Method for manufacturing laminated film

Abstract

Provided is a method for productively manufacturing a laminated film that includes a base material and a porous layer.　A method according to an embodiment of the present invention is a method for manufacturing a laminated film that includes a base material and a porous layer. The method includes: a precursor layer formation step for forming a precursor layer on at least one side of the base material; and a dealloying step for subjecting the precursor layer to a dealloying treatment to thereby form the porous layer. The precursor layer is formed while the base material is conveyed by means of a roll-to-roll process.

Description

Manufacturing method of laminated film

[0001] The present invention relates to a method for producing a laminated film, and more particularly to a method for producing a laminated film including a substrate and a porous layer.

[0002] A laminate including a substrate and a porous layer can be used in various applications. For example, an electrode using a laminated catalyst having a porous structure and a substrate has been reported as an electrode for use in a water electrolysis device (for example, Patent Document 1).

[0003] A known method for forming a porous layer is alloy dealloying. The alloy dealloying method is a method in which an alloy of a leachable element that dissolves in the dealloying solution and a metal other than the leachable element is treated with the dealloying solution. Specifically, the porous layer can be formed by treating a precursor layer containing an alloy of a leachable element that dissolves in the dealloying solution and a metal other than the leachable element with the dealloying solution. By the dealloying method, the leachable element contained in the precursor layer is dissolved into the dealloying solution, and a porous layer is formed.

[0004] Japanese Patent Application Laid-Open No. 2021-45709

[0005] Conventional laminates having a porous layer are manufactured by sequentially forming multiple constituent layers on a substrate using a batch-type film formation method, which results in poor productivity and makes them unsuitable for mass production.

[0006] An object of the present invention is to provide a method for producing a laminated film including a substrate and a porous layer with good productivity.

[0007] [1] A method for producing a laminate film according to an embodiment of the present invention is a method for producing a laminate film including a substrate and a porous layer, and includes a precursor layer forming step of forming a precursor layer on at least one side of the substrate, and a dealloying step of dealloying the precursor layer to form the porous layer, where the precursor layer is formed while the substrate is being transported by a roll-to-roll process. [2] In the method for producing a laminate film described in [1] above, the dealloying treatment may be performed while the substrate is being transported by a roll-to-roll process. [3] In the method for producing a laminate film described in [1] or [2] above, the method may include an adhesion layer forming step of forming an adhesion layer on at least one surface of the substrate, where the precursor layer forming step may be performed after the adhesion layer forming step, and the precursor layer may be formed on the surface of the adhesion layer. [4] In the method for producing a laminate film described in [3] above, the adhesion layer may be formed while the substrate is being transported by a roll-to-roll process. [5] In the method for producing a laminate film described in any one of [1] to [4] above, the precursor layer may be formed by co-sputtering or sputtering of an alloy target. [6] In the method for producing a laminated film according to any one of [3] to [5] above, the adhesion layer may be formed by sputtering a single metal target, co-sputtering, or sputtering an alloy target.

[0008] According to the present invention, it is possible to provide a method for producing a laminated film including a substrate and a porous layer with high productivity.

[0009] 1 is a schematic cross-sectional view showing an embodiment of a method for producing a laminated film of the present invention, in which an adhesion layer forming step and a precursor layer forming step are performed by a roll-to-roll process, and FIG. 2 is a schematic cross-sectional view showing an embodiment of a method for producing a laminated film of the present invention, in which a dealloying step is performed by a roll-to-roll process.

[0010] [Terminology] In this specification, when the expression "weight" appears, it may be read as "mass," which is commonly used as an SI unit indicating weight, and vice versa.

[0011] 1. Method for producing laminated film A method for producing a laminated film according to an embodiment of the present invention is a method for producing a laminated film including a substrate and a porous layer. The laminated film obtained by the production method according to an embodiment of the present invention may include any appropriate other layer as long as it includes the substrate and the porous layer, as long as the effects of the present invention are not impaired.

[0012] The laminated film obtained by the manufacturing method according to the embodiment of the present invention may have a porous layer on only one side of the substrate, or may have porous layers on both sides of the substrate.

[0013] In the laminate film obtained by the manufacturing method according to the embodiment of the present invention, the substrate and the porous layer may be directly laminated. That is, the laminate film obtained by the manufacturing method according to the embodiment of the present invention may include a laminate structure in which the substrate and the porous layer are laminated in this order. A representative example of the laminate film according to such an embodiment is a laminate film in which the substrate and the porous layer are laminated in this order.

[0014] In the laminate film obtained by the manufacturing method according to an embodiment of the present invention, the substrate and the porous layer may be laminated via an adhesive layer described later. That is, the laminate film obtained by the manufacturing method according to an embodiment of the present invention may include a laminate structure in which the substrate, the adhesive layer, and the porous layer are laminated in this order. A representative example of the laminate film according to such an embodiment is a laminate film in which the substrate, the adhesive layer, and the porous layer are laminated in this order.

[0015] A method for producing a laminated film according to an embodiment of the present invention includes a precursor layer forming step of forming a precursor layer on at least one side of a substrate, and a dealloying step of subjecting the precursor layer to a dealloying treatment to form the porous layer.

[0016] <1-1. Precursor layer forming step> In the precursor layer forming step, a precursor layer is formed on at least one side of the substrate. The precursor layer may be formed on the substrate, or may be formed on an adhesion layer formed in the adhesion layer forming step described below.

[0017] The precursor layer can be formed by any appropriate method as long as the effects of the present invention are not impaired. For example, the precursor layer is formed by a vacuum film formation method, specifically, by vapor deposition or sputtering.

[0018] The precursor layer is preferably formed by sputtering. Examples of formation by sputtering include co-sputtering using multiple targets (sometimes referred to as simultaneous sputtering) and sputtering of an alloy target. The precursor layer is more preferably formed by co-sputtering or sputtering of an alloy target, and is even more preferably formed by sputtering of an alloy target, in that the effects of the present invention can be more effectively exhibited.

[0019] Any appropriate sputtering conditions may be adopted as long as they do not impair the effects of the present invention. The atmosphere during sputtering may be, for example, a rare gas atmosphere such as argon. The pressure during sputtering may be, for example, 0.1 Pa to 10 Pa. Examples of the discharge method for sputtering include DC discharge, RF discharge, and MF-AC discharge. The sputtering temperature may be set to any appropriate temperature depending on the type of substrate, etc. The sputtering temperature may be, for example, -10°C to 150°C (e.g., sputtering onto a PET substrate), -10°C to 500°C (e.g., sputtering onto a PI substrate), or -10°C to 1000°C (e.g., sputtering onto a metal substrate).

[0020] In embodiments in which the precursor layer is formed by co-sputtering, the precursor layer is preferably formed by co-sputtering a first metal target with at least one selected from the group consisting of a second target and a second alloy target.

[0021] In an embodiment in which the precursor layer is formed by co-sputtering, the first metal target is preferably a leaching element. Examples of the leaching element include elements that dissolve in a dealloying solution in a dealloying method for an alloy. In terms of further demonstrating the effects of the present invention, the leaching element is preferably at least one element selected from the group consisting of Al, Zn, Ag, and Sn. The first metal target may be one type, or two or more types.

[0022] In an embodiment in which the precursor layer is formed by co-sputtering, the second target is preferably at least one selected from the group consisting of a metal element other than the eluted element, a metalloid element, and carbon. The second target may be one type or two or more types.

[0023] Any appropriate metal element can be used as the metal element other than the eluting element as long as it does not impair the effects of the present invention. The metal element other than the eluting element may be one type only, or two or more types. When there are two or more types of metal elements other than the eluting element, the two or more types of metals may be an alloy.

[0024] The metal elements other than the eluted elements typically include at least one selected from the group consisting of noble metal elements and base metal elements. The noble metal elements may be one type only, or two or more types. The base metal elements may be one type only, or two or more types.

[0025] Any appropriate noble metal element may be used as long as it does not impair the effects of the present invention, such as at least one selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, and Au.

[0026] Any appropriate base metal element may be used as the base metal element as long as it does not impair the effects of the present invention. Examples of the base metal element include metal elements other than noble metal elements, and preferably at least one selected from the group consisting of Mg, P, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ce, Pr, Ta, W, and Bi.

[0027] As the metalloid element, any appropriate metalloid element can be used as long as it does not impair the effects of the present invention. Examples of the metalloid element include B, Si, Ge, As, Sb, and Te, and preferably at least one element selected from the group consisting of B, Si, Ge, and Sb.

[0028] In an embodiment in which the precursor layer is formed by co-sputtering, the second alloy target is preferably an alloy composed of at least two elements selected from the group consisting of metal elements other than the eluted elements, metalloid elements, and carbon. The second alloy target may be one element or two or more elements.

[0029] In an embodiment in which the precursor layer is formed by co-sputtering, the first metal target, the second target, and the second alloy target may be selected and the sputtering conditions may be appropriately set so that the content ratio of the eluted elements in the resulting precursor layer to at least one selected from the group consisting of metal elements other than the eluted elements, metalloid elements, and carbon, expressed as atomic weight percent (at %) of [eluted elements]:[total of metal elements other than the eluted elements, metalloid elements, and carbon], is preferably in the range of 30:70 to 99.9:0.1, more preferably 50:50 to 99:1, even more preferably 60:40 to 98:2, still more preferably 70:30 to 97:3, particularly preferably 75:25 to 96:4, and most preferably 80:20 to 95:5.

[0030] In an embodiment in which the precursor layer is formed by sputtering an alloy target, the alloy target is preferably an alloy composed of a leaching element and at least one element selected from the group consisting of a metal element other than the leaching element, a metalloid element, and carbon. The alloy target may be of only one type, or of two or more types.

[0031] In an embodiment in which the precursor layer is formed by sputtering an alloy target, the alloy target may be selected and the sputtering conditions may be appropriately set so that the content ratio of the eluted elements in the resulting precursor layer to at least one selected from the group consisting of metal elements other than the eluted elements, metalloid elements, and carbon, expressed as atomic weight percent (at %) of [eluted elements]:[total of metal elements other than the eluted elements, metalloid elements, and carbon], is preferably in the range of 30:70 to 99.9:0.1, more preferably 50:50 to 99:1, even more preferably 60:40 to 98:2, still more preferably 70:30 to 97:3, particularly preferably 75:25 to 96:4, and most preferably 80:20 to 95:5.

[0032] When forming the precursor layer, film formation by sputtering may be performed multiple times for the purpose of adjusting the thickness (especially, adjusting to increase the thickness), etc. Furthermore, the number of targets may be increased for the purpose of adjusting the thickness (especially, adjusting to increase the thickness), etc.

[0033] In the precursor layer forming step, a precursor layer is preferably formed that contains an alloy of the eluted element and at least one element selected from the group consisting of a metal element other than the eluted element, a metalloid element, and carbon.

[0034] <1-2. Dealloying Step> In the dealloying step, the precursor layer obtained in the precursor layer forming step is subjected to a dealloying treatment to form a porous layer.

[0035] In the dealloying step, any appropriate method can be used as long as it is a method for removing eluted elements contained in the precursor layer. For example, a dealloying method in which the precursor layer is treated with a dealloying solution can be mentioned. This method allows the eluted elements contained in the precursor layer to be dissolved into the dealloying solution, and a porous layer having a porous structure can be formed. Any appropriate conditions for the dealloying method can be used as long as the treatment with the dealloying solution can be performed at an appropriate temperature, without impairing the effects of the present invention.

[0036] The dealloying solution may be, for example, any suitable acidic, alkaline, or neutral solution that can be used in a dealloying method. The concentration of the dealloying solution may be any suitable concentration depending on the purpose.

[0037] Examples of the acidic solution include an aqueous solution of hydrochloric acid, an aqueous solution of nitric acid, an aqueous solution of sulfuric acid, an aqueous solution of phosphoric acid, an aqueous solution of acetic acid, and a mixture thereof. Examples of the alkaline solution include an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide.

[0038] The treatment temperature in the dealloying method is, for example, 5° C. or higher, and may be 10° C. or higher, 20° C. or higher, 30° C. or higher, 40° C. or higher, 50° C. or higher, 60° C. or higher, 70° C. or higher, 80° C. or higher, 90° C. or higher, or 100° C. The upper limit of the treatment temperature in the dealloying method is, for example, less than 300° C.

[0039] In the dealloying method, the treatment with the dealloying solution may be carried out under normal pressure or under pressure. As a method for carrying out the treatment under pressure, any appropriate pressurizing method may be adopted as long as it does not impair the effects of the present invention. Such a pressurizing method may, for example, be pressurizing in a pressure-resistant vessel such as an autoclave.

[0040] <1-3. Adhesion Layer Forming Step> The method for producing a laminated film according to an embodiment of the present invention may include an adhesion layer forming step of forming an adhesion layer on at least one surface of a substrate before the precursor layer forming step. In this case, the method for producing a laminated film according to an embodiment of the present invention includes an adhesion layer forming step of forming an adhesion layer on at least one surface of a substrate, a precursor layer forming step after the adhesion layer forming step, and a dealloying step after the precursor layer forming step. In this case, one preferred embodiment of the present invention includes forming a precursor layer on the adhesion layer formed in the adhesion layer forming step by the precursor layer forming step.

[0041] The adhesion layer can be formed by any appropriate method as long as the effects of the present invention are not impaired. The adhesion layer is typically formed by a vacuum film formation method, for example, by vapor deposition or sputtering.

[0042] Examples of the formation by sputtering include single target sputtering, co-sputtering (sometimes referred to as simultaneous sputtering), and alloy target sputtering, with single target sputtering being typical.

[0043] Any appropriate sputtering conditions may be adopted as long as they do not impair the effects of the present invention. The atmosphere during sputtering may be, for example, a rare gas atmosphere such as argon. The pressure during sputtering may be, for example, 0.1 Pa to 10 Pa. Examples of the discharge method for sputtering include DC discharge, RF discharge, and MF-AC discharge. The sputtering temperature may be set to any appropriate temperature depending on the type of substrate, etc. The sputtering temperature may be, for example, -10°C to 150°C (e.g., sputtering onto a PET substrate), -10°C to 500°C (e.g., sputtering onto a PI substrate), or -10°C to 1000°C (e.g., sputtering onto a metal substrate).

[0044] In an embodiment in which the adhesion layer is formed by sputtering a single target, the single target is, for example, at least one selected from the group consisting of a metal element, a metalloid element, and carbon.

[0045] The metal element typically includes at least one selected from the group consisting of a noble metal element and a base metal element. The noble metal element may be only one type, or two or more types. The base metal element may be only one type, or two or more types.

[0046] Any appropriate noble metal element may be used as long as it does not impair the effects of the present invention, such as at least one selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, and Au.

[0047] Any appropriate base metal element may be used as the base metal element as long as it does not impair the effects of the present invention. Examples of the base metal element include metal elements other than noble metal elements, and preferably at least one selected from the group consisting of Mg, P, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ce, Pr, Ta, W, and Bi.

[0048] As the metalloid element, any appropriate metalloid element can be used as long as it does not impair the effects of the present invention. Examples of the metalloid element include B, Si, Ge, As, Sb, and Te, and preferably at least one element selected from the group consisting of B, Si, Ge, and Sb.

[0049] In one preferred embodiment, the adhesion layer contains at least one selected from the group consisting of a base metal element, a metalloid element, and carbon. In this embodiment, the adhesion layer does not necessarily contain a noble metal element.

[0050] In an embodiment in which the adhesion layer is formed by single-target sputtering, when a resin substrate (such as a polyethylene terephthalate (PET) substrate) is used as the substrate, it is a preferred embodiment in that the effects of the present invention can be more effectively exhibited by using at least one selected from the group consisting of base metal elements, metalloid elements, and carbon as the single target. On the other hand, in an embodiment in which the adhesion layer is formed by single-target sputtering, when carbon paper or carbon paper on which an MPL (Micro Porous Layer) is formed is used as the substrate, a noble metal element may be used as the single target. Therefore, it is a preferred embodiment in that the effects of the present invention can be more effectively exhibited by using at least one selected from the group consisting of metal elements (noble metal elements and base metal elements), metalloid elements, and carbon as the single target.

[0051] In an embodiment in which the adhesion layer is formed by co-sputtering, for example, it is formed by co-sputtering two of the above-mentioned single targets. When a resin substrate (such as a polyethylene terephthalate (PET) substrate) is used as the substrate, it is preferable to select at least one selected from the group consisting of base metal elements, metalloid elements, and carbon as at least one of the two single targets. When carbon paper or carbon paper with a microporous layer (MPL) formed thereon is used as the substrate, it is preferable to select at least one selected from the group consisting of metal elements (noble metal elements and base metal elements), metalloid elements, and carbon as at least one of the two single targets.

[0052] In an embodiment in which the adhesion layer is formed by sputtering an alloy target, the alloy target is an alloy composed of at least two elements selected from the group consisting of a metal element, a metalloid element, and carbon.

[0053] When a resin substrate (such as a polyethylene terephthalate (PET) substrate) is used as the substrate, it is preferable to select an alloy containing at least one selected from the group consisting of base metal elements, metalloid elements, and carbon as the alloy target. Furthermore, when carbon paper or carbon paper with a microporous layer (MPL) formed thereon is used as the substrate, an alloy containing at least one selected from the group consisting of metal elements (noble metal elements and base metal elements), metalloid elements, and carbon may be selected as the alloy target.

[0054] Before sputtering, the sputtering target (typically a substrate) may be cleaned by subjecting it to a plasma treatment, such as ion bombardment. Any appropriate conditions for the plasma treatment may be adopted as long as the effects of the present invention are not impaired.

[0055] <1-4. Roll-to-roll Process> In the method for producing a laminated film according to an embodiment of the present invention, the precursor layer is formed while the substrate is being transported by a roll-to-roll process.

[0056] In the laminate film manufacturing method according to an embodiment of the present invention, the dealloying treatment may be performed while the substrate is being transported by a roll-to-roll process. That is, in one embodiment of the laminate film manufacturing method according to the present invention, the formation of the precursor layer and the dealloying treatment are performed while the substrate is being transported by a roll-to-roll process.

[0057] In the laminated film manufacturing method according to an embodiment of the present invention, the adhesion layer may be formed while the substrate is being transported by a roll-to-roll process. That is, in one embodiment of the laminated film manufacturing method according to the present invention, the adhesion layer and the precursor layer are formed while the substrate is being transported by a roll-to-roll process.

[0058] In a method for producing a laminated film according to one embodiment of the present invention, the formation of the adhesive layer, the formation of the precursor layer, and the dealloying treatment are carried out while the substrate is being transported in a roll-to-roll process.

[0059] A schematic explanatory diagram of one preferred embodiment of the method for producing a laminated film of the present invention is shown in Figure 1 and Figures 2 and 3. However, the embodiment shown in Figure 1 and the embodiment shown in Figures 2 and 3 are merely outlines of two preferred embodiments of the method for producing a laminated film of the present invention, and the present invention is not limited to the embodiment shown in Figure 1 and the embodiment shown in Figures 2 and 3.

[0060] Fig. 1 shows an embodiment in which the adhesion layer forming process, precursor layer forming process, and dealloying process are performed in a single pass roll-to-roll process. In the embodiment shown in Fig. 1, a substrate 100 unwound from a winding roll 10 is introduced into a sputtering apparatus 1000, where the adhesion layer forming process and precursor layer forming process are performed, resulting in a laminate 150 having an adhesion layer (not shown) and a precursor layer (not shown) on the substrate 100. The laminate 150 is then introduced into a dealloying processing apparatus 2000, where the dealloying process is performed. Finally, a laminate film 200 having an adhesion layer (not shown) and a porous layer (not shown) on the substrate 100 is wound onto a winding roll 20. While Fig. 1 shows rollers 1a, 1b, 1c, and 1d, the number of rollers does not need to be limited to four; any appropriate number of rollers may be arranged in any appropriate position as long as the effects of the present invention are not impaired.

[0061] In FIG. 1, in the sputtering apparatus 1000, for example, the atmosphere and pressure during sputtering described above can be set.

[0062] 1, the atmosphere and pressure before the substrate 100 is introduced into the sputtering apparatus 1000 may be set to any appropriate conditions. The atmosphere and pressure before the substrate 100 is introduced into the sputtering apparatus 1000 may be, for example, an air atmosphere or atmospheric pressure, may be the same conditions as those inside the sputtering apparatus 1000, or may be any other appropriate conditions.

[0063] 1, the atmosphere and pressure can be set to any appropriate conditions after the stack 150 is unloaded from the sputtering apparatus 1000. The atmosphere and pressure after the stack 150 is unloaded from the sputtering apparatus 1000 may be, for example, under atmospheric pressure in the air atmosphere, may be the same conditions as those in the sputtering apparatus 1000, or may be any other appropriate conditions.

[0064] 2 and 3 show an embodiment in which the adhesion layer forming step, precursor layer forming step, and dealloying step are performed by a two-pass roll-to-roll process. Fig. 2 shows an embodiment in which the adhesion layer forming step and precursor layer forming step are performed by a roll-to-roll process, and Fig. 3 shows an embodiment in which the dealloying step is performed by a roll-to-roll process.

[0065] As shown in Fig. 2, the substrate 100 unwound from the unwinding roll 10 is introduced into a sputtering apparatus 1000, where an adhesion layer forming step and a precursor layer forming step are performed, and a laminate 150 having an adhesion layer (not shown) and a precursor layer (not shown) on the substrate 100 is taken up by a take-up roll 15. Although rollers 1a, 1b, 1c, and 1e are shown in Fig. 1, the number of rollers does not need to be limited to four, and any appropriate number of rollers may be arranged in any appropriate positions as long as the effects of the present invention are not impaired.

[0066] In FIG. 2, in the sputtering apparatus 1000, for example, the atmosphere and pressure during sputtering can be set as described above.

[0067] 2, the atmosphere and pressure before the substrate 100 is introduced into the sputtering apparatus 1000 may be set to any appropriate conditions. The atmosphere and pressure before the substrate 100 is introduced into the sputtering apparatus 1000 may be, for example, an air atmosphere or atmospheric pressure, may be the same conditions as those inside the sputtering apparatus 1000, or may be any other appropriate conditions.

[0068] 2, the atmosphere and pressure can be set to any appropriate conditions after the stack 150 is unloaded from the sputtering apparatus 1000. The atmosphere and pressure after the stack 150 is unloaded from the sputtering apparatus 1000 may be, for example, under atmospheric pressure in the air atmosphere, may be the same conditions as those inside the sputtering apparatus 1000, or may be any other appropriate conditions.

[0069] The laminate 150 wound around the winding roll 15 in FIG. 2 is then unwound from the winding roll 15 and introduced into a dealloying treatment device 2000, as shown in FIG. 3, where the dealloying process is performed. Finally, a laminate film 200 including the substrate 100 and a porous layer (not shown) is wound around the winding roll 20. While rollers 1f and 1d are shown in FIG. 3, the number of rollers does not need to be limited to these two; any appropriate number of rollers may be disposed in any appropriate positions as long as the effects of the present invention are not impaired. The atmosphere and pressure of the process shown in FIG. 3 may be set to any appropriate conditions. For example, the process may be performed under atmospheric pressure in an air atmosphere, under conditions similar to those in the sputtering device 1000, or under any other appropriate conditions.

[0070] 1 and 2 , in sputtering apparatus 1000, a substrate 100 is transported and placed on sputtering roll 50, where an adhesion layer is formed by sputtering using a sputtering target material 300 (typically a single metal target) for forming an adhesion layer, and then a precursor layer is formed on the adhesion layer by sputtering using a sputtering target material 400 (typically an alloy target) for forming a precursor layer. Details of the sputtering for forming the adhesion layer and the sputtering for forming the precursor layer are as described above.

[0071] In a laminate film manufacturing method according to an embodiment of the present invention, as shown in Figures 1 and 2-3, a laminate film including a substrate and a porous layer can be manufactured with high productivity by forming the substrate while conveying it using a roll-to-roll process. Furthermore, as shown in Figures 1 and 2, by forming multiple constituent layers on the substrate using a sputtering target material while conveying the substrate using a roll-to-roll process, the number of passes required to form the constituent layers can be reduced compared to, for example, forming multiple constituent layers sequentially using batch-type film formation. Furthermore, by reducing the number of passes required to form the constituent layers in this way, it is possible to suppress appearance abnormalities in the resulting laminate film (such as peeling of the porous layer from the substrate), ensuring a good appearance, and facilitating quality control.

[0072] According to the manufacturing method of the embodiment of the present invention, by manufacturing while conveying the substrate by a roll-to-roll process, it is possible to easily manufacture a long laminate film compared to the case of forming by a conventional batch-type film formation. The length in the longitudinal direction of such a long laminate film is, for example, 100 mm or more, or may be 500 mm or more, or may be 1000 mm or more.

[0073] 2. Laminated Film The laminated film obtained by the production method according to the embodiment of the present invention includes a substrate and a porous layer. The laminated film obtained by the production method according to the embodiment of the present invention may have a porous layer on only one side of the substrate, or may have porous layers on both sides of the substrate.

[0074] In the laminate film obtained by the manufacturing method according to the embodiment of the present invention, the substrate and the porous layer may be directly laminated. That is, the laminate film obtained by the manufacturing method according to the embodiment of the present invention may include a laminate structure in which the substrate and the porous layer are laminated in this order. A representative example of the laminate film according to such an embodiment is a laminate film in which the substrate and the porous layer are laminated in this order.

[0075] In the laminate film obtained by the manufacturing method according to an embodiment of the present invention, the substrate and the porous layer may be laminated via an adhesive layer described later. That is, the laminate film obtained by the manufacturing method according to an embodiment of the present invention may include a laminate structure in which the substrate, the adhesive layer, and the porous layer are laminated in this order. A representative example of the laminate film according to such an embodiment is a laminate film in which the substrate, the adhesive layer, and the porous layer are laminated in this order.

[0076] The total thickness of the laminate film of the present invention may be any appropriate thickness depending on the purpose, as long as the effects of the present invention are not impaired. The total thickness of the laminate film of the present invention may be, for example, 1 μm to 2000 μm, 50 μm to 1400 μm, 100 μm to 1000 μm, 130 μm to 600 μm, 150 μm to 500 μm, 150 μm to 300 μm, or 150 μm to 250 μm. For example, in an embodiment in which a porous layer is provided on only one side of the substrate, the total thickness of the laminate film of the present invention may be 1 μm to 1000 μm, 50 μm to 700 μm, 100 μm to 500 μm, 130 μm to 300 μm, or 150 μm to 250 μm.

[0077] <2-1. Substrate> Any appropriate substrate can be used as the substrate as long as it does not impair the effects of the present invention. The substrate may be composed of a single layer or may be a laminate of two or more layers.

[0078] The thickness of the substrate may be any appropriate thickness depending on the purpose as long as the effects of the present invention are not impaired. The thickness of the substrate is, for example, 1 μm to 1000 μm, or may be 50 μm to 700 μm, 100 μm to 500 μm, 130 μm to 300 μm, or 150 μm to 250 μm.

[0079] The substrate may be any appropriate material depending on the purpose, as long as the effect of the present invention is not impaired.

[0080] Examples of the substrate include resin substrates (e.g., polyethylene terephthalate (PET) substrates and polyimide (PI) substrates), composite substrates containing resin (e.g., Zirfon (registered trademark) manufactured by AGFA), metal substrates (e.g., Cu foil, Ti foil, Ti fibrous body (e.g., Pt-plated Ti fibrous body), Ni porous body), carbon composite materials (e.g., carbon paper, carbon paper on which MPL (Micro Porous Layer) is formed), cation exchange membranes (e.g., Nafion (registered trademark) and hydrocarbon-based electrolyte membranes), anion exchange membranes (e.g., polybenzimidazole (PBI) membranes), semiconductor substrates (e.g., silicon substrates), and glass substrates.

[0081] One embodiment of the substrate is an electrolyte membrane. Examples of electrolyte membranes include composite substrates containing resin (for example, Zirfon (registered trademark) manufactured by AGFA), cation exchange membranes (for example, Nafion (registered trademark) and hydrocarbon-based electrolyte membranes), and anion exchange membranes (for example, polybenzimidazole (PBI) membranes). When the substrate is an electrolyte membrane, the laminate film according to an embodiment of the present invention may be a catalyst composite for water electrolysis (a laminate composite including a porous layer as a catalyst layer and an electrolyte membrane) or a catalyst composite for fuel cells (a laminate composite including a porous layer as a catalyst layer and an electrolyte membrane), and may be a catalyst composite for water electrolysis or a catalyst composite for fuel cells that has excellent durability. Furthermore, when the substrate is an electrolyte membrane, the laminate film according to an embodiment of the present invention may be a catalyst composite for water electrolysis or a catalyst composite for fuel cells that has excellent durability. ２ It can be a catalyst composite (a laminate composite including a porous layer as a catalyst layer and an electrolyte membrane) for electrolysis (for example, for the electrolytic synthesis of formic acid or synthetic fuels), and has excellent durability. ２ It may be an electrolytic catalytic composite.

[0082] As one embodiment of the substrate, the surface on the porous layer side of the substrate may contain a resin. As the substrate of such an embodiment, any suitable substrate can be adopted as long as it contains a resin component on at least one surface, as long as the effects of the present invention are not impaired. In addition to the above-mentioned resin substrate, the substrate of such an embodiment includes, for example, the above-mentioned composite substrate containing a resin component on at least one surface, a MPL (Micro Porous Layer) composed of a resin formed on carbon paper, a cation exchange membrane containing a resin component on at least one surface, an anion exchange membrane containing a resin component on at least one surface, and a laminated substrate having a resin layer on at least one surface of a non-resin layer (such as a metal layer).

[0083] <2-2. Porous Layer> The thickness of the porous layer may be any appropriate thickness depending on the purpose, as long as the effects of the present invention are not impaired. The thickness of the porous layer is, for example, 1 nm to 3000 nm, or may be 10 nm to 2000 nm, 50 nm to 1500 nm, 100 μm to 1000 nm, or 200 nm to 800 nm.

[0084] The porous layer may be composed of one layer or may be a laminate of two or more layers.

[0085] The porous layer has a porous structure, which increases the surface area of ​​the porous layer and can provide various effects, such as increased gas diffusivity and high catalytic activity.

[0086] The porous layer contains at least one selected from the group consisting of a metal element, a metalloid element, and carbon. The porous layer may contain any other appropriate component as long as the effects of the present invention are not impaired.

[0087] Any appropriate metal element may be used as the metal element contained in the porous layer as long as the effects of the present invention are not impaired. The metal element may be one type only, or two or more types. When the porous layer contains two or more types of metal elements, the two or more types of metals may be an alloy.

[0088] The metal element typically includes at least one selected from the group consisting of a noble metal element and a base metal element. The noble metal element may be only one type, or two or more types. The base metal element may be only one type, or two or more types.

[0089] Any appropriate noble metal element may be used as long as it does not impair the effects of the present invention, such as at least one selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, and Au.

[0090] Any appropriate base metal element may be used as the base metal element as long as it does not impair the effects of the present invention. Examples of the base metal element include metal elements other than noble metal elements, and preferably at least one selected from the group consisting of Mg, P, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ce, Pr, Ta, W, and Bi.

[0091] As the metalloid element, any appropriate metalloid element can be used as long as it does not impair the effects of the present invention. Examples of the metalloid element include B, Si, Ge, As, Sb, and Te, and preferably at least one element selected from the group consisting of B, Si, Ge, and Sb.

[0092] The metal elements that can be contained in the porous layer include eluted elements (for example, at least one selected from the group consisting of Al, Zn, Ag, and Sn). However, when a porous layer having a porous structure is formed by treating a precursor layer containing an alloy of an eluted element that dissolves in a dealloying solution and at least one selected from the group consisting of a metal element other than the eluted element, a metalloid element, and carbon with a dealloying solution, the eluted elements contained in the precursor layer are eluted in the dealloying solution, so the content of the eluted elements in the formed porous layer is reduced. In this case, the content of the total of the eluted elements (preferably the total of Al, Zn, Ag, and Sn) in the porous layer is, for example, 30 atomic weight % or less, and may be 25 atomic weight % or less, 20 atomic weight % or less, 15 atomic weight % or less, 12 atomic weight % or less, 10 atomic weight % or less, 8 atomic weight % or less, 6 atomic weight % or less, 4 atomic weight % or less, 2 atomic weight % or less, 1 atomic weight % or less, 0.1 atomic weight % or less, or substantially 0 atomic weight %.

[0093] In order to further exert the effects of the present invention, the total content of metal elements, metalloid elements, and carbon other than elutable elements in the porous layer is preferably 70 atomic weight % or more, may be 75 atomic weight % or more, may be 80 atomic weight % or more, may be 85 atomic weight % or more, may be 88 atomic weight % or more, may be 90 atomic weight % or more, may be 92 atomic weight % or more, may be 94 atomic weight % or more, may be 96 atomic weight % or more, may be 98 atomic weight % or more, may be 99 atomic weight % or more, may be 99.9 atomic weight % or more, or may be substantially 100 atomic weight %.

[0094] The porous layer may contain any other appropriate component within the range that does not impair the effects of the present invention.

[0095] The porous layer can be formed by treating a precursor layer containing eluted elements that dissolve in the dealloying solution, as well as metal elements other than the eluted elements, metalloid elements, and alloys with carbon, with the dealloying solution. By the dealloying method, the eluted elements contained in the precursor layer are eluted into the dealloying solution, and a porous layer having a porous structure is formed.

[0096] The precursor layer typically contains an alloy of a soluble element with a metal element other than the soluble element, a metalloid element, and carbon. Note that the term "alloy" as used herein also includes alloy steel (an alloy of a soluble element and a metalloid element, an alloy of a soluble element and carbon, or an alloy of a soluble element, a metalloid element, and carbon). The soluble element may be of only one type, or two or more types. The metal element other than the soluble element may be of only one type, or two or more types. The metalloid element may be of only one type, or two or more types.

[0097] When the precursor layer contains an alloy of a leachable element and at least one selected from the group consisting of a metal element other than the leachable element, a metalloid element, and carbon, the content ratio of the leachable element to the at least one selected from the group consisting of a metal element other than the leachable element, a metalloid element, and carbon in the precursor layer, expressed as atomic weight percent (at %) of [leachable element]:[total of metal elements other than the leachable element, metalloid element, and carbon], may be, for example, 30:70 to 99.9, alternatively, 50:50 to 99:1, 60:40 to 98:2, 70:30 to 97:3, 75:25 to 96:4, or 80:20 to 95:5, in terms of atomic weight percent (at %).

[0098] Examples of the eluting element include elements that dissolve in a dealloying solution during alloy dealloying. In order to further enhance the effects of the present invention, the eluting element is preferably at least one element selected from the group consisting of Al, Zn, Ag, and Sn. Therefore, the precursor layer preferably contains an alloy of at least one eluting element selected from the group consisting of Al, Zn, Ag, and Sn and at least one element selected from the group consisting of a metal element, a metalloid element, and carbon other than the eluting element.

[0099] Examples of metal elements other than the eluted elements include at least one selected from the group consisting of Mg, P, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ce, Pr, Ta, W, Os, Ir, Pt, Au, and Bi.

[0100] <2-3. Adhesion Layer> The thickness of the adhesion layer may be any appropriate total thickness as long as the effects of the present invention are not impaired. In terms of further exhibiting the effects of the present invention, the thickness of the adhesion layer is, for example, 1 nm to 1000 nm, or may be 1 nm to 500 nm, 2 nm to 500 nm, 3 nm to 500 nm, 4 nm to 500 nm, 5 nm to 500 nm, 5 nm to 300 nm, or 5 nm to 200 nm.

[0101] The adhesive layer may be made of one layer or may be a laminate of two or more layers.

[0102] The adhesive layer contains at least one selected from the group consisting of a metal element, a metalloid element, and carbon. The adhesive layer may contain any other appropriate component as long as the effects of the present invention are not impaired.

[0103] As the metal element that can be contained in the adhesive layer, any appropriate metal element can be adopted as long as the effects of the present invention are not impaired. The metal element may be only one type, or may be two or more types. When the adhesive layer contains two or more types of metal elements, the two or more types of metals may be an alloy.

[0104] The metal element typically includes at least one selected from the group consisting of a noble metal element and a base metal element. The noble metal element may be only one type, or two or more types. The base metal element may be only one type, or two or more types.

[0105] Any appropriate noble metal element may be used as long as it does not impair the effects of the present invention, such as at least one selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, and Au.

[0106] Any appropriate base metal element may be used as the base metal element as long as it does not impair the effects of the present invention. Examples of the base metal element include metal elements other than noble metal elements, and preferably at least one selected from the group consisting of Mg, P, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ce, Pr, Ta, W, and Bi.

[0107] As the metalloid element, any appropriate metalloid element can be used as long as it does not impair the effects of the present invention. Examples of the metalloid element include B, Si, Ge, As, Sb, and Te, and preferably at least one element selected from the group consisting of B, Si, Ge, and Sb.

[0108] In one preferred embodiment, the adhesion layer contains at least one selected from the group consisting of a base metal element, a metalloid element, and carbon. In this embodiment, the adhesion layer does not necessarily contain a noble metal element.

[0109] When a resin substrate (such as a polyethylene terephthalate (PET) substrate) is used as the substrate, it is a preferred embodiment that the adhesion layer contains at least one selected from the group consisting of base metal elements, semi-metal elements, and carbon, as this can further demonstrate the effects of the present invention. On the other hand, when carbon paper or carbon paper with an MPL (Micro Porous Layer) formed thereon is used as the substrate, the adhesion layer may contain a precious metal element, and therefore it is a preferred embodiment that the adhesion layer contains at least one selected from the group consisting of metal elements (noble metal elements and base metal elements), semi-metal elements, and carbon, as this can further demonstrate the effects of the present invention.

[0110] 3. Uses of the Laminated Film The laminated film according to an embodiment of the present invention can suppress deterioration and alteration of the porous layer, and therefore is suitable for optical applications (refractive index control members, etc.), catalytic applications (water electrolysis catalyst composites (laminated composites including a porous layer as a catalyst layer and an electrolyte membrane), fuel cell catalyst composites (laminated composites including a porous layer as a catalyst layer and an electrolyte membrane), CO ２ The laminated film according to the embodiment of the present invention can be applied to various applications, such as catalyst composites for electrolysis (for example, for the electrolytic synthesis of formic acid or synthetic fuels) (e.g., a laminate composite including a porous layer as a catalyst layer and an electrolyte membrane), thermocompression bonding (thermal lamination), and membrane applications (e.g., water evaporation promotion membranes). In particular, because the porous layer can function as a catalyst layer, the laminated film according to the embodiment of the present invention is suitable for use in catalyst composites for water electrolysis and catalyst composites for fuel cells.

[0111] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The test and evaluation methods used in the examples are as follows.

[0112] <Thickness of Layer Formed by Sputtering> The thickness of the layer formed by sputtering each element onto the glass substrate was calculated using a stylus film thickness step meter (Dektak, manufactured by Bruker). Based on the obtained layer thickness of each element and the elemental composition of the layer actually formed by sputtering, the thickness of the layer formed by sputtering was calculated, and this calculated thickness was defined as the thickness of the layer formed by sputtering.

[0113] <Productivity evaluation> Evaluation was made according to the following criteria. ◯: A long laminate film having a length of 100 mm or more in the longitudinal direction could be produced in roll form. Δ: A long laminate film having a length of 100 mm or more in the longitudinal direction could be produced, but not in roll form, and only in sheet form. ×: A long laminate film having a length of 100 mm or more in the longitudinal direction could not be produced.

[0114] <Evaluation of the Presence or Absence of Peeling of Porous Layer from Substrate (Evaluation of Appearance Abnormality)> The obtained laminated film was visually inspected to determine whether or not the porous layer had peeled from the substrate, and evaluated according to the following criteria: ◯: No peeling was observed. Δ: Spot-like peeling was observed in some areas. ×: Peeling was observed throughout the film.

[0115] <Abbreviations for substrates in Examples and Comparative Examples> PET: polyethylene terephthalate substrate, manufactured by Toyobo Co., Ltd., trade name "A4160", thickness = 188 μm PI: polyimide substrate, manufactured by Xenomax Japan Co., Ltd., trade name "XENOMAX", thickness = 38 μm Ni porous body: thickness = 0.3 mm (300 μm) Zirfon: manufactured by AGFA, trade name "Zirfon (registered trademark)", thickness = 500 μm Cu foil: manufactured by Fukuda Metal Foil & Powder Co., Ltd., thickness = 18 μm Carbon paper and carbon paper + MPL: manufactured by Mitsubishi Chemical Corporation

[0116] <Abbreviations of sputtering targets for adhesion layers in Examples and Comparative Examples> Cr: Cr target Ni: Ni target

[0117] <Abbreviations for sputtering targets in Examples and Comparative Examples> Ni10-Al90 (at%): Ni-Al alloy target, Ni:Al=10:90 (atomic weight % ratio) Cr10-Al90 (at%): Cr-Al alloy target, Cr:Al=10:90 (atomic weight % ratio)

[0118] <Abbreviations for dealloying solutions in Examples and Comparative Examples> NaOHaq: 0.5 M NaOH aqueous solution

[0119] Example 1: As shown in the schematic diagrams of Figures 2 and 3, a laminated film was produced using a two-pass roll-to-roll process. A polyethylene terephthalate substrate was prepared as the substrate. A PET substrate was unwound from a winding roll and transported using the roll-to-roll process. The substrate was first cleaned by ion bombardment in a roll-to-roll sputtering apparatus (Ar gas atmosphere, 0.3 Pa pressure). Subsequently, a Cr target was used as the sputtering target in the roll-to-roll sputtering apparatus, and a film was deposited at room temperature (23°C) to a thickness of 3 nm under an Ar gas atmosphere and 0.3 Pa pressure to form an adhesion layer. Next, a Ni-Al alloy target (Ni:Al = 10:90 (atomic weight ratio)) was used as the sputtering target in the roll-to-roll sputtering apparatus, and a film was deposited at room temperature (23°C) to a thickness of 500 nm under an Ar gas atmosphere and 0.3 Pa pressure to form a precursor layer on the adhesion layer. The resulting laminate was removed from the roll-to-roll sputtering apparatus, exposed to the atmosphere, and wound onto a take-up roll under atmospheric pressure. The wound laminate was then unwound from the take-up roll and introduced into a dealloying treatment device via a roll-to-roll process. It was then immersed in a 0.5 M NaOH aqueous solution as a dealloying solution at room temperature (23°C) for 10 minutes to perform dealloying treatment, and the eluted element Al was dissolved into the dealloying solution. After the dealloying treatment, the laminate was immersed in ion-exchanged water and washed for 3 minutes. The resulting laminate film was then removed from the dealloying treatment device, thoroughly dried in the atmosphere, and finally wound onto a take-up roll to obtain a long laminate film measuring 300 mm x 1000 mm. The results are shown in Table 1.

[0120] [Example 2] A long laminated film of 300 mm x 1000 mm was obtained in the same manner as in Example 1, except that the adhesive layer was formed to a thickness of 5 nm as shown in Table 1. The results are shown in Table 1.

[0121] [Example 3] A long laminated film of 300 mm x 1000 mm was obtained in the same manner as in Example 1, except that the adhesive layer was formed to a thickness of 50 nm as shown in Table 1. The results are shown in Table 1.

[0122] Example 4 A long laminated film measuring 300 mm x 1000 mm was obtained in the same manner as in Example 1, except that the adhesion layer was formed using a Ni target as the sputtering target under an Ar gas atmosphere at a pressure of 0.3 Pa and at room temperature (23°C) so as to have a film thickness of 5 nm, as shown in Table 1. The results are shown in Table 1.

[0123] [Example 5] A long laminated film of 300 mm x 1000 mm was obtained in the same manner as in Example 4, except that the adhesive layer was formed to a thickness of 50 nm as shown in Table 1. The results are shown in Table 1.

[0124] Example 6 A long laminated film measuring 300 mm x 1000 mm was obtained in the same manner as in Example 4, except that Zirfon was used as the substrate, as shown in Table 1. The results are shown in Table 1.

[0125] Example 7 A long laminated film measuring 300 mm x 1000 mm was obtained in the same manner as in Example 4, except that a Ni porous body was used as the substrate, as shown in Table 1. The results are shown in Table 1.

[0126] Example 8 A long laminate film measuring 300 mm x 1000 mm was obtained in the same manner as in Example 3, except that the precursor layer was formed using a Cr-Al alloy target (Cr:Al=10:90 (atomic weight ratio)) as the sputtering target under an Ar gas atmosphere at a pressure of 0.3 Pa and at room temperature (23°C) so as to have a film thickness of 500 nm, as shown in Table 1. The results are shown in Table 1.

[0127] Example 9 A long laminated film measuring 300 mm x 1000 mm was obtained in the same manner as in Example 1, except that the adhesive layer was not formed. The results are shown in Table 1.

[0128] [Example 10] The dealloying treatment was not performed using a roll-to-roll process, but rather a batch process. The film was immersed in a 0.5 M NaOH aqueous solution as a dealloying solution and allowed to stand at room temperature (23°C) for 10 minutes to dissolve the eluted element Al into the dealloying solution. After the dealloying treatment, the film was immersed in ion-exchanged water and allowed to stand for 3 minutes, followed by two cleaning steps. Then, the film was thoroughly air-dried in the air. The same procedure as in Example 1 was repeated to obtain a long laminate film in sheet form measuring 300 mm x 1000 mm. The results are shown in Table 1.

[0129] Example 11 A long laminate film measuring 300 mm x 1000 mm was obtained in the same manner as in Example 1, except that the adhesion layer was formed to a thickness of 10 nm, and the precursor layer was formed using a Pt-Al alloy target (Pt:Al = 10:90 (atomic weight ratio)) as the sputtering target, under an Ar gas atmosphere at a pressure of 0.3 Pa and at room temperature (23°C) to a thickness of 500 nm, as shown in Table 1. The results are shown in Table 1.

[0130] Example 12 A long laminated film of 300 mm x 1000 mm was obtained in the same manner as in Example 11, except that the adhesion layer was formed using a Pt target as the sputtering target under an Ar gas atmosphere at a pressure of 0.3 Pa and at room temperature (23°C) so as to have a film thickness of 10 nm, as shown in Table 1. The results are shown in Table 1.

[0131] Example 13 A long laminated film measuring 300 mm x 1000 mm was obtained in the same manner as in Example 2, except that the precursor layer was formed using a NiFe-Al alloy target (NiFe:Al = 10:90 (atomic weight ratio)) as the sputtering target under an Ar gas atmosphere at a pressure of 0.3 Pa and at room temperature (23°C) so as to have a film thickness of 500 nm, as shown in Table 1. The results are shown in Table 1.

[0132] Comparative Example 1 A laminated film was produced by a batch process. A PET substrate was prepared as the substrate. A multi-target simultaneous sputtering device (2-inch specification) was used. First, the substrate was introduced into the device, and the pressure was increased to 5.0 × 10 -4After confirming that the pressure was below 1 Pa, the substrate was cleaned by reverse sputtering. Reverse sputtering was performed at room temperature (23 ° C.) in an Ar gas atmosphere at 0.4 Pa, 30 W, and 60 seconds. Next, a Cr target was used as the sputtering target, and a film was formed at room temperature (23 ° C.) under an Ar gas atmosphere at a pressure of 0.3 Pa to a thickness of 3 nm, forming an adhesion layer. Next, a Ni-Al alloy target (Ni:Al = 10:90 (atomic weight %)) was used as the sputtering target, and a film was formed at room temperature (23 ° C.) under an Ar gas atmosphere at a pressure of 0.3 Pa to a thickness of 500 nm, forming a precursor layer. The obtained laminate was immersed in a 0.5 M NaOH aqueous solution as a dealloying solution and left to stand at room temperature (23 ° C.) for 10 minutes to perform a dealloying treatment, and the eluted element Al was dissolved into the dealloying solution. After the dealloying treatment, the film was immersed in ion-exchanged water and left to stand for 3 minutes, followed by two washing steps, and then thoroughly air-dried in the air. Finally, a 60 mm x 60 mm laminated film was obtained. The results are shown in Table 1.

[0133]

[0134] The laminated film obtained by the manufacturing method according to the embodiment of the present invention is suitable for optical applications (refractive index control members, etc.), catalytic applications (catalyst composites for water electrolysis (laminated composites including a porous layer as a catalyst layer and an electrolyte membrane), catalyst composites for fuel cells (laminated composites including a porous layer as a catalyst layer and an electrolyte membrane), CO ２ It can be used for a variety of applications, including electrolysis (for example, for the electrolytic synthesis of formic acid or synthetic fuels), catalyst composites (laminated composites including a porous layer as a catalyst layer and an electrolyte membrane), thermocompression bonding (thermal lamination), and membrane applications (e.g., membranes for promoting water evaporation).

Claims

1. A method for producing a laminated film comprising a substrate and a porous layer, the method comprising: a precursor layer forming step of forming a precursor layer on at least one side of the substrate; and a dealloying step of subjecting the precursor layer to a dealloying treatment to form the porous layer, wherein the precursor layer is formed while the substrate is being transported in a roll-to-roll process.

2. The method for producing a laminated film according to claim 1, wherein the dealloying treatment is carried out while the substrate is being transported in a roll-to-roll process.

3. A method for producing a laminated film according to claim 1, comprising a step of forming an adhesive layer on at least one surface of the substrate, and a step of forming a precursor layer after the step of forming the adhesive layer, to form the precursor layer on the surface of the adhesive layer.

4. The method for producing a laminated film according to claim 3, wherein the adhesive layer is formed while the substrate is being transported by a roll-to-roll process.

5. The method for producing a laminated film according to claim 1, wherein the precursor layer is formed by co-sputtering or sputtering of an alloy target.

6. The method for producing a laminated film according to claim 3, wherein the adhesion layer is formed by sputtering a single metal target, co-sputtering, or sputtering an alloy target.

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