Printing layer, adhesive layer, and laminating film

Abstract

To provide a sulfide-based gas-absorbing printed layer or adhesive layer that can be applied to both sulfide-based energy storage devices and electronic equipment. [Solution] The printed layer contains a sulfide-based gas absorbent and a resin, wherein the sulfide-based gas absorbent is a transition metal-doped nanozeolite, and the coating amount is 10.0 g / m². 2 The following describes a sulfide-based gas absorbent-containing printed layer used in sulfide-based energy storage devices or electronic equipment to absorb sulfide-based gases, wherein the adhesive layer contains a sulfide-based gas absorbent and an adhesive, the sulfide-based gas absorbent being a transition metal-doped nanozeolite, and the coating amount is 10.0 g / m². 2 The following are used in sulfide-based energy storage devices or electronic equipment to absorb sulfide-based gases: This is an adhesive layer containing a sulfide-based gas absorbent.

Description

Technical Field

[0001] The present invention relates to a printing layer, an adhesive layer, and a laminate film.

Background Art

[0002] In recent years, energy-dense energy storage devices have attracted attention. In particular, all-solid-state energy storage devices using a solid electrolyte layer instead of an electrolytic solution are considered to be excellent in manufacturing cost and productivity because they do not use flammable organic solvents in the battery, enabling simplification of safety devices. Among such all-solid-state energy storage devices, sulfide-based energy storage devices using a sulfide-based solid electrolyte have attracted attention from the viewpoint of improving output current.

[0003] However, in sulfide-based all-solid-state energy storage devices, there is a problem that when the sulfide-based solid electrolyte comes into contact with moisture, sulfide-based gas is generated, and components constituting the sulfide-based all-solid-state battery are corroded, etc., resulting in deterioration of battery performance.

[0004] In addition, many various electronic devices are installed in factories such as chemical plants and water supply and drainage plants. Troubles such as frequent failures and unstable operations may occur in the electronic devices installed in the factory. Such troubles may be caused by sulfide-based corrosive gases generated in the factory.

[0005] Examples of sulfide-based corrosive gases in factories include gases generated in factories such as sewage gas leaking from drainage pipes and volatile gases from chemical drugs used in factories; gases flowing in from outside the factory such as gases flowing from hot springs, volcanoes, etc.

[0006] Furthermore, it is known that trace amounts of sulfide-based gas are released from cardboard boxes used as packaging materials for electronic devices. Electronic devices packed in such cardboard boxes and stored and transported also need to be protected from sulfide-based gases.

[0007] Due to the above circumstances, there is a demand to protect all-solid-state energy storage devices, electronic devices within a factory, and electronic devices packed in cardboard boxes from sulfide-based gases, and various countermeasures have been proposed.

[0008] For example, in Patent Document 1, there is disclosed an all-solid-state lithium secondary battery using a sulfide-based solid electrolyte material, characterized in having an oxide layer-containing power generation element in which an oxide layer formed by oxidizing the sulfide-based solid electrolyte material substantially free of moisture is formed at a site where an electrolyte-containing layer containing at least the sulfide-based solid electrolyte material comes into contact with the outside air.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0010] According to the technology of Patent Document 1, if a predetermined process proceeds as expected, the battery can exhibit its intended performance without generating sulfide-based gas from the battery. However, for example, when moisture enters the laminate pack when accommodating a sulfide-based all-solid-state battery in a laminate pack, when moisture enters through the sealing opening of the laminate pack, when pinholes occur in the laminate pack and moisture enters the laminate pack, etc., the technology of Patent Document 1 cannot cope.

[0011] Also, the technology of Patent Document 1 cannot be applied to electronic devices within a factory that are not scheduled to be accommodated in a laminate pack.

[0012] Due to the above circumstances, in the industrial fields of both sulfide-based energy storage devices and electronic devices, a sulfide-based gas absorbent element that can be applied to both is desired.

[0013] The present invention has been made in view of the above circumstances, and its objective is to provide a sulfide-based gas-absorbing element that can be applied to both sulfide-based energy storage devices and electronic equipment. [Means for solving the problem]

[0014] The present invention, which solves the above problems, is as follows.

[0015] <Aspect 1> Containing a sulfide-based gas absorbent and a resin, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. Coating amount: 10.0 g / m 2 The following: In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, Printing layer containing sulfide-based gas absorbent. <Aspect 2> The average particle size of the nanozeolite is 5 nm or more and 500 nm or less, The aforementioned average particle size is the particle size at which the cumulative mass percentage is 50% in the particle size distribution obtained from the laser diffraction method measured in accordance with JIS Z8825:2022. The printed layer described in Embodiment 1. <Aspect 3> The printing layer according to aspect 1, wherein the SAR of the nanozeolite is 20 or less. <Aspect 4> The printing layer according to aspect 1, wherein the transition metal is one or more transition metals selected from Ag, Cu, and Zn. [Aspect 5] The printing layer according to aspect 1, wherein the sulfide-based gas is hydrogen sulfide. Appearance 6: The printing layer according to any one of Appearances 1 to 5, wherein the resin is one or more selected from urethane resin, (meth)acrylic resin, polyamide resin, nitrocellulose resin, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin. [Aspect 7] A printed layer according to any one of aspects 1 to 5, used for absorbing sulfide-based gases in a sulfide-based all-solid-state battery. Appearance 8: Includes a sulfide-based gas absorbent and an adhesive, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. Coating amount: 10.0 g / m 2 The following: In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, A sulfide-based gas absorbent-containing adhesive layer. <Aspect 9> The average particle size of the nanozeolite is 5 nm or more and 500 nm or less, The aforementioned average particle size is the particle size at which the cumulative mass percentage is 50% in the particle size distribution obtained from the laser diffraction method measured in accordance with JIS Z8825:2022. The adhesive layer described in embodiment 8. <Aspect 10> The adhesive layer according to aspect 8, wherein the SAR of the nanozeolite is 20 or less. <Aspect 11> The adhesive layer according to aspect 8, wherein the transition metal is one or more transition metals selected from Ag, Cu, and Zn. <Aspect 12> The adhesive layer according to aspect 8, wherein the sulfide-based gas is hydrogen sulfide. <Aspect 13> The adhesive layer according to any one of aspects 8 to 12, wherein the adhesive is one or two selected from ester-based adhesives and ether-based adhesives. Appearance 14: An adhesive layer according to any one of Appearances 8 to 12, used for absorbing sulfide-based gases in a sulfide-based all-solid-state battery. <Aspect 15> Includes a base layer, a sulfide-based gas absorption layer, and a sealant layer, The aforementioned sulfide-based gas absorption layer, A printed layer according to any one of the embodiments 1 to 5, or Adhesive layer according to any one of embodiments 8 to 12 And, In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, Laminate film containing a sulfide-based gas absorption layer. <Aspect 16> The base material layer has a barrier function, or Further including a barrier layer, The laminating film described in embodiment 15. Appearance 17: A laminate film according to Appearance 15, used for absorbing sulfide-based gases in a sulfide-based all-solid-state battery. <Aspect 18> Containing a sulfide-based gas absorbent and a resin, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, Ink containing sulfide-based gas absorbent. [Aspect 19] The ink according to aspect 18, used to form the printing layer described in any one of aspects 1 to 5. [Aspect 20] The ink according to aspect 18, used to form a printed layer for absorbing sulfide-based gas in a sulfide-based all-solid-state battery. <Aspect 21> Containing a sulfide-based gas absorbent and an adhesive, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, Adhesive containing sulfide-based gas absorbent. Appearance 22: The adhesive according to Appearance 21, used to form the adhesive layer described in any one of Appearances 8 to 12. [Aspect 23] The adhesive according to aspect 21, used to form an adhesive layer for absorbing sulfide-based gases in a sulfide-based all-solid-state battery. [Effects of the Invention]

[0016] According to the present invention, a sulfide-based gas-absorbing printed layer, adhesive layer, and laminate film are provided that can be applied to both sulfide-based energy storage devices and electronic devices. [Modes for carrying out the invention]

[0017] The printing layer, adhesive layer, and laminate film of the present invention will be described in order below.

[0018] 《Printing layer》 The printed layer of the present invention is It contains a sulfide-based gas absorbent and a resin, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. Coating amount: 10.0 g / m 2 The following: In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, This is a printed layer containing a sulfide-based gas absorbent.

[0019] <Sulfide-based gas absorbents> The sulfide-based gas absorbent contained in the printing layer of the present invention is a transition metal-doped nanozeolite.

[0020] The zeolite used as a sulfide-based gas absorbent in the printed layer of the present invention may have pores defined by an 8-membered ring, and its skeletal structure may be, for example, AEI, AFT, AFX, CHA, DDR, ERI, ITE, ITW, KFI, LEV, LTA, MER, PAU, RHO, UFI, etc.

[0021] The sulfide-based gas absorbent contained in the printing layer of the present invention may be a hydrophilic zeolite. The hydrophilicity of a zeolite is indicated by the silica-alumina ratio (SAR, SiO2 / Al2O3 molar ratio), where a higher value indicates higher hydrophobicity and a lower value indicates higher hydrophilicity. The SAR of the zeolite in the present invention may be 20 or less, 15 or less, 10 or less, 8.0 or less, 5.0 or less, 4.0 or less, 3.0 or less, 2.5 or less, or 2.0 or less. There is no lower limit to the SAR, but generally, zeolites with an SAR of less than 1 are difficult to synthesize. From this viewpoint, the SAR of the zeolite contained in the printing layer of the present invention may be 0.8 or more, 0.9 or more, 1.0 or more, 1.5 or more, or 2.0 or more.

[0022] Furthermore, with conventional printing methods, the absorbent contained in the ink adsorbs organic solvents, causing the adsorption sites to become blocked. As a result, the resulting printed layer cannot exhibit the desired absorbency, and the absorption of the target gas is insufficient.

[0023] In contrast, if the sulfide-based gas absorbent contained in the printing layer of the present invention is a hydrophilic zeolite doped with a transition metal, its adsorption capacity is maintained without being affected by the organic solvents contained in ordinary inks. Therefore, the printing layer of the present invention containing such a zeolite as a sulfide-based gas absorbent can be easily formed by a printing method using the sulfide-based gas absorbent-containing ink described later.

[0024] The zeolite used as a sulfide-based gas absorbent in the printed layer of the present invention is doped with a transition metal. The transition metal doped into the zeolite in the present invention may be, for example, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Pd, Ag, Ce, Zn, etc., and may be one or more selected from Ag, Cu, and Zn, and especially may be one or two selected from Cu and Zn.

[0025] The amount of transition metal doping relative to the Al atoms contained in the zeolite may be, for example, 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, or 55 mol% or more, and may be less than 100 mol%, 95 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 55 mol% or less, 50 mol% or less, or 45 mol% or less.

[0026] When the transition metal is Ag, the doping amount may be, for example, 15 mol% or more, 20 mol% or more, or 25 mol% or more relative to the Al atoms contained in the zeolite, for example, 70 mol% or less, 60 mol% or less, or 55 mol% or less. When the transition metal is Cu, the doping amount may be, for example, 40 mol% or more, 50 mol% or more, or 55 mol% or more relative to the Al atoms contained in the zeolite, for example, less than 100 mol%, 95 mol% or less, or 90 mol% or less. When the transition metal is Zn, the doping amount may be, for example, 5 mol% or more, 10 mol% or more, or 15 mol% or more relative to the Al atoms contained in the zeolite, for example, 55 mol% or less, 50 mol% or less, or 45 mol% or less.

[0027] The doping of zeolites with transition metals may be carried out, for example, by known ion exchange methods.

[0028] The sulfide-based gas absorbent contained in the printed layer of the present invention is a nanozeolite with a small particle size. The average particle size of the nanozeolite may be, for example, 5 nm or more, 10 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, or 40 nm or more, and may be, for example, 500 nm or less, 400 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, 100 nm or less, or 80 nm or less.

[0029] The average particle size mentioned above is the particle size at which the cumulative mass percentage is 50% in the particle size distribution obtained from the laser diffraction method measured in accordance with JIS Z8825:2022.

[0030] The content of the sulfide-based gas absorbent in the printed layer of the present invention may be, for example, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more, based on the total mass of the printed layer, and may also be, for example, 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less.

[0031] In addition, the content of the sulfide-based gas absorbent in the printing layer, as the mass of the sulfide-based gas absorbent per unit area of the printing layer, is, for example, 0.1 g / m 2 or more, 0.2 g / m 2 or more, or 0.3 g / m 2 or more, and may be, for example, 6.0 g / m 2 or less, 4.0 g / m 2 or less, 3.0 g / m 2 or less, 2.0 g / m 2 or less, 1.5 g / m 2 or less, 1.2 g / m 2 or less, 0.8 g / m 2 or less, or 0.5 g / m 2 or less.

[0032] 〈Resin〉 The printing layer of the present invention contains a resin. The resin has a function of maintaining the layer structure of the printing layer and dispersing and holding the sulfide-based gas absorbent in the printing layer.

[0033] The resin may be, for example, one or more selected from polyurethane resin, (meth)acrylic resin, polyamide resin, nitrocellulose resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, etc.

[0034] The content of the resin in the printing layer of the present invention may be, for example, 50% by mass or more, 55% by mass or more, 60% by mass or more, or 65% by mass or more, based on the total mass of the printing layer, and may be, for example, 90% by mass or less, 85% by mass or less, 80% by mass or less, or 75% by mass or less.

[0035] 〈Optional Component〉 The printing layer of the present invention contains a sulfide-based gas absorbent and a resin. The printing layer may contain optional components other than these. The optional components in the printing layer may be, for example, fillers, colorants, defoamers, antioxidants, etc.

[0036] 〈Coating Amount of Printing Layer〉 Even when the printing layer of the present invention is thin, it functions as an adsorption layer excellent in the adsorption property of sulfide-based gas.

[0037] The coating amount of the printed layer of the present invention is, for example, 0.3 g / m² as mass per unit area. 2 More than 0.5g / m 2 More than 0.7g / m 2 Above, or 0.8g / m 2 The above is sufficient; for example, 15.0 g / m 2 Below, 12.0g / m 2 Below, 10.0g / m 2 Below 8.0g / m 2 Below 5.0g / m 2 Below 4.0g / m 2 Below 3.0g / m 2 Below 2.0g / m 2 The following, or 1.5 g / m 2 The following is acceptable:

[0038] The thickness of the printed layer of the present invention may be 0.1 μm or more, or 0.5 μm or more, and may be 10 μm or less, or 5 μm or less.

[0039] <Uses of the printed layer> The printed layer of the present invention may be used in sulfide-based energy storage devices or electronic devices to absorb sulfide-based gases. The sulfide-based gas may be, for example, hydrogen sulfide.

[0040] The sulfide-based energy storage device may be, for example, a sulfide-based all-solid-state battery.

[0041] Electronic devices may include, for example, electronic devices installed in factories such as chemical plants and water and sewage treatment plants, and electronic devices packaged in packaging materials that can generate sulfide gases (such as cardboard boxes), which may experience frequent malfunctions, unstable operation, and other problems when in contact with sulfide gases. Examples of such electronic devices include electronic devices with printed circuit boards. Specifically, examples include various measuring instruments, analytical instruments, memory devices, communication devices, medical devices, in-vehicle devices, home appliances, cooking appliances, audio equipment, and mobile devices.

[0042] Examples of how the printed layer of the present invention can be applied to sulfide-based energy storage devices or electronic devices include, for example, housing a sulfide-based energy storage device or electronic device in a laminate film containing the printed layer of the present invention, covering a printed circuit board of an electronic device with the printed layer of the present invention, and arranging the printed layer of the present invention in the housing of an electronic device.

[0043] Furthermore, the printed layer of the present invention can also be applied to piping, equipment, and the like, which may come into contact with sulfide-based gases.

[0044] Ink containing sulfide-based gas absorbent According to another aspect of the present invention, an ink containing a sulfide-based gas absorbent is provided.

[0045] The sulfide-based gas absorbent-containing ink of the present invention is It contains a sulfide-based gas absorbent and a resin, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, This ink contains a sulfide-based gas absorbent.

[0046] The sulfide-based gas absorbent-containing ink of the present invention may contain a solvent and other optional components in addition to the sulfide-based gas absorbent and resin.

[0047] The sulfide-based gas absorbent-containing ink of the present invention is suitably used to form the printed layer of the present invention. Therefore, the types of sulfide-based gas absorbent and resin contained in the sulfide-based gas absorbent-containing ink of the present invention may be the same as the sulfide-based gas absorbent and resin contained in the desired printed layer. The ratio of sulfide-based gas absorbent to resin in the ink may also be the same as the ratio of sulfide-based gas absorbent to resin in the desired printed layer.

[0048] The solvent contained in the sulfide-based gas absorbent-containing ink is not particularly limited, as long as it can disperse the sulfide-based gas absorbent and dissolve the resin. The solvent may be one or more selected from, for example, esters, alcohols, ketones, ethers, hydrocarbons, etc.

[0049] Examples of esters include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, etc. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, etc. Examples of ketones include acetone, methyl ethyl ketone, methyl-n-butyl ketone, and methylcyclohexanone; Examples of ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoethyl ether acetate; Examples of hydrocarbons include toluene, xylene, n-hexane, etc. Each can be illustrated with an example.

[0050] The amount of solvent may be appropriately set by those skilled in the art, depending on the printing method used, so that the ink has an appropriate viscosity.

[0051] The optional components contained in the sulfide-based gas absorbent-containing ink of the present invention may be any optional components contained in a desired printing layer, as well as any components that can be contained in ordinary inks. Such optional components may be, for example, penetrating agents, drying inhibitors, pH adjusters, preservatives, and the like.

[0052] 《Adhesive layer》 The adhesive layer of the present invention It includes sulfide-based gas absorbents and adhesives, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. Coating amount: 10.0 g / m 2 The following: In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, This is an adhesive layer containing a sulfide-based gas absorbent.

[0053] <Sulfide-based gas absorbents> The sulfide-based gas absorbent contained in the adhesive layer of the present invention is a transition metal-doped nanozeolite, and the above description regarding the sulfide-based gas absorbent contained in the printing layer may be applied as is.

[0054] The content of sulfide-based gas absorbent in the adhesive layer is, for example, 0.05 g / m² as the mass of sulfide-based gas absorbent per unit area of ​​the adhesive layer. 2 More than 0.10g / m 2 Above, or 0.15 g / m² 2 The above is sufficient; for example, 4.0 g / m 2 Below 3.0g / m 2 Below 2.0g / m 2 Below 1.5g / m 2 Below 1.2g / m 2 Below, 0.8g / m 2 The following, or 0.5g / m 2 The following is acceptable:

[0055] <glue> The adhesive contained in the adhesive layer of the present invention may be appropriately selected from known adhesives depending on the application.

[0056] The adhesive may be selected from, for example, ester-based adhesives, ether-based adhesives, etc. The adhesive layer of the present invention is intended for use in sulfide-based energy storage devices or electronic devices. These devices are likely to generate heat during prolonged operation. Therefore, the adhesive contained in the adhesive layer of the present invention may be highly heat-resistant, and in particular, a two-component ester-based adhesive may be used.

[0057] The adhesive content in the adhesive layer of the present invention may be, for example, 75% by mass or more, 80% by mass or more, 85% by mass or more, 88% by mass or more, or 90% by mass or more, based on the total mass of the adhesive layer, and may be, for example, 99% by mass or less, 97% by mass or less, 95% by mass or less, 93% by mass or less, or 90% by mass or less.

[0058] <Optional ingredients> The adhesive layer of the present invention comprises a sulfide-based gas absorbent and an adhesive. The adhesive layer may also contain other optional components. These optional components in the adhesive layer may be, for example, fillers, colorants, defoamers, anti-aging agents, etc.

[0059] <Amount of adhesive layer applied> The adhesive layer of the present invention functions as an adsorption layer with excellent adsorption properties for sulfide-based gases, even when it is a thin layer.

[0060] The amount of adhesive layer applied in this invention is, for example, 0.5 g / m² as mass per unit area. 2 More than 1.0g / m 2 More than 1.5g / m 2 More than 2.0g / m 2 More than 2.5g / m 2 Above, or 3.0 g / m² 2 The above is sufficient; for example, 10.0 g / m 2 Below 8.0g / m 2 Below 6.0g / m 2 Below 5.0g / m 2 The following, or 4.0 g / m 2 The following is acceptable:

[0061] The thickness of the adhesive layer of the present invention may be 0.1 μm or more, or 0.5 μm or more, and may be 10 μm or less, or 5 μm or less.

[0062] <Uses of adhesive layers> The adhesive layer of the present invention may be used in sulfide-based energy storage devices or electronic devices to absorb sulfide-based gases. The sulfide-based gas may be, for example, hydrogen sulfide.

[0063] For sulfide-based energy storage devices and electronic equipment, the above-described provisions may be applied to the application of the printed layer. Furthermore, the adhesive layer of the present invention can be applied to piping, equipment, etc., that may come into contact with sulfide-based gases, similar to the case of the printed layer of the present invention.

[0064] Examples of how the adhesive layer of the present invention can be applied to sulfide-based energy storage devices or electronic devices include, for example, housing a sulfide-based energy storage device or electronic device in a laminate film containing the adhesive layer of the present invention, placing a protective film on the surface of a printed circuit board of an electronic device via the adhesive layer of the present invention, and placing a protective layer on the housing of an electronic device via the adhesive layer of the present invention.

[0065] 《Sulfide-based gas absorbent-containing adhesive》 According to another aspect of the present invention, an adhesive containing a sulfide-based gas absorbent is provided.

[0066] The sulfide-based gas absorbent-containing adhesive of the present invention is It includes sulfide-based gas absorbents and adhesives, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, This is an adhesive containing a sulfide-based gas absorbent.

[0067] The sulfide-based gas absorbent-containing adhesive of the present invention comprises a sulfide-based gas absorbent and an adhesive, and may also contain a diluent and other optional components.

[0068] The sulfide-based gas absorbent-containing adhesive of the present invention is suitably used to form the adhesive layer of the present invention. Therefore, the types of sulfide-based gas absorbent and adhesive contained in the sulfide-based gas absorbent-containing adhesive of the present invention may be the same as the sulfide-based gas absorbent and adhesive contained in the desired adhesive layer. The ratio of sulfide-based gas absorbent to adhesive in the adhesive may also be the same as the ratio of sulfide-based gas absorbent to adhesive in the desired adhesive layer.

[0069] The diluent contained in the sulfide-based gas absorbent-containing adhesive is not particularly limited, as long as it can disperse the sulfide-based gas absorbent and dissolve the adhesive. The diluent may be an organic solvent, and may be one or more selected from, for example, esters, alcohols, ketones, ethers, hydrocarbons, etc.

[0070] Examples of esters include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, etc. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, etc. Examples of ketones include acetone, methyl ethyl ketone, methyl-n-butyl ketone, and methylcyclohexanone; Examples of ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoethyl ether acetate; Examples of hydrocarbons include toluene, xylene, n-hexane, etc. Each can be illustrated with an example.

[0071] The amount of diluent may be appropriately determined by a person skilled in the art, depending on the coating method adopted, so that the adhesive has an appropriate viscosity. The amount of diluent may be, for example, 10% or more by mass or 20% or more by mass, or for example, 90% or less by mass or 80% or less by mass, based on the total mass of the adhesive.

[0072] The optional components contained in the sulfide-based gas absorbent-containing adhesive of the present invention may be optional components contained in the desired adhesive layer, as well as components that are normally contained in adhesives. Such optional components may be, for example, plasticizers, tackifiers, fillers, thickeners, colorants, pH adjusters, antioxidants, preservatives, and the like.

[0073] Laminating film The laminate film of the present invention is It comprises a base layer, a sulfide-based gas absorption layer, and a sealant layer. The aforementioned sulfide-based gas absorption layer, The printed layer of the present invention, or The adhesive layer of the present invention And, In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, This is a laminate film containing a sulfide-based gas absorption layer.

[0074] The laminate film of the present invention is The substrate layer has a barrier function, or In addition to the base layer, sulfide-based gas absorption layer, and sealant layer, it further includes a barrier layer. It can be an object.

[0075] The laminate film of the present invention may also optionally have layers other than those described above. Examples of optional layers include a skin layer, a reinforcing layer, and the like.

[0076] The following describes each layer that constitutes the laminate film of the present invention in order.

[0077] <Base material layer> The base layer provides the necessary rigidity to the laminate film and also protects the other layers. The base layer may be made of any suitable material that can have the above functions. For example, the base layer may be made of one or more materials selected from polyolefins, vinyl chloride polymers, polyesters, polyamides, paper, etc.

[0078] Examples of polyolefins include polyethylene resins and polypropylene resins. Examples of polyethylene resins include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE). Examples of polypropylene resins include polypropylene (PP) homopolymer, random polypropylene (random PP), block polypropylene (block PP), chlorinated polypropylene, and carboxylic acid-modified polypropylene.

[0079] Examples of vinyl chloride polymers include polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polychlorotrifluoroethylene, polytetrafluoroethylene, and polyacrylonitrile (PAN).

[0080] Examples of polyesters include polyethylene terephthalate (PET) and polybutylene terephthalate.

[0081] Examples of polyamides include nylon. Nylon may be, for example, nylon 6 or nylon MXD6.

[0082] The thickness of the base material layer may be, for example, 7 μm or more, 10 μm or more, or 15 μm or more, from the viewpoint of providing the necessary rigidity to the laminate film, and may be, for example, 55 μm or less, 50 μm or less, or 45 μm or less, from the viewpoint of not excessively impairing handling.

[0083] <Substrate layer with barrier function> The laminate film of the present invention may have a substrate layer that has a barrier function, or may further include a barrier layer.

[0084] The substrate layer having a barrier function may be, for example, a laminate in which a barrier-functioning film is disposed on one or both sides of a substrate film. This barrier-functioning film may be, for example, a metal vapor-deposited film, a metal oxide vapor-deposited film, an organic coating film, and the like.

[0085] The material of the substrate film in the laminate may be appropriately selected from the materials exemplified above as materials for the substrate layer.

[0086] The metal vapor-deposited film in the laminate may be, for example, a film of aluminum or the like. The deposition film may consist of metal oxides, etc. The deposition film may consist of one or more materials selected from, for example, silica, alumina, etc.

[0087] The organic coating film in the laminate may be, for example, a polyvinylidene fluoride film.

[0088] The thickness of the base film may be, for example, 7 μm or more, 10 μm or more, or 15 μm or more, from the viewpoint of providing the necessary rigidity to the laminate film, and may be, for example, 55 μm or less, 50 μm or less, or 45 μm or less, from the viewpoint of not excessively impairing handling.

[0089] The thickness of the barrier film may be approximately 30 nm to 100 nm.

[0090] <Barrier layer> The barrier layer may be, for example, a metal foil.

[0091] The metal foil may be aluminum foil, alloyed aluminum foil, etc.

[0092] The thickness of the barrier layer may be, for example, 7 μm or more, 10 μm or more, or 15 μm or more, from the viewpoint of providing the necessary barrier properties to the laminate film, and may be, for example, 55 μm or less, 50 μm or less, or 45 μm or less, from the viewpoint of not excessively impairing handling.

[0093] <Sulfide-based gas absorption layer> The sulfide-based gas absorption layer in the laminate film of the present invention is either the printed layer of the present invention as described above, or the adhesive layer of the present invention. The above descriptions of the printed layer and adhesive layer of the present invention can be applied to these printed layer and adhesive layer.

[0094] <Sealant layer> The sealant layer is a layer that has a heat-sealing function. Therefore, a laminate pack can be formed by placing the laminate film of the present invention as the innermost layer and heat-sealing the edges of the opposing laminate films.

[0095] The sealant layer may be made of, for example, polyolefin. The material of the sealant layer may be, but is not limited to, polypropylene (PP), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), polyethylene catalyzed with metallocene, copolymer resin having repeating units of ethylene and repeating units of acrylic, or copolymer resin having repeating units of ethylene and other materials, or a combination thereof. These resins may be in the form of, for example, stretched or unstretched films, molten resins for extrusion lamination, or coatings for hot melt.

[0096] Alternatively, a commercially available easy-peel resin or easy-peel sealant film may be used as the sealant layer.

[0097] The thickness of the sealant layer is not particularly limited, but from the viewpoint of forming a strong seal by melting, it is preferably 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, or 50 μm or more, and from the viewpoint of improving handling, it is preferably 100 μm or less, 80 μm or less, or 50 μm or less.

[0098] <Reinforcement Layers> The reinforcing layer serves to impart strength, durability, and other properties to the laminate film. The reinforcing layer may be made of, for example, nylon, polypropylene, polyethylene terephthalate, etc. Stretched versions of these materials may also be used as the reinforcing layer in this invention.

[0099] The thickness of the reinforcing layer may be set appropriately depending on the type of material constituting the reinforcing layer, the intended use of the laminate film of the present invention, etc. For example, the thickness of the reinforcing layer may be 5 μm or more, 7 μm or more, 10 μm or more, or 12 μm or more, and may be 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 15 μm or less.

[0100] <Laminate structure and method for manufacturing laminate film> The laminate film of the present invention comprises a base layer, a sulfide-based gas absorption layer, and a sealant layer in this order. If the laminate film of the present invention further comprises other layers in addition to the base layer, sulfide-based gas absorption layer, and sealant layer, the sulfide-based gas absorption layer may be arranged between the sealant layer and the other layers.

[0101] When the sulfide-based gas absorption layer is a printed layer, the laminate film of the present invention may be manufactured by a method that includes printing the sulfide-based gas absorbent-containing ink of the present invention on one side of either the sealant layer or a layer or laminate other than the sealant layer.

[0102] Specifically, for example, The sulfide-based gas absorbent-containing ink of the present invention is printed onto the surface of a layer other than the sealant layer or on the surface of a laminate that is on the sealant layer side, thereby forming a printed layer. Dry lamination of a printed layer with a layer or laminate other than the printed sealant layer and the sealant layer. A laminate film is manufactured by the following process. Here, the printed layer is laminated so as to be located between the sealant layer and the layers or laminate other than the sealant layer. Furthermore, printing of the sulfide-based gas absorbent-containing ink onto the layers or laminate other than the sealant layer may be performed only once, or the thickness of the printed layer may be increased by performing printing two or more times.

[0103] To place the printed layer on the surface of each layer, the sulfide-based gas absorbent-containing ink of the present invention may be printed on the desired surface using an appropriate printing method. Examples of printing methods include letterpress printing, gravure printing, offset printing, screen printing, and inkjet printing. Lamination between the printed layer and other layers may be carried out, for example, by a known dry lamination method. Furthermore, if the layers other than the sealant layer are laminates, the manufacturing of these laminates may also be carried out, for example, by a known dry lamination method.

[0104] On the other hand, if the sulfide-based gas absorption layer is an adhesive layer, the laminate film of the present invention may be manufactured by a method that includes laminating the sealant layer and a layer or laminate other than the sealant layer with the sulfide-based gas absorbent-containing adhesive layer of the present invention.

[0105] If the layers other than the sealant layer are laminates, these laminates may be manufactured, for example, by known dry lamination methods. In manufacturing these laminates, dry lamination may be performed using the sulfide-based gas absorbent-containing adhesive of the present invention.

[0106] Furthermore, the embodiment of the laminate film of the present invention also includes having a sulfide-based gas absorbent-containing ink layer and a sulfide-based gas absorbent-containing adhesive layer superimposed on each other.

[0107] The laminate film of the present invention may have a substrate layer that has a barrier function, or may further include a barrier layer.

[0108] If the substrate layer has a barrier function, the side of the substrate layer that has the barrier function may be laminated facing the sealant layer.

[0109] If the laminate film of the present invention further includes a barrier layer in addition to the base layer, the sulfide-based gas absorption layer, and the sealant layer, the barrier layer may be disposed between the base layer and the sulfide-based gas absorption layer.

[0110] The laminate film of the present invention may further include a reinforcing layer. The reinforcing layer may be disposed between the substrate layer and the sulfide-based gas absorption layer.

[0111] If the laminate film of the present invention includes a barrier layer and a reinforcing layer in addition to the base layer, sulfide-based gas absorption layer, and sealant layer, the laminate film may be laminated in the order of base layer, barrier layer, reinforcing layer, sulfide-based gas absorption layer, and sealant layer.

[0112] <Uses of laminating film> The laminate film of the present invention can be suitably applied, for example, to laminate packs for housing sulfide-based energy storage devices, electronic devices, etc. In particular, laminate films in which the base layer has a barrier function or further includes a barrier layer can be suitably applied to sulfide-based energy storage devices (especially sulfide-based all-solid-state batteries) to absorb sulfide-based gases. [Examples]

[0113] I. Laminate film having a printed layer containing a sulfide-based gas absorbent. Preparation of inks containing sulfide-based gas absorbents A sulfide-based gas absorbent-containing ink was prepared by blending the following components. Sulfide-based gas absorbent: 7 parts by mass Rio Alpha SX R Medium (product name, manufactured by Toyo Ink Co., Ltd.), polyurethane resin and solvent-containing medium: 100 parts by mass Ethyl acetate: 40 parts by mass Isopropanol: 20 parts by mass Methyl ethyl ketone: 20 parts by mass

[0114] Example 1-1 <Manufacturing of laminating film> In Example 1-1, the sulfide-based gas absorbent was Ag-doped nanozeolite (manufactured by Nakamura Choko Co., Ltd., trade name "Zeoal(registered trademark)Ag"), and Na-A type zeolite. + 30-50% of the ions are Ag + Ionized zeolite (skeleton code: LTA, SAR=2, average particle size 50 nm) was used.

[0115] A 12 μm thick polyethylene terephthalate film (PET12), a 9 μm thick aluminum foil (AL9), and a 15 μm thick nylon film (Ny15) were dry-laminated in this order to obtain a three-layer laminate film (PET12 / / AL9 / / Ny15). Here, " / / " indicates the laminate adhesive layer. For the laminate adhesive, a two-component ester-based adhesive (manufactured by Mitsui Chemicals, Inc., main component: Takelac A-525, curing agent: Takenate A-52) was used, mixed in a mass ratio of main component to curing agent of 9:1.

[0116] A 1 μm thick sulfide-based gas absorbent-containing printed layer was formed on the Ny15 side surface of the obtained three-layer laminate film by gravure printing with an ink containing a sulfide-based gas absorbent, thereby obtaining a laminate film. The coating amount of this sulfide-based gas absorbent-containing printed layer was 1.0 g / m². 2 And here it is 0.3g / m 2 It contained a sulfide-based gas absorbent.

[0117] The surface smoothness of the printed layer of the obtained laminate film was visually observed, and the printability of the sulfide-based gas absorbent-containing ink was evaluated according to the following criteria. A: When the surface of the printed layer is smooth C: When the surface of the printed layer is not smooth.

[0118] Next, a laminate film (PET12 / / AL9 / / (Ny15 / PLHS) / / CPP50) having a sulfide-based gas absorbent-containing printed layer (PLHS) was obtained by dry laminating the printed layer side of the laminate film with a 50 μm thick unoriented polypropylene film (CPP50) as a sealant layer. Here, "(Ny15 / PLHS)" indicates that the sulfide-based gas absorbent-containing printed layer (PLHS) is printed on the nylon film (Ny15) surface. The same ester-based two-component adhesive as described above was used as the laminating adhesive.

[0119] <Evaluation of hydrogen sulfide absorption capacity> Using the obtained laminate film, a rectangular packaging bag with inner dimensions of 100 mm x 40 mm was formed by heat-sealing the edges with the sealant layer facing inward. An L-cysteine ​​aqueous solution with an initial concentration of 300 ppm or 3,000 ppm was sealed inside this packaging bag. The packaging bag containing the L-cysteine ​​aqueous solution was then placed in a constant temperature bath heated to 120°C for 30 minutes.

[0120] The hydrogen sulfide concentration in the heated L-cysteine ​​aqueous solution and the sulfurous odor were measured and evaluated using the following methods.

[0121] (Measurement of hydrogen sulfide concentration in aqueous solution) The hydrogen sulfide concentration in aqueous solutions was measured using a simple water quality meter manufactured by Kyoritsu Chemical Research Institute Co., Ltd., product name "Pack Test Sulfide (Hydrogen Sulfide) WAK-S". Three measurements were taken, and the average value was used as the hydrogen sulfide concentration in the aqueous solution.

[0122] (Sensory evaluation of sulfurous odor) The heated packaging bags were opened, and the degree of sulfurous odor inside the bags immediately after opening was checked and evaluated by five panelists according to the following criteria. A: When all panelists determined there was no sulfurous smell. B: When three or four panelists determined that there was no sulfurous odor. C: When two or fewer panelists determined that there was no sulfurous odor.

[0123] Examples 1-2 and 1-3, and Comparative Examples 1-2 to 1-8 Except for using the sulfide-based gas absorbents listed in Table 1, sulfide-based gas absorbent-containing inks were prepared in the same manner as in Example 1-1, and laminate films having a sulfide-based gas absorbent-containing printed layer were manufactured and evaluated using these inks. The evaluation results are shown in Table 1.

[0124] 《Comparative Example 1-1》 A laminate film was manufactured and evaluated in the same manner as in Example 1-1, except that the sulfide-based gas absorbent-containing ink was not printed on the Ny15 side of the three-layer laminate film. The evaluation results are shown in Table 1.

[0125] [Table 1]

[0126] The abbreviations for the types of sulfide-based gas absorbents in Table 1 have the following meanings: Zeoal-Ag: Manufactured by Nakamura Superhard Co., Ltd., Na-A type zeolite + 30-50% of the ions are Ag + Ion-exchanged zeolite, skeleton code: LTA, SAR=2, average particle size 50nm Zeoal-Cu: Manufactured by Nakamura Superhard Co., Ltd., Na-A type zeolite + 60-90% of the ions are Cu 2+ Ion-exchanged zeolite, skeleton code: LTA, SAR=2, average particle size 50nm Zeoal-Zn: Manufactured by Nakamura Superhard Co., Ltd., Na-A type zeolite + 20-40 mol% of the ions are Zn 2+ Ion-exchanged zeolite, skeleton code: LTA, SAR=2, average particle size 50nm Zeoal-4A: Manufactured by Nakamura Superhard Co., Ltd., Na-A type zeolite, skeleton code: LTA, SAR=2, average particle size 50nm Absent 3000: Manufactured by Resonaq Universal Co., Ltd., high silica zeolite, skeleton code: MFI, SAR = 400~800, average particle size 3,000~5,000 nm Nano ZSM-5: Manufactured by Nakamura Superhard Co., Ltd., Skeleton code: MFI, SAR=200, Average particle size 50nm Zeolite 4A: Manufactured by Resonaq Universal Co., Ltd., Na-A type zeolite, skeleton code: LTA, SAR=2, average particle size 3,000~5,000nm Zeomic AG10D: Manufactured by Sinanen Zeomic Co., Ltd., contains Na-A type zeolite. +5-20 mol% of ions in Ag + Ion-exchanged zeolite, skeleton code: LTA, SAR=2, average particle size 2,000~3,000nm Zeomic CA10D: Manufactured by Sinanen Zeomic Co., Ltd., contains Na-A type zeolite. + 50-70% of the ions are Cu 2+ Ion-exchanged zeolite, skeleton code: LTA, SAR=2, average particle size 2,000~3,000nm Zeomic VZA10D: Manufactured by Sinanen Zeomic Co., Ltd., contains Na-A type zeolite. + 50-90% of the ions are Zn 2+ Ion-exchanged zeolite, skeleton code: LTA, SAR=2, average particle size 2,000~3,000nm

[0127] In Table 1, a measured hydrogen sulfide concentration (ppm) of "<0.05" indicates that the hydrogen sulfide concentration was below the detection limit. A value of ">5.0" indicates that the hydrogen sulfide concentration exceeded the detection limit.

[0128] In Comparative Example 1-1, when the initial concentration of the L-cysteine ​​aqueous solution sealed inside the packaging bag was 3,000 ppm, sensory testing was not performed because the hydrogen sulfide concentration after heating may have been at a level harmful to the human body.

[0129] As shown in Table 1, compared to Comparative Example 1-1, which does not have a printed layer containing a sulfide-based gas absorbent, the laminate films of Comparative Examples 1-2 to 1-5, in which the sulfide-based gas absorbent contained in the printed layer is a zeolite not doped with transition metal ions, had insufficient hydrogen sulfide absorption capacity.

[0130] Furthermore, in the laminate films of Comparative Examples 1-6 to 1-8, where the sulfide-based gas absorbent contained in the printing layer was doped with transition metal ions but was a zeolite with a large average particle size, although the hydrogen sulfide absorption capacity was high, the ink printability was insufficient, and a flat printing layer could not be formed.

[0131] In contrast to these, the laminate films of Examples 1-1 to 1-3, in which the sulfide-based gas absorbent contained in the printing layer is doped with transition metal ions and is a nanozeolite with a small average particle size, were verified to have high hydrogen sulfide absorption capacity, excellent ink printability, and the ability to form a flat printing layer.

[0132] II. Laminate film having an adhesive layer containing a sulfide-based gas absorbent. Preparation of adhesives containing sulfide-based gas absorbents A sulfide-based gas absorbent-containing adhesive was prepared by combining the following components. Sulfide-based gas absorbent: 0.5 parts by mass Ester-based two-component adhesive (manufactured by Mitsui Chemicals, Inc., main component "Takelac A-525" and hardener "Takenate A-52") Takerack A-525: 9 Mass Units Takenate A-52: 1 part by mass Ethyl acetate: 14 parts by mass

[0133] Example 2-1 <Manufacturing of laminating film> In Example 2-1, the sulfide-based gas absorbent used was Ag-doped nanozeolite (manufactured by Nakamura Choko Co., Ltd., trade name "Zeoal(registered trademark)Ag"), and Na-A type zeolite. + 30-50% of the ions are Ag + Ionized zeolite (skeleton code: LTA, SAR=2, average particle size 50 nm) was used.

[0134] A 12 μm thick polyethylene terephthalate film (PET12), a 9 μm thick aluminum foil (AL9), and a 15 μm thick nylon film (Ny15) were dry-laminated in this order to obtain a three-layer laminate film (PET12 / / AL9 / / Ny15). Here, " / / " indicates the laminate adhesive layer. For the laminate adhesive, a two-component ester-based adhesive (manufactured by Mitsui Chemicals, Inc., main component: Takelac A-525, curing agent: Takenate A-52) was used, mixed in a mass ratio of main component to curing agent of 9:1.

[0135] The Ny15 side of the obtained three-layer laminate film was dry-laminated to a 50 μm thick unoriented polypropylene film (CPP50) as a sealant layer. At this time, the sulfide-based gas absorbent-containing adhesive prepared above was used as the dry-laminating adhesive. Through the above procedure, a laminate film (PET12 / / AL9 / / (Ny15 / ALHS / CPP50)) having a sulfide-based gas absorbent-containing adhesive layer (ALHS) was obtained. Here, "(Ny15 / ALHS / CPP50)" indicates that the nylon film (Ny15) and the unoriented polypropylene film (CPP50) are dry-laminated by a sulfide-based gas absorbent-containing adhesive layer (ALHS).

[0136] The amount of sulfide-based gas absorbent-containing adhesive layer applied to the resulting laminate film was 3.5 g / m². 2 And here it is 0.3g / m 2 It contained a sulfide-based gas absorbent.

[0137] The surface smoothness of the obtained sulfide-based gas absorbent-containing adhesive layer was visually observed, and the coating suitability of the sulfide-based gas absorbent-containing adhesive was evaluated according to the following criteria. A smooth surface of the adhesive layer means that no clumps, uncoated areas, etc., were observed on the surface. A: When the surface of the adhesive layer is smooth C: When the surface of the adhesive layer is not smooth.

[0138] <Evaluation of hydrogen sulfide absorption capacity> Using the obtained laminate film, the hydrogen sulfide absorption capacity was evaluated in the same manner as in Example 1-1 (measurement of hydrogen sulfide concentration in L-cysteine ​​aqueous solution and sensory evaluation of sulfur odor). The results are shown in Table 2.

[0139] Examples 2-2 and 2-3, and Comparative Examples 2-1 to 2-7 Except for using the sulfide-based gas absorbents listed in Table 2, sulfide-based gas absorbent-containing adhesives were prepared in the same manner as in Example 2-1. Laminate films having a sulfide-based gas absorbent-containing adhesive layer were then manufactured using these adhesives and evaluated in the same manner as in Example 2-1. The evaluation results are shown in Table 2. For reference, the results of Comparative Example 1-1 are also reproduced in Table 2.

[0140] [Table 2]

[0141] The abbreviations for the types of sulfide-based gas absorbents in Table 2 have the same meaning as the abbreviations in Table 1.

[0142] In Table 2, a measured hydrogen sulfide concentration (ppm) of "<0.05" indicates that the hydrogen sulfide concentration was below the detection limit. A value of ">5.0" indicates that the hydrogen sulfide concentration exceeded the detection limit.

[0143] Furthermore, as mentioned above, in Comparative Example 1-1, when the initial concentration of the L-cysteine ​​aqueous solution sealed inside the packaging bag was 3,000 ppm, there was a possibility that the hydrogen sulfide concentration after heating would be harmful to the human body, so a sensory evaluation was not performed.

[0144] As shown in Table 2, compared to Comparative Example 1-1, which does not have an adhesive layer containing a sulfide-based gas absorbent, the laminate films of Comparative Examples 2-1 to 2-4, in which the sulfide-based gas absorbent contained in the adhesive layer is a zeolite not doped with transition metal ions, had insufficient hydrogen sulfide absorption capacity.

[0145] Furthermore, in the laminate films of Comparative Examples 2-5 to 2-7, where the sulfide-based gas absorbent contained in the adhesive layer was doped with transition metal ions but was a zeolite with a large average particle size, although the hydrogen sulfide absorption capacity was high, the adhesive coating suitability was insufficient, and a flat adhesive layer could not be formed.

[0146] In contrast to these, the laminate films of Examples 2-1 to 2-3, in which the sulfide-based gas absorbent contained in the adhesive layer is doped with transition metal ions and is a nanozeolite with a small average particle size, were verified to have high hydrogen sulfide absorption capacity and excellent adhesive coating suitability, enabling the formation of a flat adhesive layer.

Claims

1. It contains a sulfide-based gas absorbent and a resin, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. The coating amount is 10.0 g / m². ２ The following: In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, Printing layer containing sulfide-based gas absorbent.

2. The average particle size of the nanozeolite is 5 nm or more and 500 nm or less. The aforementioned average particle size is the particle size at which the cumulative mass percentage is 50% in the particle size distribution obtained from the laser diffraction method measured in accordance with JIS Z8825:2022. The printed layer according to claim 1.

3. The printed layer according to claim 1, wherein the SAR of the nanozeolite is 20 or less.

4. The printed layer according to claim 1, wherein the transition metal is one or more transition metals selected from Ag, Cu, and Zn.

5. The printed layer according to claim 1, wherein the sulfide-based gas is hydrogen sulfide.

6. The printing layer according to any one of claims 1 to 5, wherein the resin is one or more selected from urethane resin, (meth)acrylic resin, polyamide resin, nitrocellulose resin, chlorinated polyolefin resin, and vinyl chloride / vinyl acetate copolymer resin.

7. A printed layer according to any one of claims 1 to 5, used for absorbing sulfide-based gases in a sulfide-based all-solid-state battery.

8. It includes sulfide-based gas absorbents and adhesives, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. The coating amount is 10.0 g / m². ２ The following: In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, A sulfide-based gas absorbent-containing adhesive layer.

9. The average particle size of the nanozeolite is 5 nm or more and 500 nm or less. The aforementioned average particle size is the particle size at which the cumulative mass percentage is 50% in the particle size distribution obtained from the laser diffraction method measured in accordance with JIS Z8825:2022. The adhesive layer according to claim 8.

10. The adhesive layer according to claim 8, wherein the SAR of the nanozeolite is 20 or less.

11. The adhesive layer according to claim 8, wherein the transition metal is one or more transition metals selected from Ag, Cu, and Zn.

12. The adhesive layer according to claim 8, wherein the sulfide-based gas is hydrogen sulfide.

13. The adhesive layer according to any one of claims 8 to 12, wherein the adhesive is one or two selected from ester-based adhesives and ether-based adhesives.

14. An adhesive layer according to any one of claims 8 to 12, used for absorbing sulfide-based gases in a sulfide-based all-solid-state battery.

15. It comprises a base layer, a sulfide-based gas absorption layer, and a sealant layer. The aforementioned sulfide-based gas absorption layer, The printed layer according to any one of claims 1 to 5, or Adhesive layer according to any one of claims 8 to 12 And, In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, Laminate film containing a sulfide-based gas absorption layer.

16. The substrate layer has a barrier function, or Further including a barrier layer, The laminate film according to claim 15.

17. A laminate film according to claim 15, used for absorbing sulfide-based gases in a sulfide-based all-solid-state battery.

18. It contains a sulfide-based gas absorbent and a resin, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, Ink containing sulfide-based gas absorbent.

19. The ink according to claim 18, used to form the printed layer according to any one of claims 1 to 5.

20. The ink according to claim 18, used to form a printed layer for absorbing sulfide-based gases in a sulfide-based all-solid-state battery.

21. It includes sulfide-based gas absorbents and adhesives, The aforementioned sulfide-based gas absorbent is a nanozeolite doped with a transition metal. In sulfide-based energy storage devices or electronic equipment, used to absorb sulfide-based gases, Adhesive containing sulfide-based gas absorbent.

22. The adhesive according to claim 21, used to form the adhesive layer according to any one of claims 8 to 12.

23. The adhesive according to claim 21, used to form an adhesive layer for absorbing sulfide-based gases in a sulfide-based all-solid-state battery.

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