container according to any one of [1] to

[15] further includes a deoxidizer for absorbing oxygen in the second container.

[0033]

[17] An oxygen detection material for detecting the oxygen state in the second container is provided, for the liquid-containing combined container according to any one of [1] to

[16] .

[0034]

[18] A first container that stores a liquid and has oxygen permeability, A second container that houses the first container and has oxygen barrier properties, And a deoxygenation member housed in the second container, The deoxygenation member includes a deoxidizer for absorbing 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 first film. The first film and the second film are joined in a peelable manner at a seal portion. The seal portion includes a first seal portion that faces the first container. The first seal portion bends so as to protrude to the side away from the first container in the 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 a liquid-containing combined container that is located between the first seal portion and the deoxidizing member.

[0035]

[19] The first container includes a container body including an opening and a stopper that closes the opening. The stopper has oxygen permeability. The liquid-containing combined container according to

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

[0036]

[20] The first container includes a container body including an opening and a stopper that closes the opening. The stopper has oxygen permeability. The liquid-containing combined container according to

[18] , wherein the stopper faces the first seal portion and the container body faces the deoxidizing 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 housing the first container is formed between the first side seal portion and the second side seal portion. At least one of the first side seal portion and the second side seal portion is provided with a notch. The second container according to any one of

[18] to

[20] is openable by cutting the first film and the second film starting from the notch.

[0038]

[22] The first film and the second film have an opening scheduled part that is scheduled to be cut starting from the notch, The opening scheduled part is a liquid-containing combined container of

[21] located between the deoxidizing member and the first container.

[0039]

[23] The first film and the second film each include a main part that forms a space for accommodating the first container, and an extension part connected to the main part. The sealing part includes a main sealing part that partitions the space for accommodating the first container, and an auxiliary sealing part that joins the first film and the second film in the extension part, which is a liquid-containing combined container of any one of

[18] to

[22] .

[0040]

[24] The main sealing part includes the first sealing part, a first side sealing part connected to one end of the first sealing part, and a second side sealing part connected to the other end of the first sealing part. The auxiliary sealing part includes a first auxiliary sealing part connected to the first side sealing part and a second auxiliary sealing part connected to the second side sealing part, which is a liquid-containing combined container of

[23] .

[0041]

[25] The auxiliary sealing part is separated from the main sealing part, which is a liquid-containing combined container of

[23] .

[0042]

[26] The main sealing part includes the first sealing part, a first side sealing part connected to one end of the first sealing part, and a second side sealing part connected to the other end of the first sealing part. The auxiliary sealing part includes a first auxiliary sealing part located on the extension line of the first side sealing part and a second auxiliary sealing part located on the extension line of the second side sealing part, which is a liquid-containing combined container of

[25] .

[0043]

[27] The seal part includes a first side seal part connected to one end of the first seal part, a second side seal part connected to the other end of the first seal part, and an additional seal part located between at least one of the first side seal part and the second side seal part and the first container, and is a liquid-containing combined container according to any one of

[18] to

[26] .

[0044]

[28] The additional seal part includes a first additional side seal part located between the first side seal part and the first container, and a second additional side seal part located between the second side seal part and the first container, and is a liquid-containing combined container according to

[27] .

[0045]

[29] The additional seal part is connected to at least one of the first side seal part and the second side seal part, and is a liquid-containing combined container according to

[27] .

[0046]

[30] In the direction in which the first seal part and the first container face each other, the end of the first container on the first seal part side is located at the same position as the end of the additional seal part on the first seal part side, or at a position closer to the first seal part than the end of the additional seal part on the first seal part side, and is a liquid-containing combined container according to any one of

[27] to

[29] .

[0047]

[31] The inner edge of the additional seal part facing the first container moves away from at least one of the first side seal part and the second side seal part as it approaches the first seal part in the direction in which the first seal part and the first container face each other, and is a liquid-containing combined container according to any one of

[27] to

[30] .

[0048]

[32] With the second film on the inside, the second container is bent, and the first part of the second container that houses the first container and the second part of the second container overlap. The second part is located on one side of the first part in the direction in which the first seal part and the first container face each other in the state where the second container before being bent is unfolded. A liquid-filled combined container according to any one of

[18] to

[31] , wherein the intermediate portion of the oxygen removal member is positioned on the bending apex of the second film, and the oxygen removal member is bent together with the second container.

[0049]

[33] The liquid-filled combined container according to

[32] , further comprising an oxygen detection material positioned between the oxygen removal member and the first film.

[0050]

[34] With the second film on the inside, the second container is further bent so that the first portion and the third portion of the second container overlap. The third portion is located on the other side of the first portion in the direction in which the first seal portion and the first container face each other in the state where the second container before being bent is unfolded. The liquid-filled combined container according to

[32] or

[33] , wherein the first portion, the third portion, and the second portion overlap in this order.

[0051]

[35] The liquid-filled combined container further comprises an outer box for housing the second container. The first container includes a container body including an opening and a stopper for closing the opening. The stopper has oxygen permeability. The second container houses the first container and the oxygen removal member such that one of the stopper and the container body is close to the first seal portion and the other of the stopper and the container body is close to the oxygen removal member. With the second film on the inside, the second container is bent so that the first portion of the second container housing the first container and the second portion of the second container overlap. With the second film on the inside, the second container is further bent so that the first portion and the third portion of the second container overlap. The second portion is located on one side of the first portion in the direction in which the first seal portion and the first container face each other in the state where the second container before being bent is unfolded. The third part is located on the other side of the first part in the direction in which the first seal part and the first container face each other when the second container before being bent is in a deployed state. The outer box includes a bottom part, a top part facing the bottom part, and side wall parts located between the bottom part and the top part. A second container in which the first part, the second part, and the third part are folded so as to overlap each other with the container body of the first container facing the bottom part of the outer box and the stopper of the first container facing the top part of the outer box is accommodated in the outer box. The liquid-containing combined container according to any one of

[18] to

[34] .

[0052]

[36] 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 houses the first container between the first film. The first film and the second film are joined in a peelable manner at a seal part. The seal part includes a first seal part that is located facing the first container. The first seal part is bent so as to protrude to the side away from the first container in the direction in which the first seal part and the first container face each other. The seal part further includes a first side seal part connected to one end of the first seal part, a second side seal part connected to the other end of the first seal part, and an additional seal part located between at least one of the first side seal part and the second side seal part and the first container. The liquid-containing combined container.

[0053]

[37] A method for manufacturing a liquid-containing container using the liquid-containing combined container according to any one of [1] to

[36] , A step of closing the second container containing the first container, A step of adjusting the oxygen concentration by absorbing oxygen in the second container with a deoxidizer. In the step of adjusting the oxygen concentration, oxygen in the first container permeates through the first container and moves out of the first container, and is absorbed by the oxygen scavenger in the second container, a method for manufacturing a liquid-containing container.

[0054]

[38] A first container for containing a liquid, A second container for containing the first container, and the first container has oxygen permeability, the second container has oxygen barrier properties, the second container includes a laminate, the laminate includes an inner surface facing the accommodation space of the second container and an outer surface opposite to the inner surface, the laminate includes a sealant layer, a first barrier layer, a resin layer, and a second barrier layer in this order from the inner surface to the outer surface, a container set.

[0055]

[39] A first container for containing a liquid, A second container for containing the first container, and an oxygen scavenging member contained in the second container, and the first container has oxygen permeability, the second container has oxygen barrier properties, the oxygen scavenging member includes an oxygen scavenger 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, the first film and the second film are joined in a peelable manner at a seal portion, the seal portion includes a first seal portion located facing the first container, the first seal portion bends so as to protrude to the side away from the first container in the 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 scavenging member, a container set.

[0056]

[40] A first container for containing a liquid, a second container that houses the first container; the first container has oxygen permeability; 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; the first film and the second film are joined in a peelable manner at a seal portion; the seal portion includes a first seal portion that faces the first container; the first seal portion is bent so as to protrude toward a side away from the first container in a direction in which the first seal portion and the first container face each other; the seal portion 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 located between at least one of the first side seal portion and the second side seal portion and the first container, a container set.

[0057]

[41] Comprising a laminate, 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, a container.

[0058]

[42] A laminate used for a container, 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, a laminate.

[0059] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In the drawings attached to this specification, for the sake of convenience of illustration and easy understanding, the scale, the aspect ratio of the vertical and horizontal dimensions, etc. are appropriately changed and exaggerated from those of the actual object. Configurations and the like shown in some of the drawings may be omitted in other drawings.

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

[0061] "Suppression" means to hold back or prevent realization, occurrence, etc., or to hinder realization, occurrence, etc. "Suppression" means not only to completely prevent realization, occurrence, etc., but also to reduce the possibility of realization, occurrence, etc., or to make it less likely for realization, occurrence, etc. to occur.

[0062] In this specification, when a plurality of upper limit value candidates and a plurality of lower limit value candidates are listed for a certain parameter, the numerical range of that parameter may be constituted by combining any one upper limit value candidate and any one lower limit value candidate. As an example, consider the description "Parameter B may be A1 or more, may be A2 or more, may be A3 or more. Parameter B may be A4 or less, may be A5 or less, may be A6 or less." In this example, the numerical range of Parameter B may be A1 or more and A4 or less, may be A1 or more and A5 or less, may be A1 or more and A6 or less, may be A2 or more and A4 or less, may be A2 or more and A5 or less, may be A2 or more and A6 or less, may be A3 or more and A4 or less, may be A3 or more and A5 or less, may be A3 or more and A6 or less.

[0063] Figures 1 to 26F are diagrams for explaining one embodiment of the present disclosure. The container set 20 includes a first container 30 and a second container 40. The first container 30 with liquid 30L includes the first container 30 and the liquid L contained in the first container 30. The first container 30 with liquid 30L is also called a liquid-containing container. The first container 30 has oxygen permeability. The first container 30 includes a portion that is at least partially oxygen-permeable. The second container 40 has oxygen barrier properties. The second container 40 can accommodate the first container 30 with liquid 30L. The combined container 10L with liquid includes the first container 30 with liquid 30L and the second container 40, and the first container 30 with liquid 30L is accommodated in the second container 40. According to this combined container 10L with liquid, by adjusting the oxygen concentration in the second container 40, not only the oxygen concentration in the first container 30 but also the dissolved oxygen amount of the liquid L can be adjusted. The first container 30 having oxygen permeability is an airtight container.

[0064] An airtight container means a container in which gas leakage is not detected by the liquid immersion method defined in JIS Z2330:2012. More specifically, a container that can prevent air bubbles from leaking when a container containing gas is immersed in water is determined to be an airtight container. Also, when a container containing gas is immersed in water, in a state where no air bubble leakage is confirmed from the container, the airtight container is determined to be in an airtight state. In the liquid immersion test, the container to be tested is immersed at a depth of 10 cm or more and 30 cm or less from the water surface. The presence or absence of air bubbles is determined by visual observation over 10 minutes.

[0065] With reference to the illustrated specific example, each component of the combined container 10L with liquid will be described in more detail. First, the first container 30 with liquid 30L will be described.

[0066] As described above, the first container 30 with liquid 30L includes the first container 30 and the liquid L contained in the first container 30. The first container 30 has oxygen permeability. On the other hand, the first container 30 can seal the liquid L. That is, 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 specifically 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, juice, broth, or a concentrate obtained by concentrating one or more of these. The liquid as a medicine may be an oral medicine, an external medicine, or an injection. The liquid L may be other than food or medicine. The liquid L may be blood or body fluid.

[0068] The interior of the first container 30 may be in a sterile state. The liquid L may be a liquid to be maintained in a sterile state. The liquid L to be maintained in a sterile state includes highly sensitive liquids such as food and medicine. Highly sensitive liquid L is liable to deteriorate by post-sterilization (also referred to as final sterilization) performed after production. Post-sterilization cannot be applied to highly sensitive liquids. Examples of post-sterilization include sterilization such as the high-pressure steam method, dry heat method, radiation method, ethylene oxide gas method, and hydrogen peroxide gas plasma method. The highly sensitive liquid L in this specification means a liquid in which 5% or more of the total weight ratio of all active ingredients contained in the liquid decomposes by subjecting the liquid L to post-sterilization, and one or more of the active ingredients contained in the liquid L decomposes by 1% or more in terms of weight ratio by subjecting the liquid L to post-sterilization. The highly sensitive liquid L to which post-sterilization cannot be applied can be produced using a production line arranged in a sterile environment. That is, the highly sensitive liquid L can be produced by an aseptic operation method. Examples of the highly sensitive liquid L include anticancer agents, antiviral agents, vaccines, and antipsychotics.

[0069] When attempting to adjust the oxygen amount of the liquid L produced by an aseptic operation method, the entire space in which the production line of the liquid L is arranged may be replaced with an inert gas. However, making the entire space in which the production line of the liquid L is arranged an inert gas atmosphere involves a huge capital investment and may also raise concerns about the safety of workers. Against this background, generally, the adjustment of the oxygen amount of the liquid L has been entrusted to, for example, replacing the atmosphere in the first container 30 containing the liquid L with an inert gas or bubbling the liquid L with an inert gas.

[0070] In contrast, according to the ingenuity of the inventors of the present invention described below, by accommodating the first container 30L containing the liquid in the second container 40, the dissolved oxygen amount of 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 further less than 0.015 mg / L. The effects caused by such ingenuity of the inventors of the present invention can be said to be remarkable beyond the range predicted from the prior art.

[0071] In addition, products (liquid L) labeled as "sterilized" or "aseptic" and the inside of the containers containing such products, and products (liquid L) such as pharmaceuticals for which "aseptic" is a condition for commercialization and the inside of the containers containing such products correspond to the "aseptic state" used in this specification. Products (liquid L) that satisfy the sterility assurance level (SAL) of 10 specified in JIS T0806:2014 and the inside of the containers containing such products also correspond to the "aseptic state" used in this specification. Products that are stored at a temperature of room temperature (for example, 20°C) or higher for 4 weeks without bacterial growth and the inside of the containers containing such products also correspond to the "aseptic state" used in this specification. Products that are stored in a refrigerated state (for example, 8°C or lower) for 8 weeks or longer without bacterial growth and the inside of the containers containing such products also correspond to the "aseptic state" used in this specification. Chemicals that are stored at a temperature of 28°C or higher and 32°C or lower for 2 weeks without bacterial growth and the inside of the containers containing such chemicals also correspond to the "aseptic state" used in this specification. -6 Products that are stored at a temperature of room temperature (for example, 20°C) or higher for 4 weeks without bacterial growth and the inside of the containers containing such products also correspond to the "aseptic state" used in this specification. Products that are stored in a refrigerated state (for example, 8°C or lower) for 8 weeks or longer without bacterial growth and the inside of the containers containing such products also correspond to the "aseptic state" used in this specification. Chemicals that are stored at a temperature of 28°C or higher and 32°C or lower for 2 weeks without bacterial growth and the inside of the containers containing such chemicals also correspond to the "aseptic state" used in this specification.

[0072] The first container 30 that houses the liquid L will be described. 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. For a container to have oxygen permeability means that in an atmosphere of a temperature of 23°C and a humidity of 40% RH, oxygen can permeate the container at a predetermined oxygen permeation amount or more and move between the inside and outside of the container. The predetermined oxygen permeation amount is 1×10 -1It is above [mL / (day×atm)]. The predetermined oxygen permeation amount may be 1 [mL / (day×atm)] or more, may be 1.2 [mL / (day×atm)] or more, or may be 3 [mL / (day×atm)] or more. According to the first container 30 having oxygen permeability, the amount of oxygen in the first container 30 can be adjusted by the oxygen permeation of the first container 30.

[0074] An upper limit may be set for the oxygen permeation amount passing through the first container 30. By setting the upper limit, leakage of water vapor or the like from the first container 30 can be suppressed. By setting the upper limit, the influence on the liquid L in the first container 30 due to the high gas permeation rate after the second container 40 is opened can be suppressed. The oxygen permeation amount passing through the first container 30 may be 100 [mL / (day×atm)] or less, may be 50 [mL / (day×atm)] or less, or may be 10 [mL / (day×atm)] or less.

[0075] The above-mentioned arbitrary lower limit of the oxygen permeation amount may be combined with the above-mentioned arbitrary upper limit of the oxygen permeation amount to define the range of the oxygen permeation amount.

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

[0077] The first container 30 may have oxygen permeability by making the whole of the first container 30 permeable to oxygen. The first container 30 may have oxygen permeability by making only a part of the first container 30 permeable to oxygen.

[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, may be 5×10 -12 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or more, or may be 1×10 -11 (cm 3(STP)·cm / (cm 2 ·sec·Pa)) or more is also acceptable. By setting a lower limit for the oxygen permeability coefficient, the oxygen permeation of the first container 30 is promoted, and the oxygen concentration in the headspace HS of the first container 30 can be adjusted rapidly. 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 is also acceptable.

[0079] Note that 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 measurement object does not contain rubber and is not a molded container, the oxygen permeability coefficient is a value measured using an Oxtran (OXTRAN, 2 / 21), a permeability measuring instrument manufactured by MOCON, USA, under the environment of a temperature of 23°C and a humidity of 50%RH in accordance with JIS K7126-2:2006. When the measurement object corresponds to at least one of 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 using an Oxtran (OXTRAN, 2 / 61), a permeability measuring instrument manufactured by MOCON, USA, under the environment of a temperature of 23°C and a humidity of 50%RH.

[0081] The area of the oxygen-permeable part of the first container 30 may be 1 mm 2 or more, may be 10 mm 2 or more, may be 30 mm 2 or more. Similarly, the thickness of the oxygen-permeable part of the first container 30 may be 3 mm or less, may be 1 mm or less, or may be several tenths of a mm or less. Thereby, the oxygen permeation of the first container 30 is promoted, and the amount of oxygen in the first container 30 can be adjusted rapidly.

[0082] The illustrated first container 30 includes a container body 32 including an opening 33, and a stopper 34 held in the opening 33 of the container body 32. The stopper 34 restricts leakage of the liquid L from the opening 33. In this example, the stopper 34 may have oxygen permeability. From the viewpoint of promoting the movement 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, usually, the stopper 34 is separated from the liquid L accommodated in the container body 32. That is, in the normal storage state of the first container 30, oxygen permeation through the stopper 34 of the first container 30 can be promoted. In this regard, by imparting oxygen permeability to the stopper 34, the amount of oxygen in the first container 30 can be adjusted rapidly.

[0083] The stopper 34 having oxygen permeability may be formed of a material having the oxygen permeability coefficient (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) described above. And the oxygen permeability coefficient of the material constituting the stopper 34 may be larger than the oxygen permeability coefficient of the material constituting the container body 32. Also, a part of the stopper 34 may have oxygen permeability. A part of the stopper 34 may be constituted by a material having oxygen permeability over its entire thickness. For example, the stopper 34 may have oxygen permeability over its entire thickness at a central portion spaced apart from the periphery, and may have oxygen barrier properties at 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 the oxygen concentration (%) in the first container 30 can be reduced by 5% or more by storing the first container 30 containing a liquid having an oxygen dissolved amount of 8 mg / L in the second container 40 for 4 weeks.

[0085] In the illustrated example, the area of the opening 33, that is, the opening area of the container body 32, may be 1 mm 2 or more, may be 10 mm 2 or more, may be 30 mm 2The above may also be applicable. The thickness of the stopper 34 may be 3 mm or less, or may be 1 mm or less. By these means, the oxygen permeation of the first container 30 is promoted, and the oxygen concentration in the first container 30 can be adjusted quickly. The syringe needle can pierce the stopper 34. Further, from the viewpoint of enabling a straw to pierce through, the thickness of the stopper, for example, the thickness of a film-like stopper, may be 0. several mm or less.

[0086] From the viewpoint of suppressing leakage of water vapor or the like, and 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 provided for the area of the opening 33. Specifically, the area of the opening 33 may be 5000 mm 2 or less. 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 stopper 34 having oxygen permeability is not particularly limited and may have various configurations. In the illustrated example, the stopper 34 is inserted into the opening 33 of the container body 32 to close the opening 33. The stopper 34 shown in FIG. 2A includes a plate-like portion 34a in the shape of a plate, and an insertion protrusion 34b extending from the plate-like portion 34a. The insertion protrusion 34b is, for example, cylindrical. A plurality of insertion protrusions 34b may be provided on the circumference. The insertion protrusion 34b is inserted into the opening 33. The plate-like portion 34a includes a flange portion extending radially outward from the insertion protrusion 34b. The flange portion of the plate-like portion 34a is placed on the head portion 32d of the container body 32. The stopper 34 may include an external thread or an internal thread. The stopper 34 may be attached to the container body 32 by the engagement of the threads.

[0088] The plug 34 may contain silicone. The plug 34 may be formed only of silicone. A part of the plug 34 may be formed of silicone. The silicone contained in the plug 34 is solid in the environment where the first container 30 is intended to be used. The silicone contained in the plug 34 does not have to include silicone that becomes liquid in a room temperature environment such as silicone oil. Silicone is a substance having a siloxane bond as the main chain. The plug 34 may be formed of a silicone elastomer. The plug 34 may be formed of silicone rubber.

[0089] Silicone rubber refers to a rubber-like material made of silicone. Silicone rubber is a synthetic resin mainly composed of silicone and is a rubber-like substance. Silicone rubber is a rubber-like substance having a siloxane bond as the main chain. 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, fluorosilicone rubber, etc.

[0090] The oxygen permeability coefficient of silicone and the oxygen permeability coefficient of silicone rubber are 1×10 -12 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or more, and may be 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. Silicone and silicone rubber have a hydrogen permeability coefficient about 10 times that of natural rubber, an oxygen permeability coefficient about 20 times that of natural rubber, and a nitrogen permeability coefficient about 30 times that of natural rubber. Silicone and silicone rubber have a hydrogen permeability coefficient more than 70 times that of butyl rubber, an oxygen permeability coefficient more than 40 times that of butyl rubber, and a nitrogen permeability coefficient more than 650 times that of butyl rubber.

[0091] The plug 34 may be composed of silicone at least in part. That is, the whole or a part of the plug 34 may be composed of silicone or silicone rubber. For example, a part of the plug 34 may be composed of silicone or silicone rubber over its entire thickness. The part may be the central part of the plug 34, or a part or all of the peripheral part surrounding the central part.

[0092] As shown in FIG. 2A, the container body 32 may include a bottom portion 32a, a body portion 32b, a neck portion 32c, and a head portion 32d in this order. As shown in FIG. 2A, a liquid L accommodating space is mainly formed by the bottom portion 32a and the body portion 32b. The head portion 32d forms the tip of the container body 32. The head portion 32d is thicker than other parts. The neck portion 32c is located between the body portion 32b and the head portion 32d. The neck portion 32c is narrowed in width, especially in diameter, with respect to the body portion 32b and the head portion 32d.

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

[0094] For the measurement of the transmission haze, a light source (hereinafter referred to as the D65 normal light source) simulating the spectrum of the D65 standard light is used. Before measuring the transmission haze, the D65 normal light source is turned on for 15 minutes to stabilize the output of the D65 normal light source. The incident angle to the sample when measuring the transmission haze is set to 0°. The test environment when measuring the 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 the start of the test. Other measurement conditions when measuring the transmission haze follow JIS K7136:2000. The transmission haze is the arithmetic mean value of five measurement values. The five measurement values are the measurement values measured at five measurement positions of the measurement sample to be evaluated.

[0095] The illustrated first container 30 further includes a fixture 36. The fixture 36 suppresses the plug 34 from coming off the container body 32. The fixture 36 is attached to the head 32d of the container body 32. As shown in FIGS. 1 and 2A, the fixture 36 covers the periphery of the plate-like portion 34a of the plug 34. The fixture 36 presses the flange portion of the plate-like portion 34a toward the head 32d. Thereby, the fixture 36 suppresses the plug 34 from coming off the container body 32 while exposing a part of the plug 34. In addition, the space between the plug 34 and the container body 32 can be made liquid-tight and airtight. The fixture 36 makes the first container 30 airtight. The fixture 36 may be a sheet-like metal fixed to the head 32d. The fixture 36 may also be a cap screwed onto the head 32d. The metal fixture 36 has oxygen barrier properties.

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

[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 of a resin sheet or a resin plate. In this example, the resin sheet or the resin plate may include a layer having oxygen barrier properties such as ethylene-vinyl alcohol copolymer (EVOH) or polyvinyl alcohol (PVA). Further, the container body 32 may include a laminate including a metal vapor deposition film or a vapor deposition film of a metal oxide. Transparency can be imparted to the container body 32 using a laminate or glass, in addition to 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] That a part of the container has oxygen permeability means that, in an atmosphere at a temperature of 23°C and a humidity of 40% RH, oxygen can permeate through the part of the container in an amount equal to or more than a predetermined oxygen permeation amount and move between the inside and the outside of the container. The predetermined oxygen permeation amount is 1×10 -1 (mL / (day×atm)) or more. The predetermined oxygen permeation amount may be 1 (mL / (day×atm)) or more, 1.2 (mL / (day×atm)) or more, or 3 (mL / (day×atm)) or more. By having a part of the first container 30 with oxygen permeability, the amount of oxygen in the first container 30 can also be adjusted.

[0099] The predetermined oxygen permeation amount 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 permeation amount, leakage of water vapor and the like can be suppressed, and the influence on the liquid in the first container 30 after the opening of the second container 40 due to a high oxygen permeation rate can be suppressed. The range of the oxygen permeation amount may be determined by combining any of the above-mentioned lower limits of the oxygen permeation amount with any of the above-mentioned upper limits of the oxygen permeation amount.

[0100] The oxygen permeation rate (mL / (day×atm)) through a part of the container is measured using a test container 70 including the part, as shown in FIG. 2B. The test container 70 includes a partition wall portion 71. The test container 70 includes an internal space partitioned by the partition wall portion 71. The partition wall portion 71 includes a part of the container and a main wall portion 72 having oxygen barrier properties. The permeation rate of a part 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 container 70 is maintained at 0.05% or less. The test container 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 in the second flow path 77. The oxygen measuring device 79 is an oxygen amount measuring device used in Oxtran (2 / 61) manufactured by Mocon, Inc., USA. The first flow path 76 supplies gas into the test container 70. The first flow path 76 supplies a gas that does not contain oxygen. The first flow path 76 supplies nitrogen. The second flow path 77 discharges the gas in the test container 70. The first flow path 76 and the second flow path 77 have oxygen barrier properties. The inside of the test container 70 is maintained in a situation where oxygen is substantially absent by the first flow path 76 and the second flow path 77.

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

[0103] In the illustrated example, the test container 70 is disposed within the test chamber 78. The atmosphere within the test chamber 78 is maintained at a temperature of 23°C and a humidity of 40%RH. Air is supplied into the test chamber 78 from the supply passage 78A. The gas within the test chamber 78 is discharged from the discharge passage 78B. Through the supply passage 78A and the discharge passage 78B, air circulates and the oxygen concentration within 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 passage 78A and the discharge passage 78B. If the oxygen concentration within the test chamber 78 can be maintained constant, the supply passage 78A and the discharge passage 78B shown in FIG. 2B may be open to the air atmosphere under atmospheric pressure.

[0105] FIG. 2B shows a method for measuring the oxygen permeation amount, taking a portion 30X having oxygen permeability of the first container 30 as an example. In the example shown in FIG. 2B, the partition wall portion 71 is constituted by the portion 30X having oxygen permeability of the first container 30 and the main wall portion 72 having oxygen barrier properties. For example, the partition wall portion 71 may be constituted by the portion 30X cut out from the first container 30 and the main wall portion 72 connected to the peripheral portion 30Y of the portion 30X. This main wall portion 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 peripheral portion of 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 hermetically joined to the peripheral portion of the through-hole 72A of the main wall portion 72 via an oxygen-barrier joining material 73 having oxygen barrier properties. In the example shown in FIG. 2B, the vicinity of the stopper 34 of the container set 20 shown in FIG. 2A is cut off. In this example, the stopper 34 is the portion 30X having oxygen permeability. The portions 32c, 32d forming the opening 33 of the container body 32 and the fixture 36 are hermetically connected to the main wall portion 72 via an oxygen-barrier joining material 73 as the portion 30Y adjacent to the portion 30X having oxygen permeability.

[0106] In the example shown in FIG. 2B, the container body 32 is cut at the neck portion 32c. The stopper 34 is compression-held in the opening 33 formed by the head portion 32d of the container body 32. The fixture 36 makes the space between the container body 32 and the stopper 34 airtight. The fixture 36 having an oxygen barrier property such as aluminum partially covers the stopper 34. The container body 32 and the fixture 36 having an oxygen barrier property are connected to the main wall portion 72 via the barrier bonding material 73. The stopper 34 is maintained in a state similar to the state when the first container 30 is closed during actual use, such as compression in the opening 33 and tightening by the fixture 36. Therefore, the oxygen permeation amount of the stopper 34 can be measured under the same conditions as during actual use.

[0107] As described above, the method for measuring the oxygen permeation amount (mL / (day×atm)) that permeates through a part of the container has been explained. Regarding the oxygen permeation amount (mL / (day×atm)) that permeates through the entire container, it can be specified by dividing the container into two or more parts and adding up the oxygen permeation amounts measured for each part. For example, the oxygen permeation amount of the first container 30 shown in FIG. 2A can be specified by measuring the oxygen permeation amount of the container body 32 and adding it to the oxygen permeation amount of a part 30X measured by the method shown in FIG. 2B. The oxygen permeation amount (mL / (day×atm)) of the container body 32 can be measured by using a test container 70 produced by combining the container body 32 with the 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 of, for example, borosilicate glass. This first container 30 may be a vial. A vial is a container including a container body, a stopper inserted into the opening of the container body, and a seal as a fixture 36 for fixing the stopper, and the seal is clamped together with the stopper to the head of the container body using a hand gripper or the like. The volume of the first container 30 that is a vial may be 1 mL or more, or may be 3 mL or more. The volume of the first container 30 that is a vial may be 500 mL or less, or may be 200 mL or less.

[0110] When the first container 30 is a vial, the oxygen permeability coefficient of the material constituting the stopper 34 may be greater than the oxygen permeability coefficient of the glass constituting 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 that is a vial can be stably arranged on the placement surface by bringing the bottom 32a of the container body 32 into contact with the placement surface. At this time, the stopper 34 is separated from the liquid L. The stopper 34 does not contact the liquid L. Therefore, in the normal storage state of the first container 30, oxygen permeation through the stopper 34 of the first container 30 can be promoted.

[0111] The illustrated first container 30 can maintain a negative internal pressure under atmospheric pressure. The first container 30 can accommodate the gas while maintaining the gas at a negative pressure under atmospheric pressure. The first container 30 may also be capable of accommodating the 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 be somewhat deformed under atmospheric pressure when maintaining the internal pressure at a negative or positive pressure. Examples of the first container 30 that can maintain the internal pressure at a negative or positive pressure include the above-described vial and a can made of metal.

[0112] To be able to contain a gas while maintaining a negative pressure under atmospheric pressure means that the gas can be contained without breakage while setting the internal pressure to a negative pressure of 0.80 atm or more. A container that can contain a gas while maintaining a negative pressure under atmospheric pressure may be in an airtight state when the internal pressure is 0.80 atm. In a container that can contain a gas while maintaining a negative pressure under atmospheric pressure, the volume when the internal pressure is 0.80 atm may be maintained at 95% or more of the volume when the internal pressure is 1.0 atm. To be able to contain a gas while maintaining a positive pressure in the atmosphere means that the gas can be contained without breakage while setting the internal pressure to a positive pressure of 1.2 atm or less. A container that can contain a gas while maintaining a positive pressure under atmospheric pressure may be in an airtight state when the internal pressure is 1.20 atm. In a container that can contain a gas while maintaining a positive pressure under atmospheric pressure, the volume when the internal pressure is 1.2 atm may be maintained at 105% or less of the volume when the internal pressure is 1.0 atm.

[0113] The first container 30 is intended to be housed inside a second container 40 having oxygen barrier properties. The first container 30 housed inside the second container 40 may be able to contain a gas without breakage when the difference between the internal pressure of the first container 30 and the internal pressure of the second container 40 is 0.2 atm or less. The first container 30 housed inside the second container 40 may be in an airtight state when the difference between the internal pressure of the first container 30 and the internal pressure of the second container 40 is 0.2 atm or less. The first container 30 housed inside the second container 40 may have a volume of 95% or more and 105% or less 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 when the difference between the internal pressure of the first container 30 and the internal pressure of the second container 40 is 0.2 atm or less. 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 less than the internal pressure of the second container 40, or the internal pressure of the first container 30 may be greater than the internal pressure of the second container 40.

[0114] The second container 40 has a volume capable of accommodating 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 an adhesive material. 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 having 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. That the second container 40 has oxygen barrier properties means that the oxygen permeability (mL / (m 2 ×day×atm)) of the container is 1 or less. The oxygen permeability (mL / (m 2 ×day×atm)) of a container having oxygen barrier properties may be 0.5 or less, or may be 0.1 or less. When the measurement object does not contain rubber and is not a molded container, the oxygen permeability is a value measured using an Oxtran (2 / 21), a permeability measuring machine manufactured by MOCON, Inc., USA, in an environment of a temperature of 23°C and a humidity of 50%RH in accordance with JIS K7126-2:2006. When the measurement object corresponds to at least one of 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 using an Oxtran (2 / 61), a permeability measuring machine manufactured by MOCON, Inc., USA, in an environment of a temperature of 23°C and a humidity of 50%RH.

[0116] The oxygen transmission 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, or may be 1×10 -17 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or less.

[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 part of the second container 0 may be transparent. All of the second container 40 may be transparent. The second container 40 using a laminate and the second container 40 using glass or resin can be imparted with transparency as well as oxygen barrier properties. By imparting transparency to the second container 40, the first container 30L containing liquid inside can be confirmed from the outside of the second container 40.

[0118] In the example shown in FIG. 1, the second container 40 is composed of a resin film having 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. This 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 located 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 located 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 the upper and lower edges. The films 41a to 41d are hermetically joined by welding such as heat sealing or ultrasonic bonding, or by bonding using a bonding material such as an adhesive or an adhesive.

[0119] In the second container 40 shown in FIG. 1, instead of joining separate films, one folded film may constitute two or more of the adjacent arrangements of films 41a to 41d. That is, two or more films including films 41a to 41d may be constituted by a single film material without joints. As shown in FIG. 1, the gusset bag can form a rectangular bottom surface in the second container 40. By arranging 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 together with the first film 41a and the second film 41b instead of the gusset bag. This pouch is also called a standing pouch. This pouch can also form the bottom surface, and the first container 30 can be stably stored in the second container 40.

[0120] As shown in FIGS. 7B to 7D, a second container 40 that can be unfolded flat may be used. Each of the second containers 40 shown in FIGS. 7B to 7D can be produced by joining resin films at the seal portion 49. The second container 40 shown in FIG. 7B can be produced by joining the first film 41a and the second film 41b at the seal portion 49 provided on its circumference.

[0121] The second container 40 shown in FIG. 7C has a film 41 folded at the folding portion 41x. By joining the facing portions of the folded film 41 at the seal portion 49, the second container 40 can be produced. In the second container 40 shown in FIG. 7C, an accommodation space is formed in the portion surrounded by the folding portion 41x and the three-sided seal portion 49. In the example shown in FIG. 7C, the first film 41a and the second film 41b that form a space for accommodating the first container 30 between the first film 41a are constituted by a single film material. There is no joint between the first film 41a and the second film 41b.

[0122] The second container 40 shown in FIG. 7D is also called a pillow type. By joining both ends of a single film 41 to each other as seal portions 49, the film 41 is formed into a cylindrical shape, and further by joining both end portions of the cylindrical shape as seal portions 49, the second container 40 is obtained. In the example shown in FIG. 7D, a first film 41a and a second film 41b that forms a space for accommodating the first container 30 between the first film 41a are constituted by one 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 still 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 housing portion 42a and a flange portion 42b. The housing portion 42a may form a rectangular parallelepiped housing space. The first container 30 is housed in this housing space. The housing portion 42a may have a rectangular parallelepiped outer shape with one face open. The flange portion 42b is provided at the periphery of the opening of the housing portion 42a. The lid 44 is flat. The peripheral portion of the lid 44 can be hermetically 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 or more and 2 mm or less, or may be 0.1 mm or more and 1.5 mm or less.

[0125] The second container 40 shown in FIG. 8 can maintain the internal pressure at a negative pressure under atmospheric pressure. The second container 40 can accommodate the gas while maintaining the gas at a negative pressure under atmospheric pressure. The second container 40 may be able to accommodate the 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 be somewhat deformed under atmospheric pressure when maintaining the internal pressure at a negative pressure or a positive pressure. As the second container 40 that can maintain the internal pressure at a negative pressure or a positive pressure, a can made of metal is exemplified.

[0126] Since the oxygen-permeable part of the first container 30 is at least partially separated from the second container 40 having oxygen barrier properties, the transfer of oxygen from the inside of the first container 30 into 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. By making the accommodation space of the second container 40 larger than the outer shape of the first container 30, the gap G can be secured. When the second container 40 is formed 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 container set 20 and the combined container 10 are constituted by the first container 30 and the second container 40 described above. The combined container 10L containing liquid is obtained by the first container 30L containing liquid and the second container 40.

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

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

[0130] As shown in FIG. 3, an opening 40a for accommodating the first container 30L containing liquid remains in the second container 40 before closing. In the second container 40 shown in FIG. 1, for example, the upper edge portions of the films 41a to 41d form the opening 40a without being joined to each other. In the second container 40 shown in FIG. 8, a container body 42 without a lid 44 attached is prepared. 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 the opening 40a and enters the second container 40. The discharge port 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. That is, the first container 30L containing liquid is placed in an inert gas atmosphere. Note that the inert gas is a stable gas with low reactivity. Examples of the inert gas include noble gases such as helium, neon, and argon, and nitrogen.

[0132] Note that the filling of the inert gas into the second container 40 and the placement of the first container 30L containing liquid into the second container 40 may be performed either first or in parallel.

[0133] Next, as shown in FIG. 5, with the first container 30L containing liquid and filled with the inert gas, the second container 40 is closed. In the second container 40 shown in FIG. 1, the second container 40 is closed by joining the upper edge portions of the films 41a to 41d to each other 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 portion of the lid 44 to the flange portion 42b of the container body 42. The joining may be performed using a joining material such as an adhesive or an adhesive, or may be welding such as heat sealing or ultrasonic joining. The second container 40 becomes airtight.

[0134] Alternatively, instead of supplying an inert gas from the supply pipe 15, the second container 40 containing the first container 30L with liquid may be closed in an inert gas atmosphere. Also by this method, the first container 30L with liquid is sealed in the second container 40 together with the inert gas.

[0135] In addition, the process until the second container 40 is closed may be carried out in a sterile environment. That is, the first container 30L with liquid manufactured in a sterile state and the second container 40 that has been sterilized or manufactured in a sterile state are brought into a sterile environment such as a sterile chamber, for example. If this chamber is partitioned from the air atmosphere and has an inert gas atmosphere, the supply of the inert gas by the supply pipe 15 can be omitted. Then, in the sterile environment, the second container 40 containing the first container 30L with liquid is closed. Therefore, the inside of the second container 40 containing the first container 30L with liquid also becomes sterile. That is, the first container 30L with liquid can be stored in the second container 40 in a sterile state.

[0136] Thereafter, the first container 30L with liquid is stored in the second container 40. As described above, the second container 40 has oxygen barrier properties. The permeation of oxygen through the second container 40 is effectively suppressed. The first container 30 has oxygen permeability at least in part. Also, the second container 0 is filled with an inert gas, and the oxygen concentration in the second container 40 is very low. In this combined container 10L with liquid, the oxygen in the first container 30 permeates through the first container 30 and moves into the second container 40. Along with the movement of oxygen from the first container 30 to the second container 40, the oxygen concentration in the second container 40 increases, and the oxygen concentration in the first container 30 decreases. In the final equilibrium state where the permeation of oxygen through the first container 30 reaches equilibrium, the oxygen concentration in the first container 30 may be the same as 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. And the amount of oxygen dissolved in the liquid L (mg / L) decreases.

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

[0139] Highly sensitive liquids L, such as foods and pharmaceuticals, can be decomposed by oxygen. For example, the solute of an aqueous solution as a drug can be decomposed by oxygen. The liquid as a drug or the solute of an aqueous solution as a drug can be decomposed by oxygen. The particles dispersed in the liquid of a suspension as a drug or food can be decomposed by oxygen. On the other hand, by accommodating the liquid L in the first container 30 disposed in the second container 40, the decomposition of the liquid L by oxygen can be suppressed. That is, the present embodiment in which the oxygen concentration in the first container 30 can be adjusted after enclosing the liquid L is suitable for highly sensitive liquids L, such as foods and pharmaceuticals.

[0140] Instead of filling the second container 40 with an inert gas when the second container 40 is closed or in addition to filling the second container 40 with an inert gas, an oxygen scavenger 21 for absorbing oxygen in the second container 40 may be provided. By the oxygen scavenger 21 absorbing oxygen, the oxygen concentration in the second container 40 decreases, and the oxygen in the first container 30 moves to the second container 40. By using the oxygen scavenger 21, the oxygen concentration in the second container 40 and the oxygen concentration in the first container 30 can be reduced more effectively. As confirmed by the inventors of the present case, by using a sufficient amount of the oxygen scavenger 21, the oxygen concentration in the second container 40 and the oxygen concentration in the first container 30 can be kept low, for example, maintained at less than 0.3%, 0.1% or less, 0.05% or less, less than 0.03%, and even 0%. Further, as the oxygen concentration in the first container 30 decreases, the amount of oxygen dissolved in the liquid L contained in the first container 30 also decreases. As confirmed by the inventors of the present case, by using a sufficient amount of the oxygen scavenger 21, the amount of oxygen dissolved in the liquid L can be significantly reduced, for example, maintained at 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, and even 0 mg / L.

[0141] The amount of the oxygen scavenger 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 deoxidizer 21 is not particularly limited as long as it is a composition capable of absorbing oxygen. As the deoxidizer 21, an iron-based deoxidizer or a non-iron-based deoxidizer can be used. For example, a deoxidizer composition using metal powders such as iron powder, reducing inorganic substances such as iron compounds, polyphenols, polyhydric alcohols, reducing organic substances such as ascorbic acid or its salts, or metal complexes as the main agent for the oxygen absorption reaction may be used as the deoxidizer. As shown in FIGS. 1 and 8, the combined container 10 may include a deoxygenation member 22 housed in a second container 40 together with a first container 30L containing a liquid. As shown in FIG. 9A, the deoxygenation member 22 may include a packaging body 22a having oxygen permeability and a deoxidizer 21 housed in the packaging body 22a. The deoxygenation member 22 containing the deoxidizer 21 may be an iron-based moisture-dependent FX type, an iron-based self-reactive S type, an SPE type, a ZP type, a ZI-PT type, a ZJ-PK type, or an E type available from Mitsubishi Gas Chemical Company, Inc. The deoxygenation member 22 containing the deoxidizer 21 may be an organic self-reactive GLS type, a GL-M type, or a GE type available from Mitsubishi Gas Chemical Company, Inc. The deoxygenation member 22 containing the deoxidizer 21 may be a ZH type, a Z-PK ya, a Z-PR, a Z-PKR, or a ZM type for pharmaceuticals available from Mitsubishi Gas Chemical Company, Inc.

[0143] To promote oxygen absorption by the deoxidizer 21, as shown in FIG. 9B, the deoxygenation member 22 may include a water retention agent 22b that retains moisture. 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 carrier for supporting the deoxidizer 21.

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

[0145] When the liquid L is an aqueous solution, the deoxidizing member 22 may not contain the water retention agent 22b. The first container 30 having oxygen permeability often has water vapor permeability. In this example, water can be supplied to the deoxidizing agent 21 without using the water retention agent 22b. Rather, the water 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 deoxidizing member 22 may be 5% or less of the volume (mL) of the liquid L contained in the first container 30. As storage conditions for liquids such as pharmaceuticals, during the expiration date of the pharmaceuticals (for example, 3 years), the reduction amount of the volume can be set to 5% or less. The reduction amount of the liquid L in the first container 30 can be regulated. 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, this storage condition can be satisfied.

[0146] When attempting to activate the deoxidizing agent 21 with water vapor that has passed through the first container 30 and moved into the second container 40, a part or all of the deoxidizing agent 21 or a part or all of the deoxidizing member 22 may be arranged above the oxygen-permeable portion of the first container 30 in the vertical direction. For example, when the container body 32 has oxygen barrier properties and the stopper 34 has oxygen permeability, a part or all of the deoxidizing agent 21 may be arranged above the stopper 34. When the container body 32 has oxygen barrier properties and the stopper 34 has oxygen permeability, a part or all of the deoxidizing member 22 may be arranged above the stopper 34. Water vapor is lighter compared to nitrogen, oxygen, and many inert gases. Therefore, the water vapor that has passed through the first container 30 can be efficiently used for the activation of the deoxidizing agent 21.

[0147] The oxygen scavenger 21 may be included in the oxygen scavenging film 23. FIG. 9C shows an example of a laminate 46 including the oxygen scavenging film 23. The laminate 46 including the oxygen scavenging film 23 may constitute the films 41a to 41e of the second container 40 shown in FIGS. 1 and 7A to 7C. The laminate 46 including the oxygen scavenging film 23 may constitute the container body 42 and the lid 44 of the second container 40 shown in FIG. 8. The laminate 46 including the oxygen scavenging film 23 may constitute 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 an 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 base material 23a made of a thermoplastic resin and an oxygen scavenger 21 dispersed in the base material 23a. As in the example shown in FIG. 9C, the second container 40 may include an oxygen scavenging film 23 containing the oxygen scavenger 21 as a part of the laminate 46. The oxygen scavenger 21 is not limited to the heat seal layer or the innermost layer 46c and may 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 scavenging film 23 containing the oxygen scavenger 21. The oxygen scavenger 21 may be provided separately from the first container 30 and the second container 40 as in the examples shown in FIGS. 1 and 8, or may be provided as a part of the first container 30 and 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 specified by one measuring device suitable for measuring these oxygen concentrations. As a measuring device for measuring the oxygen concentration, an oxygen amount measuring device using the headspace method, a fluorescence contact type oxygen amount measuring device, and a fluorescence non-contact type oxygen amount measuring device are known. The oxygen dissolved amount (mg / L) of the liquid contained in the first container 30 is specified by one measuring device suitable for measuring the oxygen dissolved amount of the liquid. As a measuring device for measuring the oxygen dissolved amount, a fluorescence contact type oxygen amount measuring device, a fluorescence non-contact type oxygen amount measuring device, etc. are known. As a measuring device for measuring the oxygen concentration and the oxygen dissolved amount, one appropriate measuring device is selected in consideration of the measurement limit, the stability of the measurement in the oxygen concentration band to be measured, the measurement environment, the measurement conditions, etc.

[0150] As an oxygen amount measuring device using the headspace method, the headspace analyzer FMS760 manufactured by lighthouse is used. In the measurement using this measuring device, light with a frequency that can be absorbed by oxygen is irradiated from outside the container containing the oxygen to be measured to the container, and the light emitted from the container after passing through the headspace HS of the container is received. The change in light intensity before and after transmission is measured, and based on this change in light intensity, the oxygen concentration (%) in the container can be specified. Therefore, if the first container 30 is permeable to the light from the measuring device, the oxygen concentration in the first container 30 can be specified without opening the first container 30. If the second container 40 is permeable to the light from the measuring device, for the first container 30 housed in the second container 40, light can also be irradiated from outside the second container 40 without opening the second container 40 to measure the oxygen concentration in the first container 30. The oxygen concentration (%) in the second container 40 can also be measured using the headspace analyzer FMS760 manufactured by lighthouse. The saturated solubility of oxygen in the liquid L can be specified from the measured oxygen concentration (%) and temperature of the headspace HS. Based on the specified saturated solubility, the oxygen dissolution amount (mg / L) of the liquid L can be specified. Thus, according to the headspace analyzer FMS760, the oxygen concentration in the container can be measured from outside the container. However, the lower limit value of the oxygen concentration measurable by the headspace analyzer FMS760 is higher than the lower limit value of the oxygen concentration measurable by other measuring devices.

[0151] As a fluorescence contact type oxygen amount measuring device, the oxygen amount measuring device Microx4 of PreSens of Germany is used. The oxygen amount measuring device Microx4 is a needle type device. The oxygen amount measuring device Microx4 can measure the oxygen concentration and oxygen dissolution amount in the container by puncturing the needle into the container. Although it also depends on the configuration of the part of the container where the needle is punctured, it has excellent measurement stability. By preparing a plurality of combined containers or containers manufactured under the same conditions and measuring the oxygen amount in each container with a needle type oxygen amount measuring device at different times, the change in oxygen amount over time can be evaluated.

[0152] By previously accommodating an oxygen sensor in a container, the oxygen concentration and the amount of dissolved oxygen in the first container 30 and the second container 40 can be measured using a fluorescence non-contact type oxygen measurement device. As the fluorescence non-contact type oxygen measurement device, the oxygen measurement device Fibox3 of PreSens, Germany is used. When the oxygen sensor receives light in a specific wavelength range, it emits fluorescence. The amount of the fluorescence signal of the oxygen sensor varies with an increase in the amount of oxygen around the sensor. The fluorescence non-contact type oxygen measurement device can emit light of a specific wavelength at which the oxygen sensor emits fluorescence, measure the amount of the signal due to the fluorescence emission of the oxygen sensor, and measure the oxygen concentration (%) and the amount of dissolved oxygen (mg / L). When the first container 30 is accommodated in the second container 40, the amount of dissolved oxygen in the liquid L can be measured by irradiating light from the outside of the second container 40 without opening the second container 40.

[0153] As shown in FIGS. 1 and 8, the container set 20 and the combined 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 the substance that has the property of absorbing moisture such as water vapor and water. Examples of the dehydrating agent 24 may include calcium chloride, soda lime, silica gel, and the like. The dehydrating agent 24 may be accommodated in the second container 40 together with the first container 30, and the second container 40 may be closed. In the example shown in FIG. 1, the dehydrating agent 24 is arranged in the second container 40 as a dehydrating member accommodated in a package. Similar to the above-described deoxidizing agent, a film-like dehydrating film containing a dehydrating material may be included as a 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 accommodated in the first container 30, the dehydrating agent 24 accommodated in the second container can remove moisture such as water vapor and water in the first container 30. As confirmed by the inventors of the present invention, by accommodating a dehydrating agent in the second container 40, the moisture in the first container 30 can be reduced to 100 μg or less, 50 μg or less, or 10 μg or less.

[0154] When using the dehydrating agent 24, the moisture 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 specified by the coulometric titration method using a Karl Fischer moisture meter MKC-610 manufactured by Kyoto Electronics Industry Co., Ltd. If the Karl Fischer moisture meter MKC-610 cannot be used, the moisture content in the first container 30 is specified using a Karl Fischer moisture meter MKC-710M manufactured by Kyoto Electronics Industry Co., Ltd.

[0155] The container set 20 and the combined container 10 may include an oxygen detection material 25 for detecting the oxygen state in the second container 40. The oxygen detection material 25 may display information regarding the detected oxygen state. The oxygen detection material 25 may include a display unit 26 for displaying information regarding the oxygen state. The oxygen detection material 25 may detect the oxygen concentration. The oxygen detection material 25 may display the detected oxygen concentration value. The oxygen detection material 25 may display the detected oxygen concentration value by color. The oxygen detection material 25 may display the oxygen concentration range to which the detected oxygen concentration value belongs by color.

[0156] The oxygen detection material 25 may contain a variable organic dye whose color changes reversibly by oxidation-reduction. For example, the oxygen reducing agent may contain an organic dye such as a thiazine dye, an azine dye, or an oxazine dye and a reducing agent, and may be in a solid form. The oxygen reducing agent may contain an oxygen indicator ink composition. The oxygen indicator ink composition may contain a resin solution, a thiazine dye or the like, a reducing sugar, and an alkaline substance. The thiazine dye or the like, the reducing sugar, and the alkaline substance may be dissolved or dispersed in the resin solution. The substances contained in the oxygen detection material 25 may change reversibly by oxidation and reduction. By using the oxygen detection material 25 containing a reversible substance, the display color of the oxygen detection material 25 accommodated in the container changes along with the deoxygenation in the container before the deoxygenation is completed. By observing the display of the oxygen detector 25, the state related to the oxygen in the container can be grasped. Further, the oxygen detector 25 accommodated in the container can notify, by changing the display color, the increase in the oxygen concentration after the deoxygenation is completed, for example, the state in which oxygen flows into the container due to the formation of pinholes or the like in the container during the distribution process or the like.

[0157] The oxygen detection material 25 may be a commercially available tablet-type oxygen detection material. The oxygen detection material 25 may be an oxygen detection material available from Mitsubishi Gas Chemical Company, Inc. under the trade name "Ageless Eye". The oxygen detection material 25 may also be an oxygen detection body coated with an ink composition having an oxygen detection function, for example, an oxygen detection material available from Mitsubishi Gas Chemical Company, Inc. under the trade name "Paper Eye". "Ageless Eye" and "Paper Eye" are functional products that can simply indicate by a color change that the oxygen concentration in a transparent container is in an oxygen-free state of less than 0.1% by volume. As the oxygen detection material 25, together with a deoxidizer, for example, a deoxidizer available from Mitsubishi Gas Chemical Company, Inc. under the trade name "Ageless", which can be used for maintaining the freshness of foods and the quality of medical and pharmaceutical products, may be used.

[0158] As shown in FIG. 1, the oxygen detection material 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 detection material 25 is accommodated in the second container 40, like the oxygen scavenger 21 and the oxygen scavenging member 22. The oxygen detection material 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 detection material 25 may be arranged so that its display unit 26 cannot be made unobservable by the oxygen scavenging member 22 or the dehydrating agent 24. Further, when a label is attached to the first container 30, it is preferable that the oxygen scavenging member 22, the dehydrating agent 24, and the oxygen detection material 25 are arranged so as not to cover the label.

[0159] Furthermore, the oxygen detection material 25 may detect the oxygen state in the first container 30. That is, the container set 20 and the combined container 10 may include the oxygen detection material 25 that detects the oxygen state in the first container 30. This oxygen detection material 25 may be accommodated in the first container 30. The oxygen detection material 25 may display information regarding the detected oxygen state in the first container 30. The oxygen detection material 25 may include a display unit 26 that displays information regarding the oxygen state in the first container 30. The oxygen detection material 25 may detect the oxygen concentration in the first container 30. The oxygen detection material 25 may display the detected oxygen concentration value in the first container 30. The oxygen detection material 25 may display the detected oxygen concentration value in the first container 30 by color. The oxygen detection material 25 may display the oxygen concentration range to which the detected oxygen concentration value in the first container 30 belongs by color.

[0160] Incidentally, the oxygen concentration in the space not occupied by the liquid L in the first container 30, i.e., the so-called headspace HS, can be reduced to about 1.5% or less before attaching the stopper 34 to the container body 32 by replacing the headspace HS with an inert gas, bubbling the liquid L with an inert gas, or the like. Also, by manufacturing the liquid in an atmosphere replaced with an inert gas and storing the liquid in a container having oxygen barrier properties, it is considered that the amount of oxygen dissolved in the liquid stored in the container can be reduced. However, installing the entire line for manufacturing the liquid in an atmosphere replaced with an inert gas requires a large-scale renovation of the manufacturing facility and a huge capital investment. Also, in the field of expensive chemicals and the like, in order to ensure stability against temperature, oxygen, moisture, light, etc., the chemical is freeze-dried into a powder and stored. However, making the liquid chemical into a powder for storage and returning the powdered chemical to a liquid for use have significant demerits in terms of labor, time, and cost.

[0161] In contrast, according to the present embodiment, a first container containing a liquid can be manufactured in the same manner as before using existing equipment and the like. Therefore, equipment renovation and capital investment can be avoided. In particular, in the application to liquids such as chemicals, it is also useful in that an application for approval to a public institution regarding changes in the manufacturing equipment and manufacturing process can be omitted. Also, the labor of freeze-drying the liquid L and returning the powder to a liquid can be saved. Furthermore, the first container 30 is not subject to any special restrictions. Therefore, a material that has become widely popular as a container for foods, chemicals, etc. due to its low elution amount, such as glass or resins such as polyethylene and polypropylene, can be used as the material for the first container.

[0162] In addition, 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. Conventionally, however, vials containing liquids, especially vials containing liquids in a sterile state, are made using butyl rubber or fluororubber with low oxygen permeability or even having an oxygen barrier property. In contrast, in the above-described specific example, the stopper 34 has oxygen permeability. That is, oxygen can permeate through the stopper 34. For example, the oxygen permeability coefficient (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) of the material constituting the stopper 34 is set large. The stopper 34 may be made of silicone or silicone rubber. Furthermore, the oxygen permeability coefficient of the silicone or silicone rubber constituting the stopper 34 may be larger than the oxygen permeability coefficient of the material constituting the container body 32. According to such a specific example, oxygen permeates through the stopper 34 and moves outside the first container 30. Therefore, by using the stopper 34 having oxygen permeability, oxygen permeability can be easily imparted to existing containers such as vials that have been conventionally used.

[0163] In this specific example, the time until the equilibrium state is reached depends on the oxygen permeable amount 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, the time until the oxygen permeation through the first container 30 reaches equilibrium after the first container 30 is accommodated in the second container 40 can be shortened. Thereby, the decomposition of the liquid L by oxygen can be suppressed.

[0164] Also, the partial volume of the first container 30 obtained by subtracting the volume of the liquid L from the volume of the first container 30 (the volume of the headspace HS) 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 (the volume of the headspace HS) in this way, the amount of oxygen in the volume can be reduced. Therefore, according to such a liquid-containing combined container 10L, the time until the oxygen permeation through the first container 30 reaches equilibrium after closing the second container 40 containing the first container 30 can be shortened. Thereby, the decomposition of the liquid L by oxygen can be suppressed.

[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. According to such a liquid-containing combined container 10L, after closing the second container 40 containing the first container 30, the time until the permeation of oxygen through the first container 30 reaches equilibrium can be shortened. Thereby, the decomposition of the liquid L by oxygen can be suppressed.

[0166] Furthermore, an upper limit and a lower limit may be set for the ratio (%) of the partial volume (mL) of the first container 30 obtained by subtracting the volume of the liquid L from the volume of the first container 30 (the volume of the headspace HS) 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 50% or less, or may be 20% or less. By setting such an upper limit, the oxygen concentration in the first container 30 can be sufficiently reduced. Also, a storage space for the first container 30 can be secured in the second container 40, and the first container 30 can be easily stored in the second container 40. Furthermore, after closing the second container 40 containing the first container 30, the time until the permeation of oxygen through the first container 30 reaches equilibrium can be shortened. Thereby, the decomposition of the liquid L by oxygen can be suppressed. Also, this ratio may be 5% or more, or may be 10% or more. By setting such a lower limit, the second container 40 does not become too large relative to the first container 30, and a decrease in the handleability of the combined container 10 can be suppressed.

[0167] Whether the oxygen permeation through the first container 30 is in an equilibrium state is determined based on the oxygen concentration in the first container 30. For this determination, when the difference between the oxygen concentration value (%) in the first container 30 at a certain point in time and the oxygen concentration value (%) in the first container 30 24 hours before that certain point in time is within ±5% of the oxygen concentration value (%) in the first container 30 at that certain point in time, it is determined that the equilibrium state has been reached.

[0168] As described above, it is possible to obtain the first container 30L containing a liquid and the combined container 10L containing a liquid in which the oxygen concentration and the amount of dissolved oxygen are adjusted. By only the replacement or bubbling with an inert gas in the prior art, it is often difficult to reduce the oxygen concentration (%) in the headspace HS in the first container 30 because the liquid L is contained in the first container 30. As a result, it has been difficult to reduce the dissolved oxygen that is largely dissolved in the liquid L. On the other hand, according to a specific example of the above-described embodiment, the first container 30L containing a liquid and a gas are accommodated in the second container 40, and it is not necessary to accommodate the liquid L as it is. 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 in the equilibrium state can be made less than 1%. Such an operational effect is suitable when the liquid L is a highly sensitive chemical or food.

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

[0170] If it takes a long period until the oxygen concentration and the dissolved oxygen amount are reduced, the deterioration of the liquid L due to oxygen progresses. The period or time from when the second container 40 is closed until the permeation of oxygen through the first container 30 reaches equilibrium is preferably within 4 weeks. If equilibrium is reached within 4 weeks and, for example, the oxygen concentration in the second container 40 becomes less than 1%, the deterioration of the liquid L as a chemical can be effectively suppressed. For a highly sensitive liquid L, the period until equilibrium is preferably within 20 days, more preferably within 1 week, and even more preferably within 3 days. On the other hand, it takes a certain period until the equilibrium state where the dissolved oxygen amount of the liquid L is reduced to a certain extent is reached. The period or time from when the second container 40 is closed until the permeation of oxygen through the first container 30 reaches equilibrium may be set to 1 hour or more.

[0171] Incidentally, the adjustment of the oxygen amount of 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 oxygen amount of the first container 30 in the second container 40 may be carried out until the oxygen concentration in the second container 40 rises to a predetermined value. The adjustment of the oxygen amount of the first container 30 in the second container 40 may be carried out until the oxygen concentration in the first container 30 drops to a predetermined value. The adjustment of the oxygen amount of the first container 30 in the second container 40 may be carried out until the dissolved oxygen amount of the liquid L in the first container 30 drops to a predetermined value. The adjustment of the oxygen amount of the first container 30 in the second container 40 may be carried out until the liquid L in the combined container 10 is used. Also, while the first container 30 is housed in the second container 40 and the oxygen amount is being adjusted, the combined container 10L containing liquid may be circulated.

[0172] A method of using the combined container 10L containing liquid will be described.

[0173] When using the liquid L contained in the combined container 10, first, the second container 40 is opened. Next, the first container 30L containing the liquid is taken out from the opened second container 40. After that, the liquid L is taken out from the first container 30L containing the liquid, and the liquid L can be used. Regarding the illustrated first container 30, the fixture 36 is removed from the container body 32, and further the stopper 34 is removed from the container body 32, whereby the first container 30 can be opened. Thereby, the liquid L in the first container 30 can be used.

[0174] As shown in FIG. 6, the liquid L may be a drug injected into the syringe 60. The liquid L may be a liquid contained in the first container 30 which is a vial. The liquid L may also be an injection among drugs. Examples of the injection include anticancer agents, antiviral agents, vaccines, antipsychotics, and the like. 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 enables access to the space for containing the liquid L in the cylinder body 63. The piston 66 may include a piston body 67 and a gasket 68 held by the piston body 67. The gasket 68 can be made of rubber or the like. The gasket 68 is inserted into the cylinder body 63 to partition the liquid L containing space within the cylinder body 63. The liquid L injected into this syringe 60 may be transferred from the syringe 60 to another syringe, container, or the like until it is administered to a patient or the like. In this example, it may be administered to the patient from another syringe, container, or the like.

[0175] Incidentally, it is preferable that the pressure inside the first container 30L containing the liquid is adjusted. As an example, it is preferable that the pressure inside the first container 30L containing the liquid is kept low, and particularly preferably kept at a negative pressure. According to this example, it is possible to effectively suppress the unintentional leakage of the liquid during the storage of the first container 30L containing the liquid, the scattering of the liquid L when the first container 30 is opened, etc. The problems of leakage and scattering are more serious in liquids having toxicity, such as highly pharmacologically active drugs. Further, in the example shown in FIG. 6, when the inside of the first container 30L containing the liquid is at a positive pressure, the liquid L automatically enters the syringe 60. In this case, it becomes difficult to accurately inject a desired amount of the liquid L into the syringe 60.

[0176] On the other hand, highly sensitive liquids that are deteriorated by post-sterilization treatment performed after production using, for example, gas, heat, gamma rays, etc., such as foods and drugs, more specifically, anticancer agents, antiviral agents, vaccines, antipsychotic agents, etc. are manufactured in a sterile environment and sealed in a container. That is, liquids to which the final sterilization method cannot be applied are manufactured by an aseptic operation method. This sterile environment is usually maintained at a predetermined positive pressure in order to suppress the invasion of bacteria. Therefore, the pressure inside the container becomes a predetermined positive pressure corresponding to the sterile environment, and it is difficult to adjust the internal pressure of the container after the container 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, due to the decrease in the oxygen concentration inside the second container 40 by the oxygen absorber 21 or the decrease in the oxygen concentration inside the second container 40 by inert gas replacement, the oxygen inside the first container 30 permeates through the first container 30 and moves into the second container 40. Thereby, the pressure inside the first container 30 can be decreased. That is, the pressure of the first container 30 containing the liquid L can be adjusted after the first container 30 is closed and the liquid L is sealed.

[0178] From the viewpoint of adjusting the internal pressure of the first container 30, a second container 40 capable of maintaining and storing a gas at a negative pressure under atmospheric pressure may be used. For example, using the second container 40 shown in FIG. 8, 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 will be less than atmospheric pressure. In this case, oxygen permeation from the first container 30 to the second container 40 is promoted. In particular, by ensuring a large volume for the second container 40 and significantly reducing the initial pressure of the second container 40, the pressure inside the first container 30 can be significantly adjusted. As a result, the pressure inside the first container 30, which was initially a positive pressure, can be adjusted to be below atmospheric pressure (1 atm) or even to a negative pressure by storing the first container 30 inside the second container 40. Thereby, a first container 30L containing a liquid with adjusted pressure can be manufactured without depending on the method of manufacturing the liquid L or the method of enclosing the liquid L in the first container 30 of the liquid.

[0179] Closing the second container 40 with a negative pressure will promote oxygen permeation of the first container 30. Therefore, the time until oxygen permeation through the first container 30 reaches equilibrium after closing the second container 40 containing the first container 30L with liquid can be shortened.

[0180] Note that negative pressure means a pressure below atmospheric pressure, i.e., a pressure less than 1 atm. Positive pressure means a pressure exceeding 1 atm, which is the atmospheric pressure. Whether the inside of a container is under negative pressure or not 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 the needle of a syringe is inserted into the target container, it is determined by whether the liquid or gas contained in the syringe flows into the container with only atmospheric pressure applied to the piston of the syringe. If the liquid or gas contained in the syringe flows into the container, it is determined that the inside of the container was under negative pressure. Similarly, whether the inside of a container is under positive pressure or not is determined using a pressure gauge. If the container is not equipped with a pressure gauge, it is determined using a syringe. Specifically, when the needle of a syringe is inserted into the target container, it is determined by whether the liquid or gas contained in the container flows into the syringe with only atmospheric pressure applied to the piston of the syringe. If the liquid or gas contained in the container flows into the syringe, it is determined that the inside of the container was under positive pressure.

[0181] In one embodiment described above, the container set 20 includes a first container 30 having oxygen permeability at least in part, and a second container 40 capable of accommodating the first container 30 and having oxygen barrier properties. The liquid-containing combined container 10L includes a first container 30 containing the liquid L and having oxygen permeability at least in part, and a second container 40 accommodating the first container 30 and having oxygen barrier properties. In a state where oxygen permeation through the first container 30 is balanced, the oxygen concentration in the first container 30 may be less than 1%. The method for manufacturing the first liquid-containing container 30L includes a step of closing the second container 40 containing the first liquid-containing container 30L, and a step of adjusting the amount of oxygen in the first liquid-containing container 30L contained in the second container 40. In the step of adjusting the amount of oxygen, the oxygen in the first container 30 permeates through the first container 30, whereby the oxygen concentration in the first container 30 decreases, and the amount of dissolved oxygen dissolved in the liquid L can be reduced.

[0182] As shown in FIG. 1, a gap G may be formed between the oxygen-permeable stopper 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 suppress the second container 40 having an oxygen barrier property from covering the oxygen-permeable stopper 34. Thereby, it is possible to suppress the oxygen permeation of the first container 30 from being hindered by the second container 40. Therefore, by providing the gap G, it is possible to promote the reduction of the amount of oxygen in the first container 30.

[0183] According to such an embodiment, oxygen in the first container 30 can permeate 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. Along with the decrease in the oxygen concentration (%) in the first container 30, 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 the decomposition of the liquid L by oxygen can be suppressed.

[0184] When an oxygen absorber 21 that absorbs oxygen in the second container 40 is used instead of or in addition to the inert gas replacement 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 further reduced. By using the oxygen absorber 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%, and even to 0%. Also, 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%, and even to 0%. By using the oxygen absorber 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, and even to 0 mg / L. Since the oxygen absorber 21 can be disposed outside the first container 30, the oxygen absorber 21 does not harm the aseptic state inside the first container 30.

[0185] In this combined container 10, the second container 40 is responsible for reducing the amount of oxygen and providing oxygen barrier properties. The first container 30L containing liquid may be responsible for the sterility of the interior and the liquid L contained therein. Thus, the storage environment required for the liquid L is efficiently realized by the combination of the first container 30 and the second container 40. According to the combined container 10 and the container set 20, the storage environment required for the liquid L can be realized inexpensively and simply 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 stopper 34 that closes the opening 33. The stopper 34 may have oxygen permeability. The stopper 34 may contain silicone. The oxygen permeability coefficient of the material constituting the stopper 34 is 1×10 -12 (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) or more. The oxygen permeability coefficient (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) of the material constituting the stopper 34 may be greater than the oxygen permeability coefficient (cm 3 (STP)·cm / (cm 2 ·sec·Pa)) of the material constituting the container body 32. According to such a specific example, oxygen permeates through the stopper 34 and moves outside the first container 30. Therefore, oxygen permeability can be imparted to the region exposed from the liquid L in the first container 30, such as the so-called headspace HS. As a result, the oxygen permeation of the first container 30 proceeds smoothly, and the time until the oxygen permeation through the first container 30 reaches equilibrium after the first container 30 is housed 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. The oxygen that has permeated through the first container 30 enters the region separated from the liquid L, such as the headspace HS in the first container 30. Therefore, the dissolution of the oxygen that has permeated through the first container 30 into the liquid L can be suppressed.

[0188] In a specific example of the above-described embodiment, the area of the opening 33 of the container body 32 is 10mm 2500 mm or more above 2 It may be below. The thickness of the stopper 34 may be 0.1 mm or more and 5 mm or less. According to such a liquid-containing combined container 10L, the time until the oxygen permeation through the first container 30 is balanced by accommodating the first container 40 in the second container 30 can be shortened. Thereby, the decomposition of the liquid L by oxygen can be suppressed.

[0189] Here, the results of the experiments conducted by the inventors of the present case will be described.

[0190] <Example 1> A vial with a capacity of about 9.2 mL was prepared as the first container. The first container had the configuration shown in FIG. 1. The vial forming the first container included a glass container body. The container body had oxygen barrier properties. The first container was capable of accommodating while maintaining the gas at a negative pressure under atmospheric pressure. About 4 mL of water for injection (aqueous solution) was used as the liquid L and accommodated in the first container. 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. The rubber stopper had oxygen permeability. An aluminum seal was fixed to the head of the container body using a hand clipper to produce a first container containing liquid. The aluminum seal functioned as the fixture shown in FIG. 2. That is, the aluminum seal restricted the rubber stopper from coming off the container body. In the state after sealing using the aluminum seal, the space between the container body and the rubber stopper was airtight. In the first container, a headspace with a volume of about 4.2 mL remained unfilled with water for injection. The first container was closed in the 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 oxygen dissolved in the water for injection contained in the first container was 8.84 mg / L. When the oxygen permeation amount of the stopper of the first container was measured by the method shown in FIG. 2B, it was 3 (mL / (day×atm)), and the first container of Example 1 had oxygen permeability.

[0191] Next, a second container composed of a transparent oxygen barrier packaging material was prepared. The second container had the configuration shown in FIG. 1. The second container was a so-called pouch. The liquid-filled first container and the oxygen scavenging member containing the oxygen scavenger were housed in the second container, and the second container was sealed by heat sealing. The closed second container contained about 100 mL of air. The oxygen scavenging member contained an oxygen scavenger capable of absorbing 200 mL of oxygen.

[0192] All the materials, members, etc. used for the first container in Example 1 were sterilized. The accommodation of the water for injection in the first container, the closing of the first container, the accommodation of the liquid-filled first container and the oxygen scavenger in the second container, and the closing of the second container were carried out in a sterile isolator. The use of sterilized materials and the work in the sterile isolator were the same for Comparative Example 1 and Comparative Example 2 described later.

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

[0194] <Comparative Example 2> In Comparative Example 2, the rubber stopper for closing the opening of the container body of the first container was made of butyl rubber. Comparative Example 2 was different from Example 1 in this respect, and the rest was the same as Example 1. The oxygen permeability of the butyl rubber forming the rubber stopper in Comparative Example 1 was about 80 (cm 3 / (m 2 ×24 h×atm)), which was at a level having no oxygen permeability.

[0195] <Evaluation> For Example 1 and Comparative Example 2, after closing the second container, the liquid-containing combined container was stored. For Comparative Example 1, after closing the first container, the first container containing liquid was stored. The storage environment for Example 1, Comparative Example 1, and Comparative Example 2 was under atmospheric pressure in an air atmosphere at 22°C. The changes over time in the dissolved oxygen amount (mg / L) of the water for injection, the oxygen concentration (%) in the first container, and the oxygen concentration (%) in the second container were confirmed. To measure the dissolved oxygen amount (mg / L) of the water for injection, the oxygen concentration (%) in the first container, and the oxygen concentration (%) in the second container, an oxygen amount measuring device Fibox3 from PreSens, Germany, was used. An oxygen measurement chip was housed in the first container and the second container. By using the oxygen amount measuring device Fibox3, the dissolved oxygen amount (mg / L) of the water for injection, the oxygen concentration (%) in the first container, and the oxygen concentration (%) in the second container were measured from outside the container without destroying the container. The detection limit of the oxygen concentration with the oxygen amount measuring device Fibox3 was 0.03%. The detection limit of the dissolved oxygen amount with the oxygen amount measuring 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 dissolved oxygen amount (mg / L) of the water for injection are shown in Table 3. In these tables, "0" means that oxygen was not 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 combined container of 10 L will be further described. According to the following specific example, the handling of the liquid-containing combined container of 10 L can be facilitated.

[0202] In the following description and the drawings used in the following description, the same reference numerals are used for parts that can be configured in the same manner as in the above-described example, or parts that can be configured in the same manner among some of the specific examples described later, and redundant descriptions are omitted. In the liquid-containing combined container of 10 L described below, the first container 30, the deoxygenating member 22, the oxygen detection material 25, etc. may have the same configuration as the above-described configuration.

[0203] FIGS. 10 to 25 are diagrams for explaining a specific example of the second container 40. FIGS. 10 and 11 show the liquid-containing combined container of 10 L. FIG. 10 is a front view showing the liquid-containing combined container of 10 L. FIG. 11 is a longitudinal section showing the liquid-containing combined container of 10 L. As shown in FIGS. 10 and 11, the liquid-containing combined container of 10 L includes a first container 30 L containing liquid, a second container 40, and a deoxidizer 21. In the illustrated example, the liquid-containing combined container of 10 L includes an oxygen detection material 25. The oxygen detection material 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 has oxygen permeability. That is, oxygen can permeate through the stopper 34.

[0205] The oxygen scavenger 21 may be housed in the second container 40 as the oxygen scavenging member 22. The oxygen scavenging member 22 may include a packaging body 22a having oxygen permeability and an oxygen scavenger 21 housed in the packaging body 22a. The oxygen scavenging member 22 may further include a water retention agent 22b. The second container 40 and the first container 30 may include an oxygen barrier film 23.

[0206] The second container 40 has oxygen barrier properties. The second container 40 is a film container. 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 from each other. The first film 41a and the second film 41b may be a single folded film 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 welding such as heat sealing or ultrasonic welding, or joining using an adhesive material or an adhesive. A storage space S for housing 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 a 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 can be made peelable by adjusting processing conditions at the time of joining, the material and thickness of the joining material (sealant layer), etc. The seal portion 49 may be linear.

[0208] "Peelable" means that the user of the liquid-containing combined container 10L can peel the first film 41a and the second film 41b from each other by hand, without using any devices or aids. The heat seal strength measured in accordance with JIS Z 0238 for the seal part joined in a peelable manner may be 3 N / 15 mm or more and 15 N / 15 mm or less, or may be 4 N / 15 mm or more and 7 N / 15 mm or less. The heat seal strength is the arithmetic mean value of five measured values.

[0209] The seal part 49 includes the bent first seal part 49a. The first seal part 49a may be linear. The first container 30 accommodated in the second container 40 faces the first seal part 49a. The first container 30 faces the linear first seal part 49a in the first direction D1. The first seal part 49a is bent so as to protrude toward the side away from the first container 30 in the first direction D1. The first seal part 49a is bent so as to protrude outward of the accommodation space S of the second container 40. The first seal part 49a is bent so as to protrude toward the side expanding the accommodation space S of the second container 40.

[0210] In the illustrated example, the seal part 49 includes a first side seal part 49b connected to one end of the first seal part 49a and a second side seal part 49c connected to the other end of the first seal part 49a. An accommodation space S of the second container 40 for accommodating the first container 30 is formed between the first side seal part 49b and the second side seal part 49c. The minimum distance DXa along the first film 41a between the first side seal part 49b and the second side seal part 49c may be shorter than the length L30 of the first container 30 along the direction in which the stopper 34 is inserted into the opening 33. The minimum distance DXb along the second film 41b between the first side seal part 49b and the second side seal part 49c may be shorter than the 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 stopper 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 part 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 and DXb along the films 41a and 41b between the side seal portions 49b and 49c shorter than the length L30 of the first container 30, it is possible to suppress a large change in the orientation of the first container 30 within the second container 40. That is, the orientation of the first container 30 within the second container 40 is stabilized. As a result, as will be described later, the state in which the stopper 34 of the first container 30 and the deoxygenation member 22 including the deoxidizer 21 face each other can be stably maintained, and oxygen discharge from the first container 30 can be promoted.

[0213] The seal portion 49 further includes a second seal portion 49d that faces the first seal portion 49a in the first direction D1. In the illustrated example, the seal portion 49 includes the first seal portion 49a and the second seal portion 49d that face each other in the first direction D1, and the first side seal portion 49b and the second side seal portion 49c that face each other in the second direction D2. The first seal portion 49a, the second seal portion 49d, the first side seal portion 49b, and the second side seal portion 49c form the seal portion 49 in a circumferential shape. The circumferential seal portion 49 divides the accommodation space S of the second container 40. Instead of the second seal portion 49d, a folded-back portion 41x formed by folding back a single film 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 forms an accommodation space S, and an extension portion 50b connected to the main portion 50a. The main portion 50a includes a first seal portion 49a, a second seal portion 49d, a first side seal portion 49b, and a second side seal portion 49c, and a portion surrounded by these seal portions 49a, 49d, 49b, 49c. The extension portion 50b is connected to the main portion 50a at the first seal portion 49a. The extension portion 50b may be connected to at least the bent top of the first seal portion 49a. The extension portion 50b may be connected to at least the portion of the first seal portion 49a that protrudes most from the first container 30 in the first direction D1 in which the first container 30 and the first seal 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 gripping the extension portion 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 concentrates on the bent top of the first seal portion 49a. In the illustrated example, the peeling force concentrates on the bent portion of the bent first seal portion 49a. Thereby, starting from the bent first seal portion 49a, the first film 41a and the second film 41b can be easily and smoothly peeled off. In this second container 40, the first seal portion 49a becomes a portion to be opened. The portion to be opened is a portion intended to be opened when the second container 40 is opened.

[0216] In the illustrated example, the second direction D2 is orthogonal to the first direction D1. The third direction D3 is orthogonal to both the first direction D1 and the second direction D2. The first film 41a and the second film 41b face the third direction D3. The first film 41a and the second film 41b are in a rectangular shape when flattened. 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 edge extending in the first direction D1 is the long side of the rectangular shape. The edge extending in the second direction D2 is the short side of the rectangular shape.

[0217] To clarify the relationship of directions between the drawings, in some of the drawings, common directions are indicated by arrows with common reference numerals. The tip side of the arrow is the first side of each direction. The side opposite to the tip of the arrow is the second side of each direction. An arrow pointing into the depth along the direction perpendicular to the drawing plane is indicated by a symbol with an 'x' in a circle, as shown in FIG. 10, for example. An arrow pointing forward from the drawing plane along the direction perpendicular to the drawing plane is indicated by a symbol with a dot in a circle, as shown in FIG. 11, for example.

[0218] Next, with reference to FIGS. 12 to 14, a method for manufacturing the liquid-containing combined container 10L shown in FIGS. 10 and 11 will be described.

[0219] First, as shown in FIG. 12, a liquid-containing first container 30L, a deoxidizing member 22, an oxygen detection material 25, and a second container 40 are prepared. The second container 40 is not yet closed. In the illustrated example, the first film 41a and the second film 41b are joined at the first seal portion 49a, the first side seal portion 49b, and the second side seal portion 49c. By this three-sided seal, a space S for accommodating the first container 30, the deoxidizing member 22, and the oxygen detection material 25 is generally formed. On the other hand, the first film 41a and the second film 41b are not joined at the second seal portion 49d. That is, the second container 40 has an opening 40a communicating with the accommodation space S.

[0220] As shown in FIG. 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 detection material 25 are accommodated in the accommodation space S of the second container 40. The deoxidizing member 22 is in a sheet shape. The deoxidizing member 22 is accommodated in the accommodation space S of the second container 40 such that one side edge of the sheet-shaped deoxidizing member 22 faces the stopper 34 of the first container 30. The oxygen detection material 25 is in a sheet shape. The sheet-shaped oxygen detection material 25 is overlapped with the deoxidizing member 22 in the third direction D3.

[0222] Thereafter, the second container 40 is closed by joining the first film 41a and the second film 41b at the second seal portion 49d. Thereby, the liquid-containing combined container 10L is obtained. Prior to closing the second container 40, the accommodation space S of the second container 40 may be replaced with an inert gas. The closing of the second container 40 may be performed in an inert gas atmosphere. Different from the first seal portion 49a, the second seal portion 49d can be formed linearly. Different from the first seal portion 49a, the second seal portion 49d may be joined in a non-peelable manner. Therefore, even in a state where the first container 30, the deoxidizing member 22, and the oxygen detection material 25 are accommodated, the first film 41a and the second film 41b can be easily and stably joined at the second seal portion 49d.

[0223] In the combined container 10L filled with liquid thus manufactured, the oxygen absorber 21 of the oxygen removal member 22 absorbs the oxygen in the second container 40. As a result, the oxygen concentration in the second container 40 decreases. Along with the decrease in the oxygen concentration in the second container 40, oxygen permeates through the stopper 34 having oxygen permeability and moves from the first container 30 into the second container 40. As a result, the oxygen concentration in the first container 30 decreases, and the amount of oxygen dissolved in the liquid L accommodated in the first container 30 decreases. In particular, the stopper 34 faces the oxygen removal member 22. Therefore, it is possible to effectively suppress the unintentional blocking of the oxygen movement path from the first container 30 through the stopper 34 toward the oxygen removal member 22, for example, the adhesion of the pair of films 41a and 41b to each other.

[0224] The combined container 10L filled with liquid described above includes a first container 30 that accommodates the liquid L and has oxygen permeability, a second container 40 that accommodates the first container 30 and has oxygen barrier properties, and an oxygen removal member 22 accommodated in the second container 40. The oxygen removal member 22 includes 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 accommodates the first container 30 between the first film 41a. The first film 41a and the second film 41b are joined in a peelable manner at the 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 toward the side away from the first container in the 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 removal member 22.

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

[0226] When opened, the first container 30 is positioned at the opening of the second container 40. In particular, the first container 30 is positioned in the second container 40 by a first seal portion 49a that protrudes on the side away from the first container 30. Therefore, when the second container 40 is opened, the first container 30 can be stably gripped. As a result, the first container 30 can be taken out from the second container 40. That is, when using the liquid L stored in the first container 30, the first container 30 can be easily taken out from the second container 40.

[0227] Furthermore, when the second container 40 is opened, no waste such as cut ends is generated. The deoxidation member 22 and the oxygen detection material 25 are still housed in the second container 40 after the first container 30 is taken out from the second container 40. Therefore, it is easy to handle the second container 40, the deoxidation member 22, and the oxygen detection material 25 that are discarded after the second container 40 is opened.

[0228] From the above, the above-described liquid-containing combined container 10L has the advantages of being easy to handle during use in addition to 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.

[0229] In the above specific example, an example where the first seal portion 49a is bent is shown, but 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 the second side spaced apart from the first container 30 in the first direction. As shown in FIG. 15B, only a part of the first seal portion 49a may be bent. As shown in FIG. 15C, only a part of the first seal portion 49a may be curved. As in the examples shown in FIGS. 15B and 15C, both end portions of the first seal portion 49a may extend linearly along the second direction D2. Also by these examples, the first film 41a and the second film 41b can be easily peeled off starting from the first seal portion 49a.

[0230] As shown in FIG. 15D, the portion of the first seal portion 49a that protrudes most on the side away from the first container 30 in the first direction D1 may extend most in the direction along the third direction D3 within the first seal portion 49a. That is, in the example shown in FIG. 15D, the angle formed by the outer edge 49ae of the first seal portion 49a with respect to the first direction D1 in which the first container 30 and the first seal portion 49a face each other is the smallest at the portion of the first seal portion 49a that protrudes most on the side away from the first container 30 in the first direction D1. According to such an example, starting from the first seal portion 49a, the first film 41a and the second film 41b can be more easily peeled off.

[0231] Incidentally, as shown in FIG. 10, the seal portion 49 may include a main seal portion 49X that partitions the space S for accommodating the first container 30, and an auxiliary seal portion 49Y that joins the first film 41a and the second film 41b at the extension portion 50b. In the illustrated example, the main seal portion 49X includes the above-described first seal portion 49a, the first side seal portion 49b, the second side seal portion 49c, and the second seal portion 49d. By providing the auxiliary seal portion 49Y, curling of the first film 41a and the second film 41b at the extension portion 50b can be suppressed. Therefore, by providing the auxiliary seal portion 49Y, the extension portion 50b of the first film 41a and the second film 41b can be easily gripped. Thereby, the liquid-containing combined container 10L can be made even easier to handle. Further, the rigidity of the second container 40 is improved at the portion of the extension portion 50b, and the first container 30 can be protected by the second container 40.

[0232] In the example shown in FIG. 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 linearly extend on the extension line of the first side seal portion 49b. The second auxiliary seal portion 49Yb may linearly extend on the extension line of the second side seal portion 49c. According to these examples, curling of the first film 41a and the second film 41b at the extension portion 50b can be more effectively suppressed. According to these examples, the rigidity of the second container 40 is more effectively improved at the portion of the extension portion 50b.

[0233] The configuration of the auxiliary seal portion 49Y is not limited to the configuration shown in FIG. 10 and the like. As shown in FIG. 16, the auxiliary seal portion 49Y may be separated 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 the extension line of the first side seal portion 49b and a second auxiliary seal portion 49Yb located on the extension line of the second side seal portion 49c. The first auxiliary seal portion 49Ya and the second auxiliary seal portion 49Yb may be linear, may be on a broken line, or may be dot-like as shown in FIG. 16. Also by these examples, curling of the first film 41a and the second film 41b at the extension portion 50b can be suppressed. Also by these examples, the rigidity of the second container 40 is improved at the portion of the extension portion 50b.

[0234] Also, as shown in FIG. 17, in the liquid-containing combined container 10L, the second container 40 may be further folded. In the example shown in FIG. 17, the second container 40 is bent with the second film 41b on the inside. FIG. 10 shows a first bending axis BA1 for bending the second container 40. By bending the second container 40, with respect to the first portion 40P1 of the second container 40 that houses the first container 30, the second portion 40P2 that was located on one side (the first side) in the first direction D1 from the first portion 40P1 in the unfolded state of the second container 40 faces the D3 surface from the third direction. 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 or may be separated. The first portion 40P1 and the second portion 40P2 may be joined.

[0235] The oxygen scavenging member 22 containing the oxygen scavenger 21 is in the form of a sheet. The sheet-like oxygen scavenging member 22 is bent together with the second container 40. The middle portion of the bent oxygen scavenging member 22 is located on the bending top (folding top) 41bx of the second film 41b. As shown in FIG. 17, the bending top 41bx is the position that most protrudes on the first side in the first direction D1 of the bent second film 41b. The bending top 41bx is the position that is farthest from the first container in the direction of inserting the stopper 34 into the container body 32.

[0236] As in the example shown in FIG. 17, by bending the sheet-like oxygen scavenging member 22 together with the second film 41b, it becomes easier to secure an oxygen transfer path connecting between the first container 30 and the oxygen scavenging member 22. More specifically, a gap is likely to be formed between the oxygen scavenging member 22, the stopper 34 of the first container 30, and the second film 41b. Since oxygen can stably move from the stopper 34 to the oxygen scavenging member 22 through this gap, 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] In the example shown in FIG. 17, the oxygen detection material 25 is positioned between the deoxygenation member 22 and the first film 41a. The display portion 26 of the oxygen detection material 25 arranged in this way becomes easier to observe through the transparent first film 41a. Therefore, by observing the display portion 26 of the oxygen detection material 25, information regarding 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 on the inside. FIG. 10 shows, in addition to the first bending axis BA1, a second bending axis BA2 for bending the second container 40. By bending at the second bending axis BA2, with respect to the first portion 40P1 of the second container 40 that houses the first container 30, the third portion 40P3 that was located on the other side (second side) in the first direction D1 from the first portion 40P1 in the state where the second container was unfolded faces in 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 or may be separated. The first portion 40P1 and the third portion 40P3 may be joined. The second container 40 is bent around the second bending axis BA2 so that the second film 41b is on the inside. By bending the second container 40 twice, the liquid-containing combined container 10L can be downsized.

[0239] By the two bends, the second portion 40P2 and the third portion 40P3 are located on the same side with respect to the first portion 40P1. The first film 41a in the first portion 40P1 is not covered by the second portion 40P2 and the third portion 40P3. Therefore, the first container 30 can be clearly observed through the first film 41a of the second container 40. Thereby, the state of the first container 30 and the state of the liquid L housed in the first container 30 can be made easier to observe. Also, the label attached to the first container 30 becomes easier to observe. Information regarding the liquid L may be described on this label.

[0240] In the illustrated example, the first portion 40P1, the third portion 40P3, and the second portion 40P2 overlap 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. According to this example, the bending radius of curvature of the second portion 40P2 with respect to the first portion 40P1 can be increased. Therefore, an oxygen transfer path connecting between the first container 30 and the deoxygenation member 22 can be more stably ensured. As a result, since oxygen can stably move from the stopper 34 to the deoxygenation member 22, the oxygen concentration in the first container 30 and the amount of oxygen dissolved in the liquid L stored in the first container 30 can be stably reduced.

[0241] As shown in FIG. 18, the liquid-containing combined container 10L may further include an outer box 55 that houses the second container 40. The outer box 55 includes a bottom portion 56, a top portion 57 facing the bottom portion 56, and a side wall portion 58 positioned between the bottom portion 56 and the top portion 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 dashed two-dot line in FIG. 17, the bottom portion 32a of the container body 32 of the first container 30 faces the bottom portion 56 of the outer box 55, and the stopper 34 of the first container 30 faces the top portion 57 of the outer box 55. Thus, the second container that houses the first container 30 may be housed in the outer box 55. According to this example, the liquid-containing combined container 10L can be stored such that the bottom portion 56 is positioned on a placement surface such as a desk or a shelf. At this time, the stopper 34 having oxygen permeability is separated from the liquid L and contacts the gas in the head space HS in the first container 30. By storing the liquid-containing combined container 10L in this state, the oxygen permeation of the stopper 34 is promoted, 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 housed in the second container 40.

[0242] As described above, the second container 40 has an accommodation section S between the first side seal section 49b and the second side seal section 49c. As shown in FIG. 19, the second container 40 may include a notch 51 in one or both of the first side seal section 49b and the second side seal section 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 section 49a. However, depending on the situation, 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 section 49a, the second container 40 can be opened easily and stably. Therefore, by forming the cuts of the first film 41a and the second film 41b and the notch 51 serving as the starting point at the outer edges 49ae, 49be of the side seal sections 49b, 49c, the liquid-containing combined container 10L can be handled more easily.

[0243] As shown by the dotted line in FIG. 19, the second container 40 may include a planned opening section 52. The planned opening section 52 is a portion where the cutting of the films 41a, 41b is planned when the second container 40 is opened. The planned opening section 52 may be a portion connected to the notch 51. The planned opening section 52 may have a configuration for enabling more reliable cutting at the planned opening section 52. The planned opening section 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 section 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 section 52 may be formed by performing processing such as half-cutting, laser processing, or straight cutting that cuts into the intermediate layer film on the first film 41a and the second film 41b.

[0244] One of the first film 41a and the second film 41b cut starting from the notch 51 has the first container 30 positioned thereon, and the oxygen scavenging member 22 may be positioned on the other of the first film 41a and the second film 41b cut starting from the notch 51. That is, when the second container 40 is cut starting from the notch 51, the first container 30 may be accommodated on one side of the second container 40 with the cutting line as a boundary, and the oxygen scavenging member 22 and the oxygen detection material 25 may be positioned on the other side of the second container 40. According to this example, when the second container 40 is opened, the first container 30 can be easily taken out from the second container 40. The liquid-containing combined container 10L can be easily handled. In the example shown in FIG. 19, in the first direction D1 in which the first container 30 and the oxygen scavenging member 22 face each other, the notch 51 is positioned between the first container 30 and the oxygen scavenging member 22. In the first direction D1 in which the first container 30 and the oxygen scavenging member 22 face each other, the planned opening portion 52 is positioned between the first container 30 and the oxygen scavenging member 22.

[0245] As shown in FIG. 20, the seal portion 49 may include a main seal portion 49X that partitions the accommodation space S of the second container 40, and an additional seal portion 49Z positioned 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 positioned 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 positioned between at least one of the first side seal portion 49b and the second side seal portion 49c and the first container 30. In the example shown in FIG. 20, the additional seal portion 49Z includes a first additional seal portion 49Za positioned between the first side seal portion 49b and the first container 30 in the second direction D2, and a second additional seal portion 49Zb positioned between the second side seal portion 49c and the first container 30 in the second direction D2. The additional seal portion 49Z is positioned 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, at the first seal portion 49a, the first film 41a and the second film 41b are peeled off. Next, as shown in FIG. 21, at the first side seal portion 49b and the second side seal portion 49c, the first film 41a and the second film 41b are peeled off. The peeling of the films 41a and 41b at the side seal portions 49b and 49c proceeds from the end connected to the first seal portion 49a toward the end connected to the second seal portion 49d. That is, the peeling of the films 41a and 41b at the side seal portions 49b and 49c proceeds in the second direction D2 which is the longitudinal direction of the side seal portions 49b and 49c.

[0247] When peeling off 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 so as to be separated from the other. In the example shown in FIG. 21, only the first film 41a is folded back so as to be separated from the second film 41b. Then, as the peeling of the films 41a and 41b at the side seal portions 49b and 49c proceeds, the folded edge E41 of the film reaches the additional seal portion 49Z. At this time, the bonding force between the first film 41a and the second film 41b suddenly increases. In other words, the force required to peel off the first film 41a and the second film 41b suddenly increases. Therefore, according to the additional seal portion 49Z, it is possible to prevent the first film 41a and the second film 41b from being peeled off too much unintentionally. Thereby, it is possible to prevent the first film 41a and the second film 41b from being peeled off all at once and the first container 30 from falling from the second container 40.

[0248] As shown in FIG. 20, in the first direction D1 in which the first seal portion 49a and the first container 30 face each other, the arrangement region of the additional seal portion 49Z and the arrangement region of the first container 30 may at least overlap. According to this example, when the first film 41a and the second film 41b are peeled off to open the second container 40, it is possible to effectively suppress the first container 30 from falling from the second container 40. Further, in the accommodation space S of the second container 40, it is possible to suppress a change in the orientation of the first container 30. Therefore, in the accommodation space S of the second container 40, the first container 30 and the deoxidizing member 22 can be maintained in a positioned state. Thereby, the oxygen concentration in the first container 30 and the amount of oxygen dissolved in the liquid L can be stably reduced.

[0249] In the first direction D1 in which the first seal portion 49a and the first container 30 face each other, the end portion of the first container 30 on the first seal portion 49a side may be located at the same position as the end portion of the additional seal portion 49Z on the first seal portion 49a side. As shown in FIG. 20, in the first direction D1, the end portion of the first container 30 on the first seal portion 49a side may be located at a position closer to the first seal portion 49a than the end portion of the additional seal portion 49Z on the first seal portion 49a side. According to these examples, when the folded edge E41 of the film contacts the additional seal portion 49Z, the first container 30 located between the first film 41a and the second film 41b can be easily gripped. Thereby, the handling of the liquid-containing combined container 10L can be facilitated.

[0250] As shown in FIG. 21, the film folding edge E41 when peeling off the first film 41a and the second film 41b is inclined with respect to the second direction D2 so as to approach the second seal portion 49d more in the first direction D1 on the inner side in the second direction D2. Therefore, as shown in FIG. 20, the additional seal portion 49Z may be separated from the side seal portions 49d and 49c in the second direction D2. That is, the additional seal portion 49Z may not be connected to the side seal portions 49d and 49c. Note that the inner side in the second direction D2 means the side closer to the center of the second container 40 in the second direction D2. The outer side in the second direction D2 means the side away from the center of the second container 40 in the second direction D2.

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

[0252] Also, the shape of the additional seal portion 49Z in plan view can be variously changed. The additional seal portion 49Z only needs to have a configuration that allows the film folding edge E41 when peeling the first film 41a and the second film 41b to reach. In the example shown in FIG. 22, the additional seal portions 49Za and 49Zb have a semi-circular shape in a state where the second container 40 is flattened and developed. In the example shown in FIG. 23, the additional seal portions 49Za and 49Zb have a triangular shape or a shape in which the corners of the triangle are curved in a state where the second container 40 is flattened and developed. In the example shown in FIG. 24, the additional seal portions 49Za and 49Zb have a trapezoidal shape or a shape in which the corners of the trapezoid are curved in a state where the second container 40 is flattened and developed.

[0253] As shown in FIGS. 23 and 24, the inner edge 49Ze of the additional seal portion 49Z facing the first container 30 may be away from the corresponding side seal portions 49b and 49c as it approaches the first seal portion 49a in the 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 moves away from the first side seal portion 49b in the second direction D2 and approaches the first container 30 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 moves away from the second side seal portion 49c in the second direction D2 and approaches the first container 30 toward the second side in the first direction D1. Such an inner edge 49Ze functions as a guide for guiding the first container 30 to a predetermined position when the first container 30 is inserted into the accommodation space S of the second container 40 through the opening 40a provided at the position of the second seal portion 49d, as shown in FIG. 24. According to such an inner edge 49Ze, the first container 30 can be easily and stably positioned at a predetermined relative position with respect to the deoxygenation member 22 in the accommodation 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] In addition, on the second seal portion 49d side of the first side seal portion 49b and the second side seal portion 49c, the sealing strength of the seal portion 49 may be increased. In other words, on the second seal portion 49d side of the first side seal portion 49b and the second side seal portion 49c, the bonding strength of the first film 41a and the second film 41b may be increased. The processing temperature when forming the seal portion 49 may be increased on the second seal portion 49d side of the side seal portions 49b and 49c. The number of processing times 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 such an example, it becomes easier to stop the peeling of the first film 41a and the second film 41b starting from the first seal portion 49a in the middle of the side seal portions 49b and 49c. Thereby, when the second container 40 is opened, it is possible to prevent the first container 30 from accidentally falling out of the second container 40.

[0255] In the above-described example, the first container 30 was disposed in the second container 40 such that the container body 32 faced the first seal portion 49a and the stopper 34 faced the deoxidizing member 22. As shown in FIG. 25, the first container 30 may be disposed in the second container 40 such that the stopper 34 faces the first seal portion 49a and the bottom portion 32a of the container body 32 faces the deoxidizing member 22. The liquid-containing combined container 10L shown in FIG. 25 can also be expected to have the following operational effects. That is, starting from the bent first seal portion 49a, the first film 41a and the second film 41b can be easily peeled off at the first seal portion 49a, and the second container 40 can be easily opened. Further, when the second container 40 is opened, the first container 30 is positioned at the opening portion of the second container 40. In particular, the first container 30 is positioned in the second container 40 by the first seal portion 49a that protrudes toward the side away from the first container 30. Therefore, when the second container 40 is opened, the first container 30 can be stably gripped. Thereby, the first container 30 can be taken out from the second container 40. That is, when using the liquid L stored in the first container 30, the first container 30 can be easily taken out from the second container 40. Further, when the second container 40 is opened, no waste such as a cut end is generated. The deoxidizing member 22 and the oxygen detection material 25 are still housed in the second container 40 even after the first container 30 is taken out from the second container 40. Therefore, it is easy to handle the second container 40, the deoxidizing member 22, and the oxygen detection material 25 that are discarded after the second container 40 is opened.

[0256] Next, a specific example of the laminate 47 that can be used for the second container 40 will be further described. In the following description and the drawings used in the following description, for parts that can be configured in the same manner as the above-described specific example or corresponding configurations, the same reference numerals as those used for the corresponding parts in the above-described specific example are used, and redundant descriptions are 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 in the liquid L in the first container 30 (mg / L) can be sufficiently reduced and stably maintained in the reduced state. Further, 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. In addition, when the liquid L in the first container 30 contains an aqueous solvent, the concentration of the liquid L can be stably maintained. The aqueous solvent refers to a solvent in which the main component having the largest volume ratio is water.

[0258] The laminate such as the films 41a to 41d included in the second container 40 includes a barrier layer having an oxygen barrier function and a water vapor barrier function. By increasing the thickness of the barrier layer included in the laminate, the barrier function of the laminate can be enhanced. However, usually, when the thickness of the barrier layer formed as a vapor deposition film is increased, the adhesive strength between the barrier layer and the adjacent layer decreases. Further, when the thickness of the barrier layer formed as a vapor deposition film is increased, the barrier layer is likely to crack. For these reasons, there have been limitations in the oxygen barrier property and water vapor barrier property of the laminate used in conventional containers. As a result of intensive studies by the inventors of the present case, a laminate having excellent barrier properties was created. Hereinafter, the laminate created by the inventors of the present case will be described.

[0259] The laminate described below can be applied to the second container 40 included in the combined container 10 and the container set 20. More specifically, the laminate described below may constitute the films 41a to 41e of the second container 40 shown in FIGS. 1 and 7A to 7C. The laminate described below may constitute the container body 42 and 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. Further, the laminate described below is not limited to the second container 40, and 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 accommodation space S of the container and an outer surface 47b on the side opposite to the inner surface 47a. As shown in FIG. 26A, the laminate 47 may include a sealant layer 48a, a first barrier layer 48c, a resin layer 48f, and a second barrier layer 48h in this order from the inner surface 47a toward the outer surface 47b. This laminate 47 includes two barrier layers 48c and 48h having a barrier function. Therefore, even if the thicknesses of the respective barrier layers 48c and 48h included in the laminate 47 are not increased, the laminate 47 has high barrier properties. That is, according to this laminate 47, a high barrier function can be exhibited while suppressing a decrease in the adhesiveness and cracking of the barrier layers 48c and 48h.

[0261] Also, even if defects such as pinholes and cracks occur in one of the barrier layers 48c and 48h, the laminate 47 can maintain a certain degree of barrier properties by the other barrier layer 48c or 48h. In particular, a resin layer 48f is disposed between the first barrier layer 48c and the second barrier layer 48h. By the resin layer 48f functioning as a base material of the laminate 47, it is possible to suppress the occurrence of defects such as pinholes and cracks in both the first barrier layer 48c and the second barrier layer 48h.

[0262] When the laminate 47 is applied to the container set 20 and the second container 40 of the combined container 10, the laminate 47 can exhibit a high oxygen barrier function and a 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 in a reduced state. 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 a resin layer 48f between the two barrier layers 48c and 48h, the generation of air bubbles in the laminate 47 can be suppressed. As a result, when the laminate 47 is applied to the container set 20 and the second container 40 of the combined container 10, the state of the first container 30 can be observed from the outside of the second container 40. Further, without opening the second container 40, the oxygen concentration inside the second container 40 can be measured using a non-contact oxygen measuring device. Furthermore, if the container body 32 of the first container 30 is also transparent, the liquid L inside the first container 30 can be observed from the outside of the second container 40. In this case, without opening the first container 30 and the second container 40, the oxygen concentration inside the first container 30 can be measured using a non-contact oxygen measuring device. Similarly, without opening the first container 30 and the second container 40, the amount of oxygen dissolved in the liquid L inside the first container 30 can be measured using a non-contact oxygen measuring device.

[0264] The laminate 47 may be transparent. The laminate 47 may include a transparent portion. As described above, being transparent means that the transmission haze at the target portion is 80.0% or less so that the inside of the target portion can be observed from the outside. To make the target portion more clearly observable from the outside, the transmission haze in at least a part 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. Further, without opening the second container 40, the oxygen concentration inside the second container 40 can be measured using a non-contact oxygen measuring device. Furthermore, if the container body 32 of the first container 30 is also transparent, the liquid L inside the first container 30 can be observed from the outside of the second container 40. In this case, without opening the first container 30 and the second container 40, the oxygen concentration inside the first container 30 can be measured using a non-contact oxygen measuring device. Similarly, without opening the first container 30 and the second container 40, the amount of oxygen dissolved in the liquid L inside the first container 30 can be measured using a non-contact oxygen measuring device.

[0266] The lower limit of the transmission haze in at least a part of the laminate 47 is not particularly set. The transmission haze in at least a part of the laminate 47 may be 0% or more, or may be greater than 0%.

[0267] The total light transmittance in part or all 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 the outside of the second container 40 to which the laminate 47 is applied. The lower limit of the total light transmittance of the laminate 47 is not particularly set. 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 the transmission haze within the above-described predetermined range and the total light transmittance within the above-described predetermined range.

[0269] A D65 standard light source is used for measuring the total light transmittance. Before measuring the total light transmittance, the D65 standard light source is turned on for 15 minutes to stabilize the output of the D65 standard light source. The incident angle to the sample when measuring the total light transmittance is 0°. The test environment when measuring the total light 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 the start of the test. Other measurement conditions when measuring the total light transmittance follow JIS K7361-1:1997. The total light transmittance is the arithmetic mean value of five measurement values. The five measurement values are the measurement values measured at five measurement positions of the measurement sample to be evaluated.

[0270] The yellowness degree (YI value) of part or all of the laminate 47 may be 20 or less, 15 or less, 13 or less, or 10 or less. When it is 20 or less, the color inside the package becomes easier to confirm. For example, the discrimination degree of an indicator that discriminates by a color such as an ageless eye is improved. The yellowness degree is an index indicating the degree of yellow coloring of the laminate 47. In the laminate 47, high barrier properties are exhibited by two barrier layers. By using two barrier layers as compared with using one thick barrier layer, the yellowness degree of the laminate 47 can be reduced to below the above upper limit.

[0271] By setting the above upper limit for the yellowness degree (YI value), the yellow coloring of the laminate 47 can be restricted. By setting the above upper limit for the yellowness degree (YI value), the state of the first container 30 can be clearly observed from the outside of the second container 40 to which the laminate 47 is applied.

[0272] The lower limit value of the yellowness degree (YI value) of the laminate 47 is not particularly set. The yellowness degree (YI value) of the laminate 47 may be 0 or more, or may be greater than 0.

[0273] The yellowness degree is measured by transmitted light. By a spectrophotometric color measurement method, based on the transmittance measured at 0.5 nm intervals in the range of 300 nm or more and 780 nm or less using the auxiliary illuminant C and a 2-degree field of view, the tristimulus values X, Y, Z in the XYZ color system are obtained. From the obtained values of X, Y, Z, the yellowness degree (YI value) is specified by the following formula. YI = 100(1.2769X - 1.0592Z) / Y As the geometric optical conditions for measuring the yellowness degree, the geometric optical conditions e of JIS Z 8722:2009 are adopted. In order to eliminate the influence of the scattered light from the end of the test piece, the incident light beam diameter on the test piece is made smaller than the diameter of the opening. Before measuring the yellowness degree, 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 the yellowness degree is the inner surface 47a of the laminate 47. The test environment when measuring the yellowness degree 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 the start of the test.

[0274] The yellowness (YI value) shall be the arithmetic mean value of five measurement values. The five measurement values shall be the measurement values measured at five measurement positions of the optical sheet to be evaluated. The five measurement positions are located more than 10 mm apart from each other. Other measurement conditions when measuring the yellowness (YI value) shall follow JIS K7373-1:2006.

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

[0276] The oxygen permeability of the laminate 47 may be less than 0.20 (mL / (m 2 ×day×atm)), may be 0.15 (mL / (m 2 ×day×atm)) or less, and may be 0.14 (mL / (m 2 ×day×atm)) or less. According to the oxygen permeability having such an upper limit, extremely high oxygen barrier properties are 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 to a sufficiently low level and stably maintained in the reduced state. The lower limit of the oxygen permeability of the laminate 47 is not particularly set. The oxygen permeability of the laminate 47 may be 0 (mL / (m 2 ×day×atm)) or more, and may be greater than 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, may be 0 (mL / (m 2 ×day×atm)) or more and 0.15 (mL / (m 2 ×day×atm)) or less, and may be 0 (mL / (m 2 ×day×atm)) or more and 0.14 (mL / (m 2 ×day×atm)) or less. The oxygen permeability of the laminate 47 is greater than 0 (mL / (m 2 ×day×atm)) and less than 0.20 (mL / (m 2×day×atm)) may also be below, 0 (mL / (m 2 ×day×atm)) but greater than 0.15 (mL / (m 2 ×day×atm)) may also be below, 0 (mL / (m 2 ×day×atm)) but greater than 0.14 (mL / (m 2 ×day×atm)) may also be below.

[0278] The water vapor permeability of the laminate 47 may be 0.50 (g / (m 2 ×day)) or below, 0.30 (g / (m 2 ×day)) or below, 0.20 (g / (m 2 ×day)) or below. According to such a water vapor permeability with an upper limit, extremely high water vapor barrier properties can be imparted to the second container 40. By suppressing the permeation of water vapor in the second container 40 to the outside, the evaporation amount of the liquid L can be suppressed and the concentration change can be suppressed. The lower limit of the water vapor permeability of the laminate 47 is not particularly set. The water vapor permeability of the laminate 47 may be 0 (mL / (m 2 ×day×atm)) or above, 0 (mL / (m 2 ×day×atm)) or greater.

[0279] The water vapor permeability of the laminate 47 is 0 (mL / (m 2 ×day×atm)) or above and 0.50 (g / (m 2 ×day)) or below, 0 (mL / (m 2 ×day×atm)) or above and 0.30 (g / (m 2 ×day)) or below, 0 (mL / (m 2 ×day×atm)) or above and 0.20 (g / (m 2 ×day)) or below. The water vapor permeability of the laminate 47 is 0 (mL / (m 2 ×day×atm)) but greater than 0.50 (g / (m 2 ×day)) or below, 0 (mL / (m 2 ×day×atm)) but greater than 0.30 (g / (m 2 ×day)) or below, 0 (mL / (m 2 ×day×atm)) but greater than 0.20 (g / (m2 It may also be as follows for × day).

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

[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 means the component having the largest mass ratio. A lower limit may be set for the thickness of the resin layer 48f. The thicknesses of the resin layers 48f and 48j may be 5 μm or more and 60 μm or less, or may be 7 μm or more and 30 μm or less. Among these, the resin layer 48f can function as a resin base material for the entire laminate 47.

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

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

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

[0285] Stretched polyamide and stretched nylon are excellent in puncture resistance, abrasion resistance, and flex resistance. Therefore, by using stretched polyamide or stretched nylon for the resin layer 48f, it is possible to less likely cause defects such as pinholes and cracks in the laminate 47. By using stretched polyamide or stretched nylon for the resin layer 48f, while maintaining the strength of the laminate 47, the thickness of the laminate 47 can be reduced. Further, according to the resin layer 48f containing stretched polyamide or stretched nylon, even if defects such as pinholes and cracks occur in one of the barrier layers 48c, 48h, it is possible to suppress the occurrence of defects in the other barrier layer 48c, 48h. In this regard, stretched polyamide and stretched nylon are extremely suitable as the resin layer 48f disposed between the two barrier layers 48c, 48h.

[0286] As shown in FIG. 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 joined to the sealant layer 48a and the first barrier layer 48c. Alternatively, only a layer that does not permeate water vapor, for example, a polyethylene terephthalate layer (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. According to this example, fluctuations in the water vapor concentration inside the container can be sufficiently suppressed.

[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, 48g are added to the laminate shown in FIG. 26A. FIG. 26D shows a laminate in which the adhesive layers 48e, 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 contain, for example, carbon dioxide or water vapor. The generated bubbles cannot permeate through the barrier layers 48c and 48h.

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

[0290] Also, the resin layer 48f is located 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 and the resin layer 48f can be adhered by an adhesive layer, and then the other of the first barrier layer 48c and the second barrier layer 48h and the resin layer 48f can be adhered by an adhesive layer. The resin layer 48f adhered to one barrier layer on one surface using an adhesive layer can expose the other surface. Therefore, by allowing the bubbles generated in the adhesive layer to permeate through the resin layer 48f, the bubbles can be quickly removed. At this time, by aging under appropriate conditions, the discharge of bubbles can be further promoted.

[0291] As a result, it is possible to suppress bubbles from remaining in the high-barrier laminate 47 including the two barrier layers. It is possible to suppress cloudiness of the high-barrier laminate 47 including the two barrier layers. Further, the visible light transmittance of the laminate 47 is maintained high, and the first container 30 and the liquid L can be clearly observed from the outside of the second container 40. Further, from the outside 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 in the first container 30 can be measured with high accuracy.

[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 mainly contain a polyester such as polyethylene terephthalate. The main component means the component with the largest mass ratio. The resin layer 48f may contain a polyester film such as polyethylene terephthalate. The polyester film may be a uniaxially stretched polyester film, a biaxially stretched polyester film, or a stretched polyester film. It may also be a uniaxially stretched nylon film or a biaxially stretched nylon film.

[0293] Furthermore, from the viewpoint of enhancing the puncture resistance of the laminate 47, the resin layer 48f may contain a polyamide such as nylon. The resin layer 48f may mainly contain a polyamide such as nylon. The main component means the component with the largest mass ratio. The resin layer 48f may contain a polyamide film such as nylon. The polyamide film may be a uniaxially stretched polyamide film, a biaxially stretched polyamide film, or a stretched polyamide film. It may also be a uniaxially stretched nylon film or a biaxially stretched nylon film.

[0294] As shown in FIG. 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 located between the first barrier layer 48c and the inner adhesive layer 48b. According to this arrangement, the first barrier 48c does not directly contact the sealant layer 48a that is prone to dimensional changes and deformation. By the interposition of the first barrier substrate layer 48d, the influence of dimensional changes and deformation of the sealant layer 48a on the first barrier layer 48c can be reduced. Thereby, the occurrence of defects such as cracks and pinholes in the first barrier layer 48c can be suppressed.

[0296] In the illustrated example, the second barrier layer 48h is located between the resin layer 48f and the second barrier base material layer 48i. The second barrier layer 48h is located between the second adhesive layer 48g and the second barrier base material layer 48i. That is, the second barrier base material layer 48i may be closer to the outer surface 47b than the second barrier layer 48h, or may constitute the outer surface 47b. According to this arrangement, the second barrier base material layer 48i receives the external force and the impact from the outside due to contact with the outside earlier than the second barrier layer 48h. The external force and impact received by the second barrier layer 48h are weakened by the second barrier base material layer 48i. Thereby, it is possible to suppress the occurrence of defects such as cracks and pinholes 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. According to the laminate including three or more barrier layers, the oxygen barrier property and the water vapor barrier property of the laminate 47 can be further enhanced. FIG. 26F shows the addition of the second resin layer 48j and the third barrier layer 48k to the laminate shown in FIG. 26E. Further, the laminate 47 shown in FIG. 26F includes a third barrier base material layer 48l. The third barrier base material layer 48l constitutes the outer surface 47b. The third barrier base material layer 48l may be a resin base material 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 base material layer 48i. A fourth adhesive layer may be provided between the second resin layer 48j and the third barrier layer 48k. These third adhesive layer and fourth adhesive layer may be configured in the same manner as the adhesive layers 48e and 48g.

[0299] Also in the example shown in FIG. 26F, for the reasons described above, the first barrier base material 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 base material layer 48i, and may also be located between the second adhesive layer 48g and the second barrier base material 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 base material layer 48l. The third barrier layer 48k may also be located between the fourth adhesive layer and the third barrier base material layer 48l. That is, the third barrier base material layer 48l may be closer to the outer surface 47b than the third barrier layer 48k, or may constitute the outer surface 47b. According to this arrangement, the third barrier base material layer 48l receives the external force and impact due to contact with the outside earlier than the third barrier layer 48k. Therefore, the external force and impact received by the third barrier layer 48k are weakened by the third barrier base material layer 48l. Thereby, it is possible to suppress the occurrence of defects such as cracks and pinholes in the third barrier layer 48k.

[0301] Each layer that can be included in the laminate 47 will be described in more detail.

[0302] The barrier layers 48c, 48h, 48k may contain a metal or an inorganic oxide. The barrier layer may be formed by chemical vapor deposition (CVD method) or physical vapor deposition (PVD method). The barrier layer may be a vapor deposition film. The barrier layer may contain a vapor deposition film. The vapor deposition film is a layer formed by vapor deposition. The vapor deposition film may contain a metal or an inorganic oxide. According to the vapor deposition film, a thin barrier layer with excellent barrier properties can be obtained. The barrier layer may be a transparent vapor deposition film. The barrier layer may contain a transparent vapor deposition film. The transparent vapor deposition film is a transparent layer formed by vapor deposition. According to the barrier layers 48c, 48h, 48k as the transparent vapor deposition film, the laminate 47 including the thin and highly barrier barrier layer can be made transparent together with other layers. By using the transparent laminate 47 for the second container 40, the first container 30 can be observed from the outside of the second container 40.

[0303] The metals contained in the barrier layers 48c, 48h, and 48k are not particularly limited. Examples of the metals 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 oxides contained in the barrier layers 48c, 48h, and 48k are not particularly limited. Examples of the inorganic oxides include oxides of silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium, etc. Each of the barrier layers 48c, 48h, and 48k may contain two or more of these inorganic oxides. As a specific example, the inorganic oxide contained in the barrier layers 48c, 48h, and 48k may be aluminum oxide or silicon oxide. The inorganic oxide is represented by MOX, such as AlOX, SiOX, etc. In the above formula, "M" represents an inorganic element. From the viewpoints of transparency and gas barrier property, 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, may be 3 nm or more and 100 nm or less, may be 5 nm or more and 80 nm or less, or may be 8 nm or more and 50 nm or less.

[0306] The barrier layers 48c, 48h, and 48k may include a plurality of layers. The plurality of layers may include a base barrier layer formed by chemical vapor deposition (CVD method) or physical vapor deposition (PVD method). The base barrier layer may contain a metal or an inorganic oxide. The base barrier layer may be a vapor deposition film. The base barrier layer may be a transparent vapor deposition film, that is, a transparent thin film. The vapor deposition film is a layer formed by vapor deposition. The vapor deposition film may contain a metal or an inorganic oxide.

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

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

[0309] The over layer, the first over layer, and the second over layer cover and protect any of the barrier layers. The over layer, the first over layer, and the second over layer may cover the entire barrier layer to be protected. The over layer and the first over layer may be directly formed on the first base barrier layer. The over layer and the first over layer may be in contact with the first base barrier layer. The second over layer may be directly formed on the second base barrier layer. The second over layer may be in contact with 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 formed by solidifying or curing a coating film applied on the barrier layer to be protected.

[0311] The overcoat layer, the first overcoat layer, and the second overcoat 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 curable resin composition. The overcoat layer, the first overcoat layer, and the second overcoat layer may contain the same resin material as the resin material constituting the adhesive layers 48e and 48g.

[0312] The overcoat layer, the first overcoat layer, and the second overcoat layer may contain the same resin material as the resin material constituting the resin layers 48f and 48j. They may also contain the same resin material as the resin material of the barrier substrate layers 48d, 48i, and 48l described later.

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

[0314] The overcoat layer, the first overcoat layer, and the second overcoat layer may be formed using a coating agent containing a polyvinyl alcohol-based resin and a silane compound. Acid catalysts, alkali catalysts, photoinitiators, etc. may be added to the coating agent as necessary.

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

[0316] The thicknesses of the base barrier layer, the first base barrier layer, and the second base barrier layer may be 1 nm or more and 1000 nm or less, may be 3 nm or more and 500 nm or less, may be 5 nm or more and 500 nm or less, may be 5 nm or more and 300 nm or less, may be 8 nm or more and 100 nm or less, or may be 8 nm or more and 50 nm or less. The thicknesses of the over layer, the first over layer, and the second over layer may be 10 nm or more and 10 μm or less, may be 50 nm or more and 5.0 μm or less, may be 100 nm or more and 1.0 μm or less, or may be 100 nm or more and 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 configuration. The first barrier layer 48c, the second barrier layer 48h, and the third barrier layer 48k may have different configurations. 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 film formation methods. The first barrier layer 48c, the second barrier layer 48h, and the third barrier layer 48k may have different thicknesses.

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

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

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

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

[0322] The first barrier base material layer 48d, the second barrier base material layer 48i, and the third barrier base material layer 48l may have the same configuration. The first barrier base material layer 48d, the second barrier base material layer 48i, and the third barrier base material layer 48l may have different configurations. The first barrier base material layer 48d, the second barrier base material layer 48i, and the third barrier base material layer 48l may have different materials. The first barrier base material layer 48d, the second barrier base material layer 48i, and the third barrier base material layer 48l may have different thicknesses.

[0323] The resin layers 48f and 48j function to hold each layer included in the laminate 47. 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 suppress the two barrier layers 48c, 48h, and 48k from curving with a small radius of curvature. Thereby, the occurrence of defects such as cracks in the two barrier layers 48c, 48h, and 48k can be suppressed. Also, according to the resin layers 48f and 48j, the flexibility and the firmness of the laminate 47 can be easily adjusted. Furthermore, as described above, the resin layers 48f and 48j can suppress the whitening of the laminate 47 caused by bubbles generated during the curing of the adhesive layer.

[0324] The resin layers 48f and 48j are not particularly limited. The resin layers 48f and 48j may be resin films. Examples of the resin material constituting the resin layers 48f and 48j as resin films include polyesters (chemical recycling polyester, mechanical recycling polyester, fossil fuel polyester, biomass polyester), (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 and 48j may be laminated films using two or more of these resin material films.

[0325] The resin layers 48f and 48j may be an unstretched film or a stretched film. The resin layers 48f and 48j may be a uniaxially stretched film or a biaxially stretched film. The resin layers 48f and 48j being stretched films can impart sufficient mechanical properties to the laminate 47.

[0326] The resin layers 48f and 48j may contain a thermoplastic resin. The resin layers 48f and 48j may mainly contain a thermoplastic resin. The resin layers 48f and 48j may be thermoplastic resin films. The resin layers 48f and 48j containing a thermoplastic resin can promote the discharge of air bubbles and impart low transmission haze and high total light transmittance.

[0327] The thickness of the resin layers 48f and 48j may be 5 μm or more and 60 μm or less, or may be 7 μm or more and 30 μm or less. By setting a lower limit on the thickness of the resin layer 48f, sufficient mechanical properties can be imparted 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, appropriate flexibility can be imparted to the laminate 47 applied to the second container 40. By setting an upper limit on the thickness of the resin layer 48f, the discharge of air bubbles can be promoted and low transmission haze and high total light transmittance can be imparted.

[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 have different materials. The resin layer 48f and the second resin layer 48j may have different thicknesses.

[0329] The subsequent layers 48e and 48g are layers for joining two layers. The adhesive layers 48e and 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 a radiation-curable resin composition. The radiation-curable resin composition may be an electron beam-curable resin composition or an ultraviolet-curable resin composition. The adhesive used for the adhesive layers 48e and 48g may be a one-component or two-component curable type vinyl-based, (meth)acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, or other laminate adhesives. Specific examples of the materials used for the adhesive layers 48e and 48g may include a two-component curable polyurethane-based adhesive using an isocyanate compound or the like as a curing agent, or a polyester-based adhesive.

[0330] The thickness of the adhesive layers 48e and 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 configuration. The first adhesive layer 48e, the second adhesive layer 48g, the third adhesive layer, and the fourth adhesive layer may have different configurations. 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 sealability. 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 a polyolefin. Examples of the thermoplastic resin constituting the sealant layer 48a include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, ethylene-α-olefin copolymer 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 above resin material. 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 joins the sealant layer 48a and the first barrier layer 48c. The inner adhesive layer 48b may have the same configuration as the above-described adhesive layers 48e and 48g. The inner adhesive layer 48b may contain 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 experiments conducted by the inventors of the present invention will be described.

[0337] <Example A> As the laminate according to Example A, the laminate 47 shown in FIG. 26E was produced. This laminate 47 included a sealant layer 48a, an inner adhesive layer 48b, a first barrier base material 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 base material layer 48i in order from the inner surface 47a to the outer surface 47b.

[0338] For the first barrier layer 48c and the first barrier base material layer 48d, a barrier film A formed by forming an inorganic vapor deposition film corresponding to the first barrier layer 48c on a polyethylene terephthalate film corresponding to the first barrier base material layer 48d was used. 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 barrier layer 48 included in IB-PET-PBIR as the barrier film A included a first base barrier layer, a first over layer, a second base barrier layer, and a second over layer in order from the side of the barrier base material 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] For the second barrier layer 48h and the second barrier base material layer 48i, the above-described barrier film A formed by forming an inorganic vapor deposition film corresponding to the second barrier layer 48h on a polyethylene terephthalate film corresponding to the second barrier base material layer 48i was used. That is, the second barrier layer 48h and the second barrier base material layer 48i were configured with the same barrier film A as the first barrier layer 48c and the first barrier base material layer 48d.

[0340] The resin layer 48f was Emblem ONMB-RT available from Unitika Ltd. The resin layer 48f was a biaxially stretched 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 produced using Lock Bond RU77T / H-7, a thermosetting resin available from Lock Paint Co., Ltd. The thicknesses of both the first adhesive layer 48e and the second adhesive layer 48g were 3 μm.

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

[0342] Using a dry laminator with a gravure coating unit, a laminate was produced from 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 base layer 48d via a first adhesive layer 48e. On the resin layer 48f of the obtained laminate, a barrier film A constituting the second barrier layer 48h and the second barrier base layer 48i was laminated via a second adhesive layer 48g. The sealant layer 48a was laminated on the obtained laminate via the inner adhesive layer 48b. Thus, a laminate according to Example A was obtained.

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

[0344] In the laminate according to Example B, as the first barrier layer 48c and the first barrier base material layer 48d, a barrier film B was used which was formed by forming an inorganic vapor deposition film corresponding to the first barrier layer 48c on a polyethylene terephthalate film corresponding to the first barrier base material layer 48d. The barrier film B was IB-PET-PXB2 available from Dainippon Printing Co., Ltd. The thickness of the barrier film B was 12 μm. The barrier layer included in IB-PET-PBIR as the barrier film A included a first base barrier layer, a first overcoat layer, a second base barrier layer, and a second overcoat layer in this order from the side of the barrier base material 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.

[0345] In the laminate according to Example B, as the second barrier layer 48h and the second barrier base material layer 48i, the above-described barrier film B was used which was formed by forming an inorganic vapor deposition film corresponding to the second barrier layer 48h on a polyethylene terephthalate film corresponding to the second barrier base material layer 48i. That is, the second barrier layer 48h and the second barrier base material layer 48i were IB-PET-PXB2, similar to the first barrier layer 48c and the first barrier base material layer 48d.

[0346] <Example C> As the laminate according to Example C, in the same manner as the laminate according to Example A, the laminate 47 shown in FIG. 26E was produced. The laminate according to Example C was the same as that of Example A except that the resin film used for the sealant layer 48a was different.

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

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

[0349] <Example D> As the laminate according to Example D, the laminate 47 shown in FIG. 26E was produced in the same manner as the laminate according to Example A. The laminate according to Example D was the same as that of Example A except that the resin film used for the resin layer 48f was different.

[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. The thickness of the resin layer 48f was 16 μm.

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

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

[0353] The laminate according to Comparative Example A was produced as follows. First, a barrier film A constituting the second barrier layer 48h and the second barrier base material layer 48i was laminated on the barrier film A constituting the first barrier layer 48c and the first barrier base material layer 48d via the second adhesive layer 48g. The resin layer 48f was laminated on the obtained laminate via the first adhesive layer 48e, and further, the sealant layer 48a was laminated via the inner adhesive layer 48b. Thus, 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 base material layer 48d, a first barrier layer 48c, a second adhesive layer 48g, a second barrier layer 48h, and a second barrier base material 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 base material layer 48d and the resin layer 48f were opposite to those of the laminate according to Example C.

[0355] As a result, the laminate according to Comparative Example B was the same as Comparative Example A in other respects, except that the resin film used for the sealant layer 48a was different. The sealant layer 48a of the laminate according to Comparative Example B was CF7601A available from Toray Film Processing 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 for the sealant layer was different.

[0357] <Comparative Example C> The laminate according to 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 base material layer 48d.

[0358] In the laminate according to Comparative Example C, the sealant layer 48a, the inner adhesive layer 48b, the resin layer 48f, the first adhesive layer 48e, the first barrier layer 48c, and the first barrier base material layer 48d had the same configuration as the laminate according to Example A. That is, in the laminate according to Comparative Example C, the sealant layer 48a was TPF-4 available from Okamoto Industries, Inc. The thickness of the sealant layer 48a was 30 μm. The inner adhesive layer 48b was a layer using Lockbond RU77T / H-7 as 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 produced using Lockbond RU77T / H-7 as a thermosetting resin available from Rock Paint Co., Ltd. The thickness of the first adhesive layer 48e was 3 μm. For the first barrier layer 48c and the first barrier base material layer 48d, a barrier film A formed by forming an inorganic vapor deposition film corresponding to the first barrier layer 48c on a polyethylene terephthalate film corresponding to the first barrier base material layer 48d was used. 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, the resin layer 48f was laminated on the barrier film A constituting the first barrier layer 48c and the first barrier base material layer 48d via the first adhesive layer 48e, and further, the sealant layer 48a was laminated via the inner adhesive layer 48b. Thus, the laminate according to Comparative Example C was obtained.

[0360] <Evaluation 1 (Oxygen Permeability)> The oxygen permeabilities (mL / (m 2 ×day×atm)) of the laminates according to Examples A to D and Comparative Examples A to C, and Examples E and F and Comparative Example D described below were measured. The oxygen permeability was measured using an Oxtran (2 / 21), a permeability measuring machine manufactured by MOCON, Inc., USA, in an environment of a temperature of 23°C and a humidity of 40% RH. The results are shown in the columns of "Evaluation 1" in Tables 4 and 5.

[0361] <Evaluation 2 (Water vapor permeability)> The water vapor permeabilities (g / (m 2 ×day)) of the laminates according to Examples A to D and Comparative Examples A to C were measured. The water vapor permeability was specified by measuring the change in the weight of a container containing calcium chloride as follows. First, using the laminates according to Examples A to C and Comparative Examples A to C, a test container having a four-sided seal portion shown in FIG. 7B was fabricated. The internal space of the test container had a rectangular shape of 10 cm × 10 cm in a plan view with the container laid 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 increase in the weight of the test container before and after being placed in the test environment was measured as the amount of water vapor permeation (g) per 200 cm 2 of the laminate. From the measurement results, the hydrogen permeabilities (g / (m 2 ·day)) of the laminates according to the examples and comparative examples were specified. The results were described in the column of "Evaluation 2" in Table 4.

[0362] <Evaluation 3 (Transmission haze)> Samples of 5 cm × 10 cm were cut out from the laminates according to Examples A to D and Comparative Examples A to C. It was visually confirmed that there were no abnormalities such as dust or scratches on the samples. The transmission haze of the laminate according to each example was measured by the method described above. The incident surface at the time of measurement was the inner surface 47a. For the measurement of the transmission haze, a haze meter "HM-150" manufactured by Murakami Color Research Laboratory was used. The measurement results of the transmission haze are shown in Table 4.

[0363] <Evaluation 4 (Presence or absence of bubbles)> The presence or absence of bubbles in the laminates according to the examples and comparative examples was confirmed. The laminate was 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 of "Evaluation 4" in Table 4. A: When observed with a microscope, fine bubbles were confirmed, but no bubbles were confirmed in the observation from a position 30 cm away with the naked eye, and it was judged as qualified. B: Bubbles were confirmed in the observation from a position 30 cm away with the naked eye, and it was judged as nonconforming.

[0364] [Table 4]

[0365] Regarding the appearance, the following evaluations were further carried out.

[0366] <Example E> As the laminate according to Example E, a laminate obtained by removing the sealant layer 48a and the inner adhesive layer 48b from the laminate 47 shown in FIG. 26E was produced. It included a first barrier base material 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 base material layer 48i in the order from the inner surface 47a to the outer surface 47b.

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

[0368] In the laminate according to Example E, for the second barrier layer 48h and the second barrier base material layer 48i, the above-mentioned barrier film B formed by forming an inorganic vapor deposition film corresponding to the second barrier layer 48h on a polyethylene terephthalate film corresponding to the second barrier base material layer 48i was used. That is, the second barrier layer 48h and the second barrier base material layer 48i were IB-PET-PXB2, the same as the first barrier layer 48c and the first barrier base material layer 48d.

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

[0370] Using the above materials, a laminate was produced as follows. First, the resin layer 48f was laminated onto the barrier film A constituting the first barrier layer 48c and the first barrier base layer 48d via the first adhesive layer 48e. The barrier film A constituting the second barrier layer 48h and the second barrier base layer 48i was laminated onto the resin layer 48f of the obtained laminate via the second adhesive layer 48g. The adhesive layer was applied using a bar coater. A pressure of about 10 MPa was applied to the obtained laminate with a press to make it adhere. Then, in order to cure the adhesive layer, it was stored in an oven at 40°C for 72 hours. Thus, the laminate according to Example E was obtained.

[0371] <Example F> As the laminate according to Example F, a laminate obtained by removing the sealant layer 48a and the inner adhesive layer 48b from the laminate 47 shown in Fig. 26E was produced in the same manner as the laminate according to Example E. The laminate according to Example F was the same as that of Example E except that the resin film used for the resin layer 48f was different. In the laminate according to Example F, E5102 available from Toyobo Co., Ltd. was used as the resin layer instead of Emblem ONMB-RT used as the resin layer in Example E. The resin layer 48f was a biaxially stretched polyethylene terephthalate film. The thickness of the resin layer 48f was set at 16 μm. The method for producing the laminate according to Example F was the same as the method for producing the laminate according to Example E except for the difference in the resin layer.

[0372] <Comparative Example D> The laminate according to Comparative Example D included, in order from the inner surface 47a to the outer surface 47b, a first barrier base material layer 48d, a first barrier layer 48c, a second adhesive layer 48g, a second barrier layer 48h, and a second barrier base material layer 48i. In the laminate according to Comparative Example D, it differed from Example E and Example 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 base material layer 48d and the barrier film B constituting the second barrier layer 48h and the second barrier base material layer, and in other respects, it had the same configuration as Example E and Example F.

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

[0374] <Evaluation 5 (Cloudiness)> The presence or absence of cloudiness in the laminates according to the examples and comparative examples was confirmed. 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 of "Evaluation 5" in Table 5. AA: No cloudiness was confirmed, and it was judged as qualified. A: Cloudiness was confirmed, but it was judged as qualified because it was minor. B: Cloudiness was confirmed, and it was judged as unqualified.

[0375] <Evaluation 6 (Puncture Resistance)> The puncture resistance was carried out according to the puncture strength test of JIS Z1707:2019. The test piece was fixed with a jig, and a semicircular needle with a diameter of 1.0 mm and a tip shape radius of 0.5 mm was punctured into the outer surface (the surface constituted by the second barrier base material layer) at a test speed of 50 ± 5 mm / min, and the maximum force (N) until the needle penetrated was measured. Since there was no sealant on the target sample, the puncture resistance from the outer surface 47b direction was evaluated. The maximum force (N) as the evaluation result was the arithmetic mean value of the measured values at 5 locations. The evaluation results are shown in the column of "Evaluation 6" in Table 5.

[0376]

Table 5

[0377] From the evaluation results of Example E, Example F, and Comparative Example D, it was revealed that by disposing a resin layer between the two barrier layers, the appearance (cloudiness) became good. Due to a phenomenon similar to this evaluation result, it is considered that the generation of bubbles could be effectively suppressed in Example B and Example D.

[0378] Example E using a biaxially stretched nylon film as the resin layer was excellent in puncture resistance.

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

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

[0381] The first container 30 may include a label 37 (see FIG. 10). The label 37 may indicate information regarding the liquid. The label 37 may be attached to the container body 32. The label 37 does not have to extend over the entire circumference in order to enable observation inside the container body 32. In order to enable observation of the description on the label 37, the label 37 may face the second container 40. When the first container 30 is a vial, the container body 32 may be exposed by 10 mm or more, preferably 20 mm or more, between the label 37, the stopper 34, and the fixture 36. The liquid inside the first container 30 can be observed through the transparent container body 32. By irradiating light through the transparent container body 32, the amount of oxygen inside the first container 30 can be measured. 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, the stopper 34, and the fixture 36.

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

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

[0384] In the examples shown in FIGS. 1 and 8, the container body 32 and the fixture 36 have oxygen barrier properties, and the stopper 34 has oxygen permeability. In the examples shown by the dashed-dotted lines in FIGS. 1 and 8, the deoxygenation member 22 having the deoxidizer 21 is disposed facing the oxygen-permeable stopper 34. The deoxygenation member 22 having the deoxidizer 21 may contact the oxygen-permeable stopper 34. The deoxygenation member 22 having the deoxidizer 21 may contact only a part of the oxygen-permeable stopper 34. The deoxygenation member 22 having the deoxidizer 21 may be disposed with a gap provided between it and the oxygen-permeable stopper 34. According to the deoxidizer 21 and the deoxygenation member 22 shown by the dashed-dotted lines in FIGS. 1 and 8, the movement of oxygen from the inside to the outside of the first container 30 can be promoted. Also, it is possible to suppress the second container 40 having flexibility and oxygen barrier properties from contacting the oxygen-permeable stopper 34 of the first container 30.

[0385] In order to maintain the relative position between 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 deoxidizer 21 may be fixed to the stopper 34, the fixture 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 fixture 36 so as to ensure a gap between the deoxidizing member 22 and the stopper 34.

Explanation of Signs

[0386] D1: First direction, D2: Second direction, D3: Third direction, HS: Head space, L30: Length, S: Accommodation space, E41: Folding edge, L: Liquid, 10: Combined container, 10L: Combined container with liquid, 15: Supply pipe, 15a: Discharge port, 20: Container set, 21: Deoxidizer, 22: Deoxygenation member, 22a: Package, 22b: Water retention agent, 23: Deoxygenation film, 23a: Base material, 24: Dehydrating agent, 25: Oxygen detection material, 26: Display part, 30: First container, 30X: Part, 30L: First container with liquid, 32: Container body, 33: Opening, 34: Plug, 34a: Plate-like part, 34b: Insertion protrusion, 36: Fixture, 37: Label, 40: Second container, 40a: Opening, 41a: First film, 41b: Second film, 41bx: Bending top, 41c: First gasket, 41d: Second gasket, 41x: Folding part, 42: Container body, 42a: Accommodation part, 42b: Flange part, 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 base material layer, 48e: First adhesive layer, 48f: Resin layer, 48g: Second adhesive layer, 48h: Second barrier layer, 48i: Second barrier base material layer, 48j: Second resin layer, 48k: Third barrier layer, 48l: Third barrier base material layer, 49: Seal part, 49a: First seal part, 49ae: Outer edge, 49b: First side seal part, 49be: Outer edge, 49c: Second side seal part, 49ce: Outer edge, 49d: Second seal part, 49X: Main seal part, 49Y: Auxiliary seal part, 49Ya: First auxiliary seal part, 49Yb: Second auxiliary seal part, 49Z: Additional seal part, 49Ze: Inner edge, 49Za: First additional seal part, 49Zb: Second additional seal part, 50a: Main part, 50b: Extension part, 51: Notch, 52: Scheduled opening part, 55: Outer box, 56: Bottom part, 57: Top part, 58: Side wall part, 60: Syringe, 62: Cylinder, 63: Cylinder body, 64: Needle, 66: Piston, 67: Piston body, 68: Gasket, 69: Cap, 70: Test container, 71: Partition wall part, 72: Main wall part, 72A: Through hole, 73: Barrier joint 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 that contains a liquid chemical and has oxygen permeability, and a second container that houses the first container and has oxygen barrier properties, wherein the second container includes a laminate, and at least a part of the laminate is transparent, the laminate includes an inner surface facing the accommodation space of the second container and an outer surface opposite to the inner surface, the laminate includes, in order from the inner surface toward the outer surface, a sealant layer, a first barrier layer, a first adhesive layer, a resin layer, a second adhesive layer, and a second barrier layer, the first adhesive layer and the second adhesive layer include cured products of a curable resin composition, the first adhesive layer contacts the resin layer, and the second adhesive layer contacts the resin layer, the first barrier layer includes a base barrier layer and an overcoat layer that contacts the base barrier layer and the first adhesive layer, in order from the sealant layer toward the first adhesive layer, the base barrier layer includes a metal or an inorganic oxide, the overcoat layer includes a cured product of a curable resin composition, the first container includes a transparent glass container body and a stopper inserted into the opening of the container body, and is a liquid-containing combined container.

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

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

4. The liquid-containing combined container according to claim 1, wherein the thickness of the resin layer is 5 μm or more.

5. The laminate further includes a first barrier substrate that contacts the first barrier layer, and the liquid-containing combined container according to claim 1, wherein the first barrier layer is located between the first adhesive layer and the first barrier substrate.

6. The liquid-containing combined container according to claim 1, wherein the second adhesive layer contacts the resin layer.

7. The laminate further includes a second barrier substrate that contacts the second barrier layer, and the liquid-containing combined container according to claim 6, wherein the second barrier layer is located between the second adhesive layer and the second barrier substrate.

8. The liquid-containing combined container according to claim 1, wherein the first barrier layer is a transparent vapor deposition film and the second barrier layer is a transparent vapor deposition film.

9. The liquid-containing combined container according to claim 1, wherein the resin layer includes polyamide.

10. The laminate further includes a second resin layer and a third barrier layer, The liquid-containing combined 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.

11. The oxygen permeability of the laminate is less than 0.20 mL / (m 2 × day × atm), and the liquid-containing combined container according to claim 1.

12. The liquid-containing combined container according to claim 1, further comprising an oxygen scavenger that absorbs oxygen in the second container.

13. The liquid-containing combined container according to claim 1, wherein an oxygen detection material for detecting the oxygen state in the second container is provided.

14. The liquid-containing combined container further comprises an oxygen scavenging member housed in the second container, the oxygen scavenging member includes an oxygen scavenger 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, the first film and the second film are joined at a seal portion, the seal portion includes a first seal portion that faces the first container, the first seal portion is bent so as to protrude toward a side away from the first container in a direction in which the first seal portion and the first container face each other, In a 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 scavenging member. The liquid-containing combined container according to claim 1.

15. The second container is bent with the second film on the inside, and a first portion of the second container that houses the first container and a second portion of the second container overlap, 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 in a state where the second container before being bent is unfolded, The liquid-containing combined container according to claim 14, wherein the oxygen scavenging member is bent together with the second container such that an intermediate portion of the oxygen scavenging member is located on a bending apex of the second film.

16. The second container includes a first film and a second film that houses the first container between the first film, the first film and the second film are joined at a seal portion, the seal portion includes a first seal portion that faces the first container, the first seal portion is bent so as to protrude toward a side away from the first container in a direction in which the first seal portion and the first container face each other, The seal part further includes a first side seal part connected to one end of the first seal part, a second side seal part connected to the other end of the first seal part, and an additional seal part located between at least one of the first side seal part and the second side seal part and the first container. The liquid-containing combined container according to claim 1.

17. A method for manufacturing a liquid-containing container using the liquid-containing combined container according to claim 1, comprising: a step of closing the second container containing the first container; a step of adjusting the oxygen concentration by absorbing oxygen in the second container with a deoxidizer. In the step of adjusting the oxygen concentration, the oxygen in the first container permeates through the first container and moves outside the first container, and is absorbed by the deoxidizer in the second container. A method for manufacturing a liquid-containing container.

18. A first container for containing a liquid chemical; a second container for containing the first container, wherein the first container has oxygen permeability; the second container has oxygen barrier properties; the second container includes a laminate, and at least a part of the laminate is transparent; the laminate includes an inner surface facing the accommodation 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 first adhesive layer, a resin layer, a second adhesive layer, and a second barrier layer; the first adhesive layer and the second adhesive layer include cured products of a curable resin composition; the first adhesive layer is in contact with the resin layer; the first barrier layer includes, in order from the sealant layer to the first adhesive layer, a base barrier layer and an over layer in contact with the base barrier layer and the first adhesive layer; the base barrier layer includes a metal or an inorganic oxide; the over layer includes a cured product of a curable resin composition; the first container includes a transparent glass container body and a stopper inserted into an opening of the container body. A container set.

Citation Information

Patent Citations

  • package

    JP1991111267A

  • Highly moistureproof laminate

    JP1999333966A

  • Packaging material laminate and package

    JP2001088238A

  • Packaging container and packaging method

    JP2002127293A

  • Laminate of gas barrier film

    JP2006051751A