Packaging material and packaging body for all-solid-state lithium-ion batteries

Abstract

To provide a sulfur-based gas absorption packaging material and a package for an all-solid lithium ion battery which are excellent in manufacturing suitability, and absorb sulfur-based gas generated from a sulfide-based inorganic solid electrolyte type all-solid lithium ion battery even with simple layer constitutions.SOLUTION: A sulfur-based gas absorption packaging material for a sulfide-based inorganic solid electrolyte type all-solid lithium ion battery absorbs sulfur-based gas, wherein the packaging material for the all-solid lithium ion battery contains at least a base material layer composed of a base material film, a gas barrier layer composed of a gas barrier film, and a sealant layer composed of a sulfur-based gas absorption sealant film, the sulfur-based gas absorption sealant film contains a sulfur-based gas absorbent and a heat-sealable resin, and a content of the sulfur-based gas absorbent in the layer containing the sulfur-based gas absorbent is 0.3 mass% or more and 30 mass% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a packaging material having sulfur-based gas absorbency for packaging a sulfide-based inorganic solid electrolyte type all-solid-state lithium ion battery, which absorbs sulfur-based gas generated from the sulfide-based inorganic solid electrolyte type all-solid-state lithium ion battery, and a package obtained by packaging a sulfide-based inorganic solid electrolyte type all-solid-state lithium ion battery with the packaging material. The packaging material for sulfide-based inorganic solid electrolyte type all-solid-state lithium ion batteries of the present invention can be applied to all-solid-state lithium ion battery products in various fields, and can be particularly suitably used as a packaging material for packaging large-capacity all-solid-state lithium ion batteries for home power storage systems, power sources for automobile electric motors, and the like. [Background technology]

[0002] Conventionally, packaging materials for lithium-ion batteries have been required to have improved sealing properties and water vapor barrier properties to prevent the intrusion of water vapor from the outside, chemical resistance to prevent electrolyte leakage, and heat resistance to prevent melting and electrolyte leakage when the lithium-ion battery generates heat (Patent Document 1). However, in recent years, when it is assumed that lithium-ion battery packages will be used for long periods of time, such as approximately 20 years, in automotive or home applications, there has been concern that in the case of all-solid-state lithium-ion batteries, sulfur-based gases generated by decomposition of the electrolyte during charging will accumulate, causing the lithium-ion battery package to expand or rupture. A resin film containing a flavonoid compound has been proposed as a method for removing sulfur-based gases (Patent Document 2). However, since the flavonoid compound has poor heat resistance, there are limitations on the heating conditions in the resin film manufacturing process, and the effect of removing sulfur-based gases is insufficient. Furthermore, resin films containing zeolite, copper-containing metal silicates, and antifogging agents made of glycerin esters have been proposed as resin films for removing sulfur-based gases (Patent Document 3). However, these films primarily focus on removing moisture and ethylene gas, and are insufficient in their effectiveness in removing sulfur-based gases. The adsorption and decomposition mechanism of sulfur-based gases (hydrogen sulfide) in metal silicates proceeds via an oxidation-reduction reaction. However, in a closed space such as a lithium battery packaging, the oxygen concentration (hydrogen concentration) is also limited, making the adsorption effect insufficient in terms of the durability of the adsorption effect, given the approximately 20-year lifespan required for lithium-ion batteries. The adsorption and decomposition mechanism of sulfur-based gases (hydrogen sulfide) in metal silicates proceeds via an oxidation-reduction reaction. However, in a closed space such as a lithium battery packaging, the oxygen concentration (hydrogen concentration) is also limited, making the adsorption effect insufficient in terms of the durability of the adsorption effect, given the approximately 20-year lifespan required for lithium-ion batteries. The adsorption and decomposition mechanism of sulfur-based gases (hydrogen sulfide) in metal silicates proceeds through an oxidation-reduction reaction, but in a closed space such as a lithium battery packaging, the oxygen concentration (hydrogen concentration) is also limited, and therefore the adsorption effect is insufficient in terms of sustainability, given the approximately 20-year lifespan required for lithium-ion batteries. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-38881 [Patent Document 2] Japanese Patent Application Publication No. 1-207339 [Patent Document 3] Japanese Patent Application Publication No. 2019-069817 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention addresses the above-mentioned problems and aims to provide a sulfur-based gas absorbing packaging material for all-solid-state lithium ion batteries that has excellent manufacturability and a simple layer structure, while absorbing sulfur-based gas generated from a sulfide-based inorganic solid electrolyte type all-solid-state lithium ion battery, and a sulfur-based gas-absorbing sulfide-based inorganic solid electrolyte type all-solid-state lithium ion battery package obtained by packaging an all-solid-state lithium ion battery with the sulfur-based gas absorbing packaging material. [Means for solving the problem]

[0005] As a result of various investigations, the present inventors have found that a sulfur-based gas absorbing packaging material for an all-solid-state lithium ion battery, which contains a thermoplastic resin and a specific sulfur-based gas absorbent, can achieve the above-mentioned object.

[0006] That is, the present invention is characterized by the following points. 1. A sulfur-based gas absorbing packaging material for a sulfide-based inorganic solid electrolyte type all-solid-state lithium ion battery, which absorbs sulfur-based gases, comprising: The packaging material for an all-solid-state lithium-ion battery includes at least a substrate layer made of a substrate film, a gas barrier layer made of a gas barrier film, and a sealant layer made of a sulfur-based gas absorbing sealant film, The sulfur-based gas absorbing sealant film contains a sulfur-based gas absorbent and a heat-sealable resin, the content of the sulfur-based gas absorbent in the layer containing the sulfur-based gas absorbent is 0.3% by mass or more and 30% by mass or less; Sulfur-based gas-absorbing packaging material. 2. The sulfur-based gas absorbent contains a sulfur-based gas chemical absorbent and / or a sulfur-based gas physical absorbent; 1. The sulfur-based gas-absorbing packaging material according to 1 above. 3. The sulfur-based gas absorbent has a maximum particle size of 20 μm or less and a number average particle size of 0.1 μm or more and 15 μm or less. 3. The sulfur-based gas-absorbing packaging material according to 1 or 2 above. 4. The sulfur-based gas chemical absorbent is a metal oxide and / or an inorganic material on which a metal or metal ion is supported or mixed. 4. The sulfur-based gas-absorbing packaging material according to 2 or 3 above. 5. The metal oxide contains one or more selected from the group consisting of CuO, ZnO, and AgO. 5. The sulfur-based gas-absorbing packaging material according to 4 above. 6. The metal species in the inorganic material in which the metal or metal ion is supported or mixed includes one or more selected from the group consisting of Ca, Mg, Na, Cu, Zn, Ag, Pt, Au, Fe, Al, and Ni; 6. The sulfur-based gas-absorbing packaging material according to 4 or 5 above. 7. The sulfur-based gas physical absorbent has an SiO2 / Al2O3 molar ratio of 1 / 1 to 2000 / 1. Contains one or more selected from the group consisting of hydrophobic zeolite, bentonite, and sepiolite, 7. A sulfur-based gas-absorbing packaging material according to any one of 2 to 6 above. 8. The base film contains a polyamide resin and / or a polyester resin. 8. A sulfur-based gas-absorbing packaging material according to any one of 1 to 7 above. 9. The gas barrier film is an aluminum foil. 9. A sulfur-based gas-absorbing packaging material according to any one of 1 to 8 above. 10. A sulfur-based gas-absorbing all-solid-state lithium-ion battery packaging body made from the sulfur-based gas-absorbing packaging material according to any one of 1 to 9 above. [Effects of the Invention]

[0007] The sulfur-based gas absorbing packaging material for all-solid-state lithium ion batteries of the present invention solves the above-mentioned problems, has excellent manufacturability, and has a simple layer structure, while having excellent absorbency and heat-sealability for the sulfur-based gas generated from sulfide-based inorganic solid electrolyte type all-solid-state lithium ion batteries, and can exert the effect of making peeling and swelling due to the sulfur-based gas generated from sulfide-based inorganic solid electrolyte type all-solid-state lithium ion batteries less likely to occur. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of a sulfur-based gas absorbing packaging material for an all-solid-state lithium-ion battery according to the present invention. [Figure 2] FIG. 1 is a schematic cross-sectional view showing another example of the layer structure of the sulfur-based gas absorbing packaging material for an all-solid-state lithium-ion battery of the present invention. [Figure 3] FIG. 1 is a schematic cross-sectional view showing another example of the layer structure of the sulfur-based gas absorbing packaging material for an all-solid-state lithium-ion battery according to the present invention.

[0009] In each drawing, the size and proportions of the components may be changed or exaggerated for ease of understanding. Also, for clarity, parts that are unnecessary for explanation or repeated reference numerals may be omitted. Although not shown in the drawings, an adhesive layer may be provided between the layers. Furthermore, if necessary, in order to strengthen the adhesive strength (adhesion strength) between each layer, the laminated surfaces of each layer may be subjected in advance to physical surface treatments such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, sandblasting treatment, etc., or chemical surface treatments such as oxidation treatment using chemicals. DETAILED DESCRIPTION OF THE INVENTION

[0010] The sulfur-based gas absorbing packaging material for a sulfide-based inorganic solid electrolyte type all-solid-state lithium ion battery of the present invention will be described in more detail below. Specific examples will be given, but the present invention is not limited thereto.

[0011] (gas to be absorbed) In the present invention, the gas to be absorbed is a sulfur-containing gas. In the present invention, the sulfur-based gases include hydrogen sulfide, dimethyl sulfide, methyl mercaptan, SO x Examples of sulfur oxides include sulfur oxides represented by the following formula:

[0012] <All-solid-state lithium-ion battery> A typical lithium-ion battery is composed of a positive electrode made of an oxide containing lithium, a negative electrode containing a carbon material, a separator, and an electrolyte. Here, the electrolyte can be liquid or solid, and all-solid-state lithium-ion batteries refer to those in which the electrolyte is solid. Furthermore, a typical lithium ion battery is a secondary battery that can be charged and discharged by the movement of lithium ions between a positive electrode and a negative electrode, and in the present invention, the lithium ion battery refers to such a secondary battery. Solid electrolytes include oxide-based and sulfide-based electrolytes, with sulfide-based electrolytes being preferred because they are capable of producing higher output. The sulfide-based solid electrolyte is a compound that easily reacts with moisture to generate sulfur-based gases. When an all-solid-state lithium-ion battery absorbs moisture, decomposition gas (sulfur-based gas) of the sulfide-based solid electrolyte containing sulfur-based gases is generated. The cumulative amount of sulfur-based gas generated in all-solid-state lithium-ion batteries for automotive and home energy storage systems, which are expected to be used for more than 20 years, is extremely large. The pouches used to package lithium-ion batteries contain sulfur-based gases, which can cause them to swell or tear, as well as corrode metal foil layers such as aluminum foil, so measures to prevent these problems are necessary.

[0013] <Sulfur gas absorbing packaging material> The sulfur-based gas absorbing packaging material for lithium ion batteries of the present invention is particularly suitable for use in sulfide-based inorganic solid electrolyte type all-solid-state lithium ion batteries, which generate a large amount of sulfur-based gas. The sulfur-based gas absorbing packaging material for lithium ion batteries of the present invention can absorb the above-mentioned sulfur-based gas generated from solid electrolyte type lithium ion batteries.

[0014] The sulfur-based gas absorbing packaging material for an all-solid-state lithium-ion battery of the present invention comprises at least a substrate layer made of a substrate film, a gas barrier layer made of a gas barrier film, and a sealant layer made of a sulfur-based gas absorbing sealant film, and the sulfur-based gas absorbing sealant film preferably contains a sulfur-based gas absorbent and a heat-sealable resin, and the sulfur-based gas absorbent preferably contains a chemical sulfur-based gas absorbent and / or a physical sulfur-based gas absorbent. The gas barrier layer is preferably laminated between the substrate layer and the sulfur-based gas absorbing layer. The sulfur-based gas absorbing packaging material may further include intermediate layers that perform various functions, if necessary. The layers constituting the sulfur-based gas absorbing packaging material may be laminated via an adhesive layer. The sulfur-based gas absorbing packaging material is a packaging material made from the sulfur-based gas absorbing laminate including the above-mentioned substrate layer, gas barrier layer, and sealant layer. One surface of the sulfur-based gas absorbing packaging material for an all-solid-state lithium ion battery preferably has heat-sealability, and therefore, it is preferable that the heat-sealable surface of the sulfur-based gas absorbing film be laminated so as to constitute one surface of the sulfur-based gas absorbing packaging material. The sulfur-based gas absorbing packaging material may further contain various plastic compounding agents and additives for the purpose of improving or modifying, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold releasability, flame retardancy, mildew resistance, electrical properties, strength, etc. The content of these compounds may be any amount ranging from a trace amount to several tens of percent depending on the purpose. In the above, examples of common additives that may be contained include antiblocking agents, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, modifying resins, and the like.

[0015] <Sealant layer> The sealant layer is a layer containing a sulfur-based gas absorbent and a heat-sealable resin, and has sulfur-based gas absorbency and heat-sealability. The sealant layer is preferably a layer made of a sulfur-based gas absorbing sealant film. The sulfur-based gas absorbing sealant film is a sulfur-based gas absorbing film having heat-sealing properties, and can be produced by incorporating a heat-sealing resin into the sulfur-based gas absorbing film or by laminating a layer containing a heat-sealing resin onto the sulfur-based gas absorbing film. The sealant layer can impart sulfur-based gas absorbency to the sulfur-based gas absorbent packaging material by containing a sulfur-based gas absorbent, and can impart heat-sealability to the sulfur-based gas absorbent packaging material by containing a heat-sealable resin. The outer surface of the sealant layer preferably contains a heat-sealable resin and thus has heat-sealability. Furthermore, the sealant layer may further include a layer derived from a material other than the sulfur-based gas absorbing sealant film, as necessary. For example, it may further include a support layer for reinforcing support. The sealant layer may be a single layer or may be a multi-layer consisting of two or more layers having the same or different compositions. For example, it may be a single layer containing a sulfur-based gas absorbent and a heat-sealable resin, or it may have two layers: a sulfur-based gas absorbing layer containing a sulfur-based gas absorbent and a heat-sealable layer containing no sulfur-based gas absorbent but a heat-sealable resin. Furthermore, the sulfur-based gas absorbing layer may be one or more of a layer containing only a sulfur-based gas physical absorbent, a layer containing only a sulfur-based gas chemical absorbent, or a layer containing both a sulfur-based gas physical absorbent and a sulfur-based gas chemical absorbent. Here, the sulfur-based gas absorbing layer may contain a heat-sealable resin. The thickness of the sealant layer is not particularly limited, but is preferably 10 μm or more and 100 μm or less. If it is thinner than this range, the rigidity is too low, it is easily torn, and it is difficult to exhibit a sufficient sulfur-based gas absorption effect. If it is thicker than this range, the rigidity is too strong, and it is easy to deteriorate the usability as a packaging material or packaging supply material.

[0016] <Sulfur gas absorbing film> The sulfur-containing gas absorbing film of the present invention is a gas absorbing film that absorbs sulfur-containing gases.

[0017] The sulfur-containing gas absorbing layer contains at least a thermoplastic resin and a specific sulfur-containing gas absorbent. The sulfur-based gas absorbing film exhibits sulfur-based gas absorption by containing a sulfur-based gas absorbent, and the thermoplastic resin disperses the sulfur-based gas absorbent and is contained as a resin component constituting the sulfur-based gas absorbing film. The sulfur-based gas absorbent may contain a sulfur-based gas chemical absorbent and / or a sulfur-based gas physical absorbent. Furthermore, if necessary, the sulfur-based gas absorbing film may further contain a heat-sealable resin. By further containing a heat-sealable resin, the sulfur-based gas absorbing film can exhibit heat-sealability.

[0018] The sulfur-based gas absorbing film may be composed of one layer, or two or more layers having the same or different compositions. For example, there may be two layers: a layer containing a sulfur-based gas absorbent (sulfur-based gas absorbing layer) and a layer not containing a sulfur-based gas absorbent. There may also be a layer containing only a sulfur-based gas physical absorbent and a layer containing only a sulfur-based gas chemical absorbent, or there may be a layer containing both a sulfur-based gas physical absorbent and a sulfur-based gas chemical absorbent. There may also be layers with different sulfur-based gas absorbent contents. The heat-sealable resin may be contained in the sulfur-based gas absorbing layer, or may be contained in a layer that does not contain a sulfur-based gas absorbent to form a heat-sealable layer. Furthermore, the sulfur-based gas absorbing film may have a support layer for reinforcing the support, if necessary. The layers constituting the sulfur-based gas absorbing film may be laminated via an adhesive layer.

[0019] The content of the sulfur-based gas absorbent in the layer containing the sulfur-based gas absorbent is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 29% by mass or less. If the content is less than the above range, there is a risk that sufficient sulfur-based gas absorption cannot be exhibited, and if the content is more than the above range, there is a risk that the sulfur-based gas absorption will not be particularly improved, and interlayer adhesion and heat sealability will be reduced, or the film will become brittle.

[0020] The sulfur-based gas absorbing film may contain various plastic compounding agents and additives for the purpose of improving or modifying, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, flame retardancy, mildew resistance, electrical properties, strength, etc. The content of these compounds may be any amount ranging from a trace amount to several tens of percent depending on the purpose. In the above, examples of common additives that may be contained include antiblocking agents, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, modifying resins, and the like.

[0021] Although there is no particular limitation on the thickness of the sulfur-based gas absorbing film, it is preferably 10 μm or more and 100 μm or less. If it is thinner than the above range, it will have too low rigidity, be easily torn, and will be difficult to exhibit a sufficient sulfur-based gas absorbing effect, while if it is thicker than the above range, it will have too high rigidity and will be difficult to use as a packaging material or packaging supplies.

[0022] [Sulfur-based gas absorption layer] The sulfur-based gas absorbing layer is a layer containing a sulfur-based gas absorbent and also contains a thermoplastic resin for dispersing the sulfur-based gas absorbent. The sulfur-based gas absorbing layer may also contain a heat-sealable resin, and if it has sufficient heat-sealability, it can also serve as a sealant layer. Although there is no particular limitation on the thickness of the sulfur-based gas absorbing layer, it is preferably 5 μm or more and 50 μm or less. If the thickness is thinner than the above range, it is difficult to exhibit a sufficient sulfur-based gas absorbing effect, and if the thickness is thicker than the above range, the sulfur-based gas absorbing effect is not significantly improved and the film becomes too rigid, which tends to make it difficult to use as a packaging material.

[0023] [Sulfur gas absorbent] The sulfur-based gas absorbent preferably contains a sulfur-based gas physical absorbent and / or a sulfur-based gas chemical absorbent. By using various sulfur-containing gas absorbents in combination, for example, by using a sulfur-containing gas physical absorbent and a sulfur-containing gas chemical absorbent in combination, it becomes possible to easily absorb a variety of sulfur-containing gases. The sulfur-based gas absorbent is used in the form of a powder, and the maximum particle size is preferably 20 μm or less, and the number average particle size of the powder is preferably 0.1 μm or more and 20 μm or less. If the number average particle size is smaller than the above range, the sulfur-based gas absorbent is likely to aggregate, and if the number average particle size is larger than the above range, the homogeneity of the sulfur-based gas absorbing film may be poor, and the surface area of ​​the sulfur-based gas absorbent may be reduced, resulting in poor sulfur-based gas absorption.

[0024] The sulfur-containing gas absorbent contained in the sulfur-containing gas absorbing layer is preferably contained via a masterbatch in which a powdery sulfur-containing gas absorbent is melt-blended with a thermoplastic resin. Specifically, it is preferable to prepare a masterbatch by melt-blending a powdered sulfur-based gas absorbent into a thermoplastic resin at a relatively high concentration, and then dry-blending the masterbatch with other components to achieve the desired concentration in the sulfur-based gas absorbing layer. The sulfur-based gas absorbent and the thermoplastic resin to be melt-blended may each be one type or two or more types. The content of the sulfur-containing gas absorbent in the masterbatch is preferably 20% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 70% by mass or less. Within the above range, it is easy to include a necessary and sufficient amount of the sulfur-containing gas absorbent in the sulfur-containing gas absorbing layer in a dispersed state.

[0025] (Sulfur gas physical absorbent) The sulfur-containing gas physical absorbent is a gas absorbent that has the function of physically absorbing the sulfur-containing gas to be absorbed. The sulfur gas physical absorbent is a hydrophobic material with a SiO2 / Al2O3 molar ratio of 1 / 1 to 2000 / 1. It is preferable that the inorganic filler contains one or more selected from the group consisting of zeolite, bentonite and sepiolite.

[0026] Hydrophobic zeolite is a zeolite that has excellent absorption properties for molecules with low polarity, such as sulfur-based gases, and has a porous structure. Generally, the higher the molar ratio of SiO2 / Al2O3, the more hydrophobic the zeolite is. As the hydrophobicity increases, it becomes easier to absorb molecules with low polarity such as sulfur-based gases, but conversely, it becomes less compatible with molecules with high polarity such as water, making it more difficult to absorb these molecules. The SiO2 / Al2O3 molar ratio of the hydrophobic zeolite is preferably 30 / 1 to 10,000 / 1. The ratio is preferably from 35 / 1 to 9000 / 1, more preferably from 40 / 1 to 8500 / 1. In addition, hydrophobic zeolite has high heat resistance and can maintain its absorption effect even when exposed to high temperatures of 230°C or higher. In the present invention, a hydrophobic zeolite having a molar ratio within the above range is preferably used in view of the balance between sulfur-containing gas absorption capacity and ease of availability.

[0027] Bentonite is an inorganic substance whose main component is the clay mineral montmorillonite, containing a large amount of layered aluminum phyllosilicate and containing minerals such as quartz and feldspar as impurities. Bentonite contains, for example, Na + Na-type bentonite containing a lot of ions and Ca-type bentonite 2+ stomach There are Ca-type bentonites that contain a lot of ions, and activated bentonites that are artificially converted to Na-type bentonites by adding a few wt% of sodium carbonate to Ca-type bentonite.

[0028] Sepiolite is a clay mineral whose main component is hydrous magnesium silicate, and its general chemical composition is Mg8Si 12 O 30 It is expressed as (OH2)4(OH)4·6~8H2O and has a porous structure. The pH (3% suspension) is preferably 8.0 to 9.0, more preferably 8.9 to 9.3, from the viewpoint of availability.

[0029] (Sulfur gas chemical absorbent) The sulfur-containing gas chemical absorbent is a gas absorbent that has the function of chemically absorbing or decomposing sulfur-containing gases in the gas to be absorbed. Furthermore, because the method is chemical absorption or decomposition, it is less susceptible to the influence of water, etc., and once absorbed, the sulfur-based gas molecules are less likely to desorb, allowing for efficient absorption. Furthermore, the decomposition products are absorbed by a sulfur-based gas physical absorbent or a sulfur-based gas chemical absorbent. The sulfur-based gas chemical absorbent preferably contains one or more selected from the group consisting of inorganic materials carrying metal oxides, glass mixed with metals, and glass mixed with metal ions. The metal oxide in the inorganic material carrying a metal oxide preferably contains one or more metal oxides selected from the group consisting of CuO, ZnO, and AgO. The inorganic material to be supported is preferably an inorganic porous material such as zeolite. The metal in the glass mixed with a metal, or the metal species of the metal ions in the glass mixed with metal ions, preferably includes one or more species selected from the group consisting of Ca, Mg, Na, Cu, Zn, Ag, Pt, Au, Fe, Al, and Ni.

[0030] [Thermoplastic resin] There are no particular restrictions on the thermoplastic resin contained together with the sulfur-based gas absorbent, so long as it has excellent dispersibility for the sulfur-based gas absorbent and can withstand use as a packaging material. The thermoplastic resin may also contain a heat-sealable resin. The thermoplastic resin preferably contains a polyolefin resin. Specific examples of polyolefin resins include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylic acid copolymer, ethylene-propylene copolymer, and mixtures of these resins. Of the above, polyethylene-based resins are preferred, and among polyethylene-based resins, LDPE, LLDPE, general-purpose PE, PE-based copolymers, etc. are more preferred, with LLDPE being even more preferred.

[0031] [Heat-sealable resin] The heat-sealable resin is not particularly limited, and any known resin can be used as long as it can be melted and fused by heat. Specific examples of heat-sealable resins include polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, metallocene polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl (meth)acrylate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyolefin resins obtained by modifying polyolefin resins such as polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, and the like, ethylene-(meth)acrylic acid ester-unsaturated carboxylic acid terpolymer resins, cyclic polyolefin resins, cyclic olefin copolymers, polyethylene terephthalate (PET), polyacrylonitrile (PAN), and the like. Among these, polyolefin resins are preferred, polyethylene resins are more preferred, and low-density polyethylene and linear low-density polyethylene are even more preferred.

[0032] [Heat seal layer] The heat seal layer contains a heat sealable resin and has sufficient heat sealability, and may or may not contain a sulfur-based gas absorbent.

[0033] [Support layer] The support layer is a layer that is included as needed, and is included, for example, to supplement the rigidity of the sulfur-based gas absorbing film, and can also have the effect of preventing blocking when the sulfur-based gas absorbing film is rolled or stacked. The resin contained in the support layer is preferably LDPE or LLDPE, and may also contain a heat-sealable resin. The thickness of the support layer is not particularly limited, but is preferably 1 μm or more and 50 μm or less. If it is thinner than this range, it is difficult to exert the effect of reinforcing rigidity, and if it is thicker than this range, it is too rigid and is likely to become difficult to use as a packaging material or packaging supplies.

[0034] <Adhesive layer> There are no particular limitations on the adhesive used in the adhesive layer, and adhesives for dry lamination, adhesives for EC (extrusion coating), adhesives for non-solvent lamination, any anchor coating agent, etc. can be used. The adhesive may be of any type, such as a thermosetting type, ultraviolet curing type, or electron beam curing type, and may be in any form, such as an aqueous type, solution type, emulsion type, or dispersion type. The adhesive may be in any form, such as a film / sheet type, powder type, or solid type. Furthermore, the adhesive mechanism may be any form, such as a chemical reaction type, solvent evaporation type, heat melting type, or heat pressure type.

[0035] The components that form such adhesive layers include polyvinyl acetate and vinyl acetate-ethylene Examples of adhesives include polyvinyl acetate adhesives such as copolymers, polyacrylic acid adhesives made from copolymers of polyacrylic acid and polystyrene, polyester, polyvinyl acetate, etc., cyanoacrylate adhesives, ethylene copolymer adhesives made from copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose adhesives, polyurethane adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, polyolefin adhesives such as LDPE, amino resin adhesives made from urea resin or melamine resin, phenolic resin adhesives, epoxy adhesives, reactive (meth)acrylic adhesives, elastomer adhesives made from chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc., silicone adhesives, alkali metal silicates, inorganic adhesives made from low-melting point glass, etc.

[0036] [Sulfur-based gas absorbing sealant film] The sulfur-based gas-absorbing sealant film is a sealant film made from a sulfur-based gas-absorbing film, and has sulfur-based gas absorption similar to that of the sulfur-based gas-absorbing film, and excellent heat sealability. When the sulfur-based gas absorbing film has sufficient heat-sealing properties and supportability, the sulfur-based gas absorbing film can be used as it is as a sulfur-based gas absorbing sealant film, and if necessary, a support layer can be further laminated thereon, a heat-sealing resin can be contained therein, or a layer containing a heat-sealing resin can be laminated thereon to produce a sulfur-based gas absorbing sealant film.

[0037] The sulfur-based gas absorbing sealant film may have a single layer structure or a multi-layer structure of two or more layers. In the case of a multilayer structure, a sulfur-based gas absorbing sealant film can be produced by laminating a support layer or a heat seal layer on a layer derived from a sulfur-based gas absorbing film. If necessary, various functional layers can also be laminated to produce a sulfur-based gas absorbing sealant film. Here, each layer constituting the sulfur-based gas absorbing sealant film may be laminated via an adhesive layer. It is preferable that one or both surfaces of the sulfur-based gas-absorbing sealant film have heat-sealability, and for this purpose, for example, a heat-seal layer may be laminated on one or both surfaces of the sulfur-based gas-absorbing sealant film. By providing heat sealability on both sides of the sulfur-based gas absorbing sealant film, it is possible to produce a sulfur-based gas absorbing laminate having excellent interlayer adhesion and heat sealability within the sulfur-based gas absorbing laminate.

[0038] Although there is no particular limitation on the thickness of the sulfur-based gas absorbing sealant film, it is preferably 10 μm or more and 100 μm or less. If it is thinner than this range, it will have too low rigidity, be easily torn, and will be difficult to exhibit a sufficient sulfur-based gas absorbing effect, while if it is thicker than this range, it will have too high rigidity and will be difficult to use as a packaging material or packaging supplies.

[0039] <<Method for producing sulfur-based gas absorbing film and sulfur-based gas absorbing sealant film>> The production method shown below is an example and does not limit the present invention. There are no particular limitations on the method for forming and laminating the sulfur-based gas absorbing film or sulfur-based gas absorbing sealant film, and the layers that constitute them, and any known or commonly used film forming and laminating method can be used. The sulfur-based gas absorbing film or sulfur-based gas absorbing sealant film can be produced by known film-forming and / or lamination methods such as (co)extrusion, cast molding, T-die method, cutting method, and inflation method. When the sulfur-based gas absorbing film or sulfur-based gas absorbing sealant film is composed of two or more layers, for example, the films constituting the respective layers that have been previously prepared are bonded together via an adhesive layer. Alternatively, a molten resin composition may be laminated onto a previously prepared layer by (co)extrusion, or multiple layers may be simultaneously prepared and laminated by melt-pressing, or one or more resins may be applied and dried to coat another layer. For example, an example can be described in which a sulfur-based gas absorbing sealant film is produced by laminating a heat seal layer on a sulfur-based gas absorbing film.

[0040] The sulfur-based gas absorbing layer or the heat seal layer can be laminated on another layer by extrusion or co-extrusion using an extrusion coating method, or can be laminated via an adhesive layer after film formation using an inflation method or a casting method. Even in the case of the extrusion coating method, lamination via an adhesive layer may be performed as needed. Alternatively, a film for a sulfur-based gas absorbing layer or a film for a heat-sealing layer that has been previously formed may be laminated and bonded via an adhesive layer that has been laminated by an extrusion coating method, a dry lamination method, a non-solvent lamination method, or the like. Then, an aging treatment may be carried out as necessary.

[0041] For example, when laminating a sulfur-based gas absorbing layer or a heat seal layer by an extrusion coating method, first, the resin composition that forms the layer is heated and melted, and then expanded and stretched in the required width direction using a T-die to (co)extrude in a curtain shape. The molten resin is then allowed to flow down onto the surface to be laminated and sandwiched between a rubber roll and a cooled metal roll, thereby simultaneously forming the layer and laminating and adhering it to the surface to be laminated. When laminating layers by extrusion coating, the melt flow rate (MFR) of the resin component contained in each layer is preferably 0.2 to 50 g / 10 min, more preferably 0.5 to 30 g / 10 min. If the MFR is lower or higher than the above range, the processability tends to be poor. In this specification, the MFR is a value measured by a method in accordance with JIS K7210.

[0042] When an inflation method is used, the melt flow rate (MFR) of the resin component contained in each layer is preferably 0.2 to 10 g / 10 min, more preferably 0.2 to 9.5 g / 10 min. If the MFR is lower or higher than the above range, the processability tends to be poor.

[0043] Furthermore, in order to improve the adhesion between the layers constituting the sulfur-based gas absorbing film or sulfur-based gas absorbing sealant film, the surface of each layer may be subjected to a desired surface treatment in advance, if necessary. For example, a corona-treated layer, an ozone-treated layer, a plasma-treated layer, an oxidation-treated layer, or the like can be formed by optionally carrying out pretreatment such as corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, or oxidation treatment using chemicals. Alternatively, various coating layers such as a primer coating layer, an undercoating layer, an anchor coating layer, an adhesive layer, and a vapor-deposited anchor coating layer may be optionally formed on the surface to form a surface treatment layer. The various coating agent layers described above can be made of resin compositions containing, as the main component of the vehicle, for example, polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth)acrylic resins, polyvinyl acetate resins, polyolefin resins such as polyethylene or polypropylene, or copolymers or modified resins thereof, or cellulose resins.

[0044] Each layer constituting the sulfur-based gas absorbing film or sulfur-based gas absorbing sealant film can be further uniaxially or biaxially stretched, if necessary, by a conventionally known method using a tenter system, a tubular system, or the like.

[0045] <Sulfur-based gas absorption laminate> The sulfur-based gas absorbing laminate of the present invention is a laminate obtained by laminating the sulfur-based gas absorbing film of the present invention or the sulfur-based gas absorbing sealant film of the present invention with, for example, a substrate layer or a gas barrier layer, and has sulfur-based gas absorption similar to that of the sulfur-based gas absorbing film. The sulfur-based gas absorbing laminate may further include an intermediate layer that performs various functions, if necessary. One surface of the sulfur-containing gas absorbing laminate is preferably a heat seal layer so that the sulfur-containing gas absorbing laminate has heat sealability. The gas barrier layer is preferably laminated between the substrate layer and the sulfur-based gas absorbing layer. The layers constituting the sulfur-based gas absorbent laminate may be laminated via an adhesive layer. Then, an aging treatment may be carried out as necessary.

[0046] The sulfur-based gas absorbent laminate or each layer constituting the sulfur-based gas absorbent laminate may contain various plastic compounding agents, additives, etc. for the purpose of improving or modifying, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, oxidation resistance, slipperiness, release properties, flame retardancy, mildew resistance, electrical properties, strength, etc. The content thereof may be any amount ranging from a trace amount to several tens of percent depending on the purpose. In the above, examples of common additives that may be contained include antiblocking agents, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, modifying resins, and the like.

[0047] <Base material layer> The material for the substrate layer can be a commonly known and commonly used substrate film that has excellent mechanical, physical, chemical, and other properties, and is particularly strong, tough, and heat-resistant. As the substrate film, various resin films can be used, and further, various paper substrates can be used, and a resin film and a paper substrate can also be used in combination. The substrate layer may be composed of one layer, or may be composed of two or more layers of the same or different composition laminated by any lamination means. The thickness of the base layer can be set as appropriate by those skilled in the art, but for the purpose of imparting appropriate strength and stiffness to the laminate, the thickness of the base layer is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, and even more preferably 5 to 25 μm.

[0048] Specific examples of the resin film include resin films made from tough thermoplastic resins such as polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate, polyolefin resins such as polypropylene, polyamide resins such as nylon, polyaramid resins, polycarbonate resins, polyacetal resins, fluorine-based resins, and others. The resin film may be either an unstretched film or a uniaxially or biaxially stretched film. Among the above, resin films containing polyester-based resins and / or polyamide-based resins are preferred, and biaxially oriented PET films and biaxially oriented nylon films are more preferably used.

[0049] The paper substrate can be one that can impart shapeability, flex resistance, rigidity, etc., and for example, a strong sizing bleached or unbleached paper substrate for a paper layer, or a paper substrate such as pure white roll paper, kraft paper, paperboard, processed paper, milk base paper, etc. can be used. The paper base material has a basis weight of approximately 30 g / m 2 ~600g / m 2 A basis weight of about 50 g / m is preferable. 2 ~450g / m 2 The order of is more preferable.

[0050] If necessary, plastic compounding agents and additives such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, and pigments may be added to the resin film used in the base layer for the purpose of improving or modifying processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, release properties, flame retardancy, mildew resistance, electrical properties, strength, etc., and the amount of these additives may be arbitrarily added depending on the purpose, as long as it does not adversely affect other properties. A printed layer may also be provided on one or both sides of the substrate layer.

[0051] [Print layer] The printing layer visually displays design patterns such as letters, numbers, figures, symbols, pictures, designs, etc. for decoration, indication of contents, indication of expiration date, indication of manufacturer, seller, etc., or to impart aesthetic appeal, and can form any desired design pattern. The printed layer is preferably formed on one or both sides of the base layer by a printing method such as gravure printing or flexographic printing, and the printed layer may be provided on the entire surface of the printing surface, or on a part of the surface. Forming the printed layer inside the laminate improves the adhesion of the printed layer, and prevents the ink from rubbing off or peeling off due to external impact or friction. When the printed layer is present inside the laminate, it is preferable that the layer that is on the outer side of the printed layer when the package is formed be transparent so that the printed layer can be seen.

[0052] [Gas barrier layer] The barrier layer is a layer that suppresses gas permeation, and when a sulfur-based gas absorbing package is produced, it can suppress the intrusion of oxygen and water vapor from the outside of the sulfur-based gas absorbing package into the content-accommodating section inside the package and can suppress the diffusion of gas components generated from the content to the outside of the barrier layer. In addition, it can similarly suppress the permeation of the absorption target gas in the present invention. Various barrier materials can be used for the gas barrier layer. Furthermore, the gas barrier layer may be a barrier material that has not only oxygen and water vapor barrier properties but also light-shielding properties against sunlight and the like, aroma-retaining properties for the contents, etc. Furthermore, a barrier material that has gas barrier properties against water vapor and the like, light-shielding properties against sunlight and the like, aroma-retaining properties for the contents, etc., may be used in combination.

[0053] As the barrier material, it is preferable to use a gas barrier film, and specifically, for example, one or more types selected from the group consisting of metal foil, resin film having an inorganic vapor deposition layer, and resin coating film or resin film made of oxygen barrier resin can be used. In particular, a resin film having a metal vapor deposition layer, a resin film having a metal oxide vapor deposition layer, or a resin coating film or resin film made of a barrier resin is preferred, as it has excellent barrier properties against oxygen gas, water vapor, light blocking, aroma retention, etc., and is environmentally friendly in terms of disposal of the container.

[0054] A specific example of the metal foil is aluminum foil, and the thickness of the aluminum foil is preferably 5 μm to 50 μm. Examples of inorganic compounds that form the inorganic vapor deposition layer include metals, metal oxides, metal nitrides, and metal carbides. Specific examples of metal elements constituting the above inorganic compounds include aluminum (Al), silicon (Si), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), zinc (Zn), vanadium (V), barium (Ba), and chromium (Cr).

[0055] In addition to these, Si produced by indium tin oxide (ITO) and chemical vapor deposition methods O X C Y Composite inorganic compounds such as membranes are also included.

[0056] As the inorganic material to be vapor-deposited for use in the resin film having a vapor-deposited layer, silicon oxide and aluminum oxide are preferred. The average composition of inorganic compounds is expressed as, for example, SiO x , AlO x , SiO x C y As in, MO x , M.O. x C y (In the formula, M represents a metal element, and the values ​​of x and y vary depending on the metal element.) In the case of metal oxides, the value of X can range, for example, from 0 to 2 for silicon, 0 to 1.5 for aluminum, 0 to 1.0 for magnesium, 0 to 1 for calcium, 0 to 0.5 for potassium, 0 to 2 for tin, 0 to 0.5 for sodium, 0 to 1.5 for boron, 0 to 2 for titanium, 0 to 1 for lead, 0 to 2 for zirconium, and 0 to 1.5 for yttrium. The above MO x In the case where x=0, it is, for example, a metal, and the upper limit of the range of x is This is the value when completely oxidized.

[0057] For packaging material applications, silicon oxide and aluminum oxide are preferably used, and it is preferable to use silicon oxide with x in the range of 1.0 to 2.0, and aluminum oxide with x in the range of 0.5 to 1.5. The gas barrier layer may be formed of one of these barrier materials, or a combination of two or more of them, or a mixture of two or more of them. It may also be composed of a single layer or multiple layers of the same or different compositions, and in the case of multiple layers, they do not have to be laminated adjacently.

[0058] As the resin film supporting the above-mentioned vapor deposition layer, a resin film having excellent mechanical, physical, chemical and other properties, particularly strength and toughness, and heat resistance, can be used since the vapor deposition layer is provided on it.

[0059] Specifically, in the present invention, examples of the resin film supporting the vapor-deposited layer include polyester-based resin films such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyamide-based resin films such as various nylons; polyolefin films such as polyethylene-based resins, polypropylene-based resins, cyclic polyolefin resins, polystyrene-based resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), and polybutene resin films; polyvinyl chloride-based resins, polycarbonate-based resins, polyimide-based resins, polyamideimide-based resins, polyarylphthalate resins, silicone-based resins, polysulfone-based resins, polyphenylene sulfide-based resins, polyethersulfone-based resins, polyurethane-based resins, cellulose-based resins, poly(meth)acrylic resins, polyvinylidene chloride films, acetal-based resin films, fluorine-based resins, and others. In the present invention, it is particularly preferable to use a film made of a polypropylene resin, a polyester resin, or a polyamide resin.

[0060] The inorganic vapor deposition layer can be formed on a resin film using the inorganic compounds described above as raw materials, for example, by physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, ion plating, and cluster ion beam deposition, or chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition.

[0061] More specifically, in the above-mentioned PVD method, for example, a winding type deposition machine is used, and a resin film coming off a winding roll is placed in a vacuum chamber, where a deposition source heated in a crucible is evaporated, and further, if necessary, oxygen is blown out. While oxygen or the like is being sprayed from a nozzle, an inorganic vapor deposition layer is formed through a mask on a resin film on a cooled coating drum, and then the resin film with the inorganic vapor deposition layer formed thereon is wound up on a take-up roll, thereby producing a resin film having an inorganic vapor deposition layer according to the present invention.

[0062] On the other hand, in the above-mentioned CVD method, a resin film can be produced in which a resin film unwound from a winding roll arranged in a vapor deposition chamber is cooled in the vapor deposition chamber, and a mixed gas consisting of, for example, an organosilicon compound as a monomer gas, oxygen gas, and an inert gas supplied from a vapor deposition raw material volatilization supply device is introduced onto the peripheral surface of the electrode drum, and an inorganic vapor deposition layer of silicon oxide or the like is formed by plasma. In the present invention, the resin film having the above-mentioned inorganic vapor deposition layer prevents permeation of oxygen gas, water vapor, etc., and functions as a gas barrier layer against these.

[0063] In the above, the thickness of the vapor-deposited layer is preferably 30 Å to 3000 Å, more preferably 40 Å to 2500 Å, and even more preferably 50 Å to 2000 Å, in order to obtain sufficient barrier properties. More specifically, in the above PVD method, the thickness of the vapor-deposited layer made of aluminum oxide is preferably 30 Å to 1000 Å, and more preferably about 50 Å to 500 Å. In the above CVD method, the thickness of the vapor-deposited layer made of silicon oxide is preferably 30 Å to 3000 Å, and more preferably 50 Å to 2000 Å. In the case of a vapor-deposited layer made of a metal oxide or an inorganic substance, if the thickness of the vapor-deposited layer exceeds the above range, cracks or the like are likely to occur in the vapor-deposited layer, and there is a risk of the barrier properties being reduced due to warping, as well as problems such as increased material costs, which are undesirable. On the other hand, if the thickness is less than the above range, it is undesirable because it becomes difficult to exhibit barrier properties.

[0064] The resin film having an inorganic vapor deposition layer preferably has a water vapor permeability of 3.0 g / m2 or less, as measured in accordance with JIS K7129 under an environment of a temperature of 40°C and a humidity of 100% RH. 2 ·day or less, and more preferably 2.0 g / m 2 ·day or less, and more preferably 1.5 g / m 2 If the water vapor permeability is within the above range, the packaging This can adequately prevent water vapor from entering the contents storage section inside the package from outside the body. The resin film having an inorganic vapor deposition layer preferably has an acid permeability of 3.0 cc / m2 measured in accordance with JIS K7126 under an environment of a temperature of 23°C and a humidity of 90% RH. 2 ·atm·day or less, and more preferably 2.0cc / m 2 ·atm·day or less and more preferably 1.0 cc / m 2 ·atm·day or less. Oxygen permeability is high If the above-mentioned range of values ​​is satisfied, the intrusion of oxygen from the outside of the package into the content-accommodating section inside the package can be sufficiently suppressed.

[0065] A barrier resin coating film or a barrier resin film made of a barrier resin can also be used as a barrier material and can also exhibit aroma retention properties. Examples of barrier resins that can be used include films or coatings of resins with excellent gas barrier properties, such as polyvinylidene chloride resins (PVDC), polyester resins, polyamide resins (particularly aromatic polyamides such as nylon MXD6), ethylene-vinyl alcohol copolymers (EVOH) with an ethylene content of 25 mol % to 50 mol % obtained by fully saponifying ethylene-vinyl acetate copolymers (vinyl acetate is approximately 79 wt % to 92 wt %), polyvinyl alcohol, polyacrylonitrile, and others. The thickness of the barrier resin coating film or barrier resin film is not limited, but is preferably 0.5 μm to 300 μm, and more preferably 1 μm to 100 μm. As the gas barrier film, metal foil or a resin film having a vapor-deposited layer is preferred, and aluminum foil is particularly preferred.

[0066] [Preparation of sulfur-based gas absorbing packaging material] For example, an example of producing a sulfur-based gas absorbing laminate by laminating a substrate layer and a gas barrier layer on a sulfur-based gas absorbing sealant film will be described. The production method shown below is one example and does not limit the present invention. The base layer and the gas barrier layer can be laminated by any lamination method used in the production of ordinary packaging materials, such as wet lamination, dry lamination, solventless dry lamination, extrusion lamination, T-die coextrusion molding, coextrusion lamination, inflation molding, or the like. For example, a sulfur-based gas absorbing laminate can be obtained by laminating and bonding a substrate layer, a gas barrier layer, and a sulfur-based gas absorbing sealant film via an adhesive layer laminated by an extrusion coating method, a dry lamination method, a non-solvent lamination method, or the like.

[0067] When laminating by the extrusion coating method, first, the resin composition that forms the adhesive layer is heated and melted, and then expanded and stretched in the required width direction using a T-die to (co)extrude in a curtain shape. The molten resin is then allowed to flow down onto the surface to be laminated and sandwiched between a rubber roll and a cooled metal roll, thereby simultaneously forming the adhesive layer and laminating and adhering to the surface to be laminated. Alternatively, for example, first, a dry lamination adhesive is applied to one side of a resin film for the base layer, dried, and then laminated with a film for the barrier layer, and then a dry lamination adhesive is applied to the surface of the barrier layer, dried, and then laminated with a sulfur-based gas absorbing sealant film to obtain a sulfur-based gas absorbing laminate. Then, an aging treatment may be carried out as necessary. In this manner, a sulfur-containing gas absorbing laminate can be obtained.

[0068] <Sulfur-based gas absorbing all-solid-state lithium-ion battery packaging> The sulfur-based gas-absorbing all-solid-state lithium-ion battery package of the present invention is a package produced by packaging an all-solid-state lithium-ion battery using the sulfur-based gas-absorbing packaging material of the present invention. In the sulfur-based gas-absorbing all-solid-state lithium-ion battery packaging, even if a gas to be absorbed is generated from the all-solid-state lithium-ion battery, the gas to be absorbed is absorbed by the sulfur-based gas-absorbing packaging material that constitutes the sulfur-based gas-absorbing all-solid-state lithium-ion battery packaging, and therefore peeling or swelling is unlikely to occur in the sulfur-based gas-absorbing all-solid-state lithium-ion battery packaging. [Example]

[0069] <Ingredients> The main raw materials used in the examples of the present invention are as follows:

[0070] <Sulfur gas absorbent> [Physical sulfur gas absorbent] [Chemical sulfur gas absorbent]

[0071] [Thermoplastic resin, heat-sealable resin] LDPE1: LDPE manufactured by Japan Polyethylene Co., Ltd., Novatec LC520. Density: 0.923 g / cm 3 , MFR3.6g / 10min. LLDPE1: LLDPE manufactured by Prime Polymer Co., Ltd., UltzeX 4020L. Density: 0.937 g / cm 3 , MFR2.3g / 10min. LLDPE2: Prime Polymer LLDPE, Evolue SP2020. Density 0.916g / cm 3 , MFR2.0g / 10min. PP1: PP manufactured by Japan Polypropylene Co., Ltd., Wintec WFW4M. Density: 0.9 g / cm 3 , MFR7.0g / 10min.

[0072] [others] Nylon film 1: Toyobo Co., Ltd. nylon film, Harden Film NAP02, 25 μm thick PET film 1: Toyobo Co., Ltd. Biaxially oriented PET film, E5100. 12 μm thick. Aluminum foil 1: Aluminum foil manufactured by Toyo Aluminum Co., Ltd., material 8021. Thickness: 40 μm. DL Adhesive 1: Dry laminating adhesive, RU-004 / H-1, manufactured by Rock Paint Co., Ltd. EC adhesive 1: Mitsui Chemicals, Inc. acid-modified polyethylene, Admer NF528. EC adhesive 2: Mitsui Chemicals, Inc. acid-modified polypropylene, Admer QF551,

[0073] <Preparation of master batch> [Preparation of Masterbatch 1] LDPE 1 and chemical absorbent 1, a chemical absorbent for sulfur-based gases, were melt-blended in the following ratio to obtain master batch 1 (MB1). LDPE1 90 parts by mass Chemical absorbent 1 10 parts by mass

[0074] [Preparation of Masterbatches 2 to 22] According to the formulations in Tables 1 and 2, melt blending was carried out in the same manner as for Masterbatch 1 to obtain Masterbatches 2 to 22 (MB2 to 22).

[0075] [Table 1]

[0076] [Table 2]

[0077] [Example 1] The following raw materials were mixed by dry blending to obtain a resin composition for a sulfur-based gas absorbing layer. MB1 50 parts by mass LLDPE1 50 parts by mass Next, nylon film 1 for the base layer and aluminum foil 1 for the gas barrier layer were bonded to each other with DL adhesive 1 (coating amount 3.5 g / m 2 ) via dry lamination (drying temperature 70℃) The nylon film 1 (25 μm) and DL adhesive 1 (3.5 g / m 2 ) / aluminum foil 1 (40 μm) laminated film was prepared. Then, the EC adhesive 1 and the above-obtained adhesive were applied to the aluminum foil 1 side of the laminated film obtained above. The resin composition for a sulfur-based gas absorbing layer was co-extruded with the resin composition for a sulfur-based gas absorbing layer, and a sulfur-based gas absorbing packaging material having the following layer structure was obtained by a co-extrusion lamination method. Various evaluations were then carried out. Layer structure: Nylon film 1 (thickness 25 μm) / DL adhesive 1 (coating amount 3.0 g / m2) / aluminum foil 1 (thickness 40 μm) / EC adhesive 1 (thickness 15 μm) / sulfur-based gas absorbing layer (thickness 30 μm)

[0078] [Examples 2 to 26, Comparative Examples 3 and 4] According to the descriptions in Tables 3 to 8, a masterbatch is selected to prepare a resin composition for a sulfur-based gas absorbing layer, Materials for each layer were selected and the procedure was the same as in Example 1 to obtain a sulfur-based gas absorbing packaging material, which was then evaluated in the same manner.

[0079] [Comparative Example 1] According to the description in Table 5, the same procedure as in Example 1 was carried out, except that a heat seal layer made of LLDPE1 was formed instead of the sulfur-based gas absorbing layer, to obtain a packaging material, which was similarly evaluated.

[0080] Comparative Example 2 According to the description in Table 5, the same procedure as in Example 1 was carried out, except that a heat seal layer made of PP1 was formed instead of the sulfur-based gas absorbing layer, to obtain a packaging material, which was similarly evaluated.

[0081] <Summary of results> The sulfur-based gas absorbing laminates of all the examples of the present invention exhibited good manufacturability, heat sealability, and reduced sulfur-based gas concentration. However, Comparative Example 1, which did not contain a sulfur-based gas absorbent, was inferior in the effect of reducing the sulfur-based gas concentration, and Comparative Example 2, which contained too much sulfur-based gas absorbent, was inferior in heat sealability. In Comparative Examples 3 and 4, the heat sealability was poor, so the subsequent evaluation was discontinued and the measurement of the sulfur-based gas concentration was discontinued. No fixed evaluation was performed.

[0082] [Table 3]

[0083] [Table 4]

[0084] [Table 5]

[0085] [Table 6]

[0086] [Table 7]

[0087] [Table 8]

[0088] <Evaluation>

[0089] [Manufacturing suitability] The appearance of the laminate was visually observed, and the presence or absence of defects was evaluated according to the following evaluation criteria. ◯: The laminate had no wrinkles, bumps, or peeling. ×: Wrinkles, bumps, or peeling were observed in the laminate.

[0090] [Heat sealability] The laminate was cut into 10 cm x 10 cm pieces, the sealant sides were overlapped, and a 1 cm x 10 cm area was heat-sealed under the following conditions using a heat seal tester (TP-701-A manufactured by Tester Sangyo Co., Ltd.). The edges were not heat-sealed or bonded, and a test piece for peel strength was prepared in a bifurcated state. This test piece was cut into a 15 mm wide strip, and each bifurcated end was attached to a tensile tester to measure the peel strength (N / 15 mm) under the conditions below, and the result was judged as pass / fail according to the pass / fail criteria below. Heat sealing conditions Temperature: 160℃ Pressure: 1kgf / cm 2 Time: 1 second Test conditions Test speed: 300 mm / min Load range: 50N Pass / fail criteria ○: 30N / 15mm or more, passed. ×: Less than 30N / 15mm, failed.

[0091] [Sulfur gas concentration] The laminate was cut into 20 x 20 cm pieces, and 1000 ml of test gas adjusted to sulfur-based gas components of hydrogen sulfide: 30 ppm and dimethyl sulfide: 50 ppm was placed in a gas sampling bag (SMART BAG PA series, manufactured by GL Sciences Inc.). After leaving the bag at 25°C for 48 hours, the concentrations of hydrogen sulfide and dimethyl sulfide were measured using a detector tube. [Explanation of symbols]

[0092] 1. Sulfur gas absorbing packaging materials 2 Base material layer 3. Middle class 4 Gas barrier layer 5 Sealant Layer 6 Sulfur gas absorption layer 7. Sulfur gas absorbents 8 Heat-seal layer

Claims

1. A sulfur-based gas-absorbing packaging material for a sulfide-based inorganic solid electrolyte type all-solid-state lithium ion battery, which absorbs sulfur-based gases, comprising: The packaging material for an all-solid-state lithium-ion battery includes, in this order, at least a substrate layer made of a substrate film, an adhesive layer, a gas barrier layer made of a gas barrier film, and a sealant layer made of a sulfur-based gas absorbing sealant film; The sulfur-based gas absorbing sealant film contains a sulfur-based gas absorbent and a heat-sealable resin, The sulfur-based gas absorbent contains a sulfur-based gas chemical absorbent and / or a sulfur-based gas physical absorbent, The sulfur-based gas chemical absorbent is a metal oxide and / or an inorganic material in which a metal or metal ion is supported or mixed, The metal oxide contains one or more selected from the group consisting of CuO, ZnO, and AgO, the metal species in the inorganic material carrying or containing the metal or metal ion includes one or more selected from the group consisting of Ca, Mg, Na, Cu, Ag, Pt, Au, Fe, Al, and Ni; The sulfur-based gas physical absorbent is SiO ２ / Al ２ O ３ The present invention comprises one or more hydrophobic zeolites and bentonites in a molar ratio of 30 / 1 to 2000 / 1, the content of the sulfur-based gas absorbent in the layer containing the sulfur-based gas absorbent is 0.3 mass% or more and 30 mass% or less; Sulfur-based gas-absorbing packaging material.

2. The sulfur-based gas absorbent has a maximum particle size of 20 μm or less and a number average particle size of 0.1 μm or more and 15 μm or less. The sulfur-based gas-absorbing packaging material according to claim 1 .

3. The base film contains a polyamide resin and / or a polyester resin. The sulfur-based gas-absorbing packaging material according to claim 1 or 2.

4. The gas barrier film is an aluminum foil. The sulfur-based gas absorbing packaging material according to any one of claims 1 to 3.

5. A sulfur-based gas-absorbing all-solid-state lithium-ion battery packaging body made from the sulfur-based gas-absorbing packaging material according to any one of claims 1 to 4.

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