WO2015068819A1 - Liquid-filling bag, container housing said bag, and multiple film for forming said bag - Google Patents

Liquid-filling bag, container housing said bag, and multiple film for forming said bag Download PDF

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Publication number
WO2015068819A1
WO2015068819A1 PCT/JP2014/079638 JP2014079638W WO2015068819A1 WO 2015068819 A1 WO2015068819 A1 WO 2015068819A1 JP 2014079638 W JP2014079638 W JP 2014079638W WO 2015068819 A1 WO2015068819 A1 WO 2015068819A1
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WO
WIPO (PCT)
Prior art keywords
film
liquid
bag
container
filled
Prior art date
Application number
PCT/JP2014/079638
Other languages
French (fr)
Japanese (ja)
Inventor
倫子 熊澤
怜 原田
弘旭 後藤
孝之 池田
克行 甕
Original Assignee
大日本印刷株式会社
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Priority to JP2015527593A priority Critical patent/JPWO2015068819A1/en
Publication of WO2015068819A1 publication Critical patent/WO2015068819A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
    • B65D75/52—Details
    • B65D75/58—Opening or contents-removing devices added or incorporated during package manufacture
    • B65D75/5861—Spouts
    • B65D75/5872—Non-integral spouts
    • B65D75/5883—Non-integral spouts connected to the package at the sealed junction of two package walls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
    • B67D—DISPENSING, DELIVERING OR TRANSFERRING LIQUIDS, NOT OTHERWISE PROVIDED FOR
    • B67D7/00—Apparatus or devices for transferring liquids from bulk storage containers or reservoirs into vehicles or into portable containers, e.g. for retail sale purposes
    • B67D7/02—Apparatus or devices for transferring liquids from bulk storage containers or reservoirs into vehicles or into portable containers, e.g. for retail sale purposes for transferring liquids other than fuel or lubricants
    • B67D7/0238—Apparatus or devices for transferring liquids from bulk storage containers or reservoirs into vehicles or into portable containers, e.g. for retail sale purposes for transferring liquids other than fuel or lubricants utilising compressed air or other gas acting directly or indirectly on liquids in storage containers
    • B67D7/0255—Apparatus or devices for transferring liquids from bulk storage containers or reservoirs into vehicles or into portable containers, e.g. for retail sale purposes for transferring liquids other than fuel or lubricants utilising compressed air or other gas acting directly or indirectly on liquids in storage containers squeezing collapsible or flexible storage containers

Definitions

  • the present invention relates to a liquid-filled bag, a container containing the bag, and a multilayer film for forming the bag. More specifically, the present invention relates to a liquid-filled bag that can suppress the influence of moisture on the liquid to be filled as much as possible and has a higher durability, a container that contains the bag, and a multilayer film for forming the bag.
  • a liquid such as an electrolyte for a lithium ion battery is filled in a container such as a canister can (also referred to as a metal can) and conveyed.
  • a container such as a canister can (also referred to as a metal can) and conveyed.
  • the container after the liquid is used after the transport is cleaned and reused.
  • the liquid is taken out from the inside of the container as needed and used.
  • the inside of the container from which the liquid has been taken out is then cleaned, and the liquid is again stored and transported.
  • Patent Document 1 proposes a method for cleaning a container filled with high-purity isopropyl alcohol with high accuracy.
  • a container contaminated with fine particles having a diameter of 0.3 ⁇ m or more is ultrapure in which the presence of fine particles having a diameter of 0.3 ⁇ m or more is 20 particles / mL or less and the specific resistance value is 10 M ⁇ ⁇ cm or more.
  • This is a method of washing with water, followed by washing with high-purity isopropyl alcohol having fine particles having a diameter of 0.3 ⁇ m or more of 10 particles / mL or less and a water content of 50 ppm or less.
  • a container containing a packaging bag with a spout for containing a fluid content inside the container has been proposed.
  • a special high-purity resin composition as a resin composition formed on a member (packaging bag) that comes into contact with a high-purity chemical prevents leaching of impure fine particles into the high-purity chemical.
  • Techniques for reducing the number of proposals have been proposed.
  • a container that accommodates a packaging bag formed of such a resin composition can be reused simply by taking a used packaging bag out of the outer packaging and setting a new packaging bag in the outer packaging. For example, it is said that there is an advantage that it is possible to save labor and the like for cleaning as compared with the case where the outer container is directly filled with the fluid content without using the packaging bag.
  • the electrolyte solution for lithium ion batteries has a problem that it is hydrolyzed by reacting with moisture and the battery characteristics are deteriorated. Therefore, it needs to be handled in an environment with a small amount of moisture.
  • Patent Document 3 it is common to produce an electrolyte for a lithium ion battery in an environment with a dew point of about ⁇ 50 ° C.
  • or lower include, for example, a method of reducing the amount of water contained in the electrolyte itself to a predetermined value or less, and filling of an ion battery electrolyte A method in which the dew point in the container in the previous step is ⁇ 50 ° C. or lower is employed.
  • the container proposed in Patent Document 2 contains a packaging bag therein.
  • an electrolyte solution for lithium ion batteries also simply referred to as an electrolyte solution
  • the dew point temperature control in which the dew point in the container including the packaging bag is set to ⁇ 50 ° C. and the water content is set to 38 ppm or less before the electrolytic solution is filled after the packaging bag is accommodated in the container.
  • such dew point temperature control is not always sufficient.
  • the packaging bag accommodated in the container is usually prepared by being folded, expanded at the time of mounting, and inserted into the container. Further, the packaging bag inserted into the container is rubbed with the inner surface of the container. Such folding of the packaging bag and rubbing between the containers add a mechanical load to the film constituting the packaging bag, so that depending on the film constituting the packaging bag, pinholes and cracks may occur, for example, lithium ion It is not suitable as a film for a packaging bag for filling the battery electrolyte.
  • the present invention has been made in order to solve the above-described problems, and an object of the present invention is to provide a liquid-filled bag that can suppress the influence of moisture on the liquid to be filled as much as possible and that is more durable. . Another object of the present invention is to provide a container containing the liquid filling bag and a multiple film for forming the liquid filling bag.
  • the present inventors conducted extensive research.
  • the material of the film of the packaging bag greatly affects.
  • the inventors of the present invention paying attention to this point and conducting intensive research to select a material having a moisture content of the film of 0.5% by mass or less, thereby stably controlling the dew point temperature in the container including the packaging bag.
  • the present invention has been completed.
  • a liquid-filled bag according to the present invention for solving the above-mentioned problems is a liquid-filled bag for filling and using a liquid after being accommodated in an outer container, and is an inner film on the side in contact with the liquid And an outer film on the side in contact with the outer container, and is formed into a bag shape, and the outer film is a flex-resistant film and has a moisture content of 0.5% by mass or less. .
  • the outer film is preferably a polybutylene terephthalate film.
  • the outer film can be configured to be a laminated film further having a barrier layer.
  • the liquid-filled bag according to the present invention can be configured to be a double bag type bag in which peripheral edges of the inner film and the outer film are joined.
  • the liquid-filled bag according to the present invention can be configured to further include a barrier film having a barrier layer between the inner film and the outer film.
  • the liquid-filled bag according to the present invention is a liquid-filled bag for filling and using a liquid after being accommodated in an outer container, and is formed into a bag shape with a film, and the film is a flex-resistant film
  • the water content is 0.5% by mass or less.
  • the liquid can be configured to be an electrolyte for a lithium ion battery.
  • a container according to the present invention for solving the above problems includes an exterior container having an opening, and a liquid-filled bag that is accommodated in the exterior container and includes a spout corresponding to the opening.
  • the outer film is a flexible film and has a moisture content of 0.5% by mass or less.
  • the container according to the present invention is a container having an exterior container having an opening and a liquid filling bag that is accommodated in the exterior container and includes a spout corresponding to the opening.
  • the bag is formed into a bag shape with a film, and the film is a flexible film and has a water content of 0.5% by mass or less.
  • the container according to the present invention can be configured such that the liquid is an electrolyte for a lithium ion battery.
  • a multiple film according to the present invention for solving the above-mentioned problems is a multiple film for a liquid-filled bag for filling and using a liquid after being accommodated in an outer container, and the side in contact with the liquid And an outer film on the side in contact with the outer packaging container, wherein the outer film is a flex-resistant film and has a water content of 0.5% by mass or less.
  • the outer film is preferably a polybutylene terephthalate film.
  • the liquid can be configured to be an electrolyte for a lithium ion battery.
  • moisture content with respect to the liquid to fill can be suppressed as much as possible, and also the durable liquid filling bag, the container which accommodated the liquid filling bag, and the multiple film for forming the liquid filling bag are provided. can do.
  • the liquid filling bag according to the present invention has two aspects. Hereinafter, each aspect will be described.
  • the liquid filling bag 1 which concerns on this aspect is the bag 1 for filling and using the liquid 11 after accommodating in the exterior container 5 (refer FIG. 3). It is.
  • the liquid-filled bag 1 is formed in a bag shape with a multiple film 2 having an inner film 21 on the side in contact with the liquid 11 and an outer film 20 on the side in contact with the outer container 5.
  • the outer film 20 constituting the multiple film 2 is a flex-resistant film and is configured to have a moisture content of 0.5% by mass or less.
  • the electrolytic solution has a problem that the electrolytic solution is hydrolyzed due to the presence of moisture and the battery characteristics are deteriorated. More specifically, when the water content in the container including the packaging bag is such that the dew point in the container including the packaging bag is higher than ⁇ 50 ° C., the electrolytic solution is hydrolyzed and the battery characteristics are May decrease. Therefore, it is desired that the moisture content in the container including the packaging bag is such that the dew point in the container including the packaging bag is ⁇ 50 ° C. or less.
  • the dew point in the container including the packaging bag is set to ⁇ 50 ° C. and the water content is set to 38 ppm or less.
  • the dew point temperature control is not always sufficient.
  • the dew point of the container including the packaging bag may be difficult to set the dew point of the container including the packaging bag to ⁇ 50 ° C. or lower due to moisture contained in the outer film itself.
  • the dew point of the container including the packaging bag can be temporarily reduced to ⁇ 50 ° C. or lower, the dew point in the container is increased by dewatering from the outer film, and the dew point of the container including the packaging bag is reduced. There is concern that it will be difficult to stabilize.
  • the material of the packaging bag film greatly affects the dew point temperature control in the container including the packaging bag.
  • the inventors of the present invention paying attention to this point and conducting intensive research to select a material having a moisture content of the film of 0.5% by mass or less, thereby stably controlling the dew point temperature in the container including the packaging bag.
  • the present invention has been completed.
  • this liquid-filled bag 1 since the outer film 20 on the side in contact with the outer container 5 has a water content of 0.5% by mass or less, the dew point temperature can be easily reduced to ⁇ 50 ° C. or less. The influence of moisture can be suppressed as much as possible. As a result, when this liquid-filled bag 1 is used as, for example, a bag for an electrolytic solution for a lithium ion battery, it is possible to suppress degradation of the battery characteristics due to hydrolysis of the electrolytic solution due to the presence of moisture.
  • the liquid-filled bag 1 has good durability because the outer film 20 on the side in contact with the outer container 5 is a flex-resistant film.
  • the multiple film is formed by folding the bag 1 or rubbing with the outer container 5. Even if a mechanical load is applied to 2, the occurrence of pinholes, cracks, and the like can be suppressed.
  • a mechanical load is applied to 2
  • problems caused by such pinholes, cracks, and the like can be suppressed.
  • the liquid-filled bag 1 that does not cause a problem even when folded can be conveniently transported without taking up a storage place.
  • the liquid-filled bag 1 can be accommodated in the outer container 5 such as a canister can, the outer container 5 does not need to be cleaned, and the outer container 5 need not be frequently reused.
  • the multiple film 2 includes an inner film 21 and an outer film 20.
  • the inner film 21 is disposed on the side in contact with the liquid 11, and the outer film 20 is disposed on the side in contact with the exterior container 5.
  • the liquid-filled bag 1 is obtained by cutting the multiple film 2 into an arbitrary shape, superimposing the multiple film 2 so that the inner film 21 faces, and then setting the peripheral edge 3 (3a, 3b, 3c) of three sides or four sides. It is formed by bonding.
  • the inner film 21 is disposed on the side in contact with the liquid 11.
  • the inner film 21 is not particularly limited as long as it is a film in which the components of the inner film 21 do not dissolve in the liquid 11 or a film that does not easily dissolve.
  • Examples of the inner film 21 include additive-free polyolefin films such as additive-free polyethylene film, additive-free polypropylene film, and additive-free polyisobutylene film. “No additive” means that it does not contain various additives that are generally contained in polyolefin films. Examples of such additives include antioxidants, slip agents, antiblocking agents and the like that preferably act during film production.
  • the film components can be prevented or suppressed from dissolving in the liquid 11.
  • the additive-free polyethylene film has flexibility and can reduce costs.
  • an additive-free polyethylene film is used as a representative example.
  • the inner film 21 may be a single layer or a laminate of two or more layers.
  • the layer provided on the side in contact with the liquid 11 is preferably the above-described additive-free polyolefin layer.
  • the other layers are not particularly limited, but the layer on the outer film 20 side is preferably a layer that can be bonded to the outer film 20, and specifically, a heat-sealable polyolefin layer is preferable.
  • a barrier layer having gas barrier properties may be provided. About a barrier layer, what is demonstrated by the term of the outer film mentioned later can be used.
  • the thickness of the inner film 21 is not particularly limited, but is usually in the range of 10 ⁇ m to 120 ⁇ m, and preferably in the range of 30 ⁇ m to 100 ⁇ m.
  • Such an inner film 21 can be formed by a normal film forming means such as an inflation method.
  • the outer film 20 is disposed on the side in contact with the outer container 5.
  • the outer film 20 is a bend resistant film and has a moisture content of 0.5% by mass or less.
  • the outer film 20 is not particularly limited as long as it has such characteristics.
  • a particularly preferable outer film 20 for example, a polybutylene terephthalate film can be exemplified.
  • the dew point temperature can be easily reduced to ⁇ 50 ° C. or less, and the influence of moisture on the liquid 11 to be filled can be suppressed as much as possible.
  • production of the pinhole in a bending test can be suppressed and high bending resistance can be shown.
  • a polyethylene film can be used as the outer film.
  • the polyethylene film used for the outer film include a polyethylene film 125FN manufactured by Ube Maruzen Polyethylene Co., Ltd. and a polyethylene film Kernel KF273 manufactured by Nippon Polyethylene Co., Ltd.
  • the moisture content of the outer film 20 is 0.5% by mass or less, preferably 0.2% by mass or less.
  • the outer film 20 having a moisture content within this range can easily have a dew point temperature of ⁇ 50 ° C. or lower.
  • the dew point temperature is ⁇ 50 ° C. or lower
  • the moisture content of the outer film 20 becomes 38 ppm or less, and the moisture content is remarkably reduced.
  • the dew point temperature is ⁇ 60 ° C.
  • the lower limit of the moisture content is not particularly limited, but is about 0.005% by mass.
  • the moisture content can be measured by, for example, the Karl Fischer method, the drying method, the infrared absorption method, the dielectric constant method, or the like.
  • the outer film 20 has good bending resistance.
  • the bending resistance of the outer film 20 can be confirmed by a gelbo flex test (durability test). Specifically, pinholes generated when a film of A4 size (210 mm ⁇ 297 mm) is bent 1000 times at room temperature (about 23 ° C. ⁇ 2 ° C.) are visualized with a colored liquid, and the number of pin holes is measured. Can be confirmed. When the number of pinholes is 15 or less, it can be said that the bending resistance is excellent.
  • the number of pinholes is preferably 10 or less, more preferably 5 or less.
  • the outer film 20 is at least flexible and has a moisture content of 0.5% by mass or less. If this outer film 20 is arranged as a layer (outer layer) 20b on the outer container 5 side, the other layers
  • the configuration is not particularly limited.
  • a layer that can be bonded to the inner film 21 may be provided, or a gas barrier layer may be provided, or they may be laminated. May be. Since joining can be preferably performed by heat sealing or the like, it is preferable to provide a heat-sealable polyolefin layer as the inner layer (inner layer) 20a of the outer film 20.
  • the same additive-free polyolefin film as that of the inner film 21 can be preferably applied.
  • the material of the barrier layer is not particularly limited as long as it can impart a desired gas barrier property to the outer film, for example, vapor deposition of silica.
  • examples thereof include a film, a vapor deposition film of alumina, a binary vapor deposition film of silica and alumina, a vapor deposition film of aluminum, and an aluminum foil.
  • Preferred are a vapor deposition film of silica, a vapor deposition film of alumina, and a binary vapor deposition film of silica and alumina, and a vapor deposition film of silica is more preferred.
  • the metal ions contained in the liquid-filled bag can be reduced.
  • a liquid-filled bag that can be suitably used for a liquid that is easily affected by metal ions. be able to.
  • the method for forming the barrier layer can be the same as the method for forming a barrier layer of a general film, and examples thereof include a vacuum deposition method.
  • the outer film is a laminated film further having a barrier layer
  • the outer film, the barrier layer and the inner layer are preferably laminated films. This is because the inner film and the outer film can be easily joined by heat sealing or the like. Moreover, it is because pinhole-proof property can be made higher by setting it as the laminated
  • the thickness of the outer film 20 is not particularly limited, but is usually in the range of 10 ⁇ m to 120 ⁇ m, preferably in the range of 30 ⁇ m to 80 ⁇ m, and preferably in the range of 60 ⁇ m to 80 ⁇ m. This is because, by setting the thickness of the outer film within the above range, the pinhole resistance, durability, and handling properties of the outer film can be improved.
  • Such an outer film 20 can be formed by a normal film forming means such as an inflation method.
  • the outer film 20 provided with the inner layer 20a can be formed by a normal film forming means such as a T-die extrusion method.
  • barrier film which has a barrier layer between an inner film and an outer film.
  • a multiple film in which the inner film, the barrier film, and the outer film are superposed is used for the liquid-filled bag.
  • a barrier film it usually has a base film as a base and a barrier layer formed on the base film.
  • the substrate film is not particularly limited as long as it can support the barrier layer.
  • a film that can be heat-sealed with the inner film is preferable, and more specifically, a polyolefin film is preferable.
  • the barrier film is also preferably a laminated film of a polyolefin layer, a barrier layer and a polyolefin layer.
  • the barrier film is a polyolefin film, a laminated film of a barrier layer and a polyolefin layer, pinhole resistance can be increased.
  • the barrier layer can be the same as described above.
  • the liquid-filled bag 1 can be formed by superposing the inner film 21 and the outer film 20 to form the multi-film 2 and superimposing the multi-film 2 on each other. Specifically, the formation can be performed by bonding the multiple films 2 so that the inner film 21 is on the liquid 11 side, and bonding the facing inner films 21, 21 together. Bonding is usually preferably performed by heat sealing, but is not limited thereto.
  • Examples of the shape of the liquid filling bag 1 include a bag shape, a box shape, and a cylindrical shape.
  • the bag-like, particularly double-bag-type liquid-filled bag 1 can be formed, for example, by superposing two multiplex films 2 and 2 and joining the peripheral edges thereof. More specifically, by overlapping the multiple films 2 in which only the peripheral edges of the inner film 21 and the outer film 20 are bonded to each other so that the inner film 21 of the multiple film 2 is in contact, and further bonding at the peripheral edge Can be formed.
  • the inner film 21 and the outer film 20 can be formed by joining the multiple films 2 obtained by simply superimposing the inner films 21 and the outer film 20 so that the inner films 21 of the multiple films 2 are in contact with each other.
  • the bonding of the peripheral edge may be performed by bonding by, for example, heat sealing.
  • the four sides of the multiple film 2 may be heat sealed, or when the folded multiple films 2 are overlapped, the three sides may be heat sealed.
  • the outer film 20 has a water content of 0.5% by mass or less. Therefore, the dew point temperature can be easily set to ⁇ 50 ° C. or lower, and the influence of moisture on the liquid 11 to be filled can be suppressed as much as possible. Moreover, even if the moisture contained in the outer film 20 moves toward the inner film 21, the inner film 21 can suppress the moisture from being transferred to the liquid 11. Therefore, the liquid filling bag 1 which is a double bag type bag can suppress the influence of moisture on the liquid 11 to be filled as much as possible. Furthermore, the double bag type bag can provide the liquid-filled bag 1 with good durability. In addition, joining of the periphery of the inner side film 21 and the outer side film 20 can be easily performed by providing a heat seal layer in the side which the inner side film 21 and the outer side film 20 face, for example.
  • the method for manufacturing the liquid-filled bag 1 is not limited to the heat sealing method described above, and a method such as a coextrusion method or a lamination method may be used.
  • a method such as a coextrusion method or a lamination method may be used.
  • the inner bag 21 filled with the liquid 11 by the inner film 21 of the multiple film 2 (the same symbol “21” is used because the inner bag is constituted by the inner film 21).
  • an outer bag 20 that accommodates the inner bag by the outer film 20 of the multiplex film 2 (the outer bag is constituted by the outer film 20 and therefore has the same reference numeral “20”). ) Is formed.
  • the multiple film 2 is not particularly limited as long as it includes two or more films including the inner film 21 and the outer film 20.
  • stacked the outer film 20 on the inner film 21 may be sufficient.
  • the film of another layer may be provided between the inner film 21 and the outer film 20, or the outer side of the outer film 20, or these combinations.
  • the liquid 11 is filled in the liquid filling bag 1 and is not particularly limited.
  • an electrolyte for lithium ion batteries, polylactic acid, and the like are preferable.
  • These liquids are solutions (excluding organic solvents) that are hydrolyzed by moisture.
  • a resist removal liquid, an etching liquid, or other chemical liquid used in the semiconductor manufacturing process can be used.
  • Other examples include resist removal liquid and etching liquid used in the lead frame manufacturing process, resist removal liquid or etching liquid used in the suspension board manufacturing process, printing ink used in the printing process, high-purity liquid or liquid medicine, etc. You can also.
  • LiPF 6 , LiClO 4 , LiBF 4 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2, etc., which are lithium salts are dissolved.
  • some liquids such as electrolytes for lithium ion batteries have an adverse effect on not only moisture but also halogen and metal ions. Therefore, when filling these liquids in the inner bag, moisture, halogen, and metal It is preferable to use the inner film 21 having a low content of ions or the like.
  • the liquid filling bag which concerns on this aspect is a liquid filling bag for filling and using a liquid after accommodating in an exterior container, Comprising: It forms in a bag shape with a film, The said film is bending resistance It is a film and has a water content of 0.5% by mass or less.
  • this liquid-filled bag since the film has a moisture content of 0.5% by mass or less, the dew point temperature can be easily reduced to ⁇ 50 ° C. or less, and the influence of moisture on the liquid to be filled can be suppressed as much as possible.
  • this liquid-filled bag is used as, for example, a bag for an electrolyte solution for a lithium ion battery, it is possible to suppress degradation of the battery characteristics due to hydrolysis of the electrolyte solution due to the presence of moisture.
  • the film used for the outer film in the first aspect described above can be used.
  • a film having a predetermined moisture content is used as a layer (outer layer) on the outer container side and an additive-free polyolefin layer (inner layer) is laminated on the liquid side.
  • a liquid filling bag can be manufactured easily using heat sealing etc.
  • a laminated film having a barrier layer between the outer layer and the inner layer may be used as the film.
  • the barrier layer can be the same as described above.
  • the formation of the liquid-filled bag and the liquid can be the same as the contents described in the section “1. First aspect” described above, and thus the description thereof is omitted here.
  • the container 30 is a liquid including an outer container 5 having an opening 22 and a spout 4 accommodated in the outer container 5 and corresponding to the opening 22.
  • a filling bag 1; The container 30 is used by filling the liquid 11 after the liquid filling bag 1 is accommodated in the outer container 5.
  • the liquid-filled bag 1 is the same as the liquid-filled bag 1 described above, and is formed into a bag shape with a multiple film 2 having an inner film 21 on the side in contact with the liquid 11 and an outer film 20 on the side in contact with the outer container 5.
  • the outer film 20 is a flexible film and has a water content of 0.5% by mass or less.
  • the liquid filling bag 1 constituting the container 30 is the same as that described above, and the effect thereof is also the same.
  • the container 30 is configured such that the liquid filling bag 1 accommodated in the outer container 5 is inserted between the outer container 5 and the liquid filling bag 1 (space portion 23). Therefore, the liquid 11 in the liquid filling bag 1 is poured through the nozzle tip 24 and the dispensing nozzle 6 without directly contacting the liquid 7 with the gas 7a. It can be poured out from the outlet 4.
  • the container 30 includes an outer container 5, a liquid filling bag 1, and a lid portion 8.
  • the outer container 5 may be a metal can (canister) or a resin can.
  • the metal can is preferably made of, for example, a stainless material.
  • the liquid filling bag 1 is a bag-like container accommodated in the outer container 5.
  • the lid 8 is for sealing the outer container 5.
  • the liquid filling bag 1 includes an inner bag 21, an outer bag 20, a lid portion 8, and a dispensing nozzle 6.
  • the inner bag 21 is filled with the liquid 11 and formed by the inner film 21 described above.
  • the outer bag 20 accommodates the inner bag 21 and is formed by the outer film 20 described above.
  • the bag body 3 of the liquid filling bag 1 seals the inner bag 21 and the outer bag 20 together, and the upper edge 3a, the lower edge 3b, and the side edge 3c have an upper edge heat seal portion 10a, a bottom edge heat seal portion 10b, and It can manufacture by forming the side edge heat seal part 10c, respectively.
  • the lid portion 8 is for connecting to both the liquid filling bag 1 and the outer container 5.
  • the spout attachment portion 4a of the spout 4 connected to the lid portion 8 is inserted into the opening 25 of the inner bag 21 and the outer bag 20, and the inner bag 21 and the outer bag 20 are integrally sealed to seal the inner bag 21. It is pinched and fixed.
  • the dispensing nozzle 6 is a tube for dispensing the liquid 11 in the inner bag 21 to the outside. The dispensing nozzle 6 is inserted into the hole of the lid portion 8.
  • the lid 8 opens and closes the spout of the liquid filling bag 1.
  • the opening 22 is configured so that the spout 4 of the liquid filling bag 1 can be detachably connected.
  • the dispensing nozzle 6 is for dispensing liquid.
  • the dispensing nozzle 6 is provided in the hole of the dispensing port 4.
  • the gas injection nozzle 7 is a passage for injecting the gas 7 a into the space 23 between the outer container 5 and the liquid filling bag 1. Examples of the gas 7a injected into the gas injection nozzle 7 include nitrogen, air, oxygen, carbon dioxide, and the like.
  • the gas injection nozzle 7 is provided on the flange 9 at the top of the outer container 5.
  • the spout engaging portion 4b and the lid portion 8 are connected to hold the liquid filling bag 1 accommodated in the outer container 5, but the spout engaging portion 4b and the lid portion 8 are connected to each other.
  • the liquid filling bag 1 may be accommodated and held in the outer container 5 through the opening 22 provided in the outer container 5.
  • the lid portion 8 is fixed in contact with the outer container 5 and hermetically seals the inside of the liquid filling bag 1.
  • the lid 8 can be fixed to the outer container 5 with, for example, a bolt or the like.
  • the liquid 11 is poured into the space 23 between the outer container 5 and the liquid filling bag 1 through the gas injection nozzle 7 as shown in FIG. This is done by injecting 7a. That is, by injecting the gas 7a into the space between the outer container 5 and the liquid filling bag 1, the space is inflated, whereby the liquid filling bag 1 is pressed and the liquid is extracted.
  • the inner bag 21 of the liquid filling bag 1 may be directly filled with the liquid via the pouring port 4 and the pouring nozzle 6, but when the liquid filling bag 1 is folded. May inject the liquid after injecting an inert gas such as nitrogen into the inner bag 21 to inflate the inner bag 21 and the outer bag 20.
  • an inert gas such as nitrogen
  • the liquid such as an electrolyte for a lithium ion battery is vulnerable to moisture, so that the dew point in the liquid filled bag 1 can be appropriately managed. is necessary. That is, it is desirable to reduce the moisture contained in the air by lowering the dew point temperature to about ⁇ 50 ° C. to ⁇ 70 ° C., and then filling the inner bag 21 with a liquid such as an electrolyte for a lithium ion battery. .
  • Example 1 Water content of various films
  • Nylon film manufactured by Kojin Film & Chemicals Co., Ltd., trade name: Bonyl RX, thickness: 25 ⁇ m
  • polyethylene terephthalate film trade name: S105, thickness: 25 ⁇ m by Toray Industries, Inc.
  • polybutylene terephthalate film Toyobo Co., Ltd., trade name: toughness polyester, thickness: 12 ⁇ m
  • polyetherimide film Shin-Etsu polymer, thickness: 20 ⁇ m
  • polyethylene film Ube Maruzen Polyethylene Co., Ltd., trade name: polyethylene film 125FN, thickness S: 80 ⁇ m
  • Each of these films was cut into approximately 40 mm ⁇ 10 mm. The weight was 0.15 g.
  • Each film was stably stored in an environment of room temperature of about 24 ° C. and humidity of about 45%.
  • the nylon film exceeded 2.5% by mass, whereas the polybutylene terephthalate film was the same as the polyethylene terephthalate film having a low water content, and was 0.20% by mass. . Moreover, it has confirmed that a moisture content became 0.5 mass% or less also about a polyetherimide film and a polyethylene film.
  • Example 2 (Dew point measurement of various films) A dew point meter (manufactured by VAISALA) was set in the logging mode and placed in a vacuum chamber together with a nylon film or polybutylene terephthalate film, and measurement of the dew point temperature was started. The measurement was performed by evacuating the vacuum chamber from T0 to T1 for 5 minutes, and then stopping the evacuation when the temperature reached T2 and leaving it for 5 minutes. As a comparative control experiment, the dew point temperature was measured without placing the film in a vacuum chamber. The results are shown in FIG. Table 2 shows the dew point arrival temperature 15 minutes after the start of evacuation.
  • Example 3 Evaluation of bending resistance
  • the nylon film, polyethylene terephthalate film, polybutylene terephthalate film, and polyethylene film used in Experiment 1 were each cut into A4 size (210 mm x 297 mm), and a gelbo flex tester with a thermostatic bath (manufactured by Tester Sangyo Co., Ltd.) was used.
  • a bending test was performed. In the bending test, bending was locally repeated 1000 times at 24 ° C.
  • the polyethylene terephthalate film has more than 90 pinholes, whereas the polybutylene terephthalate film has the same degree of flexibility as a nylon film and has 5 pinholes. It was suggested that the resistance to bending is excellent at less than the number. In addition, it was suggested that the polyethylene film also has better bending resistance than the polyethylene terephthalate film.
  • the dew point temperature in the canister can was measured using the apparatus 40 shown in FIG.
  • the apparatus 40 includes an air compressor 41 that supplies air, a membrane dryer 42 that dries the air to dry air 7d, a connection portion 43 that connects the air compressor 41 and the membrane dryer 42, and a spout 44 of the dry air 7d.
  • a canister 46 having a discharge port 45, an injection nozzle 47 for injecting dry air 7 d into the canister can 46, and a dew point meter 48 disposed in the vicinity of the discharge port 45.
  • 19L canister can, the membrane type air dryer made from Japan Machinery, and the handy type dew point meter DM70 made from VAISALA were used.
  • the film 50 was placed in the canister 46.
  • the amount of film was 3742 mm 3 minutes for a 19 L canister can. That is, the film amount with respect to the can capacity was about 197 mm 3 / L.
  • the pouring and discharging port of the canister can was opened, dry air having a dew point of about ⁇ 60 ° C. was supplied by a membrane air dryer at a flow rate of 25 L / min (0.2 MPa), and the air in the canister can was replaced with dry air.
  • the dew point change and the arrival time at ⁇ 50 ° C. were measured with a dew point meter.
  • the change in the dew point and the arrival time at ⁇ 50 ° C. were measured with a dew point meter.
  • films include nylon films (manufactured by Kojin Film & Chemicals Co., Ltd., trade name: Bonil RX), polybutylene terephthalate films (trade name: tough polyester by Toyobo Co., Ltd.), and polyetherimide films (manufactured by Shin-Etsu Polymer). Measured for each film. The results are shown in FIG.
  • Example 4-2 Except for the following conditions, the change in the dew point and the arrival time at ⁇ 50 ° C. were measured in the same manner as in Experiment 4-1. A 200 L canister can was used, and the amount of film was 58867 mm 3 minutes relative to a 200 L canister can. That is, the film amount with respect to the can capacity was set to about 294 mm 3 / L. As a film, it measured with respect to each film of the nylon film in experiment 1, and a polybutylene terephthalate film. The results are shown in FIG.
  • the dew point reached ⁇ 50 ° C. in 75 minutes when the film amount relative to the can capacity was about 197 mm 3 / L.
  • the amount was about 294 mm 3 / L, the dew point did not reach ⁇ 50 ° C. even after 8 hours. Therefore, it was confirmed that when the film amount with respect to the can capacity was increased, it took longer time to reach the dew point of ⁇ 50 ° C.
  • the moisture content of the film is 0.5% by mass or less, it is possible to reduce the time loss until the dew point reaches ⁇ 50 ° C. even when the film amount with respect to the can capacity is increased.
  • the polybutylene terephthalate film has a water content of 0.5% by mass or less, has good flexibility, and the above dew point measurement results show that It was suggested that the film can be suitably used as an outer film, and when used in a liquid-filled bag, the water content in the container can be well managed at a dew point of -50 ° C. or lower.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Packages (AREA)
  • Bag Frames (AREA)

Abstract

　To provide a liquid-filling bag, etc., that is durable and in which the effect of water on the filling liquid can be minimized. The above problem is addressed by a liquid-filling bag to be used by housing the bag in an exterior container and then filling the bag with a liquid, wherein the bag is formed into a bag shape by a multiple film having an inside film on the side in contact with the liquid and an outside film on the side in contact with the external container, the outside film is a flex-resistant film, and the water content is 0.5 mass% or less. The outside film is preferably a polybutylene terephthalate film, the bag being configured as a double-bag-type in which the peripheral edges of the inside film and the outside film are bonded together. The liquid is configured as an electrolyte for a lithium-ion cell.

Description

液体充填バッグ、そのバッグを収容した容器及びそのバッグ形成用多重フィルムLiquid-filled bag, container containing the bag, and multilayer film for forming the bag
　本発明は、液体充填バッグ、そのバッグを収容した容器、及びそのバッグ形成用多重フィルムに関する。さらに詳しくは、充填する液体に対する水分の影響を極力抑えることができ、さらに耐久性のよい液体充填バッグ、そのバッグを収容した容器、及びそのバッグ形成用多重フィルムに関する。 The present invention relates to a liquid-filled bag, a container containing the bag, and a multilayer film for forming the bag. More specifically, the present invention relates to a liquid-filled bag that can suppress the influence of moisture on the liquid to be filled as much as possible and has a higher durability, a container that contains the bag, and a multilayer film for forming the bag.
　例えばリチウムイオン電池用電解液等の液体は、キャニスター缶（金属缶ともいう。）等の容器に充填され、搬送されている。搬送後に液体が使用された後の容器は、内部が洗浄されて再利用される。そして、必要に応じて容器内部から液体が取出され、使用される。液体が取出された容器は、その後に内部が洗浄され、再び液体を収容して搬送される。ところで、リチウムイオン電池用電解液は、その取扱いを慎重に行う必要があり、一度リチウムイオン電池用電解液を収容した容器の洗浄にあたっても、高精度に洗浄する必要がある。 For example, a liquid such as an electrolyte for a lithium ion battery is filled in a container such as a canister can (also referred to as a metal can) and conveyed. The container after the liquid is used after the transport is cleaned and reused. Then, the liquid is taken out from the inside of the container as needed and used. The inside of the container from which the liquid has been taken out is then cleaned, and the liquid is again stored and transported. By the way, it is necessary to handle the electrolytic solution for lithium ion batteries carefully, and it is necessary to clean the container containing the electrolytic solution for lithium ion batteries with high accuracy once.
　高精度の洗浄方法は、種々提案されている。例えば特許文献１には、高純度イソプロピルアルコールを充填する容器を高精度に洗浄する方法が提案されている。この技術は、直径が０．３μｍ以上の微粒子により汚染された容器を、該直径が０．３μｍ以上の微粒子の存在が２０個／ｍＬ以下であり比抵抗値が１０ＭΩ・ｃｍ以上である超純水により洗浄し、次いで、該直径が０．３μｍ以上の微粒子の存在が１０個／ｍＬ以下であり含水量が５０ｐｐｍ以下の高純度イソプロピルアルコールで洗浄する方法である。 A variety of highly accurate cleaning methods have been proposed. For example, Patent Document 1 proposes a method for cleaning a container filled with high-purity isopropyl alcohol with high accuracy. In this technology, a container contaminated with fine particles having a diameter of 0.3 μm or more is ultrapure in which the presence of fine particles having a diameter of 0.3 μm or more is 20 particles / mL or less and the specific resistance value is 10 MΩ · cm or more. This is a method of washing with water, followed by washing with high-purity isopropyl alcohol having fine particles having a diameter of 0.3 μm or more of 10 particles / mL or less and a water content of 50 ppm or less.
　一方、容器の洗浄コストを低減するため、容器の内部に流動性内容物を収容する注出口付き包装袋を収容した容器が提案されている。例えば、特許文献２には、高純度薬品と接触する部材（包装袋）に成形される樹脂組成物として特別な高純度樹脂組成物を用いることにより、高純度薬品中への不純微粒子の浸出が極めて少なくする技術が提案されている。このような樹脂組成物で成形された包装袋を収容する容器は、使用済みの包装袋を外装容器から取り出し、新たな包装袋を外装容器内にセットするだけで再使用することができるために、例えば、包装袋を使用せずに直に外装容器に流動性内容物を充填する場合に比べて、洗浄する手間等が省けるなどの利点があるとされている。 On the other hand, in order to reduce the cleaning cost of the container, a container containing a packaging bag with a spout for containing a fluid content inside the container has been proposed. For example, in Patent Document 2, the use of a special high-purity resin composition as a resin composition formed on a member (packaging bag) that comes into contact with a high-purity chemical prevents leaching of impure fine particles into the high-purity chemical. Techniques for reducing the number of proposals have been proposed. A container that accommodates a packaging bag formed of such a resin composition can be reused simply by taking a used packaging bag out of the outer packaging and setting a new packaging bag in the outer packaging. For example, it is said that there is an advantage that it is possible to save labor and the like for cleaning as compared with the case where the outer container is directly filled with the fluid content without using the packaging bag.
特開平１０－４３６号公報Japanese Patent Laid-Open No. 10-436 特開平９－９５５６５号公報JP-A-9-95565 特開２０１３－１６６６８０号公報JP 2013-166680 A
　ところで、リチウムイオン電池用電解液は、水分と反応することにより加水分解し、電池特性が低下するという問題があることから、水分量の少ない環境下で取り扱う必要がある。例えば、特許文献３に示すように、リチウムイオン電池用電解液は露点－５０℃程度の環境下で製造することが一般的である。また、リチウムイオン電池用電解液は上記露点－５０℃以下の環境下で取り扱うことが一般的である。また、イオン電池用電解液を露点－５０℃以下の環境下で保管する方法としては、例えば、電解液自体に含有される水分量を所定の値以下とする方法、イオン電池用電解液の充填前における容器内の露点を－５０℃以下とする方法が採用されている。 By the way, the electrolyte solution for lithium ion batteries has a problem that it is hydrolyzed by reacting with moisture and the battery characteristics are deteriorated. Therefore, it needs to be handled in an environment with a small amount of moisture. For example, as shown in Patent Document 3, it is common to produce an electrolyte for a lithium ion battery in an environment with a dew point of about −50 ° C. Moreover, it is common to handle the electrolyte solution for a lithium ion battery in an environment having the above dew point of −50 ° C. or less. Examples of a method for storing an ion battery electrolyte in an environment having a dew point of −50 ° C. or lower include, for example, a method of reducing the amount of water contained in the electrolyte itself to a predetermined value or less, and filling of an ion battery electrolyte A method in which the dew point in the container in the previous step is −50 ° C. or lower is employed.
　特許文献２で提案されている容器は、その中に包装袋を収容している。しかしながら、その包装袋の種類によっては、包装袋に充填される液体の特性が低下するという問題がある。特にリチウムイオン電池用電解液（単に電解液ともいう。）は、水分の存在により電解液が加水分解して電池特性が低下するという問題がある。こうした問題に対しては、容器内に包装袋を収容した後に電解液を充填する前に、包装袋を含む容器内の露点を－５０℃にして水分量を３８ｐｐｍ以下にするという露点温度管理によって対応しているが、一般的に用いられているナイロンを用いた場合では、そうした露点温度管理が必ずしも十分ではなかった。 The container proposed in Patent Document 2 contains a packaging bag therein. However, depending on the type of the packaging bag, there is a problem that the characteristics of the liquid filled in the packaging bag are deteriorated. In particular, an electrolyte solution for lithium ion batteries (also simply referred to as an electrolyte solution) has a problem that the electrolyte properties are hydrolyzed due to the presence of moisture, resulting in deterioration of battery characteristics. To solve this problem, the dew point temperature control in which the dew point in the container including the packaging bag is set to −50 ° C. and the water content is set to 38 ppm or less before the electrolytic solution is filled after the packaging bag is accommodated in the container. Correspondingly, in the case of using commonly used nylon, such dew point temperature control is not always sufficient.
　また、容器に収容される包装袋は、通常、折り畳まれて準備され、装着時に拡げられて容器内に挿入される。また、容器内に挿入された包装袋は、容器の内面との間で擦れが生じる。こうした包装袋の折り畳みや容器との間の擦れは、包装袋を構成するフィルムに機械的な負荷が加わることから、その包装袋を構成するフィルムによっては、ピンホールや亀裂が生じ、例えばリチウムイオン電池用電解液を充填するための包装袋用のフィルムとしては適切ではない。 In addition, the packaging bag accommodated in the container is usually prepared by being folded, expanded at the time of mounting, and inserted into the container. Further, the packaging bag inserted into the container is rubbed with the inner surface of the container. Such folding of the packaging bag and rubbing between the containers add a mechanical load to the film constituting the packaging bag, so that depending on the film constituting the packaging bag, pinholes and cracks may occur, for example, lithium ion It is not suitable as a film for a packaging bag for filling the battery electrolyte.
　本発明は、上記課題を解決するためになされたものであって、その目的は、充填する液体に対する水分の影響を極力抑えることができ、さらに耐久性のよい液体充填バッグを提供することにある。また、その液体充填バッグを収容した容器、及びその液体充填バッグ形成用の多重フィルムを提供することにある。 The present invention has been made in order to solve the above-described problems, and an object of the present invention is to provide a liquid-filled bag that can suppress the influence of moisture on the liquid to be filled as much as possible and that is more durable. . Another object of the present invention is to provide a container containing the liquid filling bag and a multiple film for forming the liquid filling bag.
　上記課題を解決するために、本発明者らは鋭意研究を行なった。包装袋を含む容器内の露点温度管理においては、包装袋のフィルムの材料が大きく影響する。本発明者らはこの点に着目し鋭意研究を重ねることにより、フィルムの水分量が０．５質量％以下となる材料を選定することにより、安定して包装袋を含む容器内の露点温度管理を行うことができることを見出し、本発明を完成させるに至った。 In order to solve the above problems, the present inventors conducted extensive research. In the dew point temperature control in the container including the packaging bag, the material of the film of the packaging bag greatly affects. The inventors of the present invention paying attention to this point and conducting intensive research to select a material having a moisture content of the film of 0.5% by mass or less, thereby stably controlling the dew point temperature in the container including the packaging bag. The present invention has been completed.
　（１）上記課題を解決するための本発明に係る液体充填バッグは、外装容器内に収容した後に液体を充填して使用するための液体充填バッグであって、前記液体に接する側の内側フィルムと、前記外装容器に接する側の外側フィルムとを有する多重フィルムで袋状に形成され、前記外側フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする。 (1) A liquid-filled bag according to the present invention for solving the above-mentioned problems is a liquid-filled bag for filling and using a liquid after being accommodated in an outer container, and is an inner film on the side in contact with the liquid And an outer film on the side in contact with the outer container, and is formed into a bag shape, and the outer film is a flex-resistant film and has a moisture content of 0.5% by mass or less. .
　本発明に係る液体充填バッグにおいて、前記外側フィルムがポリブチレンテレフタレートフィルムであることが好ましい。 In the liquid-filled bag according to the present invention, the outer film is preferably a polybutylene terephthalate film.
　本発明に係る液体充填バッグにおいて、前記外側フィルムが、バリア層をさらに有する積層フィルムであるように構成できる。 In the liquid-filled bag according to the present invention, the outer film can be configured to be a laminated film further having a barrier layer.
　本発明に係る液体充填バッグにおいて、前記内側フィルムと前記外側フィルムとの周縁が接合されている二重袋型バッグであるように構成できる。 The liquid-filled bag according to the present invention can be configured to be a double bag type bag in which peripheral edges of the inner film and the outer film are joined.
　本発明に係る液体充填バッグにおいて、前記内側フィルムと前記外側フィルムとの間に、バリア層を有するバリアフィルムをさらに有するように構成できる。 The liquid-filled bag according to the present invention can be configured to further include a barrier film having a barrier layer between the inner film and the outer film.
　また、本発明に係る液体充填バッグは、外装容器内に収容した後に液体を充填して使用するための液体充填バッグであって、フィルムで袋状に形成され、前記フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする。 Further, the liquid-filled bag according to the present invention is a liquid-filled bag for filling and using a liquid after being accommodated in an outer container, and is formed into a bag shape with a film, and the film is a flex-resistant film The water content is 0.5% by mass or less.
　本発明に係る液体充填バッグにおいて、前記液体がリチウムイオン電池用電解液であるように構成できる。 In the liquid-filled bag according to the present invention, the liquid can be configured to be an electrolyte for a lithium ion battery.
　（２）上記課題を解決するための本発明に係る容器は、開口部を有する外装容器と、該外装容器内に収容されるとともに前記開口部に対応した注出口を備える液体充填バッグとを有する容器であって、前記液体充填バッグが、前記外装容器内に収容した後に液体を充填して用いられ、前記液体に接する側の内側フィルムと、前記外装容器に接する側の外側フィルムとを有する多重フィルムで袋状に形成され、前記外側フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする。 (2) A container according to the present invention for solving the above problems includes an exterior container having an opening, and a liquid-filled bag that is accommodated in the exterior container and includes a spout corresponding to the opening. A container, wherein the liquid-filled bag is used after being filled in the outer container and filled with the liquid, and has an inner film on the side in contact with the liquid and an outer film on the side in contact with the outer container The outer film is a flexible film and has a moisture content of 0.5% by mass or less.
　また、本発明に係る容器は、開口部を有する外装容器と、該外装容器内に収容されるとともに前記開口部に対応した注出口を備える液体充填バッグとを有する容器であって、前記液体充填バッグが、フィルムで袋状に形成され、前記フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする。 The container according to the present invention is a container having an exterior container having an opening and a liquid filling bag that is accommodated in the exterior container and includes a spout corresponding to the opening. The bag is formed into a bag shape with a film, and the film is a flexible film and has a water content of 0.5% by mass or less.
　本発明に係る容器において、前記液体がリチウムイオン電池用電解液であるように構成できる。 The container according to the present invention can be configured such that the liquid is an electrolyte for a lithium ion battery.
　（３）上記課題を解決するための本発明に係る多重フィルムは、外装容器内に収容した後に液体を充填して使用するための液体充填バッグ用の多重フィルムであって、前記液体に接する側の内側フィルムと、前記外装容器に接する側の外側フィルムとを有し、前記外側フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする。 (3) A multiple film according to the present invention for solving the above-mentioned problems is a multiple film for a liquid-filled bag for filling and using a liquid after being accommodated in an outer container, and the side in contact with the liquid And an outer film on the side in contact with the outer packaging container, wherein the outer film is a flex-resistant film and has a water content of 0.5% by mass or less.
　本発明に係る多重フィルムにおいて、前記外側フィルムがポリブチレンテレフタレートフィルムであることが好ましい。 In the multiple film according to the present invention, the outer film is preferably a polybutylene terephthalate film.
　本発明に係る多重フィルムにおいて、前記液体がリチウムイオン電池用電解液であるように構成できる。 In the multiple film according to the present invention, the liquid can be configured to be an electrolyte for a lithium ion battery.
　本発明によれば、充填する液体に対する水分の影響を極力抑えることができ、さらに耐久性のよい液体充填バッグ、その液体充填バッグを収容した容器、及びその液体充填バッグ形成用の多重フィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the influence of the water | moisture content with respect to the liquid to fill can be suppressed as much as possible, and also the durable liquid filling bag, the container which accommodated the liquid filling bag, and the multiple film for forming the liquid filling bag are provided. can do.
本発明に係る液体充填バッグの一例を示す正面図である。It is a front view which shows an example of the liquid filling bag which concerns on this invention. 本発明に係る多重フィルムの一例を示す断面図である。It is sectional drawing which shows an example of the multiplex film which concerns on this invention. 本発明に係る容器の一例を示す断面図である。It is sectional drawing which shows an example of the container which concerns on this invention. 図３に示す容器に気体を注入して液体充填バッグを圧縮し、液体充填バッグ内の液体を抽出する形態を示す説明図である。It is explanatory drawing which shows the form which inject | pours gas into the container shown in FIG. 3, compresses a liquid filling bag, and extracts the liquid in a liquid filling bag. 多重フィルムを構成する外側フィルムの種類を変えて露点を測定した結果を示すグラフである。It is a graph which shows the result of having measured the dew point by changing the kind of outer film which comprises a multiple film. 実験４における露点温度の測定方法について説明する模式図である。It is a schematic diagram explaining the measuring method of the dew point temperature in Experiment. 実験４－１における露点温度の測定結果を示すグラフである。It is a graph which shows the measurement result of the dew point temperature in Experiment 4-1. 実験４－２における露点温度の測定結果を示すグラフである。It is a graph which shows the measurement result of the dew point temperature in Experiment 4-2.
　以下、本発明に係る液体充填バッグ、そのバッグを収容した容器及びそのバッグ形成用多重フィルムについて、図面を参照しつつ説明する。なお、本発明は、以下の実施形態に限定されない。 Hereinafter, a liquid-filled bag according to the present invention, a container containing the bag, and a multilayer film for forming the bag will be described with reference to the drawings. The present invention is not limited to the following embodiment.
　［液体充填バッグ］
　本発明に係る液体充填バッグは、２つの態様を有する。以下、各態様について説明する。 [Liquid filling bag]
The liquid filling bag according to the present invention has two aspects. Hereinafter, each aspect will be described.
　１．第１態様
　本態様に係る液体充填バッグ１は、図１及び図２に示すように、外装容器５（図３を参照。）内に収容した後に液体１１を充填して使用するためのバッグ１である。この液体充填バッグ１は、液体１１に接する側の内側フィルム２１と、外装容器５に接する側の外側フィルム２０とを有する多重フィルム２で袋状に形成されている。多重フィルム２を構成する外側フィルム２０は、耐屈曲性フィルムであり、水分量０．５質量％以下であるように構成されている。 1. 1st aspect As shown in FIG.1 and FIG.2, the liquid filling bag 1 which concerns on this aspect is the bag 1 for filling and using the liquid 11 after accommodating in the exterior container 5 (refer FIG. 3). It is. The liquid-filled bag 1 is formed in a bag shape with a multiple film 2 having an inner film 21 on the side in contact with the liquid 11 and an outer film 20 on the side in contact with the outer container 5. The outer film 20 constituting the multiple film 2 is a flex-resistant film and is configured to have a moisture content of 0.5% by mass or less.
　ここで、上述したように、従来の包装袋を含む容器においては、包装袋の種類によっては、包装袋に充填される液体の特性が低下するという問題がある。特に電解液は、水分の存在により電解液が加水分解して電池特性が低下するという問題がある。より具体的には、包装袋を含む容器内の水分量が、包装袋を含む容器内の露点が－５０℃よりも高くなるような水分量である場合、電解液が加水分解して電池特性が低下する場合がある。そのため、包装袋を含む容器内の水分量を、包装袋を含む容器内の露点が－５０℃以下とすることが望まれる。 Here, as described above, in the container including the conventional packaging bag, there is a problem that the characteristics of the liquid filled in the packaging bag are deteriorated depending on the type of the packaging bag. In particular, the electrolytic solution has a problem that the electrolytic solution is hydrolyzed due to the presence of moisture and the battery characteristics are deteriorated. More specifically, when the water content in the container including the packaging bag is such that the dew point in the container including the packaging bag is higher than −50 ° C., the electrolytic solution is hydrolyzed and the battery characteristics are May decrease. Therefore, it is desired that the moisture content in the container including the packaging bag is such that the dew point in the container including the packaging bag is −50 ° C. or less.
　また、上述の問題に対しては、従来から、容器内に包装袋を収容した後に電解液を充填する前に、包装袋を含む容器内の露点を－５０℃にして水分量を３８ｐｐｍ以下にするという露点温度管理によって対応しているが、一般的に用いられているナイロンでは、そうした露点温度管理が必ずしも十分ではなかった。 In addition, for the above-mentioned problem, conventionally, after the packaging bag is stored in the container and before the electrolytic solution is filled, the dew point in the container including the packaging bag is set to −50 ° C. and the water content is set to 38 ppm or less. However, in the case of commonly used nylon, such dew point temperature control is not always sufficient.
　すなわち、ナイロン等の従来の外側フィルムにおいては、外側フィルム自体に含まれる水分により、包装袋を含む容器の露点を－５０℃以下とすること自体が困難となる場合がある。また、上記包装袋を含む容器の露点を一時的に－５０℃以下とすることができた場合も、外側フィルムからの脱水蒸気により容器内の露点が上がり、上記包装袋を含む容器の露点を安定させることが困難となることが懸念される。 That is, in a conventional outer film such as nylon, it may be difficult to set the dew point of the container including the packaging bag to −50 ° C. or lower due to moisture contained in the outer film itself. In addition, even when the dew point of the container including the packaging bag can be temporarily reduced to −50 ° C. or lower, the dew point in the container is increased by dewatering from the outer film, and the dew point of the container including the packaging bag is reduced. There is concern that it will be difficult to stabilize.
　このように、包装袋を含む容器内の露点温度管理においては、包装袋のフィルムの材料が大きく影響する。本発明者らはこの点に着目し鋭意研究を重ねることにより、フィルムの水分量が０．５質量％以下となる材料を選定することにより、安定して包装袋を含む容器内の露点温度管理を行うことができることを見出し、本発明を完成させるに至った。 As described above, the material of the packaging bag film greatly affects the dew point temperature control in the container including the packaging bag. The inventors of the present invention paying attention to this point and conducting intensive research to select a material having a moisture content of the film of 0.5% by mass or less, thereby stably controlling the dew point temperature in the container including the packaging bag. The present invention has been completed.
　この液体充填バッグ１は、外装容器５に接する側の外側フィルム２０が水分量０．５質量％以下であるので、露点温度を容易に－５０℃以下にすることができ、充填する液体１１に対する水分の影響を極力抑えることができる。その結果、この液体充填バッグ１を例えばリチウムイオン電池用電解液のバッグとして用いた場合に、水分の存在により電解液が加水分解して電池特性が低下するのを抑制することができる。 In this liquid-filled bag 1, since the outer film 20 on the side in contact with the outer container 5 has a water content of 0.5% by mass or less, the dew point temperature can be easily reduced to −50 ° C. or less. The influence of moisture can be suppressed as much as possible. As a result, when this liquid-filled bag 1 is used as, for example, a bag for an electrolytic solution for a lithium ion battery, it is possible to suppress degradation of the battery characteristics due to hydrolysis of the electrolytic solution due to the presence of moisture.
　また、この液体充填バッグ１は、外装容器５に接する側の外側フィルム２０が耐屈曲性フィルムであるので、耐久性が良く、例えばバッグ１の折り畳みや外装容器５との間の擦れによって多重フィルム２に機械的な負荷が加わったとしても、ピンホールや亀裂等の発生を抑制できる。その結果、例えばリチウムイオン電池用電解液の充填バッグとして用いた場合に、そうしたピンホールや亀裂等によって起こる問題を抑制することができる。折り畳んでも問題を生じない液体充填バッグ１は、折り畳むことにより保管場所をとらず、運搬にも便利である。 The liquid-filled bag 1 has good durability because the outer film 20 on the side in contact with the outer container 5 is a flex-resistant film. For example, the multiple film is formed by folding the bag 1 or rubbing with the outer container 5. Even if a mechanical load is applied to 2, the occurrence of pinholes, cracks, and the like can be suppressed. As a result, for example, when used as a filling bag for an electrolyte solution for a lithium ion battery, problems caused by such pinholes, cracks, and the like can be suppressed. The liquid-filled bag 1 that does not cause a problem even when folded can be conveniently transported without taking up a storage place.
　さらに、この液体充填バッグ１は、キャニスター缶等の外装容器５内に収容することができるので、外装容器５の洗浄が不要となり、外装容器５の再利用を頻繁な洗浄を行う必要がない。 Furthermore, since the liquid-filled bag 1 can be accommodated in the outer container 5 such as a canister can, the outer container 5 does not need to be cleaned, and the outer container 5 need not be frequently reused.
　以下、液体充填バッグ１の構成について詳しく説明する。 Hereinafter, the configuration of the liquid-filled bag 1 will be described in detail.
　（多重フィルム）
　多重フィルム２は、内側フィルム２１と外側フィルム２０とで構成されている。内側フィルム２１は、液体１１に接する側に配置され、外側フィルム２０は、外装容器５に接する側に配置されている。液体充填バッグ１は、多重フィルム２を任意の形状に切断加工し、内側フィルム２１が向かい合うように多重フィルム２を重ね合わせ、その後、３辺又は４辺の周縁３（３ａ，３ｂ，３ｃ）を貼り合わせて形成される。 (Multiple film)
The multiple film 2 includes an inner film 21 and an outer film 20. The inner film 21 is disposed on the side in contact with the liquid 11, and the outer film 20 is disposed on the side in contact with the exterior container 5. The liquid-filled bag 1 is obtained by cutting the multiple film 2 into an arbitrary shape, superimposing the multiple film 2 so that the inner film 21 faces, and then setting the peripheral edge 3 (3a, 3b, 3c) of three sides or four sides. It is formed by bonding.
　（内側フィルム）
　内側フィルム２１は、液体１１に接する側に配置されている。内側フィルム２１としては、液体１１中に内側フィルム２１の成分が溶け出さないフィルム、又は溶け出しにくいフィルムであれば特に制限されるものではない。内側フィルム２１としては、例えば、無添加のポリエチレンフィルム、無添加のポリプロピレンフィルム、無添加のポリイソブチレンフィルム等の無添加のポリオレフィンフィルムを挙げることができる。「無添加」とは、一般的にポリオレフィンフィルムに含まれているような各種の添加剤を含まないという意味である。そうした添加剤としては、フィルム製造時に好ましく作用する酸化防止剤、スリップ剤、アンチブロッキング剤等を挙げることができる。 (Inner film)
The inner film 21 is disposed on the side in contact with the liquid 11. The inner film 21 is not particularly limited as long as it is a film in which the components of the inner film 21 do not dissolve in the liquid 11 or a film that does not easily dissolve. Examples of the inner film 21 include additive-free polyolefin films such as additive-free polyethylene film, additive-free polypropylene film, and additive-free polyisobutylene film. “No additive” means that it does not contain various additives that are generally contained in polyolefin films. Examples of such additives include antioxidants, slip agents, antiblocking agents and the like that preferably act during film production.
　無添加のポリオレフィンフィルムを用いることにより、フィルムの成分が液体１１に溶け出すのを防ぐ又は抑制することができる。特に無添加ポリエチレンフィルムは、柔軟性を有し、コストの低減を図ることができる。なお、後述の実施例では、代表例として無添加のポリエチレンフィルムを使用している。 By using an additive-free polyolefin film, the film components can be prevented or suppressed from dissolving in the liquid 11. In particular, the additive-free polyethylene film has flexibility and can reduce costs. In the examples described later, an additive-free polyethylene film is used as a representative example.
　内側フィルム２１は、単層であっても、２層以上のフィルムを積層したものであってもよい。２層以上のフィルムを積層した内側フィルム２１は、液体１１に接触する側に設けられた層が、上記した無添加のポリオレフィン層であることが好ましい。それ以外の層は特に限定されないが、外側フィルム２０側の層は外側フィルム２０との間で接合できる層であることが好ましく、具体的には、ヒートシール可能なポリオレフィン層であることが好ましい。また、ガスバリア性を有するバリア層が設けられていてもよい。バリア層については、後述する外側フィルムの項で説明するものを用いることができる。 The inner film 21 may be a single layer or a laminate of two or more layers. In the inner film 21 in which two or more films are laminated, the layer provided on the side in contact with the liquid 11 is preferably the above-described additive-free polyolefin layer. The other layers are not particularly limited, but the layer on the outer film 20 side is preferably a layer that can be bonded to the outer film 20, and specifically, a heat-sealable polyolefin layer is preferable. Further, a barrier layer having gas barrier properties may be provided. About a barrier layer, what is demonstrated by the term of the outer film mentioned later can be used.
　内側フィルム２１の厚さは特に限定されないが、通常、１０μｍ以上１２０μｍ以下の範囲内であり、３０μｍ以上１００μｍ以下の範囲内であることが好ましい。こうした内側フィルム２１は、インフレーション法等の通常のフィルム形成手段によって形成することができる。 The thickness of the inner film 21 is not particularly limited, but is usually in the range of 10 μm to 120 μm, and preferably in the range of 30 μm to 100 μm. Such an inner film 21 can be formed by a normal film forming means such as an inflation method.
　（外側フィルム）
　外側フィルム２０は、外装容器５に接する側に配置されている。外側フィルム２０は、耐屈曲性フィルムであり、水分量０．５質量％以下である。こうした特徴を有するものであれば、外側フィルム２０は特に制限されるものではない。特に好ましい外側フィルム２０としては、例えば、ポリブチレンテレフタレートフィルムを挙げることができる。このように、外側フィルム２０がポリブチレンテレフタレートフィルムである場合には、露点温度を容易に－５０℃以下にすることができ、充填する液体１１に対する水分の影響を極力抑えることができる。また、屈曲試験でのピンホールの発生を抑制でき、高い耐屈曲性を示すことができる。 (Outer film)
The outer film 20 is disposed on the side in contact with the outer container 5. The outer film 20 is a bend resistant film and has a moisture content of 0.5% by mass or less. The outer film 20 is not particularly limited as long as it has such characteristics. As a particularly preferable outer film 20, for example, a polybutylene terephthalate film can be exemplified. Thus, when the outer film 20 is a polybutylene terephthalate film, the dew point temperature can be easily reduced to −50 ° C. or less, and the influence of moisture on the liquid 11 to be filled can be suppressed as much as possible. Moreover, generation | occurrence | production of the pinhole in a bending test can be suppressed and high bending resistance can be shown.
　また、外側フィルムとしては、ポリエチレンフィルムを用いることもできる。外側フィルムに用いられるポリエチレンフィルムとしては、例えば、宇部丸善ポリエチレン株式会社製　ポリエチレンフィルム　１２５ＦＮ、日本ポリエチレン株式会社製　ポリエチレンフィルム　カーネルＫＦ２７３を挙げることができる。 Also, a polyethylene film can be used as the outer film. Examples of the polyethylene film used for the outer film include a polyethylene film 125FN manufactured by Ube Maruzen Polyethylene Co., Ltd. and a polyethylene film Kernel KF273 manufactured by Nippon Polyethylene Co., Ltd.
　外側フィルム２０の水分量は、０．５質量％以下であり、好ましくは０．２質量％以下である。この範囲内の水分量を有する外側フィルム２０は、露点温度を容易に－５０℃以下にすることができる。露点温度が－５０℃以下になると、外側フィルム２０の水分量は、３８ｐｐｍ以下になり、水分量が著しく減少する。特に露点温度が－６０℃になると、水分量は１１ｐｐｍになり、水分量が僅かになる。なお、水分量の下限は特に限定されないが、０．００５質量％程度である。水分量の測定は、例えば、カールフィッシャー法、乾燥法、赤外線吸収法、誘電率法等により測定することができる。 The moisture content of the outer film 20 is 0.5% by mass or less, preferably 0.2% by mass or less. The outer film 20 having a moisture content within this range can easily have a dew point temperature of −50 ° C. or lower. When the dew point temperature is −50 ° C. or lower, the moisture content of the outer film 20 becomes 38 ppm or less, and the moisture content is remarkably reduced. In particular, when the dew point temperature is −60 ° C., the water content becomes 11 ppm and the water content becomes slight. The lower limit of the moisture content is not particularly limited, but is about 0.005% by mass. The moisture content can be measured by, for example, the Karl Fischer method, the drying method, the infrared absorption method, the dielectric constant method, or the like.
　外側フィルム２０は耐屈曲性が良い。外側フィルム２０の耐屈曲性は、ゲルボフレックス試験（耐久性試験）によって確認することができる。具体的には、室温（２３℃±２℃程度）で、Ａ４サイズ（２１０ｍｍ×２９７ｍｍ）のフィルムを１０００回屈曲させた際に生じるピンホールを着色液で可視化し、ピンホール数を計測することにより確認することができる。ピンホール数が１５個以下である場合は、耐屈曲性に優れているということができる。ピンホール数は、好ましくは１０個以下であり、より好ましくは５個以下である。 The outer film 20 has good bending resistance. The bending resistance of the outer film 20 can be confirmed by a gelbo flex test (durability test). Specifically, pinholes generated when a film of A4 size (210 mm × 297 mm) is bent 1000 times at room temperature (about 23 ° C. ± 2 ° C.) are visualized with a colored liquid, and the number of pin holes is measured. Can be confirmed. When the number of pinholes is 15 or less, it can be said that the bending resistance is excellent. The number of pinholes is preferably 10 or less, more preferably 5 or less.
　外側フィルム２０は、少なくとも、耐屈曲性が良く、水分量０．５質量％以下であり、この外側フィルム２０が外装容器５側の層（外層）２０ｂとして配置されていれば、それ以外の層構成は特に限定されない。例えば、内側フィルム２１の側の層（内層）２０ａとして、内側フィルム２１に対して接合可能な層を設けてもよいし、ガスバリア性のバリア層を設けてもよいし、それらを積層して設けてもよい。接合は、ヒートシール等で好ましく行うことができるので、ヒートシール可能なポリオレフィン層を外側フィルム２０の内側の層（内層）２０ａとして設けることが好ましい。特に、内側フィルム２１と同じ無添加のポリオレフィンフィルムを好ましく適用することができる。 The outer film 20 is at least flexible and has a moisture content of 0.5% by mass or less. If this outer film 20 is arranged as a layer (outer layer) 20b on the outer container 5 side, the other layers The configuration is not particularly limited. For example, as the layer (inner layer) 20a on the inner film 21 side, a layer that can be bonded to the inner film 21 may be provided, or a gas barrier layer may be provided, or they may be laminated. May be. Since joining can be preferably performed by heat sealing or the like, it is preferable to provide a heat-sealable polyolefin layer as the inner layer (inner layer) 20a of the outer film 20. In particular, the same additive-free polyolefin film as that of the inner film 21 can be preferably applied.
　外側フィルムが、バリア層をさらに有する積層フィルムである場合、バリア層の材料としては、外側フィルムに所望のガスバリア性を付与することが可能なものであれば特に限定されず、例えば、シリカの蒸着膜、アルミナの蒸着膜、シリカとアルミナの二元蒸着膜、アルミニウムの蒸着膜、アルミニウム箔などを挙げることができる。好ましくは、シリカの蒸着膜、アルミナの蒸着膜、シリカとアルミナの二元蒸着膜であり、より好ましくはシリカの蒸着膜である。シリカの蒸着膜を用いた場合は、液体充填バッグに含有される金属イオンを少なくすることができることから、例えば金属イオンの影響を受けやすい液体等に好適に用いることが可能な液体充填バッグとすることができる。 When the outer film is a laminated film further having a barrier layer, the material of the barrier layer is not particularly limited as long as it can impart a desired gas barrier property to the outer film, for example, vapor deposition of silica. Examples thereof include a film, a vapor deposition film of alumina, a binary vapor deposition film of silica and alumina, a vapor deposition film of aluminum, and an aluminum foil. Preferred are a vapor deposition film of silica, a vapor deposition film of alumina, and a binary vapor deposition film of silica and alumina, and a vapor deposition film of silica is more preferred. When a vapor deposition film of silica is used, the metal ions contained in the liquid-filled bag can be reduced. For example, a liquid-filled bag that can be suitably used for a liquid that is easily affected by metal ions. be able to.
　バリア層の厚さとしては、特に限定されず、本発明の液体充填バッグの用途に応じて適宜選択することができる。
　バリア層の形成方法としては、一般的なフィルムのバリア層の形成方法と同様とすることができ、例えば、真空蒸着法等を挙げることができる。 It does not specifically limit as thickness of a barrier layer, According to the use of the liquid filling bag of this invention, it can select suitably.
The method for forming the barrier layer can be the same as the method for forming a barrier layer of a general film, and examples thereof include a vacuum deposition method.
　外側フィルムがバリア層をさらに有する積層フィルムである場合、上記外層、バリア層および内層（ポリオレフィン層）の積層フィルムであることが好ましい。内側フィルムと外側フィルムとヒートシール等で接合しやすくすることができるからである。また、上記外層、バリア層および内層の積層フィルムとすることにより、耐ピンホール性をより高くすることができるからである。 When the outer film is a laminated film further having a barrier layer, the outer film, the barrier layer and the inner layer (polyolefin layer) are preferably laminated films. This is because the inner film and the outer film can be easily joined by heat sealing or the like. Moreover, it is because pinhole-proof property can be made higher by setting it as the laminated | multilayer film of the said outer layer, a barrier layer, and an inner layer.
　外側フィルム２０の厚さは特に限定されないが、通常、１０μｍ以上１２０μｍ以下の範囲内であり、３０μｍ以上８０μｍ以下の範囲内であることが好ましく、６０μｍ以上８０μｍ以下の範囲内であることが好ましい。外側フィルムの厚さを上記範囲内とすることにより、外側フィルムの耐ピンホール性、耐久性、ハンドリング性を良好なものとすることができるからである。こうした外側フィルム２０は、インフレーション法等の通常のフィルム形成手段によって形成することができる。また、内層２０ａを設けた外側フィルム２０は、Ｔダイ押出成形法等の通常のフィルム形成手段によって形成することができる。 The thickness of the outer film 20 is not particularly limited, but is usually in the range of 10 μm to 120 μm, preferably in the range of 30 μm to 80 μm, and preferably in the range of 60 μm to 80 μm. This is because, by setting the thickness of the outer film within the above range, the pinhole resistance, durability, and handling properties of the outer film can be improved. Such an outer film 20 can be formed by a normal film forming means such as an inflation method. The outer film 20 provided with the inner layer 20a can be formed by a normal film forming means such as a T-die extrusion method.
　（バリアフィルム）
　本態様においては、内側フィルムと外側フィルムとの間に、バリア層を有するバリアフィルムをさらに有していてもよい。この場合、内側フィルムとバリアフィルムと外側フィルムとを重ね合わせた多重フィルムが液体充填バッグに用いられる。バリアフィルムとしては、通常、基材となる基材フィルムと基材フィルム上に形成されたバリア層とを有する。基材フィルムとしては、バリア層を支持することができれば特に限定されないが、例えば、内側フィルムとヒートシール可能なフィルムであることが好ましく、より具体的にはポリオレフィンフィルムであることが好ましい。また、バリアフィルムとしては、ポリオレフィン層、バリア層およびポリオレフィン層の積層フィルムであることも好ましい。内側フィルムとバリアフィルムと外側フィルムとヒートシール等で接合しやすくすることができるからである。また、バリアフィルムがポリオレフィン層、バリア層およびポリオレフィン層の積層フィルムである場合は、耐ピンホール性を高くすることができるからである。なお、バリア層については、上述した内容と同様とすることができる。 (Barrier film)
In this aspect, you may further have the barrier film which has a barrier layer between an inner film and an outer film. In this case, a multiple film in which the inner film, the barrier film, and the outer film are superposed is used for the liquid-filled bag. As a barrier film, it usually has a base film as a base and a barrier layer formed on the base film. The substrate film is not particularly limited as long as it can support the barrier layer. For example, a film that can be heat-sealed with the inner film is preferable, and more specifically, a polyolefin film is preferable. The barrier film is also preferably a laminated film of a polyolefin layer, a barrier layer and a polyolefin layer. This is because the inner film, the barrier film, the outer film, and the heat sealing can be easily joined. Further, when the barrier film is a polyolefin film, a laminated film of a barrier layer and a polyolefin layer, pinhole resistance can be increased. The barrier layer can be the same as described above.
　（液体充填バッグの形成）
　液体充填バッグ１は、内側フィルム２１と外側フィルム２０とを重ね合わせて多重フィルム２を構成し、重ね合わせた多重フィルム２で形成することができる。その形成は、具体的には、内側フィルム２１が液体１１側になるように、多重フィルム２を向かい合わせ、向かい合った内側フィルム２１、２１同士を貼り合わせて行うことができる。貼り合わせは、通常、ヒートシールによって行うことが好ましいが、それに限定されない。 (Formation of liquid-filled bag)
The liquid-filled bag 1 can be formed by superposing the inner film 21 and the outer film 20 to form the multi-film 2 and superimposing the multi-film 2 on each other. Specifically, the formation can be performed by bonding the multiple films 2 so that the inner film 21 is on the liquid 11 side, and bonding the facing inner films 21, 21 together. Bonding is usually preferably performed by heat sealing, but is not limited thereto.
　液体充填バッグ１の形状は、例えば、袋状、箱状、筒状等を挙げることができる。袋状、特に二重袋型の液体充填バッグ１は、例えば、２枚の多重フィルム２、２を重ね合わせてその周縁を接合することによって形成できる。より具体的には、内側フィルム２１と外側フィルム２０との周縁のみが接合された多重フィルム２同士を、該多重フィルム２の内側フィルム２１が接するように重ね合わせて、さらに周縁で接合することによって形成できる。また、内側フィルム２１と外側フィルム２０とを接合しないでそれらを単に重ね合わせた多重フィルム２同士を、該多重フィルム２の内側フィルム２１が接するように重ね合わせて周縁で接合することによって形成できる。 Examples of the shape of the liquid filling bag 1 include a bag shape, a box shape, and a cylindrical shape. The bag-like, particularly double-bag-type liquid-filled bag 1 can be formed, for example, by superposing two multiplex films 2 and 2 and joining the peripheral edges thereof. More specifically, by overlapping the multiple films 2 in which only the peripheral edges of the inner film 21 and the outer film 20 are bonded to each other so that the inner film 21 of the multiple film 2 is in contact, and further bonding at the peripheral edge Can be formed. Alternatively, the inner film 21 and the outer film 20 can be formed by joining the multiple films 2 obtained by simply superimposing the inner films 21 and the outer film 20 so that the inner films 21 of the multiple films 2 are in contact with each other.
　上記周縁の接合は、例えばヒートシールによって貼り合わせて行ってもよい。貼り合わせは、図１に示すように、多重フィルム２の四辺をヒートシールしてもよいし、折り返した多重フィルム２を重ね合わせた場合には３辺をヒートシールしてもよい。なお、ヒートシールした部分の内縁角部は、その内縁が弧状になるように形成してもよい。これによって、角部に流動性収容物が残りにくい構造となる。 The bonding of the peripheral edge may be performed by bonding by, for example, heat sealing. As shown in FIG. 1, the four sides of the multiple film 2 may be heat sealed, or when the folded multiple films 2 are overlapped, the three sides may be heat sealed. In addition, you may form the inner edge corner | angular part of the heat-sealed part so that the inner edge may become arc shape. Thereby, it becomes a structure where a fluid accommodation thing hardly remains in a corner | angular part.
　上述のように、液体充填バッグ１が、内側フィルム２１と外側フィルム２０との周縁が接合された二重袋型バッグである場合には、外側フィルム２０が水分量０．５質量％以下であるので、露点温度を容易に－５０℃以下にすることができ、充填する液体１１に対する水分の影響を極力抑えることができる。また、外側フィルム２０に含まれる水分が内側フィルム２１の方に移行したとしても、内側フィルム２１によって該水分の液体１１への移行を抑制することができる。したがって、二重袋型バッグである液体充填バッグ１は、充填する液体１１に対する水分の影響を極力抑えることができる。さらに、二重袋型バッグは、耐久性のよい液体充填バッグ１を提供することができる。なお、内側フィルム２１と外側フィルム２０との周縁の接合は、内側フィルム２１と外側フィルム２０の向かい合う側に例えばヒートシール層を設けることによって容易に行うことができる。 As described above, when the liquid-filled bag 1 is a double bag type bag in which the peripheral edges of the inner film 21 and the outer film 20 are joined, the outer film 20 has a water content of 0.5% by mass or less. Therefore, the dew point temperature can be easily set to −50 ° C. or lower, and the influence of moisture on the liquid 11 to be filled can be suppressed as much as possible. Moreover, even if the moisture contained in the outer film 20 moves toward the inner film 21, the inner film 21 can suppress the moisture from being transferred to the liquid 11. Therefore, the liquid filling bag 1 which is a double bag type bag can suppress the influence of moisture on the liquid 11 to be filled as much as possible. Furthermore, the double bag type bag can provide the liquid-filled bag 1 with good durability. In addition, joining of the periphery of the inner side film 21 and the outer side film 20 can be easily performed by providing a heat seal layer in the side which the inner side film 21 and the outer side film 20 face, for example.
　液体充填バッグ１の製造方法は、上記したヒートシール法に限定されるものではなく、共押出法、ラミネート法等の方法を用いてもよい。このようにして液体充填バッグ１を製造することにより、多重フィルム２の内側フィルム２１によって液体１１が充填される内袋２１（内袋は内側フィルム２１によって構成されているため同じ符号「２１」を付している。）が形成され、多重フィルム２の外側フィルム２０によって内袋を収容する外袋２０（外袋は外側フィルム２０によって構成されているため同じ符号「２０」を付している。）が形成される。 The method for manufacturing the liquid-filled bag 1 is not limited to the heat sealing method described above, and a method such as a coextrusion method or a lamination method may be used. By manufacturing the liquid-filled bag 1 in this way, the inner bag 21 filled with the liquid 11 by the inner film 21 of the multiple film 2 (the same symbol “21” is used because the inner bag is constituted by the inner film 21). And an outer bag 20 that accommodates the inner bag by the outer film 20 of the multiplex film 2 (the outer bag is constituted by the outer film 20 and therefore has the same reference numeral “20”). ) Is formed.
　多重フィルム２は、内側フィルム２１と外側フィルム２０とを含む２層又はそれ以上のフィルムを含むものであれば特に制限されるものではない。例えば、内側フィルム２１に外側フィルム２０を重ね合わせて積層したフィルムであってもよい。また、内側フィルム２１と外側フィルム２０との間に、又は、外側フィルム２０の外側に、又はこれらの組み合わせにおいて、別の層のフィルムが設けられていてもよい。 The multiple film 2 is not particularly limited as long as it includes two or more films including the inner film 21 and the outer film 20. For example, the film which laminated | stacked the outer film 20 on the inner film 21 may be sufficient. Moreover, the film of another layer may be provided between the inner film 21 and the outer film 20, or the outer side of the outer film 20, or these combinations.
　（液体）
　液体１１は、液体充填バッグ１に充填させるものであり、特に限定されないが、例えば、リチウムイオン電池用電解液、ポリ乳酸等が好ましい。これらの液体は、水分により加水分解される溶液（但し、有機溶媒を除く。）である。他にも、半導体製造工程で用いられるレジスト除去用液体、エッチング用液体又は他の化学液体等を挙げることができる。その他、リードフレーム製造工程で用いられるレジスト除去液体、エッチング液、サスペンション基板製造工程で用いられるレジスト除去用液体又はエッチング液、印刷工程で用いられる印刷用インキ、高純度液体又は液体医薬品等を挙げることもできる。 (liquid)
The liquid 11 is filled in the liquid filling bag 1 and is not particularly limited. For example, an electrolyte for lithium ion batteries, polylactic acid, and the like are preferable. These liquids are solutions (excluding organic solvents) that are hydrolyzed by moisture. In addition, a resist removal liquid, an etching liquid, or other chemical liquid used in the semiconductor manufacturing process can be used. Other examples include resist removal liquid and etching liquid used in the lead frame manufacturing process, resist removal liquid or etching liquid used in the suspension board manufacturing process, printing ink used in the printing process, high-purity liquid or liquid medicine, etc. You can also.
　リチウムイオン電池用電解液としては、リチウム塩であるＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２等が溶解されている有機電解液を挙げることができる。なお、リチウムイオン電池用電解液等のいくつかの液体は、水分だけでなく、ハロゲンや金属イオン等も悪影響を及ぼすため、これらの液体を内袋に充填する場合には、水分、ハロゲン、金属イオン等の含有量が低い内側フィルム２１を用いることが好ましい。 As an electrolytic solution for a lithium ion battery, an organic electrolytic solution in which LiPF 6 , LiClO 4 , LiBF 4 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2, etc., which are lithium salts, are dissolved. Can be mentioned. In addition, some liquids such as electrolytes for lithium ion batteries have an adverse effect on not only moisture but also halogen and metal ions. Therefore, when filling these liquids in the inner bag, moisture, halogen, and metal It is preferable to use the inner film 21 having a low content of ions or the like.
　２．第２態様
　本態様に係る液体充填バッグは、外装容器内に収容した後に液体を充填して使用するための液体充填バッグであって、フィルムで袋状に形成され、前記フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする。 2. 2nd aspect The liquid filling bag which concerns on this aspect is a liquid filling bag for filling and using a liquid after accommodating in an exterior container, Comprising: It forms in a bag shape with a film, The said film is bending resistance It is a film and has a water content of 0.5% by mass or less.
　この液体充填バッグは、フィルムが水分量０．５質量％以下であるので、露点温度を容易に－５０℃以下にすることができ、充填する液体に対する水分の影響を極力抑えることができる。その結果、この液体充填バッグを例えばリチウムイオン電池用電解液のバッグとして用いた場合に、水分の存在により電解液が加水分解して電池特性が低下するのを抑制することができる。 In this liquid-filled bag, since the film has a moisture content of 0.5% by mass or less, the dew point temperature can be easily reduced to −50 ° C. or less, and the influence of moisture on the liquid to be filled can be suppressed as much as possible. As a result, when this liquid-filled bag is used as, for example, a bag for an electrolyte solution for a lithium ion battery, it is possible to suppress degradation of the battery characteristics due to hydrolysis of the electrolyte solution due to the presence of moisture.
　フィルムとしては、上述した第１態様における外側フィルムに用いられるフィルムを用いることができる。また、本態様においては、フィルムとして、所定の水分量のフィルムを外装容器側の層（外層）とし、液体側に無添加のポリオレフィン層（内層）が積層された積層フィルムを用いることが好ましい。内層が無添加のポリオレフィン層であることにより、フィルムの成分が液体に溶け出すのを防ぐ又は抑制することができるからである。また、ヒートシール等を用いて、液体充填バッグを容易に製造することができるからである。また、フィルムとしては、上記外層および上記内層の間にバリア層を有する積層フィルムを用いてもよい。なお、バリア層については、上述した内容と同様とすることができる。 As the film, the film used for the outer film in the first aspect described above can be used. In this embodiment, it is preferable to use a laminated film in which a film having a predetermined moisture content is used as a layer (outer layer) on the outer container side and an additive-free polyolefin layer (inner layer) is laminated on the liquid side. It is because it can prevent or suppress that the component of a film melt | dissolves in a liquid because an inner layer is an additive-free polyolefin layer. Moreover, it is because a liquid filling bag can be manufactured easily using heat sealing etc. Further, as the film, a laminated film having a barrier layer between the outer layer and the inner layer may be used. The barrier layer can be the same as described above.
　液体充填バッグの形成、液体については、上述した「１．第１態様」の項で説明した内容と同様とすることができるため、ここでの説明は省略する。 The formation of the liquid-filled bag and the liquid can be the same as the contents described in the section “1. First aspect” described above, and thus the description thereof is omitted here.
　［容器］
　本発明に係る容器３０は、図３及び図４に示すように、開口部２２を有する外装容器５と、その外装容器５内に収容されるとともに開口部２２に対応した注出口４を備える液体充填バッグ１とを有する。この容器３０は、液体充填バッグ１が、外装容器５内に収容した後に液体１１を充填して用いられている。その液体充填バッグ１は、上記した液体充填バッグ１と同じであり、液体１１に接する側の内側フィルム２１と、外装容器５に接する側の外側フィルム２０とを有する多重フィルム２で袋状に形成されており、その外側フィルム２０が、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする。 [container]
As shown in FIGS. 3 and 4, the container 30 according to the present invention is a liquid including an outer container 5 having an opening 22 and a spout 4 accommodated in the outer container 5 and corresponding to the opening 22. A filling bag 1; The container 30 is used by filling the liquid 11 after the liquid filling bag 1 is accommodated in the outer container 5. The liquid-filled bag 1 is the same as the liquid-filled bag 1 described above, and is formed into a bag shape with a multiple film 2 having an inner film 21 on the side in contact with the liquid 11 and an outer film 20 on the side in contact with the outer container 5. The outer film 20 is a flexible film and has a water content of 0.5% by mass or less.
　この容器３０を構成する液体充填バッグ１は、上記したものと同様であり、その効果も同様である。なお、この容器３０は、図４に示すように、外装容器５内に収容される液体充填バッグ１を、外装容器５と液体充填バッグ１との間（空間部２３）に気体注入用ノズル７を介して送り込んだ気体７ａにより圧縮することができるので、その気体７ａを液体１１に直接触れさせることなく、液体充填バッグ１内の液体１１をノズル先端２４と注出用ノズル６を通って注出口４から注出することができる。 The liquid filling bag 1 constituting the container 30 is the same as that described above, and the effect thereof is also the same. As shown in FIG. 4, the container 30 is configured such that the liquid filling bag 1 accommodated in the outer container 5 is inserted between the outer container 5 and the liquid filling bag 1 (space portion 23). Therefore, the liquid 11 in the liquid filling bag 1 is poured through the nozzle tip 24 and the dispensing nozzle 6 without directly contacting the liquid 7 with the gas 7a. It can be poured out from the outlet 4.
　容器３０の概略について図３を用いて説明する。 The outline of the container 30 will be described with reference to FIG.
　容器３０は、外装容器５と、液体充填バッグ１と、蓋部８とを備えている。外装容器５は、金属製の缶（キャニスター）でもよいし、樹脂製の缶でもよい。金属製の缶は、例えば、ステンレス材料によって構成されていることが好ましい。液体充填バッグ１は、外装容器５内に収容される袋状の容器である。蓋部８は、外装容器５を密閉するためのものである。液体充填バッグ１は、内袋２１と、外袋２０と、蓋部８と、注出用ノズル６とを備える。 The container 30 includes an outer container 5, a liquid filling bag 1, and a lid portion 8. The outer container 5 may be a metal can (canister) or a resin can. The metal can is preferably made of, for example, a stainless material. The liquid filling bag 1 is a bag-like container accommodated in the outer container 5. The lid 8 is for sealing the outer container 5. The liquid filling bag 1 includes an inner bag 21, an outer bag 20, a lid portion 8, and a dispensing nozzle 6.
　内袋２１は、液体１１を充填し、上記した内側フィルム２１によって形成される。外袋２０は、内袋２１を収容し、上記した外側フィルム２０によって形成される。液体充填バッグ１の袋本体３は、内袋２１と外袋２０を一体にしてシールし、上縁３ａ、下縁３ｂ及び側縁３ｃに上縁ヒートシール部１０ａ、底縁ヒートシール部１０ｂ及び側縁ヒートシール部１０ｃをそれぞれ形成することにより製造できる。 The inner bag 21 is filled with the liquid 11 and formed by the inner film 21 described above. The outer bag 20 accommodates the inner bag 21 and is formed by the outer film 20 described above. The bag body 3 of the liquid filling bag 1 seals the inner bag 21 and the outer bag 20 together, and the upper edge 3a, the lower edge 3b, and the side edge 3c have an upper edge heat seal portion 10a, a bottom edge heat seal portion 10b, and It can manufacture by forming the side edge heat seal part 10c, respectively.
　蓋部８は、液体充填バッグ１と外装容器５の両方に接続するためのものである。蓋部８に接続する注出口４の注出口取付部４ａは、内袋２１と外袋２０との開口部２５に挿入され、内袋２１と外袋２０を一体にシールすることにより内袋２１に挟持されて固定される。注出用ノズル６は、内袋２１内の液体１１を外部に注出するための管である。注出用ノズル６は、蓋部８の孔部に挿入されている。 The lid portion 8 is for connecting to both the liquid filling bag 1 and the outer container 5. The spout attachment portion 4a of the spout 4 connected to the lid portion 8 is inserted into the opening 25 of the inner bag 21 and the outer bag 20, and the inner bag 21 and the outer bag 20 are integrally sealed to seal the inner bag 21. It is pinched and fixed. The dispensing nozzle 6 is a tube for dispensing the liquid 11 in the inner bag 21 to the outside. The dispensing nozzle 6 is inserted into the hole of the lid portion 8.
　蓋部８は、液体充填バッグ１の注出口の開閉を行うものである。開口部２２は、液体充填バッグ１の注出口４を着脱可能に接続できるように構成される。 The lid 8 opens and closes the spout of the liquid filling bag 1. The opening 22 is configured so that the spout 4 of the liquid filling bag 1 can be detachably connected.
　注出用ノズル６は、液体を注出するためのものである。注出用ノズル６は、注出口４の孔部に設けられる。気体注入用ノズル７は、外装容器５と液体充填バッグ１との間の空間部２３に気体７ａを注入するための通路である。気体注入用ノズル７に注入される気体７ａとしては、例えば、窒素、空気、酸素、二酸化炭素等を挙げることができる。気体注入用ノズル７は、外装容器５の上部にあるフランジ９に設けられている。 The dispensing nozzle 6 is for dispensing liquid. The dispensing nozzle 6 is provided in the hole of the dispensing port 4. The gas injection nozzle 7 is a passage for injecting the gas 7 a into the space 23 between the outer container 5 and the liquid filling bag 1. Examples of the gas 7a injected into the gas injection nozzle 7 include nitrogen, air, oxygen, carbon dioxide, and the like. The gas injection nozzle 7 is provided on the flange 9 at the top of the outer container 5.
　なお、注出口４の注出口係合部４ｂと蓋部８を接続して固定した場合には、注出口４の孔部と蓋部８の孔部が合わさり、注出口４と注出ノズル６が接続される。この場合、注出口４を介して、液体充填バッグ１内の液体を注出用ノズル６から注出することができる。 When the spout engaging portion 4b of the spout 4 and the lid 8 are connected and fixed, the hole of the spout 4 and the hole of the lid 8 are combined, and the spout 4 and the spout nozzle 6 are combined. Is connected. In this case, the liquid in the liquid filling bag 1 can be poured out from the pouring nozzle 6 through the pouring port 4.
　本実施形態では、注出口係合部４ｂと蓋部８を接続して、外装容器５内に収容した液体充填バッグ１を保持することとしているが、注出口係合部４ｂと蓋部８を一体型とし、外装容器５に設けられた開口部２２を通して、外装容器５内に液体充填バッグ１を収容して保持できるようにしてもよい。この場合、蓋部８は、外装容器５に接触している状態で固定され、液体充填バッグ１内を密閉にする。なお、蓋部８の外装容器５への固定は、例えば、ボルト等で行うことができる。 In the present embodiment, the spout engaging portion 4b and the lid portion 8 are connected to hold the liquid filling bag 1 accommodated in the outer container 5, but the spout engaging portion 4b and the lid portion 8 are connected to each other. The liquid filling bag 1 may be accommodated and held in the outer container 5 through the opening 22 provided in the outer container 5. In this case, the lid portion 8 is fixed in contact with the outer container 5 and hermetically seals the inside of the liquid filling bag 1. The lid 8 can be fixed to the outer container 5 with, for example, a bolt or the like.
　なお、注出用ノズル６を介した液体１１の注出は、図４に示すように、気体注入用ノズル７を介して、外装容器５と液体充填バッグ１との間の空間部２３に気体７ａを注入することにより行われる。すなわち、外装容器５と液体充填バッグ１との間の空間に気体７ａを注入することによって該空間が膨張され、これにより液体充填バッグ１が圧迫されて液体が抽出される。 As shown in FIG. 4, the liquid 11 is poured into the space 23 between the outer container 5 and the liquid filling bag 1 through the gas injection nozzle 7 as shown in FIG. This is done by injecting 7a. That is, by injecting the gas 7a into the space between the outer container 5 and the liquid filling bag 1, the space is inflated, whereby the liquid filling bag 1 is pressed and the liquid is extracted.
　一方、液体の注入は、注出口４と注出ノズル６を介して、液体充填バッグ１の内袋２１に液体を直接充填してもよいが、液体充填バッグ１が折畳まれている場合には、内袋２１の内部に窒素等の不活性ガスを注入して内袋２１と外袋２０を膨らませた後、液体を注入してもよい。 On the other hand, in the liquid injection, the inner bag 21 of the liquid filling bag 1 may be directly filled with the liquid via the pouring port 4 and the pouring nozzle 6, but when the liquid filling bag 1 is folded. May inject the liquid after injecting an inert gas such as nitrogen into the inner bag 21 to inflate the inner bag 21 and the outer bag 20.
　リチウムイオン電池用電解液等の液体を内袋２１に充填する場合には、リチウムイオン電池用電解液等の液体は、湿気に弱いため、液体充填バッグ１内の露点を適切に管理することが必要である。すなわち、露点温度を－５０℃～－７０℃程度まで低下させることにより、空気中に含まれる水分を低下させ、それから、内袋２１にリチウムイオン電池用電解液等の液体を充填することが望ましい。 When filling the inner bag 21 with a liquid such as an electrolyte for a lithium ion battery, the liquid such as an electrolyte for a lithium ion battery is vulnerable to moisture, so that the dew point in the liquid filled bag 1 can be appropriately managed. is necessary. That is, it is desirable to reduce the moisture contained in the air by lowering the dew point temperature to about −50 ° C. to −70 ° C., and then filling the inner bag 21 with a liquid such as an electrolyte for a lithium ion battery. .
　実験例によって本発明をさらに詳しく説明する。本発明は、以下の実験例で採用する材料等に限定されるものではない。なお、後述の各実験は、多重フィルムを構成する外側フィルムの種類を変えて袋の擬似評価を行ったものであり、袋の形態での評価結果を示すものではない。 The present invention will be described in more detail by experimental examples. The present invention is not limited to materials used in the following experimental examples. In addition, each below-mentioned experiment changed the kind of the outer film which comprises a multiplex film, performed the pseudo evaluation of the bag, and does not show the evaluation result in the form of a bag.
　［実験１］
　（各種フィルムの水分量）
　ナイロンフィルム（興人フィルム＆ケミカルズ株式会社製、商品名：ボニールＲＸ、厚さ：２５μｍ）、ポリエチレンテレフタレートフィルム（東レ株式会社製、商品名：Ｓ１０５、厚さ：２５μｍ）、及びポリブチレンテレフタレートフィルム（東洋紡株式会社製、商品名：タフネスポリエステル、厚さ：１２μｍ）、ポリエーテルイミドフィルム（信越ポリマー製、厚さ：２０μｍ）、ポリエチレンフィルム（宇部丸善ポリエチレン株式会社製、商品名：ポリエチレンフィルム　１２５ＦＮ、厚さ：８０μｍ）を準備した。これらの各フィルムを約４０ｍｍ×１０ｍｍに切断した。重さは０．１５ｇであった。
　各フィルムは、室温約２４℃、湿度約４５％の環境下で安定して保管されたものである。 [Experiment 1]
(Water content of various films)
Nylon film (manufactured by Kojin Film & Chemicals Co., Ltd., trade name: Bonyl RX, thickness: 25 μm), polyethylene terephthalate film (trade name: S105, thickness: 25 μm by Toray Industries, Inc.), and polybutylene terephthalate film ( Toyobo Co., Ltd., trade name: toughness polyester, thickness: 12 μm, polyetherimide film (Shin-Etsu polymer, thickness: 20 μm), polyethylene film (Ube Maruzen Polyethylene Co., Ltd., trade name: polyethylene film 125FN, thickness S: 80 μm) was prepared. Each of these films was cut into approximately 40 mm × 10 mm. The weight was 0.15 g.
Each film was stably stored in an environment of room temperature of about 24 ° C. and humidity of about 45%.
　各フィルムの水分量を、電量法用カールフィッシャー水分計（株式会社ダイアインスツルメンツ社製、製品名：微量水分計）を用いて水分量測定を行った。なお、使用溶媒としては、アクアミクロン（登録商標）ＡＸ／ＣＸＵ（株式会社三菱化学アナリテック製）を用い、測定は、２００℃の条件下で行った。その結果を表１に示した。 The moisture content of each film was measured using a coulometric Karl Fischer moisture meter (manufactured by Dia Instruments Co., Ltd., product name: trace moisture meter). In addition, Aquamicron (registered trademark) AX / CXU (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used as the solvent used, and the measurement was performed at 200 ° C. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、ナイロンフィルムは２．５質量％を超えているのに対して、ポリブチレンテレフタレートフィルムは、水分量の低いポリエチレンテレフタレートフィルムと同程度で、０．２０質量％であった。また、ポリエーテルイミドフィルム、ポリエチレンフィルムについても、水分量が０．５質量％以下となることが確認できた。 As shown in Table 1, the nylon film exceeded 2.5% by mass, whereas the polybutylene terephthalate film was the same as the polyethylene terephthalate film having a low water content, and was 0.20% by mass. . Moreover, it has confirmed that a moisture content became 0.5 mass% or less also about a polyetherimide film and a polyethylene film.
　［実験２］
　（各種フィルムの露点測定）
　露点計（ＶＡＩＳＡＬＡ社製）をロギングモードにセットし、ナイロンフィルム又はポリブチレンテレフタレートフィルムとともに真空チャンバー内に入れ、露点温度の測定を開始した。測定は、真空チャンバーの真空引きをＴ０～Ｔ１まで５分間実施し、その後、Ｔ２に至ったときに真空引きを止めて５分間放置することにより行った。また、比較対照実験として、フィルムを真空チャンバーに入れないで露点温度の測定を行った。結果を図５に示した。また、真空引き開始から１５分後での露点到達温度を表２に示す。 [Experiment 2]
(Dew point measurement of various films)
A dew point meter (manufactured by VAISALA) was set in the logging mode and placed in a vacuum chamber together with a nylon film or polybutylene terephthalate film, and measurement of the dew point temperature was started. The measurement was performed by evacuating the vacuum chamber from T0 to T1 for 5 minutes, and then stopping the evacuation when the temperature reached T2 and leaving it for 5 minutes. As a comparative control experiment, the dew point temperature was measured without placing the film in a vacuum chamber. The results are shown in FIG. Table 2 shows the dew point arrival temperature 15 minutes after the start of evacuation.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　図５に示すように、ナイロンフィルム（図５中のｂ）は、露点－５０℃への到達時間の増加が確認でき、真空引き終了後のナイロンフィルムからの脱水蒸気の懸念があることが示された。一方、ポリブチレンテレフタレートフィルム（図５中のａ）は、フィルム無し（図５中のｃ）の状態と同等の露点処理スピードであり、ナイロンフィルムと比べると露点処理に与える影響が極めて小さいことが示された。 As shown in FIG. 5, in the nylon film (b in FIG. 5), an increase in the time to reach the dew point of −50 ° C. can be confirmed, indicating that there is a concern of dewatering from the nylon film after evacuation. It was done. On the other hand, the polybutylene terephthalate film (a in FIG. 5) has the same dew point treatment speed as that of the state without film (c in FIG. 5), and the influence on the dew point treatment is extremely small compared to the nylon film. Indicated.
　［実験３］
　（耐屈曲性の評価）
　実験１で用いたナイロンフィルム、ポリエチレンテレフタレートフィルム、及びポリブチレンテレフタレートフィルム、ポリエチレンフィルムをそれぞれＡ４サイズ（２１０ｍｍ×２９７ｍｍ）にカットし、恒温槽付きゲルボフレックステスタ（テスター産業株式会社製）を用いて屈曲試験を行った。なお、屈曲試験は、２４℃で、局所的に屈曲を１０００回繰り返し行った。屈曲試験後、フィルムを取出して白い紙に張り付け、フィルムの上から着色液（三菱瓦斯化学株式会社製、商品名：エージレスシールチェック）を塗り付け、下の白い紙にシールチェックのインクが付いた箇所をピンホールとみなし、その数を計測した。計測は目視で行った。結果を表３に示した。
　また、ポリエチレンフィルム（日本ポリエチレン株式会社製、商品名：ポリエチレンフィルム　カーネルＫＦ２７３、厚さ　８０μｍ）についても同様の屈曲試験を行ない、計測を行なった。結果を表３に示す。 [Experiment 3]
(Evaluation of bending resistance)
The nylon film, polyethylene terephthalate film, polybutylene terephthalate film, and polyethylene film used in Experiment 1 were each cut into A4 size (210 mm x 297 mm), and a gelbo flex tester with a thermostatic bath (manufactured by Tester Sangyo Co., Ltd.) was used. A bending test was performed. In the bending test, bending was locally repeated 1000 times at 24 ° C. After the bending test, the film was taken out and pasted on white paper, and a colored liquid (Mitsubishi Gas Chemical Co., Ltd., trade name: Ageless Seal Check) was applied from the top of the film, and the seal check ink was applied to the white paper below. The locations were considered pinholes and the number was counted. The measurement was performed visually. The results are shown in Table 3.
Moreover, the same bending test was also performed on the polyethylene film (manufactured by Nippon Polyethylene Co., Ltd., trade name: polyethylene film kernel KF273, thickness 80 μm), and measurement was performed. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３に示すように、ポリエチレンテレフタレートフィルムは、ピンホール数が９０を超えているのに対し、ポリブチレンテレフタレートフィルムは、耐屈曲性に優れたナイロンフィルムと同程度で、ピンホールの数が５個以下で耐屈曲性に優れていることが示唆された。また、ポリエチレンフィルムについても、ポリエチレンテレフタレートフィルムに比べて、耐屈曲性が良好であることが示唆された。 As shown in Table 3, the polyethylene terephthalate film has more than 90 pinholes, whereas the polybutylene terephthalate film has the same degree of flexibility as a nylon film and has 5 pinholes. It was suggested that the resistance to bending is excellent at less than the number. In addition, it was suggested that the polyethylene film also has better bending resistance than the polyethylene terephthalate film.
　［実験４］
　［実験４－１］
　図６に示す装置４０を用いて、キャニスター缶内の露点温度の測定を行なった。装置４０は、エア（空気）を供給するエアコンプレッサ４１、エアを乾燥させてドライエア７ｄとする膜式ドライヤ４２、エアコンプレッサ４１および膜式ドライヤ４２を接続する接続部４３、ドライエア７ｄの注出口４４および排出口４５を有するキャニスター缶４６、キャニスター缶４６にドライエア７ｄを注入する注入用ノズル４７、排出口４５の近傍に配置された露点計４８を有する。また、上記装置においては、１９Ｌのキャニスター缶、ジャパンマシナリー製の膜式エアドライヤ、ＶＡＩＳＡＬＡ製ハンディタイプ露点計ＤＭ７０を用いた。 [Experiment 4]
[Experiment 4-1]
The dew point temperature in the canister can was measured using the apparatus 40 shown in FIG. The apparatus 40 includes an air compressor 41 that supplies air, a membrane dryer 42 that dries the air to dry air 7d, a connection portion 43 that connects the air compressor 41 and the membrane dryer 42, and a spout 44 of the dry air 7d. A canister 46 having a discharge port 45, an injection nozzle 47 for injecting dry air 7 d into the canister can 46, and a dew point meter 48 disposed in the vicinity of the discharge port 45. Moreover, in the said apparatus, 19L canister can, the membrane type air dryer made from Japan Machinery, and the handy type dew point meter DM70 made from VAISALA were used.
　図６に示すように、キャニスター缶４６内に、フィルム５０を入れた。フィルムの量は、１９Ｌのキャニスター缶に対して３７４２ｍｍ３分の量とした。すなわち、缶容量に対するフィルム量は約１９７ｍｍ３／Ｌとした。その後、キャニスター缶の注排出口を開放し、膜式エアドライヤにより露点約－６０℃にしたドライエアを流量２５Ｌ／ｍｉｎ（０．２ＭＰａ）で供給し、キャニスター缶内の空気をドライエアで置換した。露点計で露点の変化および露点－５０℃の到達時間を計測した。また、キャニスター缶内にフィルムを入れない場合（Ｂｌａｎｋ）についても同様にして、露点計で露点の変化および露点－５０℃の到達時間を計測した。
　フィルムとしては、ナイロンフィルム（興人フィルム＆ケミカルズ株式会社製、商品名：ボニールＲＸ）、ポリブチレンテレフタレートフィルム（東洋紡株式会社製、商品名：タフネスポリエステル）、ポリエーテルイミドフィルム（信越ポリマー製）の各フィルムに対して測定した。結果を図７および表４に示す。 As shown in FIG. 6, the film 50 was placed in the canister 46. The amount of film was 3742 mm 3 minutes for a 19 L canister can. That is, the film amount with respect to the can capacity was about 197 mm 3 / L. Thereafter, the pouring and discharging port of the canister can was opened, dry air having a dew point of about −60 ° C. was supplied by a membrane air dryer at a flow rate of 25 L / min (0.2 MPa), and the air in the canister can was replaced with dry air. The dew point change and the arrival time at −50 ° C. were measured with a dew point meter. Similarly, when no film was placed in the canister can (Blank), the change in the dew point and the arrival time at −50 ° C. were measured with a dew point meter.
Examples of films include nylon films (manufactured by Kojin Film & Chemicals Co., Ltd., trade name: Bonil RX), polybutylene terephthalate films (trade name: tough polyester by Toyobo Co., Ltd.), and polyetherimide films (manufactured by Shin-Etsu Polymer). Measured for each film. The results are shown in FIG.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　［実験４－２］
　下記の条件以外については、実験４－１と同様にして露点の変化および露点－５０℃の到達時間を計測した。
　２００Ｌのキャニスター缶を用い、フィルムの量を、２００Ｌのキャニスター缶に対して、５８８６７ｍｍ３分の量とした。すなわち、缶容量に対するフィルム量を約２９４ｍｍ３／Ｌとした。
　フィルムとしては、実験１におけるナイロンフィルム、ポリブチレンテレフタレートフィルムの各フィルムに対して測定した。結果を図８および表５に示す。 [Experiment 4-2]
Except for the following conditions, the change in the dew point and the arrival time at −50 ° C. were measured in the same manner as in Experiment 4-1.
A 200 L canister can was used, and the amount of film was 58867 mm 3 minutes relative to a 200 L canister can. That is, the film amount with respect to the can capacity was set to about 294 mm 3 / L.
As a film, it measured with respect to each film of the nylon film in experiment 1, and a polybutylene terephthalate film. The results are shown in FIG.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　実験４－１に示すように、ポリブチレンテレフタレートフィルムおよびポリイミドフィルムについては、ナイロンフィルムに比べて露点－５０℃の到達時間が短いことが確認された。
　また、実験４－１および実験４－２に示すように、缶容量に対するフィルム量が約１９７ｍｍ３／Ｌである場合と、約２９４ｍｍ３／Ｌである場合とを比較した場合、空のキャニスター缶においてはそれぞれ１０分、４３分で露点－５０℃に到達し、フィルムの水分量が０．２５質量％であるポリブチレンテレフタレートフィルムにおいてはそれぞれ２０分、５６分で露点－５０℃に到達した。一方、フィルムの水分量が２．５質量％であるナイロンフィルムにおいては、缶容量に対するフィルム量が約１９７ｍｍ３／Ｌである場合は７５分で露点－５０℃に到達したが、缶容量に対するフィルム量が約２９４ｍｍ３／Ｌである場合は８時間経過後も露点－５０℃に到達しなかった。
　よって、缶容量に対するフィルム量を大きくした場合は、露点－５０℃に到達させるまでにかかる時間が長くなることが確認された。この際、フィルムの水分量が０．５質量％以下である場合は、缶容量に対するフィルム量を大きくした場合も露点－５０℃に到達するまでの時間ロスを少なくすることが可能となるのに対して、フィルムの水分量が０．５質量％よりも多い場合は、缶容量に対するフィルム量を大きくした場合に露点－５０℃に到達するまでの時間が顕著に長くなり、実際の液体充填バッグとして外装容器とともに用いた場合に、容器内を露点－５０℃に管理することが困難となることが示唆された。 As shown in Experiment 4-1, it was confirmed that the polybutylene terephthalate film and the polyimide film had a shorter dew point at −50 ° C. than the nylon film.
Further, as shown in Experiment 4-1 and Experiment 4-2, when compared with the case where the film weight with respect to the can capacity is about 197 mm 3 / L, and the case is about 294 mm 3 / L, empty canister cans The dew point reached −50 ° C. in 10 minutes and 43 minutes, respectively, and the dew point reached −50 ° C. in 20 minutes and 56 minutes in the polybutylene terephthalate film having a water content of 0.25% by mass, respectively. On the other hand, in the case of a nylon film having a moisture content of 2.5% by mass, the dew point reached −50 ° C. in 75 minutes when the film amount relative to the can capacity was about 197 mm 3 / L. When the amount was about 294 mm 3 / L, the dew point did not reach −50 ° C. even after 8 hours.
Therefore, it was confirmed that when the film amount with respect to the can capacity was increased, it took longer time to reach the dew point of −50 ° C. At this time, when the moisture content of the film is 0.5% by mass or less, it is possible to reduce the time loss until the dew point reaches −50 ° C. even when the film amount with respect to the can capacity is increased. On the other hand, when the moisture content of the film is more than 0.5% by mass, the time until the dew point reaches −50 ° C. becomes significantly longer when the amount of the film with respect to the can capacity is increased. It was suggested that it would be difficult to control the inside of the container at a dew point of −50 ° C. when used with an outer container.
　実験１～実験４から、ポリブチレンテレフタレートフィルムは、その水分量を０．５質量％以下とすることができ、屈曲性が良好であること、また上述した露点測定の結果から、液体充填バッグの外側フィルムとして好適に用いることができ、液体充填バッグに使用した場合に、容器内の水分量を露点－５０℃以下に良好に管理することが可能であることが示唆された。 From Experiment 1 to Experiment 4, the polybutylene terephthalate film has a water content of 0.5% by mass or less, has good flexibility, and the above dew point measurement results show that It was suggested that the film can be suitably used as an outer film, and when used in a liquid-filled bag, the water content in the container can be well managed at a dew point of -50 ° C. or lower.
　１　液体充填バッグ
　２　多重フィルム
　３　袋本体
　３ａ　上縁
　３ｂ　下縁
　３ｃ　側縁
　４　注出口
　４ａ　注出口取付部
　４ｂ　注出口係合部
　５　外装容器
　６　注出用ノズル
　７　気体注入用ノズル
　７ａ　気体
　８　蓋部
　９　フランジ
　１０　ヒートシール部
　１０ａ　上縁ヒートシール部
　１０ｂ　底縁ヒートシール部
　１０ｃ　側縁ヒートシール部
　１１　液体
　２０　外側フィルム（外袋）
　２０ａ　内層
　２０ｂ　外層
　２１　内側フィルム（内袋）
　２２　開口部
　２３　空間部
　２４　ノズル先端
　２５　開口部
　３０　容器 DESCRIPTION OF SYMBOLS 1 Liquid filling bag 2 Multiple film 3 Bag main body 3a Upper edge 3b Lower edge 3c Side edge 4 Outlet 4a Outlet attaching part 4b Outlet engaging part 5 Outer container 6 Outlet nozzle 7 Gas injection nozzle 7a Gas 8 Lid Part 9 Flange 10 Heat seal part 10a Upper edge heat seal part 10b Bottom edge heat seal part 10c Side edge heat seal part 11 Liquid 20 Outer film (outer bag)
20a inner layer 20b outer layer 21 inner film (inner bag)
22 Opening portion 23 Space portion 24 Nozzle tip 25 Opening portion 30 Container

Claims (13)

  1. 　外装容器内に収容した後に液体を充填して使用するための液体充填バッグであって、
    　前記液体に接する側の内側フィルムと、前記外装容器に接する側の外側フィルムとを有する多重フィルムで袋状に形成され、
    　前記外側フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする液体充填バッグ。     A liquid-filled bag for filling and using a liquid after being housed in an outer container,
    The inner film on the side in contact with the liquid and the outer film on the side in contact with the outer container are formed in a bag shape with a multiple film,
    The liquid filling bag, wherein the outer film is a flex-resistant film and has a water content of 0.5% by mass or less.
  2. 　前記外側フィルムがポリブチレンテレフタレートフィルムである、請求の範囲第１項に記載の液体充填バッグ。 The liquid-filled bag according to claim 1, wherein the outer film is a polybutylene terephthalate film.
  3. 　前記外側フィルムが、バリア層をさらに有する積層フィルムである、請求の範囲第１項または第２項に記載の液体充填バッグ。 The liquid-filled bag according to claim 1 or 2, wherein the outer film is a laminated film further having a barrier layer.
  4. 　前記内側フィルムと前記外側フィルムとの周縁が接合されている二重袋型バッグである、請求の範囲第１項から第３項までのいずれかに記載の液体充填バッグ。 The liquid-filled bag according to any one of claims 1 to 3, which is a double bag-type bag in which peripheral edges of the inner film and the outer film are joined.
  5. 　前記内側フィルムと前記外側フィルムとの間に、バリア層を有するバリアフィルムをさらに有する、請求の範囲第１項から第４項までのいずれかに記載の液体充填バック。 The liquid-filled bag according to any one of claims 1 to 4, further comprising a barrier film having a barrier layer between the inner film and the outer film.
  6. 　外装容器内に収容した後に液体を充填して使用するための液体充填バッグであって、
    　フィルムで袋状に形成され、
    　前記フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする液体充填バッグ。     A liquid-filled bag for filling and using a liquid after being housed in an outer container,
    Formed in a bag shape with film,
    The liquid-filled bag, wherein the film is a flex-resistant film and has a water content of 0.5% by mass or less.
  7. 　前記液体がリチウムイオン電池用電解液である、請求の範囲第１項から第６項までのいずれかに記載の液体充填バッグ。 The liquid-filled bag according to any one of claims 1 to 6, wherein the liquid is an electrolyte for a lithium ion battery.
  8. 　開口部を有する外装容器と、該外装容器内に収容されるとともに前記開口部に対応した注出口を備える液体充填バッグとを有する容器であって、
    　前記液体充填バッグが、前記外装容器内に収容した後に液体を充填して用いられ、前記液体に接する側の内側フィルムと、前記外装容器に接する側の外側フィルムとを有する多重フィルムで袋状に形成され、
    　前記外側フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする容器。     A container having an exterior container having an opening, and a liquid-filled bag that is accommodated in the exterior container and includes a spout corresponding to the opening,
    The liquid-filled bag is used after being filled in the outer container and filled with a liquid, and is formed into a bag shape with a multiple film having an inner film on the side in contact with the liquid and an outer film on the side in contact with the outer container Formed,
    The outer film is a flexible film and has a water content of 0.5% by mass or less.
  9. 　開口部を有する外装容器と、該外装容器内に収容されるとともに前記開口部に対応した注出口を備える液体充填バッグとを有する容器であって、
    　前記液体充填バッグが、フィルムで袋状に形成され、
    　前記フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする容器。     A container having an exterior container having an opening, and a liquid-filled bag that is accommodated in the exterior container and includes a spout corresponding to the opening,
    The liquid filling bag is formed into a bag shape with a film,
    The container is a flexible film and has a moisture content of 0.5% by mass or less.
  10. 　前記液体がリチウムイオン電池用電解液である、請求の範囲第８項または第９項に記載の容器。 The container according to claim 8 or 9, wherein the liquid is an electrolyte for a lithium ion battery.
  11. 　外装容器内に収容した後に液体を充填して使用するための液体充填バッグ用の多重フィルムであって、
    　前記液体に接する側の内側フィルムと、前記外装容器に接する側の外側フィルムとを有し、
    　前記外側フィルムが、耐屈曲性フィルムであり、水分量０．５質量％以下であることを特徴とする多重フィルム。     A multiplex film for a liquid-filled bag for filling and using a liquid after being housed in an outer container,
    An inner film on the side in contact with the liquid, and an outer film on the side in contact with the outer container,
    The outer film is a flexible film and has a moisture content of 0.5% by mass or less.
  12. 　前記外側フィルムがポリブチレンテレフタレートフィルムである、請求の範囲第１１項に記載の多重フィルム。 The multiple film according to claim 11, wherein the outer film is a polybutylene terephthalate film.
  13. 　前記液体がリチウムイオン電池用電解液である、請求の範囲第１１項または第１２項に記載の多重フィルム。 The multiple film according to claim 11 or 12, wherein the liquid is an electrolyte for a lithium ion battery.
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