JP2016201219A - Catalyst layer transfer base material, manufacturing method for membrane electrode assembly, and membrane electrode assembly - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst layer transfer base material capable of suppressing exposure of a polymer electrolyte membrane from between an electrode catalyst layer and a gasket layer, and to provide a manufacturing method for a membrane electrode assembly, and a membrane electrode assembly.SOLUTION: A catalyst layer transfer base material 10C includes a base material layer 11C, and a multilayer structure layer 15C for sectioning an opening 21C to be filled with a material for forming an electrode catalyst layer on a first surface 11a. The multilayer structure layer 15C has such a structure that a first junction layer 16C, a second junction layer 17C, a gasket layer 18C, and a third junction layer 19C are arranged in this order from the side close to the first surface 11a. The force required for peeling the second junction layer 17C from the gasket layer 18C is smaller than the force required for peeling the first junction layer 16C from the gasket layer 18C, and smaller than the force required for peeling the third junction layer 19C from the gasket layer 18C.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a catalyst layer transfer substrate used for manufacturing a membrane electrode assembly provided in a polymer electrolyte fuel cell, a method for manufacturing a membrane electrode assembly using the catalyst layer transfer substrate, and a membrane electrode assembly About.

  A polymer electrolyte fuel cell is a fuel cell that uses a polymer membrane having proton conductivity as an electrolyte. FIG. 11 is a cross-sectional view showing an example of the structure of a polymer electrolyte fuel cell.

  As shown in FIG. 11, the polymer electrolyte membrane 110 has a cathode contact surface 110a as one side surface and an anode contact surface 110b as a side surface opposite to the cathode contact surface 110a. The electrode catalyst layer 120C is in contact with the cathode contact surface 110a, and the electrode catalyst layer 120C and the porous diffusion layer 130C are laminated in this order. The electrode catalyst layer 120A is in contact with the anode contact surface 110b, and the electrode catalyst layer 120A and the porous diffusion layer 130A are laminated in this order. The electrode catalyst layer 120C constitutes an air electrode that is a cathode, and the electrode catalyst layer 120A constitutes a fuel electrode that is an anode.

  At the cathode contact surface 110a, a gasket layer 140C is disposed outside the outer peripheral edge of the electrode catalyst layer 120C and the outer peripheral edge of the porous diffusion layer 130C. At the anode contact surface 110b, a gasket layer 140A is disposed outside the outer peripheral edge of the electrode catalyst layer 120A and the outer peripheral edge of the porous diffusion layer 130A. The gasket layers 140C and 140A are attached to the polymer electrolyte membrane 110. The membrane / electrode assembly 100 includes a polymer electrolyte membrane 110, electrode catalyst layers 120C and 120A, porous diffusion layers 130C and 130A, and gasket layers 140C and 140A. The pair of separators 150C and 150A includes membrane electrode assemblies. The body 100 is clamped.

  An oxidant gas containing oxygen is supplied to the cathode-side electrode catalyst layer 120C from a gas flow path 160C formed in the separator 150C. A fuel gas containing hydrogen is supplied to the anode-side electrode catalyst layer 120A from a gas flow path 160A formed in the separator 150A. And an electromotive force arises between a cathode and an anode because oxidant gas and fuel gas advance electrode reaction in presence of a catalyst. During this time, the gasket layers 140C and 140A suppress the leakage of the gas supplied to the electrode catalyst layers 120C and 120A from the polymer electrolyte fuel cell.

  As a method of forming the electrode catalyst layers 120C and 120A in the manufacturing process of the membrane electrode assembly 100, a liquid or paste mixture in which a catalyst and an electrolyte are mixed is printed on the surface of the polymer electrolyte membrane 110. A method of forming electrode catalyst layers 120C and 120A by applying a coating method or a spray method, and a method of forming electrode catalyst layers 120C and 120A by applying the mixture on the surfaces of the porous diffusion layers 130C and 130A. It is done. Whether the electrode catalyst layers 120C and 120A are formed on the surface of the polymer electrolyte membrane 110 or the electrode catalyst layers 120C and 120A are formed on the surfaces of the porous diffusion layers 130C and 130A, the electrode catalyst layer 120C , 120A, the polymer electrolyte membrane 110 and the porous diffusion layers 130C, 130A are joined by hot pressing or the like (see, for example, Patent Documents 1 to 3).

  On the other hand, as another method of forming the electrode catalyst layers 120C and 120A, the electrode catalyst layers 120C and 120A are formed by applying the above mixture on a substrate different from the polymer electrolyte membrane 110 and the porous diffusion layers 130C and 130A. Then, there is a method of transferring the formed electrode catalyst layers 120C and 120A from the base material to the polymer electrolyte membrane 110 by hot pressing or hot roll (for example, see Patent Document 4). Such a method is easy to control the film thickness of the electrode catalyst layers 120C and 120A, and can easily improve the uniformity of the electrode catalyst layers 120C and 120A, so that the battery performance can be improved. Is superior in terms of high production efficiency.

Japanese Patent Laid-Open No. 06-203849 Japanese Patent Laid-Open No. 08-88011 Japanese Patent Laid-Open No. 08-106915 Japanese Patent Laid-Open No. 10-64574

  In the method of disposing the electrode catalyst layers 120C and 120A on the surface of the polymer electrolyte membrane 110 by transfer from the substrate, the polymer is disposed after the electrode catalyst layers 120C and 120A are disposed on the surface of the polymer electrolyte membrane 110. Gasket layers 140C and 140A are disposed around the electrode catalyst layers 120C and 120A on the surface of the electrolyte membrane 110.

  However, since it is difficult to precisely match the dimensions of the gasket layers 140C and 140A and the dimensions of the electrode catalyst layers 120C and 120A in advance, when the gasket layers 140C and 140A and the polymer electrolyte membrane 110 are bonded, A gap may be formed between the electrode catalyst layer 120C and the gasket layer 140C and between the electrode catalyst layer 120A and the gasket layer 140A. The part facing the gap is a part exposed to the separator 150C or the separator 150A and is directly exposed to the oxidant gas or the fuel gas. Further, since the exposed portion is not pressed by any of the electrode catalyst layers 120C and 120A and the gasket layers 140C and 140A, stress due to swelling and shrinkage of the polymer electrolyte membrane 110 during power generation is concentrated on the exposed portion. To do. Thus, the exposed part in the polymer electrolyte membrane 110 is one of the factors that promote the deterioration of the polymer electrolyte membrane 110.

  The present invention provides a catalyst layer transfer base material, a method for producing a membrane electrode assembly, and a membrane electrode assembly capable of suppressing exposure of a polymer electrolyte membrane from between an electrode catalyst layer and a gasket layer. For the purpose.

  The catalyst layer transfer base material that solves the above-mentioned problems is a base material layer having a first surface and a second surface that is the surface opposite to the first surface, and a frame shape disposed on the first surface. A multilayer structure layer having an opening for embedding a material for forming an electrode catalyst layer on the first surface, wherein the multilayer structure layer is a first junction. A layer, a second bonding layer, a gasket layer, and a third bonding layer are arranged in this order from the side closer to the first surface, and is required for peeling the second bonding layer from the gasket layer. The force is smaller than the force required to peel the first bonding layer from the base material layer, and smaller than the force required to peel the third bonding layer from the gasket layer.

  According to the above configuration, since the opening in which the electrode catalyst layer is formed is defined by the multilayer structure layer including the gasket layer, the electrode catalyst layer is formed in this opening, thereby forming the electrode catalyst layer. Sometimes the dimensions of the gasket layer and the electrocatalyst layer are matched. Then, by performing transfer using this catalyst layer transfer substrate, the electrode catalyst layer and the gasket layer are simultaneously transferred to the polymer electrolyte membrane, so that a gap is formed between the electrode catalyst layer and the gasket layer. Thus, exposure of the polymer electrolyte membrane can be suppressed.

Then, since the peeling of the second bonding layer from the gasket layer is easier than the peeling of the first bonding layer from the base material layer and the peeling of the third bonding layer from the gasket layer, the base material after the transfer When the layers are peeled off, the peeling at the interface between the second bonding layer and the gasket layer is smoothly realized. In particular, since there are two bonding layers disposed between the base material layer and the gasket layer, the adhesive strength of the bonding layer to the base material layer and the gasket are compared with the case where such a bonding layer is a single layer. The degree of freedom of adjustment with the adhesive strength of the bonding layer to the layer is increased. As a result, when adjusting the adhesive force, the restrictions imposed by the material of the base material layer and the material of the gasket layer are reduced, and even when various materials are used as such materials, the base material layer can be easily removed from the gasket layer. A peelable catalyst layer transfer substrate can be realized.
The said structure WHEREIN: The reinforcement layer which suppresses the deformation | transformation of the said base material layer by a temperature change is arrange | positioned at the said 2nd surface of the said base material layer.

  According to the said structure, even if it is a case where the temperature of a catalyst layer transfer base material changes a lot by the drying process at the time of formation of an electrode catalyst layer, it is suppressed that a base material layer generate | occur | produces curvature. As a result, workability in the manufacturing process of the membrane electrode assembly using the catalyst layer transfer substrate is improved. In addition, since a layer different from the base material layer is disposed on the front and back of the base material layer, the rigidity of the catalyst layer transfer base material is increased, and this also improves workability.

  In the above configuration, the peel strength of the first bonding layer with respect to the base material layer is larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths is 0.01 N / 25 mm or more, And it is preferable that it is less than 10N / 25mm.

  According to the above configuration, the base material layer can be easily peeled at the interface between the second bonding layer and the gasket layer together with the first bonding layer and the second bonding layer when the base material layer after transfer is peeled off. .

  In the above configuration, the peel strength of the third bonding layer with respect to the gasket layer is larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between the peel strengths is 0.01 N / 25 mm or more, and It is preferable that it is less than 10N / 25mm.

According to the above configuration, the base material layer can be easily peeled at the interface between the second bonding layer and the gasket layer together with the first bonding layer and the second bonding layer when the base material layer after transfer is peeled off. .
The said structure WHEREIN: It is preferable that the peeling strength of the said 1st joining layer with respect to the said base material layer is 0.02 N / 25mm or more and less than 10 N / 25mm.

  According to the said structure, since the adhesiveness of a base material layer and a 1st joining layer becomes high, the adhesiveness of a base material layer and a multilayered structure layer is improved. As a result, it is possible to suppress the formation of a gap between the base material layer and the multilayer structure layer. Therefore, when the electrode catalyst layer is formed, the material for forming the electrode catalyst layer is between the base material layer and the multilayer structure layer. It is suppressed to enter the gap.

  In the above-described configuration, an electrode catalyst layer disposed in the opening is further provided, and the thickness of the multilayer structure layer is larger than the thickness of the electrode catalyst layer, and the thickness of the multilayer structure layer and the thickness of the electrode catalyst layer are The difference is preferably 100 μm or less.

  According to the above configuration, since the difference between the thickness of the multilayer structure layer and the thickness of the electrode catalyst layer is not too large, the effect of the step between the edge of the multilayer structure layer and the edge of the electrode catalyst layer on the transfer is reduced. The transfer between the electrode catalyst layer and the gasket layer can be performed satisfactorily.

The said structure WHEREIN: It is preferable that the thickness of the said gasket layer is 1 micrometer or more and 100 micrometers or less.
According to the said structure, the function as a gasket is exhibited suitably. Moreover, it is easy to ensure the depth of the opening in which the electrode catalyst layer is formed within an appropriate range for film formation and transfer of the electrode catalyst layer.

  The manufacturing method of the membrane electrode assembly which solves the said subject WHEREIN: On the said 1st surface of the base material layer which has a 1st surface and the 2nd surface which is a surface on the opposite side to the said 1st surface, said 1st A multilayer structure layer that divides an opening on the surface, and a first bonding layer, a second bonding layer, a gasket layer, and a third bonding layer included in the multilayer structure layer are arranged in this order from the side closer to the first surface. A step of arranging them in a line and an electrode catalyst layer are formed in the openings by applying ink to form a catalyst layer transfer substrate having the substrate layer, the multilayer structure layer, and the electrode catalyst layer. And a step of pressing the catalyst layer transfer substrate against a polymer electrolyte membrane having a contact surface and press-bonding the electrode catalyst layer and the third bonding layer in the multilayer structure layer to the contact surface. An adhesive force of the first bonding layer to the base material layer, and the first bonding layer to the gasket layer. The adhesion of the bonding layer is greater than the adhesive strength of the second bonding layer with respect to the gasket layer.

  According to the above method, when the electrode catalyst layer is formed, the dimensions of the gasket layer and the electrode catalyst layer are matched, and the electrode catalyst layer and the gasket layer are simultaneously transferred to the polymer electrolyte membrane. Therefore, a gap is formed between the electrode catalyst layer and the gasket layer, and the polymer electrolyte membrane is prevented from being exposed.

  In addition, the peeling of the second bonding layer from the gasket layer is easier than the peeling of the first bonding layer from the base material layer and the peeling of the third bonding layer from the gasket layer. When the base polymer layer needs to be peeled when the polymer electrolyte fuel cell is used, peeling at the interface between the second bonding layer and the gasket layer is smoothly realized. In particular, since there are two bonding layers disposed between the base material layer and the gasket layer, the adhesive strength of the bonding layer to the base material layer and the gasket are compared with the case where such a bonding layer is a single layer. The degree of freedom of adjustment with the adhesive strength of the bonding layer to the layer is increased. As a result, when adjusting the adhesive force, the restrictions imposed by the material of the base material layer and the material of the gasket layer are reduced, and even when various materials are used as such materials, the base material layer can be easily removed from the gasket layer. It can be made peelable.

  The method includes the base material layer, the first bonding layer, and the second material from the electrode catalyst layer and the gasket layer transferred from the catalyst layer transfer base material to the contact surface of the polymer electrolyte membrane. It is preferable to further include a step of peeling the bonding layer.

  According to the above method, since the base material layer can be easily peeled off at the interface between the second bonding layer and the gasket layer together with the first bonding layer and the second bonding layer, it is suitable for a polymer electrolyte fuel cell. A membrane electrode assembly used in the above is obtained.

  A membrane electrode assembly that solves the above problems is a polymer electrolyte membrane having a contact surface, an electrode catalyst layer positioned on the contact surface, and is positioned around the electrode catalyst layer in the surface direction of the contact surface; A gasket layer in contact with a peripheral end surface of the electrode catalyst layer, a base material layer covering the electrode catalyst layer and the gasket layer, and disposed between the gasket layer and the base material layer. A first bonding layer that is in contact; a second bonding layer that is disposed between the gasket layer and the base layer and is in contact with the gasket layer and the first bonding layer; and the polymer electrolyte membrane and the gasket layer. A third bonding layer disposed between and in contact with the polymer electrolyte membrane and the gasket layer, and the force required to peel the second bonding layer from the gasket layer is from the base material layer to the first bonding layer. 1Peel off the bonding layer Less than the force required to, and less than the force required to peel the third bonding layer from said gasket layer.

  The membrane electrode assembly is manufactured using the catalyst layer transfer substrate. Therefore, in the membrane / electrode assembly, the polymer electrolyte membrane is suppressed from being exposed between the electrode catalyst layer and the gasket layer. Furthermore, since the base material layer functions as a protective layer for the electrode catalyst layer, for example, the membrane / electrode assembly is transported to a location different from the production location of the membrane / electrode assembly and used for the production of the polymer electrolyte fuel cell. In such a case, the electrode catalyst layer can be protected without separately providing a protective sheet. Therefore, the process of attaching the protective sheet becomes unnecessary, and the number of members used is reduced.

  According to the present invention, exposure of the polymer electrolyte membrane from between the electrode catalyst layer and the gasket layer can be suppressed.

It is sectional drawing which shows the cross-section of the catalyst layer transfer base material in one Embodiment. It is a top view which shows the planar structure of the catalyst layer transfer base material in one Embodiment. It is a figure which shows the arrangement | positioning process of a multilayer structure layer and a reinforcement layer in the manufacturing method of the membrane electrode assembly of one Embodiment. It is a figure which shows the film-forming process of an electrode catalyst layer in the manufacturing method of the membrane electrode assembly of one Embodiment. It is a figure which shows the transfer process of an electrode catalyst layer and a gasket layer in the manufacturing method of the membrane electrode assembly of one Embodiment. It is a figure which shows the peeling process of a base material layer in the manufacturing method of the membrane electrode assembly of one Embodiment. It is sectional drawing which shows the cross-section of the membrane electrode assembly manufactured by the manufacturing method of the membrane electrode assembly of one Embodiment. FIG. 8 is a cross-sectional view showing a part of the cross-sectional structure of the membrane / electrode assembly manufactured by the method for manufacturing a membrane / electrode assembly according to an embodiment, and is an enlarged view of a portion A surrounded by a dashed line in FIG. 7. It is. It is a perspective view which shows the perspective structure of a polymer electrolyte fuel cell provided with the membrane electrode assembly manufactured by the manufacturing method of the membrane electrode assembly of one Embodiment. It is sectional drawing which shows the cross-section of the membrane electrode assembly of a modification. It is sectional drawing which shows the cross-section of the polymer electrolyte fuel cell in a prior art example.

  With reference to FIGS. 1-9, embodiment of a catalyst layer transfer base material, the manufacturing method of a membrane electrode assembly, and a membrane electrode assembly are described.

[Configuration of catalyst layer transfer substrate]
With reference to FIG. 1 and FIG. 2, the structure of a catalyst layer transfer base material is demonstrated.
As shown in FIG. 1, the catalyst layer transfer substrate 10C includes a substrate layer 11C, a reinforcing layer 12C, and a multilayer structure layer 15C having a frame shape. The reinforcing layer 12C includes a support layer 14C and a reinforcing bonding layer 13C. The multilayer structure layer 15C includes a first bonding layer 16C, a second bonding layer 17C, a gasket layer 18C, and a third bonding layer 19C. It is configured.

The base material layer 11C has a first surface 11a and a second surface 11b which is a surface opposite to the first surface 11a. A multilayer structure layer 15C is disposed on the first surface 11a side with respect to the base material layer 11C, and a reinforcing layer 12C is disposed on the second surface 11b side with respect to the base material layer 11C.
Specifically, the reinforcing bonding layer 13C covers the entire second surface 11b, and the support layer 14C is attached to the base material layer 11C by the reinforcing bonding layer 13C.

  The first bonding layer 16C is in contact with the first surface 11a along the outer edge of the first surface 11a in a region surrounding the central portion of the first surface 11a, and the first bonding layer 16C and the second bonding layer 17C. The gasket layer 18C and the third bonding layer 19C are arranged in this order from the side closer to the first surface 11a. That is, the second bonding layer 17C is in contact with the first bonding layer 16C, and the gasket layer 18C is adhered to the base material layer 11C by these two bonding layers 16C and 17C. The surface of the gasket layer 18C opposite to the surface in contact with the second bonding layer 17C is covered with the third bonding layer 19C. The surface of the third bonding layer 19C opposite to the surface in contact with the gasket layer 18C is covered with the coating layer 20C. The coating layer 20C covers the third bonding layer 19C when the electrode catalyst layer is formed, and is peeled off from the third bonding layer 19C when the electrode catalyst layer is transferred.

  The force required to peel the second bonding layer 17C from the gasket layer 18C is smaller than the force required to peel the first bonding layer 16C from the base material layer 11C, and the third bonding layer 19C from the gasket layer 18C. It is smaller than the force required to peel off.

As shown in FIG. 2, the base material layer 11C has a substantially rectangular outer shape, and the multilayer structure layer 15C and the covering layer 20C have an annular shape along the outer edge of the base material layer 11C, that is, a rectangular frame shape. have. On the first surface 11a of the base layer 11C, a substantially rectangular opening in which the material for forming the electrode catalyst layer is embedded by the inner peripheral edges of the multilayer structure layer 15C and the coating layer 20C in the plane direction of the base layer 11C. 21C is partitioned.
The reinforcing layer 12C has a substantially rectangular outer shape, and the outer dimension of the reinforcing layer 12C substantially matches the outer dimension of the base material layer 11C.

[Production method of membrane electrode assembly]
With reference to FIGS. 3-6, the manufacturing method of the membrane electrode assembly using the above-mentioned catalyst layer transfer base material is demonstrated.
As shown in FIG. 3, the multilayer structure layer 15C with the coating layer 20C is disposed on the first surface 11a of the base material layer 11C, and the reinforcing layer 12C is disposed on the second surface 11b of the base material layer 11C. Thus, the catalyst layer transfer base material 10C is formed.

  When the multilayer structure layer 15C and the covering layer 20C are disposed on the first surface 11a, first, a laminate of the multilayer structure layer 15C and the covering layer 20C is formed, and an opening 21C is formed in the laminate. . Thereafter, the base layer 11C and the first bonding layer 16C are in contact with each other, that is, the first bonding layer 16C, the second bonding layer 17C, the gasket layer 18C, and the third bonding layer 19C are in the first surface 11a. A laminated body of the multilayer structure layer 15C and the covering layer 20C is arranged on the first surface 11a of the base material layer 11C so as to be arranged in this order from the side closer to.

  The reinforcing layer 12C is disposed on the second surface 11b after the multilayer structure layer 15C and the covering layer 20C are disposed on the first surface 11a of the base material layer 11C. The reinforcing layer 12C may be disposed on the second surface 11b before the multilayer structure layer 15C and the covering layer 20C are disposed on the first surface 11a.

  The base material layer 11C can transfer a sheet formed from a material capable of transferring the electrode catalyst layer formed on the surface of the base material layer 11C, or an electrode catalyst layer formed on the surface of the base material layer 11C. Thus, the sheet is subjected to surface treatment.

Examples of the material of the base layer 11C include ethylene tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroperfluoroalkyl vinyl ether copolymer (PFA), poly Fluorine resin such as tetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polytetrafluoroethylene (PTFE), polyimide (PI), etc. are used. It is done. Examples of the surface treatment include silicone treatment.
The thickness of the base material layer 11C is preferably about 1 μm to 100 μm, and is appropriately selected according to the material so that strength and heat resistance are appropriately ensured.

  As the first bonding layer 16C, the second bonding layer 17C, and the third bonding layer 19C, an adhesive layer that does not need to be solidified when bonding the objects may be used, or an adhesive layer that needs to be solidified when bonding the objects may be used. Good. As the material of these bonding layers 16C, 17C, 19C, for example, an epoxy resin-based, acrylic resin-based, urethane resin-based, silicone resin-based, rubber-based pressure-sensitive adhesive or adhesive can be used. As a material for forming the bonding layers 16C, 17C, and 19C, a material capable of exhibiting an adhesive force required for each bonding layer is selected for each bonding layer. In the present embodiment, the terms “adhesion” and “adhesive force” are also used for joining the objects with the pressure-sensitive adhesive.

  The first bonding layer 16C and the second bonding layer 17C are preferably formed from different materials, and the second bonding layer 17C and the third bonding layer 19C are preferably formed from different materials. The first bonding layer 16C and the third bonding layer 19C may be formed of the same material or different materials.

  As a forming material of each of the first bonding layer 16C and the second bonding layer 17C, the adhesive force of the first bonding layer 16C to the second bonding layer 17C, that is, between the first bonding layer 16C and the second bonding layer 17C. Is at least larger than the adhesive force of the second bonding layer 17C to the gasket layer 18C, and preferably the adhesive force of the first bonding layer 16C to the base material layer 11C and the second bonding layer 17C to the gasket layer 18C. A material that is sufficiently larger than each of the adhesive force and the adhesive force of the third bonding layer 19C to the gasket layer 18C is selected. Further, as a forming material of the third bonding layer 19C, the adhesive force of the third bonding layer 19C with respect to the polymer electrolyte membrane is at least larger than the adhesive force of the second bonding layer 17C with respect to the gasket layer 18C. A material that is sufficiently larger than the adhesive force of the first bonding layer 16C to the layer 11C, the adhesive force of the second bonding layer 17C to the gasket layer 18C, and the adhesive force of the third bonding layer 19C to the gasket layer 18C is selected. Is done.

  The adhesive force of the first bonding layer 16C to the base material layer 11C is larger than the adhesive force of the second bonding layer 17C to the gasket layer 18C. Further, each of the adhesive force of the first bonding layer 16C to the base material layer 11C and the adhesive force of the second bonding layer 17C to the gasket layer 18C was measured at a peeling rate of 300 mm / min using a tensile tester. When expressed as peel strength (JIS-K-6854-2: 1999), the difference in peel strength is preferably 0.01 N / 25 mm or more and less than 10 N / 25 mm. When the difference in peel strength is within the above range, the second bonding layer 17C is easily peeled off at the interface with the gasket layer 18C when the base layer 11C is peeled after the electrode catalyst layer is transferred.

  Further, the adhesive force of the third bonding layer 19C to the gasket layer 18C is larger than the adhesive force of the second bonding layer 17C to the gasket layer 18C. Further, 180 ° peeling was performed by measuring the adhesive strength of the third bonding layer 19C with respect to the gasket layer 18C and the adhesive strength of the second bonding layer 17C with respect to the gasket layer 18C using a tensile tester at a peeling speed of 300 mm / min. When expressed as strength (JIS-K-6854-2: 1999), the difference in peel strength is preferably 0.01 N / 25 mm or more and less than 10 N / 25 mm. When the difference in peel strength is within the above range, the second bonding layer 17C is easily peeled off at the interface with the gasket layer 18C when the base layer 11C is peeled after the electrode catalyst layer is transferred.

  Moreover, when the adhesive force of the 1st joining layer 16C with respect to the base material layer 11C is represented as 180 degree peeling strength (JIS-K-6854-2: 1999) measured with the peeling rate of 300 mm / min using the tensile tester. 0.02 N / 25 mm or more and preferably less than 10 N / 25 mm. When the peel strength is in the above range, the adhesion between the base material layer 11C and the first bonding layer 16C is increased, and therefore the adhesion between the base material layer 11C and the multilayer structure layer 15C is enhanced. As a result, since a gap is prevented from being generated between the base material layer 11C and the multilayer structure layer 15C, the catalyst ink is placed in the gap between the base material layer 11C and the multilayer structure layer 15C when the electrode catalyst layer is formed. Intrusion is suppressed, and the linearity of the outer peripheral edge of the electrode catalyst layer is improved.

The thickness of each of the bonding layers 16C, 17C, and 19C is not particularly limited, but is preferably 0.1 μm or more and 40 μm or less. When the thickness of each of the bonding layers 16C, 17C, and 19C is 0.1 μm or more, it is possible to suppress uneven coating of the material when the bonding layer is formed.
Moreover, the peeling strength between joining layers can be set by selecting suitably the adhesive and adhesive agent from which adhesive force (adhesive strength) differs so that the difference in peeling strength may arise between joining layers.

The gasket layer 18C is formed of a resin generally used for polymer electrolyte fuel cells among thermoplastic resins. For example, as a material of the gasket layer 18C, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polytetrafluoroethylene (PTFE), polyimide (PI), or the like is used.
The thickness of the gasket layer 18C is preferably 1 μm or more and 100 μm or less, and is appropriately selected depending on the material so that strength and heat resistance are appropriately ensured.

  The material of the support layer 14C and the reinforcing joint layer 13C in the reinforcing layer 12C is not particularly limited, and a generally circulating material may be used. For example, as the material of the support layer 14C, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polytetrafluoroethylene (PTFE), polyimide (PI), or the like is used, and reinforcement bonding is performed. As a material for the layer 13C, epoxy resin, acrylic resin, urethane resin, silicone resin, rubber, or the like is used.

  The thickness of the reinforcing layer 12C is not particularly limited, but the thickness of the support layer 14C is preferably about 1 μm to 100 μm, and particularly preferably the same thickness as the gasket layer 18C. When the thickness of the support layer 14C is equal to the thickness of the gasket layer 18C, it is preferable to prevent the base material layer 11C from warping due to a temperature change when the electrode catalyst layer is formed.

The material of the covering layer 20C is not particularly limited, and a generally circulating resin may be used. For example, as a material of the coating layer 20C, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polycarbonate (PC), polyethylene naphthalate (PEN), syndiotactic polystyrene ( SPS), polytetrafluoroethylene (PTFE), polyimide (PI), or the like is used. For example, a separate film pasted on the third bonding layer 19C may be used as the coating layer 20C.
The thickness of the coating layer 20C is not particularly limited, but is preferably about 1 μm to 40 μm.

  As shown in FIG. 4, the catalyst ink is applied to the inside of the opening 21 </ b> C and dried to be exposed from the multilayer structure layer 15 </ b> C and the coating layer 20 </ b> C in the first surface 11 a of the base material layer 11 </ b> C. An electrode catalyst layer 22C is formed on the portion. The coating layer 20C may be peeled off after the electrode catalyst layer 22C is formed and before the electrode catalyst layer 22C is transferred. After the electrode catalyst layer 22C is formed, the catalyst layer transfer substrate 10C is provided with the coating layer 20C. The cover layer 20C may be handled in a state in which the coating layer 20C is peeled off.

In the case where the base material layer 11C and the gasket layer 18C are made of different materials, the base material layer after cooling is caused by a temperature change that occurs during the drying process of the catalyst ink applied in the opening 21C. 11C may be warped due to stress. On the other hand, in this embodiment, since the reinforcing layer 12C that suppresses deformation of the base material layer 11C due to temperature change is disposed on the second surface 11b of the base material layer 11C, warping of the base material layer 11C is reduced. Thus, workability in the manufacture of the membrane electrode assembly is improved.
The catalyst ink includes a polymer electrolyte, a catalyst substance, and an ink solvent.

  As the polymer electrolyte contained in the catalyst ink, for example, a polymer material having proton conductivity such as a fluorine-based polymer electrolyte or a hydrocarbon-based polymer electrolyte is used. Examples of the fluoropolymer electrolyte include NAFION (registered trademark) manufactured by DuPont, FLEMION (registered trademark) manufactured by Asahi Glass Co., Ltd., ACIPLEX (registered trademark) manufactured by Asahi Kasei Co., Ltd., and GORE-SELECT (registered trademark) manufactured by Gore. ) And the like. Among these materials, NAFION (registered trademark) manufactured by DuPont is preferably used in order to increase the output voltage of the polymer electrolyte fuel cell. Examples of the hydrocarbon polymer electrolyte include electrolytes such as sulfonated polyetherketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene.

  As the catalyst substance, for example, platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), chromium (Cr), cobalt (Co), iron (Fe), or the like is used. In particular, it is preferable to use platinum as the catalyst material. The catalyst material is preferably supported on carbon particles that are conductive carriers, but a single catalyst material may be used. As the carbon particles, for example, carbon black or the like is used.

  The ink solvent is a solvent that does not erode the catalyst material-supporting carbon body, which is a carbon particle supporting the catalyst material, and the polymer electrolyte, and dissolves the polymer electrolyte in a fluid state or is fine. It is preferable to use a solvent that disperses the polymer electrolyte as the gel. Such an ink solvent preferably contains a volatile organic solvent. Examples of the organic solvent contained in the ink solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, Alcohols such as isobutyl alcohol, tert-butyl alcohol and pentanol, ketone solvents such as acetone, methyl ethyl ketone, pentanone, methyl isobutyl ketone, heptanone, cyclohexanone, methylcyclohexanone, acetonyl acetone, diisobutyl ketone, tetrahydrofuran, dioxane, diethylene glycol Ether solvents such as dimethyl ether, anisole, methoxytoluene, dibutyl ether, and dimethylformamide, dimethylacetamide, N-methylpyrrole Emissions, ethylene glycol, diethylene glycol, diacetone alcohol, polar solvents such as 1-methoxy-2-propanol. Two or more kinds of these organic solvents may be mixed and used as the ink solvent.

  When a lower alcohol is used as the organic solvent, the ink solvent is preferably a mixed solvent of an organic solvent and water in order to increase the ignition temperature of the ink solvent. Also, in order to increase the affinity between the polymer electrolyte and the ink solvent, the ink solvent contains water to such an extent that the polymer electrolyte is separated from the ink solvent to cause white turbidity or the polymer electrolyte does not gel. It is preferable.

  The solid content in the catalyst ink, such as the polymer electrolyte and the catalyst substance-supporting carbon body, is preferably 1% by mass or more and 50% by mass or less. If the solid content in the catalyst ink is 50% by mass or less, the viscosity of the catalyst ink does not become too high, and cracks are unlikely to occur on the surface of the electrode catalyst layer 22C to be formed. On the other hand, if the solid content is 1% by mass or more, the viscosity of the catalyst ink does not become too low, so that the film formation speed of the electrode catalyst layer 22C is ensured moderately, and the productivity of the electrode catalyst layer 22C decreases. Is suppressed.

  Even if the catalyst ink has the same content of the polymer electrolyte and the catalyst substance-supporting carbon body, the viscosity of the catalyst ink increases as the ratio of the carbon particles in the solid content increases. The smaller the is, the lower the viscosity of the catalyst ink. Therefore, the concentration of the carbon particles in the solid content contained in the catalyst ink is preferably 10% by mass or more and 80% by mass or less.

  Also, by adjusting the solid content in the catalyst ink, adjusting the concentration of carbon particles in the solid content, and in addition to these, a dispersing agent is added to the catalyst ink during the dispersion process of the solid content in the ink solvent. The viscosity of the catalyst ink can be adjusted to a predetermined value. Moreover, it is preferable that the mass ratio of the polymer electrolyte with respect to a catalyst substance carrying | support carbon body is 0.04 mass% or more and 3.00 mass% or less.

  As a method of applying the catalyst ink to the base material layer 11C, a coating method such as a doctor blade method, a dipping method, a screen printing method, a roll coating method, or a spray method is used. Of these coating methods, spray methods such as a pressure spray method, an ultrasonic spray method, and an electrostatic spray method are preferably used. According to these methods, since the catalyst ink hardly aggregates when the coated catalyst ink is dried, it is possible to obtain a homogeneous electrode catalyst layer 22C having a high porosity.

  In the catalyst ink coating process, when the ink temperature of the catalyst ink is 10 ° C. or higher, the viscosity of the catalyst ink does not become too high, and the uniformity of the electrode catalyst layer 22C to be formed is improved. Further, when the ink temperature is 50 ° C. or lower, it is possible to suppress volatilization of the ink solvent during application of the catalyst ink. The thickness of the electrode catalyst layer 22C is not particularly limited, but is preferably about 1 μm to 30 μm.

  The thickness of the electrode catalyst layer 22C is smaller than the thickness of the multilayer structure layer 15C, and the difference between the thickness of the multilayer structure layer 15C and the thickness of the electrode catalyst layer 22C is preferably 100 μm or less.

  As shown in FIG. 5, in the manufacture of the membrane electrode assembly, a catalyst layer transfer substrate 10A having the same configuration as that of the catalyst layer transfer substrate 10C is further formed. That is, the catalyst layer transfer substrate 10A includes a substrate layer 11A, a reinforcing layer 12A composed of a support layer 14A and a reinforcing bonding layer 13A, a first bonding layer 16A, a second bonding layer 17A, a gasket layer 18A, and And a multilayer structure layer 15C composed of the third bonding layer 19A. The base material layer 11A has the same configuration as the base material layer 11C, the support layer 14A has the same configuration as the support layer 14C, and the reinforcing bonding layer 13A has the same configuration as the reinforcing bonding layer 13C. The first bonding layer 16A has the same configuration as the first bonding layer 16C, the second bonding layer 17A has the same configuration as the second bonding layer 17C, and the gasket layer 18A has the same configuration as the gasket layer 18C. The third bonding layer 19A has the same configuration as the third bonding layer 19C.

Similarly to the electrode catalyst layer 22C, the above-described catalyst ink is applied and dried in the opening 21A of the catalyst layer transfer substrate 10A, whereby the electrode catalyst layer 22A is formed.
The catalyst layer transfer base material 10C on which the electrode catalyst layer 22C is formed and the catalyst layer transfer base material 10A on which the electrode catalyst layer 22A is formed are arranged with the polymer electrolyte membrane 30 interposed therebetween.

  The polymer electrolyte membrane 30 is a polymer membrane having proton conductivity. As a material for the polymer electrolyte membrane 30, for example, a fluorine-based polymer electrolyte or a hydrocarbon-based polymer electrolyte is used. Examples of the fluoropolymer electrolyte include NAFION (registered trademark) manufactured by DuPont, FLEMION (registered trademark) manufactured by Asahi Glass Co., Ltd., ACIPLEX (registered trademark) manufactured by Asahi Kasei Co., Ltd., and GORE-SELECT (registered trademark) manufactured by Gore. ) Is used. In particular, NAFION (registered trademark) manufactured by DuPont is suitably used to increase the output voltage of the polymer electrolyte fuel cell.

  As the hydrocarbon polymer electrolyte membrane, electrolyte membranes such as sulfonated polyether ketone, sulfonated polyethersulfone, sulfonated polyetherethersulfone, sulfonated polysulfide, and sulfonated polyphenylene are used. In order to improve the adhesion between the electrode catalyst layers 22C and 22A and the polymer electrolyte membrane 30, the polymer electrolyte contained in the electrode catalyst layers 22C and 22A and the polymer electrolyte constituting the polymer electrolyte membrane 30 are combined. The same material is preferable.

  The polymer electrolyte membrane 30 has a cathode contact surface 30a and an anode contact surface 30b opposite to the cathode contact surface 30a, and the electrode catalyst layer 22C and the third bonding layer 19C are composed of the cathode contact surface 30a. The electrode catalyst layer 22A and the third bonding layer 19A face the anode contact surface 30b.

  These members are heated and pressurized while the polymer electrolyte membrane 30 is sandwiched between the two catalyst layer transfer substrates 10C and 10A. As a result, the electrode catalyst layer 22C and the third bonding layer 19C are pressure-bonded to the cathode contact surface 30a of the polymer electrolyte membrane 30. Further, the electrode catalyst layer 22 </ b> A and the third bonding layer 19 </ b> A are pressure-bonded to the anode contact surface 30 b of the polymer electrolyte membrane 30.

  As shown in FIG. 6, after the electrode catalyst layers 22C and 22A and the third bonding layers 19C and 19A are pressure-bonded to the polymer electrolyte membrane 30, the base material layers 11C and 11A and the reinforcing layers 12C and 12A are peeled off. The At this time, the first bonding layer 16C and the second bonding layer 17C are peeled together with the base material layer 11C in a state where the second bonding layer 17C is attached to the first bonding layer 16C attached to the base material layer 11C. . That is, the second bonding layer 17C is peeled off at the interface with the gasket layer 18C. Similarly, the first bonding layer 16A and the second bonding layer 17A are peeled together with the base material layer 11A in a state where the second bonding layer 17A is attached to the first bonding layer 16A attached to the base material layer 11A. . That is, the second bonding layer 17A is peeled off at the interface with the gasket layer 18A.

  The adhesive strength of the first joining layers 16C, 16A to the base material layers 11C, 11A and the adhesive strength of the third joining layers 19C, 19A to the gasket layers 18C, 18A are the second joining layers 17C, 18C, 18A. By being larger than the adhesive strength of 17A, peeling at the interface between the second bonding layers 17C and 17A and the gasket layers 18C and 18A is smoothly realized.

  As a result, the electrode catalyst layers 22C and 22A, the third bonding layers 19C and 19A, and the gasket layers 18C and 18A are transferred to the polymer electrolyte membrane 30 to form a membrane electrode assembly. In a state where the electrode catalyst layers 22C and 22A, the third bonding layers 19C and 19A, and the gasket layers 18C and 18A are transferred to the polymer electrolyte membrane 30, the thickness of the electrode catalyst layers 22C and 22A is set to be the third bonding layer 19C, The thickness may be the same as the total thickness of 19A and gasket layers 18C and 18A, or may be smaller than the total thickness of third bonding layers 19C and 19A and gasket layers 18C and 18A. When the thickness of the electrode catalyst layers 22C and 22A is smaller than the total thickness of the third bonding layers 19C and 19A and the gasket layers 18C and 18A, the base material layer 11C laminated on the electrode catalyst layers 22C and 22A. , 11 </ b> A is pressed, and the electrode catalyst layers 22 </ b> C, 22 </ b> A are transferred to the polymer electrolyte membrane 30.

  The transfer of each member to the cathode contact surface 30a of the polymer electrolyte membrane 30 and the transfer of each member to the anode contact surface 30b of the polymer electrolyte membrane 30 may be performed simultaneously or one by one. It may be broken.

[Configuration of membrane electrode assembly]
The detailed structure of the membrane electrode assembly manufactured by the above-described manufacturing method will be described.
As shown in FIG. 7, the membrane electrode assembly 35 includes a polymer electrolyte membrane 30, a pair of electrode catalyst layers 22C and 22A, a pair of gasket layers 18C and 18A, a gasket layer 18C, and the polymer electrolyte membrane 30. And a third bonding layer 19A for bonding the gasket layer 18A and the polymer electrolyte membrane 30 to each other.
The cathode contact surface 30a is located on the opposite side of the anode contact surface 30b, and the cathode contact surface 30a and the anode contact surface 30b are located substantially in parallel.

  An electrode catalyst layer 22C, a third bonding layer 19C, and a gasket layer 18C are disposed at a position facing the cathode contact surface 30a. The electrode catalyst layer 22C constitutes the cathode of the polymer electrolyte fuel cell. The electrode catalyst layer 22A, the third bonding layer 19A, and the gasket layer 18A are disposed at a position facing the anode contact surface 30b. The electrode catalyst layer 22A constitutes the anode of the polymer electrolyte fuel cell.

  The electrode catalyst layer 22C and the third bonding layer 19C are in surface contact with the cathode contact surface 30a, and the third bonding layer 19C and the gasket layer 18C are on the outer periphery of the electrode catalyst layer 22C on the surface of the cathode contact surface 30a. The electrode catalyst layer 22C is in contact with the electrode catalyst layer 22C. The electrode catalyst layer 22A and the third bonding layer 19A are in surface contact with the anode contact surface 30b, and the third bonding layer 19A and the gasket layer 18A are on the outer peripheral edge of the electrode catalyst layer 22A on the surface of the anode contact surface 30b. The electrode catalyst layer 22A is in contact with the electrode catalyst layer 22A. That is, in the surface direction of the contact surfaces 30a and 30b, the gasket layers 18C and 18A are positioned around the electrode catalyst layers 22C and 22A and are in contact with the peripheral end surfaces of the electrode catalyst layers 22C and 22A.

  In such a configuration, the third bonding layers 19C and 19A are sandwiched between the gasket layers 18C and 18A and the polymer electrolyte membrane 30 and are in contact with these members, and the gasket layers 18C and 18A and the polymer electrolyte membrane 30 are the third. Since the bonding is performed by the bonding layers 19C and 19A, the adhesion between the gasket layers 18C and 18A and the polymer electrolyte membrane 30 is improved.

  In addition, for each set of the electrode catalyst layer 22C and the electrode catalyst layer 22A, the third bonding layer 19C and the third bonding layer 19A, and the gasket layer 18C and the gasket layer 18A, the positions of the two members constituting each set are as follows: It is preferable that the polymer electrolyte membrane 30 is sandwiched in plane symmetry.

  As shown in FIG. 8, in the portion where the electrode catalyst layer 22C and the third bonding layer 19C are in contact, the third bonding layer 19C is embedded in the electrode catalyst layer 22C. That is, the third bonding layer 19C protrudes to the electrode catalyst layer 22C side, which is inside the inner peripheral edge of the gasket layer 18C, when viewed from the facing direction that is the direction facing the cathode contact surface 30a.

  Usually, the electrode catalyst layer 22C and the third bonding layer 19C have lower rigidity than the gasket layer 18C. Further, the electrode catalyst layer 22C has lower rigidity than the third bonding layer 19C. For this reason, due to the pressurization at the time of pressure bonding, the inner peripheral edge of the third bonding layer 19C is crushed by the gasket layer 18C and sunk into the outer peripheral edge of the electrode catalyst layer 22C in contact with the inner peripheral edge of the third bonding layer 19C. That is, when the electrode catalyst layer 22C, the third bonding layer 19C, and the gasket layer 18C are transferred, these members are pressed against the polymer electrolyte membrane 30. As a result, the third bonding layer 19C is embedded in the electrode catalyst layer 22C. It is formed.

Since the third bonding layer 19C is pressed from both the gasket layer 18C and the polymer electrolyte membrane 30, an intermediate position in the thickness direction at the inner periphery of the third bonding layer 19C is in the thickness direction. It is easier to sink into the electrode catalyst layer 22C than at both ends.
Similarly, in a portion where the electrode catalyst layer 22A and the third bonding layer 19A are in contact with each other, a structure in which the third bonding layer 19A is recessed into the electrode catalyst layer 22A is formed.

  Note that the membrane electrode assembly 35 may include a porous diffusion layer overlaid on each of the electrode catalyst layers 22C and 22A. The porous diffusion layer includes a base material formed of a material having gas diffusibility and conductivity. As the material of the base material, for example, porous carbon materials such as carbon cloth, carbon paper, and non-woven fabric are used. The porous diffusion layer is pressure-bonded to the electrode catalyst layers 22C and 22A by being superimposed on the electrode catalyst layers 22C and 22A and heated and pressurized after the transfer of the electrode catalyst layers 22C and 22A.

[Configuration of polymer electrolyte fuel cell]
With reference to FIG. 9, the structure of a polymer electrolyte fuel cell provided with the above-mentioned membrane electrode assembly is demonstrated.
As shown in FIG. 9, the polymer electrolyte fuel cell 40 includes a membrane electrode assembly 35 including a pair of porous diffusion layers 23C and 23A, and a pair of separators 41C and 41A. The membrane electrode assembly 35 is sandwiched between the separator 41C and the separator 41A. In the separator 41C, a gas flow path 42C is recessed in a surface facing the membrane electrode assembly 35, and a cooling water flow path 43C is recessed in a surface opposite to the membrane electrode assembly 35. ing. In the separator 41A, a gas flow path 42A is recessed on the surface facing the membrane electrode assembly 35, and a cooling water flow path 43A is recessed on the surface opposite to the membrane electrode assembly 35. ing.

  Separators 41C and 41A are assembled to the membrane electrode assembly 35, and further, a supply mechanism of an oxidant gas and a fuel gas is provided, and a single cell solid polymer fuel cell 40 is manufactured. The polymer electrolyte fuel cell 40 is used in a single cell state or in a state where a plurality of polymer electrolyte fuel cells 40 are combined.

  When the polymer electrolyte fuel cell 40 is used, an oxidant gas is caused to flow through the gas passage 42C of the cathode-side separator 41C, and a fuel gas is caused to flow into the gas passage 42A of the anode-side separator 41A. Further, cooling water flows through the cooling water flow paths 43C and 43A of the separators 41C and 41A. Then, gas is supplied from the gas flow path 42C to the cathode, and gas is supplied from the gas flow path 42A to the anode, whereby an electrode reaction accompanied by proton conduction in the polymer electrolyte membrane 30 proceeds. An electromotive force is generated between the cathode and the anode.

[Action]
The operation of the method for producing a membrane / electrode assembly using the catalyst layer transfer substrate of the present embodiment will be described.
In the manufacturing method described above, the electrode catalyst layers 22C and 22A are formed on the catalyst layer transfer base materials 10C and 10A in a state where the gasket layers 18C and 18A are arranged on the base material layers 11C and 11A. Then, the catalyst layer transfer base material 10C on which the electrode catalyst layer 22C is formed and the catalyst layer transfer base material 10A on which the electrode catalyst layer 22A is formed are pressed against the polymer electrolyte membrane 30, whereby the electrode catalyst layer 22C, 22A and gasket layers 18C and 18A are transferred to the polymer electrolyte membrane 30.

  According to such a manufacturing method, since the electrode catalyst layers 22C and 22A are formed on the surfaces of the base material layers 11C and 11A on which the gasket layers 18C and 18A are arranged, when the electrode catalyst layers 22C and 22A are formed, The dimensions of the inner peripheral edge of the gasket layers 18C and 18A and the outer peripheral edge of the electrode catalyst layers 22C and 22A are matched. The electrode catalyst layer 22C and the gasket layer 18C are simultaneously transferred to the cathode contact surface 30a of the polymer electrolyte membrane 30, and the electrode catalyst layer 22A and the gasket layer 18A are transferred to the anode contact surface 30b of the polymer electrolyte membrane 30. Transcribed at the same time. Therefore, it is possible to suppress the formation of a gap between the electrode catalyst layer 22C and the gasket layer 18C or between the electrode catalyst layer 22A and the gasket layer 18A. As a result, the polymer electrolyte membrane 30 is suppressed from being exposed between the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A.

  In addition, since the first bonding layers 16C and 16A and the second bonding layers 17C and 17A are peeled off together with the base material layers 11C and 11A, the membrane electrodes are transferred during the transfer between the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A. In the joined body 35, unnecessary members are not disposed on the polymer electrolyte membrane 30.

  Here, in this embodiment, the relative relationship of the adhesive force in each joining layer is defined as follows. That is, the force required to peel the second bonding layers 17C, 17A from the gasket layers 18C, 18A is smaller than the force required to peel the first bonding layers 16C, 16A from the base material layers 11C, 11A, and The force required to peel the third bonding layers 19C and 19A from the gasket layers 18C and 18A is made smaller. Thereby, peeling at the interface between the second bonding layers 17C and 17A and the gasket layers 18C and 18A is smoothly realized.

  In particular, by using two bonding layers disposed between the base material layers 11C and 11A and the gasket layers 18C and 18A, the base material layers 11C and 11C The range of adjustment between the adhesive strength of the joining layer to 11A and the adhesive strength of the joining layer to gasket layers 18C and 18A is widened. As a result, in adjusting the adhesive force, restrictions imposed by the material of the base material layers 11C and 11A and the material of the gasket layers 18C and 18A are reduced, and even when various materials are used as such materials, the base material layer Catalyst layer transfer base materials 10C and 10A that can easily peel 11C and 11A from gasket layers 18C and 18A can be realized.

  In addition, the separate film attached to the third bonding layer 19C can be used as the covering layer 20C, and the separate film can be used as the covering layer for the third bonding layer 19A as well. Since the coating layer 20C functions as a cover that suppresses exposure of the mask and the adhesive during the formation of the electrode catalyst layer 22C, it is possible to reduce members necessary for the formation of the electrode catalyst layers 22C and 22A.

  Conventionally, a structure has been proposed in which a gasket layer is disposed on the surface of the electrode catalyst layer to suppress the exposure of the polymer electrolyte membrane from between the electrode catalyst layer and the gasket layer. Compared with such a structure, in the membrane electrode assembly 35 according to the present embodiment, the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A do not overlap with each other when viewed from the opposite direction. Generation of portions that do not contribute to power generation in the catalyst layers 22C and 22A is suppressed. As a result, even if an expensive platinum group noble metal is used for the electrode catalyst layers 22C and 22A, an increase in cost required for manufacturing the membrane electrode assembly 35 is suppressed. In addition, there is no variation in the thickness of the membrane electrode assembly due to the presence of a portion where the electrode catalyst layer and the gasket layer overlap and a portion where they do not overlap in the facing direction.

As described above, according to the catalyst layer transfer substrate, the method for manufacturing a membrane electrode assembly, and the membrane electrode assembly of the present embodiment, the effects listed below can be obtained.
(1) In the catalyst layer transfer base materials 10C and 10A, the openings 21C and 21A in which the electrode catalyst layers 22C and 22A are formed are partitioned by the multilayer structure layers 15C and 15A including the gasket layers 18C and 18A. By forming the electrode catalyst layers 22C and 22A in the openings 21C and 21A, the dimensions of the gasket layers 18C and 18A and the electrode catalyst layers 22C and 22A are matched when the electrode catalyst layers 22C and 22A are formed. Then, by performing transfer using the catalyst layer transfer base materials 10C and 10A, the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A are simultaneously transferred to the polymer electrolyte membrane 30, and therefore the electrode catalyst layer 22C. , 22A and the gasket layers 18C, 18A, a gap is formed and the polymer electrolyte membrane 30 is prevented from being exposed.

  Then, the peeling of the second bonding layers 17C and 17A from the gasket layers 18C and 18A includes the peeling of the first bonding layers 16C and 16A from the base material layers 11C and 11A and the third bonding from the gasket layers 18C and 18A. Since peeling of the layers 19C and 19A is easier, peeling at the interface between the second bonding layers 17C and 17A and the gasket layers 18C and 18A is smoothly realized when peeling the base material layers 11C and 11A after transfer. The In particular, since there are two bonding layers disposed between the base material layers 11C and 11A and the gasket layers 18C and 18A, the base material layers 11C and 11A are compared with the case where such a bonding layer is a single layer. And the degree of freedom in adjusting the adhesive force of the bonding layer to the gasket layers 18C and 18A is increased. As a result, even when various materials are used as the base material layers 11C and 11A and the gasket layers 18C and 18A, the base material layers 11C and 11A can be easily separated from the gasket layers 18C and 18A. 10C and 10A can be realized.

  (2) Since the reinforcing layers 12C and 12A are disposed on the second surfaces of the base material layers 11C and 11A, the catalyst layer transfer base material 10C, Even when the temperature of 10A changes greatly, it is possible to suppress warping of the base material layers 11C and 11A. As a result, workability in the manufacturing process of the membrane electrode assembly 35 using the catalyst layer transfer base materials 10C and 10A is improved. Moreover, since layers different from the base material layers 11C and 11A are arranged on the front and back of the base material layers 11C and 11A, the rigidity of the catalyst layer transfer base materials 10C and 10A is increased, and this also improves the workability. .

  (3) The difference between the peel strength of the first bonding layers 16C and 16A with respect to the base material layers 11C and 11A and the peel strength of the second bonding layers 17C and 17A with respect to the gasket layers 18C and 18A is 0.01 N / 25 mm or more, In addition, since it is less than 10 N / 25 mm, the base material layers 11C and 11A, together with the first joining layers 16C and 16A and the second joining layers 17C and 17A, are peeled off when the base material layers 11C and 11A after transfer are peeled off. It can be easily peeled off at the interface between the bonding layers 17C and 17A and the gasket layers 18C and 18A.

  (4) The difference between the peel strength of the third bonding layers 19C and 19A with respect to the gasket layers 18C and 18A and the peel strength of the second bonding layers 17C and 17A with respect to the gasket layers 18C and 18A is 0.01 N / 25 mm or more, and Since it is less than 10 N / 25 mm, when the base material layers 11C and 11A after transfer are peeled off, the base material layers 11C and 11A together with the first joining layers 16C and 16A and the second joining layers 17C and 17A are second joined. It can be easily peeled off at the interface between the layers 17C and 17A and the gasket layers 18C and 18A.

  (5) Since the peel strength of the first bonding layers 16C, 16A with respect to the base layers 11C, 11A is 0.02 N / 25 mm or more and less than 10 N / 25 mm, the base layers 11 C, 11 A and the multilayer structure layer 15 C , 15A is improved. As a result, a gap is suppressed from being generated between the base material layers 11C and 11A and the multilayer structure layers 15C and 15A. Therefore, when the electrode catalyst layers 22C and 22A are formed, the catalyst ink and the base material layers 11C and 11A are multi-layered. It is possible to suppress the gap between the structural layers 15C and 15A.

  (6) The thickness of the multilayer structure layers 15C and 15A is larger than the thickness of the electrode catalyst layers 22C and 22A, and the difference between these thicknesses is 100 μm or less. Therefore, since the difference between the thickness of the multilayer structure layers 15C and 15A and the thickness of the electrode catalyst layers 22C and 22A is not too large, the step between the end portions of the multilayer structure layers 15C and 15A and the end portions of the electrode catalyst layers 22C and 22A. Can reduce the influence of the transfer on the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A.

  (7) Since the thickness of the gasket layers 18C and 18A is 1 μm or more and 100 μm or less, the function as a gasket in the polymer electrolyte fuel cell is suitably exhibited. Moreover, it is easy to ensure the depth of the openings 21C and 21A in which the electrode catalyst layers 22C and 22A are formed within a suitable range for the film formation and transfer of the electrode catalyst layers 22C and 22A.

  (8) The inner peripheral edge of the third bonding layers 19C and 19A sinks into the outer peripheral edge of the electrode catalyst layers 22C and 22A due to the pressurization during the transfer between the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A. The formation of gaps between the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A is appropriately suppressed.

(Modification)
The above embodiment can be implemented with the following modifications.
As shown in FIG. 10, the base material layers 11C and 11A, the first bonding layers 16C and 16A, the second bonding layers 17C and 17A, and the reinforcing layers 12C and 12A are not peeled off, and these layers are membranes. You may use as a protective layer for protecting each layer which comprises an electrode assembly from the outside. For example, when the membrane / electrode assembly is transported to a location different from the manufacturing location of the membrane / electrode assembly and used for the manufacture of the polymer electrolyte fuel cell, the electrode catalyst layers 22C and 22A are transported when transporting the membrane / electrode assembly. It is necessary to attach a protective sheet for protecting the electrode catalyst layers 22C and 22A. Here, if the base material layers 11C and 11A, the first bonding layers 16C and 16A, the second bonding layers 17C and 17A, and the reinforcing layers 12C and 12A are used as a protective layer without being peeled off, a protective sheet is attached. Is eliminated, and the number of members used is reduced. In addition, when the protective sheet is peeled off, a part of the adhesive layer of the protective sheet is prevented from remaining on the electrode catalyst layers 22C and 22A.

  In this case, the membrane electrode assembly 36 is added to the polymer electrolyte membrane 30, the electrode catalyst layers 22C and 22A, the third bonding layers 19C and 19A, and the gasket layers 18C and 18A that function as constituent members of the solid polymer fuel cell. The base layers 11C and 11A, the first bonding layers 16C and 16A, the second bonding layers 17C and 17A, and the reinforcing layers 12C and 12A are provided. The base material layers 11C and 11A cover the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A, and the first bonding layers 16C and 16A are disposed between the gasket layers 18C and 18A and the base material layers 11C and 11A. The second bonding layers 17C and 17A are disposed between the gasket layers 18C and 18A and the base material layers 11C and 11A so that the gasket layers 18C and 18A and the first bonding layer 16C are in contact with the base material layers 11C and 11A. , 16A. The base material layers 11C and 11A, the first bonding layers 16C and 16A, the second bonding layers 17C and 17A, and the reinforcing layers 12C and 12A are peeled when the solid polymer fuel cell is manufactured.

The members constituting the catalyst layer transfer base materials 10C and 10A may or may not include the electrode catalyst layers 22C and 22A. That is, the layered body before the electrode catalyst layers 22C and 22A are formed may be used as the catalyst layer transfer base materials 10C and 10A, and the layered body after the electrode catalyst layers 22C and 22A are formed is the electrode catalyst layer 22C, It is good also as catalyst layer transfer base materials 10C and 10A including 22A. In short, the members constituting the catalyst layer transfer base materials 10C and 10A may include only some or all of the members transferred to the polymer electrolyte membrane 30.
The reinforcing layers 12C and 12A may be omitted from the catalyst layer transfer base materials 10C and 10A. Even with such a configuration, the effect (1) can be obtained.

  In the membrane electrode assemblies 35 and 36, the shape of the electrode catalyst layers 22C and 22A and the shape of the gasket layers 18C and 18A viewed from the opposite direction, that is, in the catalyst layer transfer base materials 10C and 10A, The shape of the openings 21C and 21A and the shape of the multilayer structure layers 15C and 15A viewed from the direction facing the first surface of 11A may be a triangular shape or a polygonal shape of a pentagon or more. The shape may be circular or elliptical. Further, the inner peripheral edges of the gasket layers 18C and 18A may be inclined with respect to the facing direction. For example, the inner peripheral edge of the gasket layer 18C may have a reverse taper shape when viewed from the base material layer 11C side so that the cross-sectional area of the opening 21C becomes smaller as the portion is closer to the base material layer 11C. That is, the inner surface of the multilayer structure layer 15C that defines the opening 21C has a truncated cone shape, and the electrode catalyst layer 22C fills the bottom of the opening 21C having such a shape. In this case, in the membrane electrode assembly 35, 36, the inner peripheral edge of the gasket layer 18C has a forward tapered shape when viewed from the polymer electrolyte membrane 30 side. According to such a manufacturing method, the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A are separated from each other on the surface of the polymer electrolyte membrane 30 as in the prior art, and the electrode catalyst layers 22C and 22A and the gasket layers 18C and 18A are separately provided. Depending on the manufacturing method to be disposed in, it can be formed into a shape that is difficult to form.

The catalyst layer transfer substrate described above and the method for producing a membrane electrode structure using the catalyst layer transfer substrate will be described using specific examples and comparative examples.
[Example 1]
Using a pressure-sensitive adhesive sheet having separate films on both sides, a laminate of a bonding layer and a gasket layer was formed and bonded to a base material layer. An acrylic pressure-sensitive adhesive having a thickness of 10 μm is used as the first bonding layer, an acrylic pressure-sensitive adhesive having a thickness of 10 μm is used as the second bonding layer, and the thickness is set as the third bonding layer. An acrylic pressure-sensitive adhesive having a thickness of 10 μm was used. Further, a PTFE (polytetrafluoroethylene) sheet having a thickness of 50 μm was used as the base material layer, and a PET (polyethylene terephthalate) film having a thickness of 25 μm was used as the gasket layer.

  The peel strength of the first bonding layer with respect to the base material layer was larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was 0.2 N / 25 mm. Further, the peel strength of the third bonding layer with respect to the gasket layer was larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was set to 1.4 N / 25 mm. The peel strength was determined by measuring 180 ° peel strength at a peel speed of 300 mm / min according to JIS-K-6854-2: 1999 using a tensile tester (manufactured by A & D: STA-1225).

A separate film pasted on one surface of the third bonding layer was used as a coating layer, and a 5 cm ² square opening was formed in the laminate of the bonding layer and the gasket layer. A reinforcing layer was disposed on the opposite surface of the base material layer to which the laminate was bonded. As the reinforcing layer, PET with a bonding layer having a thickness of 25 μm was used.

  Subsequently, a catalyst ink was applied to the base material layer through the opening by the doctor blade method, and the applied catalyst ink was dried in an air atmosphere at a temperature of 80 ° C. for 5 minutes to form an electrode catalyst layer. This obtained the catalyst layer transfer base material of Example 1.

  Using NAFION (registered trademark) 212 (manufactured by DuPont) as the polymer electrolyte membrane, the two catalyst layers are transferred so that each of the two catalyst layer transfer substrates faces each of the two contact surfaces of the polymer electrolyte membrane. A layer transfer substrate and a polymer electrolyte membrane were disposed. After that, the polymer electrolyte membrane sandwiched between these two catalyst layer transfer substrates is heated to 130 ° C. and hot pressed for 10 minutes under pressure to transfer the electrode catalyst layer and gasket layer to the polymer electrolyte membrane. By doing so, the membrane electrode assembly of Example 1 was obtained. In the peeling process of the base material layer after the transfer, the base material layer could be peeled off at the interface between the second joining layer and the gasket layer together with the first joining layer and the second joining layer.

[Example 2]
A catalyst layer transfer substrate of Example 2 was obtained in the same manner as Example 1 except for the peel strength of the bonding layer. The peel strength of the first bonding layer with respect to the base material layer was larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was set to 0.1 N / 25 mm. Further, the peel strength of the third bonding layer with respect to the gasket layer was larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was set to 3.5 N / 25 mm.

  Using the catalyst layer transfer substrate of Example 2, a membrane electrode assembly of Example 2 was obtained in the same manner as Example 1. In the peeling process of the base material layer after the transfer of the electrode catalyst layer and the gasket layer, the base material layer could be peeled together with the first joining layer and the second joining layer at the interface between the second joining layer and the gasket layer.

[Example 3]
A catalyst layer transfer substrate of Example 3 was obtained in the same manner as Example 1 except for the peel strength of the bonding layer. The peel strength of the first joining layer with respect to the base material layer was larger than the peel strength of the second joining layer with respect to the gasket layer, and the difference between these peel strengths was 8.5 N / 25 mm. Further, the peel strength of the third bonding layer with respect to the gasket layer was larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was set to 6.2 N / 25 mm.

  Using the catalyst layer transfer substrate of Example 3, a membrane electrode assembly of Example 3 was obtained in the same manner as in Example 1. In the peeling process of the base material layer after the transfer of the electrode catalyst layer and the gasket layer, the base material layer could be peeled together with the first joining layer and the second joining layer at the interface between the second joining layer and the gasket layer.

[Example 4]
A catalyst layer transfer substrate of Example 4 was obtained in the same manner as Example 1 except for the peel strength of the bonding layer. The peel strength of the first joining layer with respect to the base material layer was larger than the peel strength of the second joining layer with respect to the gasket layer, and the difference between these peel strengths was 0.05 N / 25 mm. Further, the peel strength of the third bonding layer with respect to the gasket layer was larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was 0.07 N / 25 mm.

  Using the catalyst layer transfer substrate of Example 4, a membrane electrode assembly of Example 4 was obtained in the same manner as Example 1. In the peeling process of the base material layer after the transfer of the electrode catalyst layer and the gasket layer, the base material layer could be peeled together with the first joining layer and the second joining layer at the interface between the second joining layer and the gasket layer.

[Example 5]
A catalyst layer transfer substrate of Example 5 was obtained in the same manner as Example 1 except for the peel strength of the bonding layer. The peel strength of the first bonding layer with respect to the base material layer was larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was set to 0.1 N / 25 mm. Further, the peel strength of the third bonding layer with respect to the gasket layer was larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was 3.7 N / 25 mm.

  Using the catalyst layer transfer substrate of Example 5, a membrane electrode assembly of Example 5 was obtained in the same manner as Example 1. In the peeling process of the base material layer after the transfer of the electrode catalyst layer and the gasket layer, the base material layer could be peeled together with the first joining layer and the second joining layer at the interface between the second joining layer and the gasket layer.

[Comparative Example 1]
A catalyst layer transfer substrate of Comparative Example 1 was obtained in the same manner as in Example 1 except for the peel strength of the bonding layer. The peel strength of the first bonding layer with respect to the base material layer was smaller than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was 1.5 N / 25 mm. Further, the peel strength of the third bonding layer with respect to the gasket layer was larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was set to 0.1 N / 25 mm.

  Using the catalyst layer transfer substrate of Comparative Example 1, a membrane / electrode assembly of Comparative Example 1 was obtained in the same manner as in Example 1. In the peeling process of the base material layer after the transfer of the electrode catalyst layer and the gasket layer, peeling occurred at the interface between the first bonding layer and the base material layer, and peeling at the interface between the second bonding layer and the gasket layer could not be performed.

[Comparative Example 2]
A catalyst layer transfer substrate of Comparative Example 2 was obtained in the same manner as in Example 1 except for the peel strength of the bonding layer. The peel strength of the first bonding layer with respect to the base material layer was smaller than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was 1.5 N / 25 mm. Further, the peel strength of the third bonding layer with respect to the gasket layer was smaller than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths was set to 0.7 N / 25 mm.

  Using the catalyst layer transfer substrate of Comparative Example 2, a membrane / electrode assembly of Comparative Example 2 was obtained in the same manner as in Example 1. In the peeling process of the base material layer after the transfer of the electrode catalyst layer and the gasket layer, peeling occurred at the interface between the first bonding layer and the base material layer, and peeling at the interface between the second bonding layer and the gasket layer could not be performed.

From the above examples and comparative examples, in the configuration in which the adhesive force of the first bonding layer to the base material layer and the adhesive force of the third bonding layer to the gasket layer are larger than the adhesive force of the second bonding layer to the gasket layer. It was shown that the base material layer can be peeled off at the interface between the second bonding layer and the gasket layer together with the first bonding layer and the second bonding layer.
(Appendix)
Means for solving the above-mentioned problems include the following supplementary notes as technical ideas derived from the above-described embodiment and the above-described modifications.

(Additional remark 1) It is a membrane electrode assembly manufactured using the said catalyst layer transfer base material, Comprising: The polymer electrolyte membrane which has a contact surface, The electrode catalyst layer located in the said contact surface, The surface of the said contact surface A gasket layer positioned around the electrode catalyst layer in the direction, and a bonding layer positioned around the electrode catalyst layer at the contact surface and sandwiched between the polymer electrolyte membrane and the gasket layer, The membrane electrode assembly in which the inner peripheral edge of the bonding layer is embedded in the outer peripheral edge of the electrode catalyst layer.
(Appendix 2) A polymer electrolyte fuel cell comprising the membrane electrode assembly according to appendix 1 and a pair of separators sandwiching the membrane electrode assembly.

  The membrane electrode assembly or the polymer electrolyte fuel cell having the above configuration is manufactured by using the manufacturing method described in the above embodiment. Therefore, in the membrane / electrode assembly, the polymer electrolyte membrane is suppressed from being exposed between the electrode catalyst layer and the gasket layer.

  10C, 10A ... catalyst layer transfer substrate, 11C, 11A ... substrate layer, 11a ... first surface, 11b ... second surface, 12C, 12A ... reinforcing layer, 13C, 13A ... reinforcing joint layer, 14C, 14A ... support Layers, 15C, 15A ... multilayered structure layer, 16C, 16A ... first joining layer, 17C, 17A ... second joining layer, 18C, 18A ... gasket layer, 19C, 19A ... third joining layer, 20C ... covering layer, 21C , 21A ... opening, 22C, 22A ... electrode catalyst layer, 23C, 23A ... porous diffusion layer, 30 ... polymer electrolyte membrane, 30a ... cathode contact surface, 30b ... anode contact surface, 35, 36 ... membrane electrode assembly, 40: Solid polymer fuel cell, 41C, 41A: Separator.

Claims (10)

A base material layer having a first surface and a second surface opposite to the first surface;
A multilayer structure layer having a frame shape disposed on the first surface, the multilayer structure layer defining an opening in which a material for forming an electrode catalyst layer is embedded on the first surface;
With
The multilayer structure layer has a structure in which a first bonding layer, a second bonding layer, a gasket layer, and a third bonding layer are arranged in this order from the side closer to the first surface,
The force required to peel the second bonding layer from the gasket layer is smaller than the force required to peel the first bonding layer from the base material layer, and the third bonding layer from the gasket layer. The catalyst layer transfer base material is smaller than the force required to peel off the catalyst layer. The catalyst layer transfer substrate according to claim 1, wherein a reinforcing layer that suppresses deformation of the substrate layer due to a temperature change is disposed on the second surface of the substrate layer. The peel strength of the first bonding layer with respect to the base material layer is larger than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between these peel strengths is 0.01 N / 25 mm or more and 10 N / The catalyst layer transfer substrate according to claim 1 or 2, wherein the catalyst layer transfer substrate is less than 25 mm. The peel strength of the third bonding layer with respect to the gasket layer is greater than the peel strength of the second bonding layer with respect to the gasket layer, and the difference between the peel strengths is 0.01 N / 25 mm or more and 10 N / 25 mm. The catalyst layer transfer substrate according to any one of claims 1 to 3. The catalyst layer transfer substrate according to any one of claims 1 to 4, wherein the peel strength of the first bonding layer with respect to the substrate layer is 0.02 N / 25 mm or more and less than 10 N / 25 mm. Further comprising an electrode catalyst layer disposed in the opening;
The thickness of the multilayer structure layer is larger than the thickness of the electrode catalyst layer, and the difference between the thickness of the multilayer structure layer and the thickness of the electrode catalyst layer is 100 µm or less. The catalyst layer transfer substrate according to 1. The catalyst layer transfer substrate according to claim 1, wherein the gasket layer has a thickness of 1 μm or more and 100 μm or less. A multilayer structure layer that defines an opening on the first surface is formed on the first surface of a base material layer having a first surface and a second surface that is a surface opposite to the first surface. Arranging the first bonding layer, the second bonding layer, the gasket layer, and the third bonding layer of the structural layer so as to be arranged in this order from the side closer to the first surface;
Forming an electrode catalyst layer in the opening by applying an ink to form a catalyst layer transfer substrate having the substrate layer, the multilayer structure layer, and the electrode catalyst layer;
Pressing the catalyst layer transfer substrate against a polymer electrolyte membrane having a contact surface, and crimping the electrode catalyst layer and the third bonding layer in the multilayer structure layer to the contact surface;
Including
The adhesive force of the first bonding layer to the base material layer and the adhesive force of the third bonding layer to the gasket layer are larger than the adhesive force of the second bonding layer to the gasket layer. Production method. The substrate layer, the first bonding layer, and the second bonding layer are peeled from the electrode catalyst layer and the gasket layer transferred from the catalyst layer transfer substrate to the contact surface of the polymer electrolyte membrane. The manufacturing method of the membrane electrode assembly according to claim 8, further comprising: A polymer electrolyte membrane having a contact surface;
An electrode catalyst layer located on the contact surface;
A gasket layer located around the electrode catalyst layer in the surface direction of the contact surface and in contact with the peripheral end surface of the electrode catalyst layer;
A base material layer covering the electrode catalyst layer and the gasket layer;
A first bonding layer disposed between the gasket layer and the base material layer and in contact with the base material layer;
A second bonding layer disposed between the gasket layer and the base material layer and in contact with the gasket layer and the first bonding layer;
A third bonding layer disposed between the polymer electrolyte membrane and the gasket layer and in contact with the polymer electrolyte membrane and the gasket layer;
With
The force required to peel the second bonding layer from the gasket layer is smaller than the force required to peel the first bonding layer from the base material layer, and the third bonding layer from the gasket layer. The membrane electrode assembly is smaller than the force required to peel off the film.

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