Ultraviolet-curable resin composition, polymer electrolyte membrane, solid polymer fuel cell, solid polymer water electrolysis device, and method for producing polymer electrolyte membrane

Abstract

The UV-curable resin composition comprises: urethane (meth)acrylate with a weight-average molecular weight of 1,500 to 20,000 and a double bond equivalent of 600 g / mol to 7,500 g / mol; (meth)acrylate monomer with a molecular weight of 150 to 300; vinyl monomer having an acidic functional group; and a photopolymerization initiator.

Description

Technical Field

[0001] This invention relates to ultraviolet-curable resin compositions, polymeric electrolyte membranes, solid polymeric fuel cells, solid polymeric water electrolysis devices, and methods for manufacturing polymeric electrolyte membranes. Background Technology

[0002] Proton-conducting membranes composed solely of polymers with phosphate groups on their side chains are prone to rupture and have low strength. As an alternative, Patent Document 1 discloses a proton-conducting membrane in which a polymer with phosphate groups on its side chains is polymerized within the pores of a porous membrane, thereby loading the polymer within the pores. This proton-conducting membrane can, for example, be used as a polymer electrolyte membrane for solid-state molecular fuel cells.

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent No. 4621344 Summary of the Invention

[0004] The problem that the invention aims to solve Because the pores of the porous membrane that makes up the proton-conducting membrane are micropores, it is difficult to load polymers into all the pores, making it difficult for the membrane to exhibit excellent proton conductivity as a whole.

[0005] The present invention was made in view of the above circumstances, and its object is to provide a polymeric electrolyte membrane with excellent proton conductivity and high strength, a solid polymeric fuel cell and a solid polymeric water electrolysis device having the polymeric electrolyte membrane, a method for manufacturing the polymeric electrolyte membrane, and an ultraviolet-curable resin composition that can be used as a resin composition constituting the polymeric electrolyte membrane.

[0006] Methods for solving problems The present invention is described below.

[0007] [1] The ultraviolet-curable resin composition involved in this invention comprises: Carbamate (meth) acrylates with a weight-average molecular weight of 1,500 to 20,000 and a double bond equivalent of 600 g / mol to 7,500 g / mol; (Meth)acrylate monomers with a molecular weight of 150 to 300; Vinyl monomers with acidic functional groups; and Photopolymerization initiator, The content of the urethane (meth)acrylate is between 20% and 45% by weight relative to the total of 100% by weight of the urethane (meth)acrylate, the (meth)acrylate monomer, and the vinyl monomer. The content of the (meth)acrylate monomer is between 15% by weight and 45% by weight relative to the total of 100% by weight of the urethane (meth)acrylate, the (meth)acrylate monomer, and the vinyl monomer. The content of the vinyl monomer is between 20% and 55% by weight relative to the total of 100% by weight of the urethane (meth)acrylate, the (meth)acrylate monomer, and the vinyl monomer.

[0008] [2] Alternatively, the acidic functional group may be composed of at least one group selected from the group consisting of carboxyl, phosphonic acid, sulfonic acid and phosphate groups.

[0009] [3] Alternatively, the number of acidic functional groups in the vinyl monomer may be 1 or 2.

[0010] [4] The polymeric electrolyte membrane involved in this invention is composed of a UV-curable resin composition of any one of [1] to [3] that has been cured.

[0011] [5] The solid polymer fuel cell of the present invention comprises: [4] The polymer electrolyte membrane described above; An anode catalyst layer is formed on one side of the polymer electrolyte membrane; A cathode catalyst layer is formed on the other side of the polymer electrolyte membrane; The first gas diffusion layer is formed on the opposite side of the anode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The second gas diffusion layer is formed on the opposite side of the cathode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The first diaphragm is disposed on the opposite side of the first gas diffusion layer, i.e., the other side, relative to the side where the anode catalyst layer is formed; and The second diaphragm is disposed on the opposite side of the second gas diffusion layer relative to the side on which the cathode catalyst layer is formed, i.e., the other side.

[0012] [6] The solid polymer water electrolysis device involved in this invention comprises: [4] The polymer electrolyte membrane described above; An anode catalyst layer is formed on one side of the polymer electrolyte membrane; A cathode catalyst layer is formed on the other side of the polymer electrolyte membrane; The first gas diffusion layer is formed on the opposite side of the anode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The second gas diffusion layer is formed on the opposite side of the cathode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The first diaphragm is disposed on the opposite side of the first gas diffusion layer, i.e., the other side, relative to the side where the anode catalyst layer is formed; and The second diaphragm is disposed on the opposite side of the second gas diffusion layer relative to the side on which the cathode catalyst layer is formed, i.e., the other side.

[0013] [7] The method for manufacturing the polymer electrolyte membrane involved in this invention includes: Preparation process: Prepare the ultraviolet-curable resin composition described in any one of [1] to [3]; The resin layer forming process involves forming a resin layer composed of the UV-curable resin composition on a release film. In the film preparation process, another release film is prepared on the opposite side of the resin layer, i.e., the other side, which is opposite to the side on which the first release film is prepared. In the curing process, the resin layer is irradiated with ultraviolet light through one or more release films to cure the resin layer; and The peeling process involves peeling one release film and the other release film from the cured resin layer.

[0014] The effects of the invention According to the present invention, it is possible to provide a polymeric electrolyte membrane with excellent proton conductivity and high strength, a solid polymeric fuel cell and a solid polymeric water electrolysis device having the polymeric electrolyte membrane, a method for manufacturing the polymeric electrolyte membrane, and an ultraviolet-curable resin composition that can be used as a resin composition constituting the polymeric electrolyte membrane. Attached Figure Description

[0015] [ Figure 1 [ ] is a schematic cross-sectional view of the polymer electrolyte membrane as an embodiment.

[0016] [ Figure 2 [This is a schematic cross-sectional view showing the structure of a proton exchange solid polymer fuel cell.]

[0017] [ Figure 3 [This is a schematic cross-sectional view showing the structure of a proton exchange type solid polymer water electrolysis device.] Detailed Implementation

[0018] The following provides a detailed description of the ultraviolet-curable resin composition, polymeric electrolyte membrane, solid-state polymeric fuel cell, solid-state polymeric water electrolysis device, and method for manufacturing the polymeric electrolyte membrane, which are used to implement the present invention (hereinafter referred to as embodiments). These embodiments are illustrative examples of the present invention and are not intended to limit the invention to the following content. The present invention can be appropriately modified and implemented within its scope.

[0019] In this invention, urethane (meth)acrylate refers to urethane acrylate or urethane methacrylate. (meth)acrylate monomer refers to acrylate monomer or methacrylate monomer. Weight, for example, refers to the weight of the resin alone, excluding volatile components such as organic solvents contained in the resin, and the weight of non-volatile components.

[0020] [UV-curable resin composition] The UV-curable resin composition of the embodiments comprises urethane (meth)acrylate, (meth)acrylate monomer, vinyl monomer, and photopolymerization initiator. Such a UV-curable resin composition is suitable for use as a resin composition for constituting a polymeric electrolyte membrane with excellent proton conductivity and high strength.

[0021] The components contained in the UV-curable resin composition of the embodiments will be described below.

[0022] (Carbamate (meth)acrylate) Examples of urethane (meth)acrylates used in the embodiments include addition-type urethane (meth)acrylates, polycarbonate-based urethane (meth)acrylates, and polyester-based urethane (meth)acrylates. From the viewpoint of obtaining a polymeric electrolyte membrane with excellent proton conductivity and high strength, addition-type urethane (meth)acrylates and polycarbonate-based urethane (meth)acrylates are preferred. One type of urethane (meth)acrylate may be used alone or in combination of two or more types. It should be noted that addition-type urethane (meth)acrylates are also called adduct-based urethane (meth)acrylates.

[0023] From the viewpoint of obtaining a high-strength polymeric electrolyte membrane, the weight-average molecular weight of urethane (meth)acrylate is 1,500 to 20,000, preferably 1,500 to 15,000, more preferably 1,700 to 15,000, and even more preferably 5,000 to 15,000. It should be noted that the weight-average molecular weight of hydroxy (meth)acrylate can be determined using standard polymethyl methacrylate and gel permeation chromatography (GPC).

[0024] From the viewpoint of obtaining a polymeric electrolyte membrane with excellent proton conductivity and high strength, the double bond equivalent of urethane (meth)acrylate is 600 g / mol or more and 7500 g / mol or less, preferably 750 g / mol or more and 7500 g / mol or less, more preferably 800 g / mol or more and 7500 g / mol or less, and even more preferably 800 g / mol or more and 2500 g / mol or less. The urethane (meth)acrylate may have double bonds in its side chains and / or at its ends; from the viewpoint of improving reactivity, it is preferable to have double bonds in both the side chains and at the ends. It should be noted that the double bond equivalent can be calculated using the formula: double bond equivalent (g / mol) = weight-average molecular weight of the monomer / number of polymerizable double bonds in the same molecule (mol).

[0025] The aforementioned addition-type urethane (meth)acrylates can be obtained, for example, by reacting hydroxy (meth)acrylates with diisocyanates. Examples of hydroxy (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and caprolactone-modified 2-hydroxyethyl (meth)acrylate. Furthermore, from the viewpoint of easy availability, hydroxy (meth)acrylates are preferably 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. Examples of diisocyanates include (i) aromatic diisocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and naphthalene diisocyanate; (ii) aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; and (iii) alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylene diisocyanate. Furthermore, from the viewpoint of easy availability, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate are preferred.

[0026] The aforementioned polycarbonate-based urethane (meth)acrylates can be obtained, for example, by reacting polycarbonate diols with hydroxy (meth)acrylates and diisocyanates. Examples of polycarbonate diols include propylene carbonate diol, hexamethylene carbonate diol, and 3-methylpentene carbonate diol. Furthermore, from a reactivity point of view, propylene carbonate diol and hexamethylene carbonate diol are preferred.

[0027] The aforementioned polyester-based urethane (meth)acrylates can be obtained, for example, by reacting polyester polyols with hydroxy (meth)acrylates and diisocyanates.

[0028] Examples of polyester polyols include reactants of alcohol and acid components. Examples of alcohol components include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, nonanediol, cyclohexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and neopentyl glycol hydroxypentanoate. Furthermore, from a reactivity point of view, preferred alcohol components include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, nonanediol, and cyclohexanediol.

[0029] Examples of acid components include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, or their anhydrides, or ring-opening reactants of polycarbonate diol and caprolactone. Furthermore, from the viewpoint of efficiently facilitating polycondensation, adipic acid or phthalic acid are preferred acid components.

[0030] The content of urethane (meth)acrylate in the UV-curable resin composition is 20% to 45% by weight, preferably 25% to 40% by weight, relative to the total of urethane (meth)acrylate, (meth)acrylate monomers, and vinyl monomers, for a total of 100% by weight. By including urethane (meth)acrylate in the UV-curable resin composition in the above proportion, the proton conduction performance is not reduced, and the strength of the polymer electrolyte membrane is improved.

[0031] ((meth)acrylate monomer) Examples of (meth)acrylate monomers used in the embodiments include butyl (meth)acrylate, stearate (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and diethylene glycol di(meth)acrylate. Furthermore, from the viewpoint of compatibility with other materials constituting the UV-curable resin composition, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and diethylene glycol di(meth)acrylate are more preferred (meth)acrylate monomers.

[0032] From the viewpoint of using (meth)acrylate monomers to dilute urethane (meth)acrylate, vinyl monomers, and photopolymerization initiators, the molecular weight of the (meth)acrylate monomer is, for example, 150 or more and 300 or less, preferably 150 or more and 250 or less, and more preferably 175 or more and 225 or less.

[0033] From the viewpoint of reducing the viscosity of the UV-curable resin composition, the content of (meth)acrylate monomers in the UV-curable resin composition is 15% to 45% by weight, preferably 15% to 40% by weight, relative to the total of 100% by weight of urethane (meth)acrylate and (meth)acrylate monomers and vinyl monomers. This ensures that the vinyl monomers, which have acidic functional groups that affect proton conductivity, are uniformly dispersed in the UV-curable resin composition. By curing the UV-curable resin composition in this uniformly dispersed state of vinyl monomers, a polymeric electrolyte membrane with acidic functional groups present throughout the thickness direction and the main surface of the membrane can be obtained. Such a polymeric electrolyte membrane exhibits excellent proton conductivity as a whole.

[0034] (Vinyl monomer) Vinyl monomers possess acidic functional groups. Examples of vinyl monomers possessing acidic functional groups include monofunctional phosphate (meth)acrylates (2-methacryloyloxyethyl phosphate), monofunctional sulfonic acid (meth)acrylates (2-[methacryloyloxy]ethanesulfonic acid), phosphonic acid (meth)acrylates, phosphonic acid di(meth)acrylates (bis[2-(methacryloyloxyethyl)] phosphate), vinylphosphonic acid, and vinylsulfonic acid. From the viewpoint of storage stability, monofunctional phosphate (meth)acrylates (2-methacryloyloxyethyl phosphate), monofunctional sulfonic acid (meth)acrylates (2-[methacryloyloxy]ethanesulfonic acid), phosphonic acid di(meth)acrylates, vinylphosphonic acid, and vinylsulfonic acid are preferred.

[0035] The acidic functional group is selected from at least one group chosen from the group consisting of carboxyl, phosphonic acid, sulfonic acid, and phosphoric acid groups. From the viewpoint of obtaining a polymeric electrolyte membrane with excellent proton conductivity, the acidic functional group is preferably phosphonic acid, sulfonic acid, and / or phosphoric acid. From the viewpoint of obtaining a polymeric electrolyte membrane with excellent proton conductivity, the number of acidic functional groups in the vinyl monomer is preferably 1 or 2. Examples of vinyl monomers having phosphonic acid, sulfonic acid, and / or phosphoric acid include vinylphosphonic acid, vinylsulfonic acid, monofunctional phosphate (meth)acrylate (2-methacryloyloxyethyl phosphate), and monofunctional sulfonic acid (meth)acrylate (2-[methacryloyloxy]ethanesulfonic acid).

[0036] From the viewpoint of obtaining a polymeric electrolyte membrane with excellent proton conductivity, the molecular weight of the vinyl monomer is, for example, 100 or more and 1000 or less, preferably 100 or more and 700 or less, and more preferably 100 or more and 400 or less.

[0037] The content of vinyl monomers in the UV-curable resin composition is 20% to 55% by weight, preferably 20% to 50% by weight, relative to the total of 100% by weight of urethane (meth)acrylate and (meth)acrylate monomers and vinyl monomers. The polymeric electrolyte membrane obtained by curing such a UV-curable resin composition exhibits excellent proton conductivity.

[0038] (Photopolymerization initiator) Examples of photopolymerization initiators include short-wavelength absorption photopolymerization initiators that absorb light with wavelengths less than 400 nm and long-wavelength absorption photopolymerization initiators that absorb light with wavelengths greater than 400 nm. Examples of short-wavelength absorption photopolymerization initiators include Omnirad 2959, Omnirad 651, Omnirad 379, and Omnirad 907 from IGM PreSIN. Examples of long-wavelength absorption photopolymerization initiators include Omnirad 184, Omnirad TPO, Omnirad 819, and Omnirad EMK from IGM PreSIN.

[0039] From the viewpoint of ensuring uniform curing of the UV-curable resin composition along its thickness direction, a long-wavelength absorption type photopolymerization initiator is preferred as the photopolymerization initiator. One type of photopolymerization initiator may be used alone or in combination of two or more. From the viewpoint of promoting the photocuring reaction, the content of the photopolymerization initiator is preferably 1% to 10% by weight relative to the total 100% by weight of urethane (meth)acrylate and (meth)acrylate monomers and vinyl monomers, more preferably 1% to 7% by weight, and even more preferably 1% to 3% by weight.

[0040] (Other ingredients) Additives may be added to the UV-curable resin composition of the embodiments, provided that the proton conductivity and strength of the polymer electrolyte membrane are not compromised. Examples of additives include chain transfer agents, sensitizers, dispersants, softeners, heat aging resistant agents, and silane coupling agents.

[0041] The UV-curable resin composition of the embodiment is obtained by placing a specified amount of the above-mentioned material into a container and mixing them.

[0042] [Polymer electrolyte membrane] Next, the structure of the polymer electrolyte membrane in the embodiment will be described.

[0043] Figure 1 The polymeric electrolyte membrane 40 shown in the embodiment is composed of the UV-curable resin composition of the embodiment. From the viewpoint of operability and maintaining membrane strength, the thickness of the polymeric electrolyte membrane 40 of the embodiment is, for example, 10 μm or more and 300 μm or less, more preferably 50 μm or more and 200 μm or less.

[0044] The polymeric electrolyte membrane 40 is obtained, for example, through the following steps. The above-mentioned amounts of urethane (meth)acrylate, (meth)acrylate monomers, vinyl monomers, and a photopolymerization initiator are added to a container and mixed to prepare a UV-curable resin composition (preparation step). The obtained UV-curable resin composition is coated onto a first release film using, for example, a coating apparatus, to form a resin layer composed of the UV-curable resin composition (resin layer formation step). Next, a second release film is disposed on the surface of the formed resin layer (film placement step). The resin layer is irradiated with ultraviolet light through the first or second release film to cure the resin layer (curing step). The first and second release films disposed on both sides of the resin layer are peeled off (peeling step) to obtain the resin layer, i.e., the polymeric electrolyte membrane 40.

[0045] Examples of coating apparatus used in the resin layer formation process include die coaters and comma coaters. During the curing process, the wavelength of the ultraviolet light irradiating the resin layer is, for example, 200 nm to 800 nm. The cumulative intensity of the ultraviolet light irradiating the resin layer is, for example, 1000 mJ / cm². 2 Above 10000mJ / cm 2 From the viewpoint of ensuring uniform curing of the UV-curable resin composition constituting the resin layer along its thickness direction, the wavelength of the UV light is preferably 400 nm or more and 800 nm or less. Furthermore, when irradiating the UV-curable resin composition with UV light of 400 nm or more and 800 nm or less, the photopolymerization initiator contained in the UV-curable resin composition is preferably Omnirad 819 or Omnirad EMK, which absorb UV light with wavelengths of 400 nm or more.

[0046] From the viewpoint of easy preparation or easy peeling of the release film, the thickness of the first and second release films used in the resin layer formation and film preparation processes is, for example, 25 μm to 100 μm, preferably 75 μm to 100 μm. Examples of materials for the release film include polyethylene, polypropylene, polyimide, polyamide, polyethylene naphthalate, and polyethylene terephthalate. From the viewpoint of efficiently irradiating the resin layer with ultraviolet light during the curing process, the release film is preferably a colorless and transparent film. Furthermore, from the viewpoint of easy peeling of the release film from the resin layer, a demolding treatment can be performed on the surface of the release film. Examples of demolding treatment agents include silicone-based agents and fluorine-based agents.

[0047] In the resin layer formation process, the formed resin layer can also be heated. This cures the resin layer, thus preventing changes in its thickness when the second release film is laminated in the next process. Furthermore, the polymeric electrolyte membrane 40 of the embodiment is manufactured in the order of resin layer formation, membrane preparation, curing, and peeling; however, the polymeric electrolyte membrane 40 can also be obtained without performing the membrane preparation process. That is, the polymeric electrolyte membrane 40 can be obtained by performing a curing process (irradiating the resin layer obtained in the resin layer formation process with ultraviolet light to cure the resin layer) and a peeling process without preparing the second release film.

[0048] The obtained polymer electrolyte membrane 40 can be used as a polymer electrolyte membrane for use in solid polymer fuel cells, and more specifically, it can be used as a polymer electrolyte membrane for use in proton exchange solid polymer fuel cells.

[0049] In addition, the obtained polymer electrolyte membrane 40 can be used as a polymer electrolyte membrane in a solid polymer water electrolysis device, and more specifically, it can be used as a polymer electrolyte membrane in a proton exchange solid polymer water electrolysis device.

[0050] Solid polymer fuel cells The following explanation will use a proton exchange type solid polymer fuel cell 10 that utilizes the polymer electrolyte membrane 40 of the embodiment as an example. Figure 2 As shown, the proton exchange type solid polymer fuel cell 10 includes an anode electrode 20, a cathode electrode 30, a polymer electrolyte membrane 40, a membrane 51, and a membrane 52.

[0051] The anode electrode 20 includes an anode catalyst layer 41 and a gas diffusion layer 43. The anode catalyst layer 41 is formed on one side of the polymer electrolyte membrane 40. The gas diffusion layer 43 is formed on the opposite side of the anode catalyst layer 41 relative to the side where the polymer electrolyte membrane 40 is formed. That is, the anode catalyst layer 41 and the gas diffusion layer 43 are stacked on the polymer electrolyte membrane 40 in order from near to far from the polymer electrolyte membrane 40. The gas diffusion layer 43 corresponds to the first gas diffusion layer.

[0052] The cathode electrode 30 includes a cathode catalyst layer 42 and a gas diffusion layer 44. The cathode catalyst layer 42 is stacked on the other side of the polymer electrolyte membrane 40. The gas diffusion layer 44 is formed on the opposite side of the cathode catalyst layer 42 relative to the side where the polymer electrolyte membrane 40 is formed. That is, the cathode catalyst layer 42 and the gas diffusion layer 44 are stacked on the polymer electrolyte membrane 40 in order from near to far from the polymer electrolyte membrane 40. The gas diffusion layer 44 is equivalent to a second gas diffusion layer.

[0053] The anode catalyst layer 41 functions as a catalyst to promote the oxidation reaction of hydrogen. Examples of materials for the anode catalyst layer 41 include a carbon support with a platinum loading of 50 wt%. Specifically, TEC10E50E (manufactured by Tanaka Precious Metals Industry Co., Ltd.) is an example.

[0054] The cathode catalyst layer 42 has a catalytic function that promotes the reduction reaction of oxygen. Examples of materials for the cathode catalyst layer 42 include carbon supports with a platinum loading of 50 wt%. Specifically, TEC10E50E (manufactured by Tanaka Precious Metals Industry Co., Ltd.) is an example.

[0055] The gas diffusion layer 43 functions to diffuse externally supplied hydrogen (H2) 63 into the anode catalyst layer 41. The gas diffusion layer 44 functions to diffuse externally supplied oxygen (O2) 61 into the cathode catalyst layer 42. Examples of materials for the gas diffusion layers 43 and 44 include carbon paper with a hydrophobic surface treatment. Specifically, SGL24-BCH (manufactured by SGL Carbon) is an example.

[0056] The polymer electrolyte membrane 40 allows protons (H+) generated during the oxidation of hydrogen in the anode catalyst layer 41 to pass through. ＋ )72 passed.

[0057] To protect the anode electrode 20, the polymer electrolyte membrane 40, and the cathode electrode 30, a pair of diaphragms 51 and 52 are arranged to clamp the anode electrode 20, the polymer electrolyte membrane 40, and the cathode electrode 30. Diaphragm 51 is disposed on the opposite side of the gas diffusion layer 43 relative to the side where the anode catalyst layer 41 is formed. Diaphragm 52 is disposed on the opposite side of the gas diffusion layer 44 relative to the side where the cathode catalyst layer 42 is formed. Figure 2 As shown, diaphragms 51 and 52 have a plurality of grooves 53 and 54 on one side. The grooves 53 and 54 are arranged parallel to each other on one side in a direction orthogonal to the length direction of the grooves 53 and 54. For example, metal diaphragms manufactured by MIKURABO can be used as diaphragms 51 and 52.

[0058] A diaphragm 51 with grooves 53 on its surface is disposed on the gas diffusion layer 43 such that the surface with grooves 53 is in contact with the gas diffusion layer 43. The grooves 53 are connected to a supply path 65 for supplying hydrogen (H2) 63 and have the function of allowing hydrogen (H2) 63 to flow. In addition, the grooves 53 are also connected to a discharge path 66 for discharging hydrogen (H2) 63.

[0059] A diaphragm 52 with grooves 54 on its surface is disposed on the gas diffusion layer 44 such that the surface with grooves 54 is in contact with the gas diffusion layer 44. The grooves 54 are connected to the supply path 67 for supplying oxygen (O2) 61 and have the function of allowing oxygen (O2) 61 to flow. In addition, the grooves 54 are also connected to the discharge of oxygen (O2) 61 and protons (H2O) from the cathode catalyst layer 42. ＋ The water (H2O) produced by the reduction reaction of 72 is discharged through the outlet path 68.

[0060] Diaphragm 51 is equivalent to the first diaphragm. Diaphragm 52 is equivalent to the second diaphragm.

[0061] Next, the mechanism by which the proton exchange solid polymer fuel cell 10 generates electromotive force will be explained.

[0062] Hydrogen (H2) 63 supplied from the outside via supply path 65 passes through the tank 53 of diaphragm 51, through gas diffusion layer 43, and reaches anode catalyst layer 41. The hydrogen (H2) 63 reaching anode catalyst layer 41 undergoes a hydrogen oxidation reaction within the anode catalyst layer 41, i.e., H2 → 2H+. ＋ +2e - The reaction produces protons (H). ＋ )72 and electrons (e - 71. Unreacted hydrogen (H2) 63 in the anode catalyst layer 41 is discharged to the outside of the proton exchange solid polymer fuel cell 10 via the discharge path 66. Electrons (e -)71 returns to the proton exchange solid polymer fuel cell 10 via external circuit 70. At this time, an electromotive force is generated in the proton exchange solid polymer fuel cell 10.

[0063] Proton (H) ＋ Oxygen (O2) 61 supplied from supply path 67 passes through tank 54 and gas diffusion layer 44 to reach cathode catalyst layer 42. In cathode catalyst layer 42, oxygen (O2) 61 reacts with protons (H2O) to form protons (H2O). ＋ The reduction reaction of H₂O₆₂ produces water (H₂O)₆₂. The specific reduction reaction is 4H₂O₆₂. ＋ +O2+4e - The reaction → 2H2O. The water (H2O) 62 generated by this reaction is discharged to the outside of the proton exchange solid polymer fuel cell 10 via the discharge path 68.

[0064] Regarding the polymeric electrolyte membrane 40, which is an embodiment with acidic functional groups throughout, it is able to facilitate the generation of protons (H+) in the anode catalyst layer 41. ＋ )72 moves efficiently to the cathode catalyst layer 42, thus exhibiting excellent proton conductivity.

[0065] [Solid Polymer Water Electrolysis Device] Next, the proton exchange type solid polymer water electrolysis device 100 using the polymer electrolyte membrane 40 of the embodiment will be described as an example. Figure 3 As shown, the proton exchange type solid polymer water electrolysis device 100 includes an anode electrode 120, a cathode electrode 130, a polymer electrolyte membrane 40, a diaphragm 151, and a diaphragm 152.

[0066] The anode electrode 120 includes an anode catalyst layer 141 and a gas diffusion layer 143. The anode catalyst layer 141 is formed on one side of the polymer electrolyte membrane 40. The gas diffusion layer 143 is formed on the opposite side of the anode catalyst layer 141 relative to the side where the polymer electrolyte membrane 40 is formed. That is, the anode catalyst layer 141 and the gas diffusion layer 143 are stacked on the polymer electrolyte membrane 40 in order from near to far from the polymer electrolyte membrane 40. The gas diffusion layer 143 corresponds to the first gas diffusion layer.

[0067] The cathode electrode 130 includes a cathode catalyst layer 142 and a gas diffusion layer 144. The cathode catalyst layer 142 is formed on the other side of the polymer electrolyte membrane 40. The gas diffusion layer 144 is formed on the opposite side of the cathode catalyst layer 142 relative to the side where the polymer electrolyte membrane 40 is formed. That is, the cathode catalyst layer 142 and the gas diffusion layer 144 are stacked on the polymer electrolyte membrane 40 in order from near to far from the polymer electrolyte membrane 40. The gas diffusion layer 144 is equivalent to a second gas diffusion layer.

[0068] The anode catalyst layer 141 functions as a catalyst to promote the water splitting reaction. Examples of materials for the anode catalyst layer 141 include, for instance, a carbon support containing iridium oxide. Specifically, ELC-0110 (iridium content 1 mg / cm³) is an example. 2 (Made by Tanaka Precious Metals Industry Co., Ltd.)

[0069] The cathode catalyst layer 142 functions as a catalyst to promote the reduction reaction of hydrogen. Examples of materials for the cathode catalyst layer 142 include a carbon support with a platinum loading of 50 wt%. Specifically, TEC10E50E (platinum loading 1 mg / cm³) is an example. 2 (Made by Tanaka Precious Metals Industry Co., Ltd.)

[0070] The gas diffusion layer 143 functions to diffuse water (H2O) 163 supplied from the tank 153 of the diaphragm 151 throughout the entire anode catalyst layer 141. The gas diffusion layer 144 functions to diffuse protons (H2O) generated in the cathode catalyst layer 142 by the hydrolysis reaction of the anode catalyst layer 141. ＋ )172 and electrons (e) supplied from power source 170 - The hydrogen (H2) 161 produced by the reaction of 171 diffuses into the membrane 152 as a whole, thus efficiently inducing the function of the tank 154.

[0071] As a material for the gas diffusion layer 143, porous titanium materials with excellent corrosion resistance and high strength can be cited. Specifically, WEBTi (registered trademark)-K (manufactured by Toho Titanium Co., Ltd.) can be cited.

[0072] As a material for the gas diffusion layer 144, carbon paper with a hydrophobic surface treatment can be cited as an example. Specifically, SIGRACET 39BC (manufactured by SLG Carbon Japan Co., Ltd.) can be cited as an example.

[0073] The polymer electrolyte membrane 40 allows only the protons (H+) generated during the water decomposition reaction in the anode catalyst layer 141 to pass through. ＋ 172 passed.

[0074] To protect the anode electrode 120, the polymer electrolyte membrane 140, and the cathode electrode 130, a pair of diaphragms 151 and 152 are arranged to clamp the anode electrode 120, the polymer electrolyte membrane 140, and the cathode electrode 130. Diaphragm 151 is disposed on the opposite side of the gas diffusion layer 143 relative to the side where the anode catalyst layer 141 is formed. Diaphragm 152 is disposed on the opposite side of the gas diffusion layer 144 relative to the side where the cathode catalyst layer 142 is formed. Figure 3 As shown, diaphragms 151 and 152 have a plurality of grooves 153 and 154 on one side. The grooves 153 and 154 are arranged parallel to each other on one side in a direction orthogonal to the length direction of the grooves 153 and 154. For example, a gold-plated titanium diaphragm (manufactured by MIKURABO) can be used as diaphragm 151. For example, a gold-plated titanium diaphragm (manufactured by MIKURABO) can be used as diaphragm 152.

[0075] A diaphragm 151 with grooves 153 on its surface is disposed on a gas diffusion layer 143 such that the surface with grooves 153 is in contact with the gas diffusion layer 143. The grooves 153 are connected to a supply path 165 for supplying water (H2O) 163 and have the function of allowing water (H2O) 163 to flow. In addition, the grooves 153 are also connected to a discharge path 166 for discharging water (H2O) 163 and oxygen (O2) 162.

[0076] A diaphragm 152 having grooves 154 on its surface is disposed on the gas diffusion layer 144 such that the surface with grooves 154 is in contact with the gas diffusion layer 144. The grooves 154 are also connected to an exhaust path 168 for discharging hydrogen (H2) 161.

[0077] Diaphragm 151 is equivalent to the first diaphragm. Diaphragm 152 is equivalent to the second diaphragm.

[0078] Power supply 170 supplies power to proton exchange type polymer water electrolysis device 100.

[0079] Next, the mechanism for generating hydrogen from the proton exchange type polymer water electrolysis device 100 will be explained.

[0080] Water (H2O) 163 supplied from the outside via supply path 165 passes through tank 153 of diaphragm 151, and reaches anode catalyst layer 141 via gas diffusion layer 143. The water (H2O) 163 reaching anode catalyst layer 141 is then converted into electrons (electrons) by electricity supplied from power source 170 within the anode catalyst layer 141. - 171) Electrolysis. Through the electrolysis of this water, i.e., 2H₂O → 4H₂O ＋ +4e - The reaction of +O2 produces protons (H+) from water (H2O). ＋ ), electron (e- The unreacted water (H2O) 163 and the oxygen (O2) 162 produced by the reaction are discharged to the proton exchange type solid polymer water electrolysis device 100 via the discharge path 166.

[0081] Proton (H) ＋ Protons (H172) pass through the polymer electrolyte membrane 40 and reach the cathode catalyst layer 142. In the cathode catalyst layer 142, protons (H172) pass through the polymer electrolyte membrane 40 and reach the cathode catalyst layer 142. ＋ )172 and electrons (e) supplied from power source 170 - The reaction of 171 is 2H ＋ +2e - →H2 produces hydrogen (H2). The produced hydrogen (H2) 161 passes through the tank 154 of the membrane 152 via the gas diffusion layer 144 and is stored outside the proton exchange type solid polymer water electrolysis device 100 via the discharge path 168.

[0082] In embodiments where the polymeric electrolyte membrane 40 has acidic functional groups throughout its thickness direction and main surface, it enables the generation of protons (H+) in the anode catalyst layer 141 to... ＋ The protons move efficiently to the cathode catalyst layer 142, resulting in excellent proton conductivity.

[0083] Example The invention is illustrated in more detail by way of the following embodiments. The invention is not limited to any of the following embodiments.

[0084] The following materials were used as components in the UV-curable resin compositions used as examples and comparative examples.

[0085] (Ester-based carbamate (meth)acrylates) (1) CWD8E26 (made by Nejou Kogyo Co., Ltd.) It has a weight-average molecular weight of 20,000, a double bond equivalent of 5,000 g / mol, a glass transition temperature (Tg) of -19℃, a viscosity of 150,000 mPa·s at 25℃, and 4 functional groups.

[0086] (2) CWD11N (made by Negami Kogyo Co., Ltd.) Weight-average molecular weight 10,500, double bond equivalent 3,500 g / mol, Tg -37℃, viscosity at 25℃ 30,000 Pa·s, number of functional groups 3.

[0087] (Adduct system urethane (meth)acrylate) (3) SMT001 (made by Nejou Kogyo Co., Ltd.) It has a weight-average molecular weight of 1700, a double bond equivalent of 567 g / mol, a Tg of 103℃, a viscosity of 1,000,000 Pa·s at 25℃, a viscosity of 250,000 Pa·s at 60℃, and 3 functional groups.

[0088] (4) UN2701 (made by Nejou Industrial Company) The weight-average molecular weight is 1500, the double bond equivalent is 750 g / mol, the Tg is 57℃, the viscosity at 25℃ is 600000 Pa·s, and the number of functional groups is 2.

[0089] (5) UN2600 (made by Nejou Kogyo Co., Ltd.) Weight-average molecular weight 1600, double bond equivalent 800 g / mol, Tg 10℃, viscosity at 25℃ 10000 Pa·s, number of functional groups 2.

[0090] (Carbohydrate-based urethane (meth)acrylates) (6) UN9000PEP (made by Nejou Kogyo Co., Ltd.) Weight-average molecular weight 5000, double bond equivalent 2500 g / mol, Tg -7℃, viscosity at 25℃ 2000000 Pa·s, number of functional groups 2.

[0091] (7) UN9200 (made by Nejou Kogyo Co., Ltd.) Weight-average molecular weight 15000, double bond equivalent 7500 g / mol, Tg -27℃, viscosity at 25℃ 2000000 Pa·s, number of functional groups 2.

[0092] ((meth)acrylate monomer) (1) Light Ester PO (made by Kyoei Chemical Co., Ltd.) Weight-average molecular weight 201, double bond equivalent 201 g / mol, viscosity at 25℃ 7 Pa·s, number of functional groups 1.

[0093] (Vinyl monomer) Vinylphosphonic acid CAS RN 1746-03-8 (manufactured by Tokyo Chemical Industry Co., Ltd.) Weight-average molecular weight 108, double bond equivalent 108 g / mol, number of functional groups 1.

[0094] (Photopolymerization initiator) Omnirad 819 (made by IGM RESIN).

[0095] (Example 1) (Preparation of UV-curable resin composition) 33.3 parts by weight of Light Ester PO and 3.0 parts by weight of Omnirad 819 were added to a reaction vessel and stirred at 70°C. Then, 33.3 parts by weight of CWD8E26 heated to 70°C were added to the same reaction vessel and stirred until homogeneous. The mixture was then cooled to room temperature. Next, 33.3 parts by weight of CAS RN 1746-03-8 were added to the reaction vessel and stirred to obtain a UV-curable resin composition. It should be noted that the preparation was carried out in a room using a yellow lamp to suppress the reaction of the initiator caused by visible light.

[0096] (Preparation of polymer electrolyte membrane) Using a die-coating machine, a UV-curable resin composition was applied to the release surface of a first release PET film (Lintec PET75X) with a thickness of 75 μm, to a cured thickness of 150 μm. Next, a second release PET film (Lintec PET75X) was placed on the resin surface, with the coated resin surface in contact with the release surface. Then, the UV-curable resin composition was cured by irradiation with a high-pressure mercury lamp (TOPCON TECHNOHOUSE, industrial UV detector, UVR-T1). The irradiation conditions were an illuminance of 150 ± 20 W / cm². 2 Cumulative light intensity 2000 mJ / cm 2 The first and second release PET films are peeled off from the laminate consisting of a first release PET film, a resin layer, and a second release PET film, thereby obtaining the resin layer, which is the polymer electrolyte membrane.

[0097] (Evaluation of proton conductivity) The proton conductivity of the obtained polymer electrolyte membrane was evaluated. First, the resistance, thickness, and electrode area of ​​the polymer electrolyte membrane were measured. The obtained values ​​were substituted into equation (1) to calculate the proton conductivity. Then, the proton conductivity was evaluated according to the following criteria.

[0098] Equation (1) Proton conductivity (mS / cm) = 1000 × membrane thickness of polymer electrolyte membrane (cm) / (electrode area (cm²)) 2 () × resistance value (Ω)), where S represents Siemens, the unit of proton conductivity (mS / cm).

[0099] Excellent (≥8mS / cm); Good quality: ≥3mS / cm, <8mS / cm; The difference is less than 3 mS / cm.

[0100] When determining the "resistance value" in equation (1), the AC impedance of the polymer electrolyte membrane was measured. The AC impedance was measured using an electrochemical measuring device (made by Beidou Electric Co., Ltd., Hz-Pro S4) and a high-precision resistance measuring device (made by Jingyuan Manufacturing Co., Ltd., IMC-008D(A)).

[0101] Specifically, a polymer electrolyte membrane cut into 4 cm squares was immersed in ion-exchange water at 25°C for 24 hours. After being removed from the ion-exchange water, the polymer electrolyte membrane, after wiping off the water droplets, was used as the sample for measurement. Next, the sample was clamped between a pair of gold-plated electrodes of a high-precision resistance measuring device under a pressure of 1 MPa. Then, the active electrode of the electrochemical measuring device was connected to one of the gold-plated electrodes, and the reference electrode of the electrochemical measuring device was connected to the other of the gold-plated electrodes. Additionally, the counter electrode of the electrochemical measuring device was connected to the reference electrode, and the AC impedance of the polymer electrolyte membrane was measured. The measurement conditions were 25°C, 50% RH relative humidity, a measurement frequency of 1 kHz to 1 MHz, and an AC amplitude of 10 mV.

[0102] Based on the measured AC impedance, the Nyquist plot was obtained using specialized software (made by Beidou Electric Co., Ltd., EIS1.2.2), and the resistance value of the polymer electrolyte membrane was calculated. It should be noted that the "Nyquist plot" refers to a graph plotted on a complex plane by changing the frequency to measure the AC impedance of the measured object, setting the X-axis as the real component and the Y-axis as the imaginary component.

[0103] The proton conductivity of the polymer electrolyte membrane composed of the UV-curable resin composition of Example 1, determined by the above method, is 7.5 mS / cm, and is rated as "good".

[0104] Next, the strength of the polymer electrolyte membrane was evaluated. The gas leakage rate and tensile strength of the polymer electrolyte membrane were measured and evaluated.

[0105] (Gas leakage amount) Regarding the gas leakage of the polymer electrolyte membrane, the air leakage was measured. Specifically, an air leakage tester (Cosmo Instruments, LS-R910) was used to measure the air leakage. First, the polymer electrolyte membrane, cut into 90mm squares, was immersed in ion-exchange water at 25°C for 24 hours. Next, the polymer electrolyte membrane was removed from the ion-exchange water, and the surface water droplets were wiped off. The polymer electrolyte membrane was then placed in the chamber of the air leakage tester without creating gaps. Next, air was flowed into the chamber at a pressure of 50 kPa for 30 seconds, and the amount of air leaked out was taken as the gas leakage.

[0106] Based on the results of the gas leakage, the following evaluation is conducted.

[0107] The high molecular weight electrolyte membrane remained intact, and the gas leakage was less than 100 ml. Poor quality: The polymer electrolyte membrane is ruptured, or although the polymer electrolyte membrane is not ruptured, the gas leakage is more than 100ml.

[0108] The gas leakage of the polymer electrolyte membrane in Example 1, as determined by the above method, was less than 1.0 ml, and the polymer electrolyte membrane did not rupture, thus it was rated as good.

[0109] (Tensile strength) Regarding the tensile strength of the polymer electrolyte membrane, it was determined using a tensile testing machine (Shimadzu Corporation, EZ-TEST EZ–SX 100N) according to JIS K 7161-2. Specifically, the polymer electrolyte membrane was cut into dumbbell shapes (test piece No. 2 as specified in JIS K7161-2) and immersed in ion-exchange water at 25°C for 24 hours. Then, the polymer electrolyte membrane was removed from the ion-exchange water, and the surface water droplets were wiped off, thus obtaining the sample. The sample was placed in the tensile testing machine and measured at a test speed of 50 mm / min.

[0110] The tensile strength obtained is evaluated as follows.

[0111] 4MPa or above; Good, with an pressure of 1 MPa or higher and less than 3 MPa; The difference is less than 1 MPa.

[0112] The tensile strength of the polymer electrolyte membrane of Example 1, as measured by the above method, is below 1.2 MPa, and is rated as good.

[0113] As described above, the polymer electrolyte membrane of Example 1 exhibits a proton conductivity of 7.5 mS / cm, low gas leakage, and a strength exceeding 1 MPa. These results demonstrate that the polymer electrolyte membrane of Example 1 possesses excellent proton conductivity and high strength. The polymer electrolyte membrane of Example 1 is suitable for use as a polymer electrolyte membrane in solid-state polymer fuel cells and solid-state polymer water electrolysis devices.

[0114] Examples 2 to 11 and Comparative Examples 1 to 7 The types and contents of each component contained in the UV-curable resin compositions of each embodiment and each comparative example are shown in Table 1 and Table 2. For the UV-curable resin compositions of Examples 2 to 11 and Comparative Examples 1 to 7, except for changing the types and contents of each component, the UV-curable resin compositions were prepared by the same method as in Example 1 to produce polymer electrolyte membranes.

[0115] [Table 1] [Table 2] In addition, the results of proton conductivity, gas leakage, and tensile strength of the polymer electrolyte membranes of each embodiment and comparative example are shown in Tables 3 and 4. The proton conductivity, gas leakage, and tensile strength of the polymer electrolyte membranes of Examples 2-11 and Comparative Examples 1-7 were determined by the same method as that used to determine the proton conductivity and gas leakage of the polymer electrolyte membrane of Example 1. It should be noted that unless otherwise specified, the units of content in the tables are "parts by weight".

[0116] [Table 3] [Table 4] As shown in Table 3, the polymer electrolyte membranes of Examples 2-11 also exhibit excellent proton conductivity and high strength. Furthermore, the polymer electrolyte membranes of Examples 2-11 are also suitable for use as polymer electrolyte membranes in solid-state polymer fuel cells and solid-state polymer water electrolysis devices.

[0117] The polymer electrolyte membranes of Comparative Examples 1-5 shown in Table 4 were rated as "poor" for at least one of proton conductivity, gas leakage, and tensile strength. The polymer electrolyte membrane of Comparative Example 6 could not be formed. The polymer electrolyte membrane of Comparative Example 7 could be formed. However, because the membrane dissolved upon immersion in ion-exchanged water, its proton conductivity, gas leakage, and tensile strength could not be measured.

[0118] As can be seen from the above results, the polymer electrolyte membrane composed of the UV-curable resin composition of this embodiment has excellent proton conductivity and high strength.

[0119] Furthermore, for the polymeric electrolyte membranes of Examples 1 to 11, chemical resistance, water resistance, initial viscosity, and pot life were evaluated. Hereinafter, the UV-curable resin composition of Example 3 and the polymeric electrolyte membrane derived from the UV-curable resin composition of Example 3 will be used as examples for explanation.

[0120] (Drug resistance) Chemical resistance was evaluated as follows. First, 30% by weight of hydrogen peroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a plastic container, followed by the addition of ferric sulfate heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) until Fe... 2＋The ion concentration was 95 ppm, yielding a solution. 100 ml of this solution was added to another plastic container, and a polymer electrolyte membrane cut into 4 cm squares was immersed in it. The container was then left at room temperature (23℃±5℃) for one week. Afterward, the membrane was removed from the solution, and its condition was visually confirmed.

[0121] Drug resistance was evaluated according to the following criteria.

[0122] The appearance of the high molecular weight electrolyte membrane remained unchanged. A portion of the good polymer electrolyte membrane dissolves but can still be used as a polymer electrolyte membrane for solid polymer fuel cells; The polymer electrolyte membrane completely dissolved.

[0123] Regarding the polymer electrolyte membrane of Example 3, although a portion of the polymer electrolyte membrane dissolved, it can still be used as a polymer electrolyte membrane for solid polymer fuel cells and is rated as "good".

[0124] (Water resistance) After immersing the polymer electrolyte membrane, cut into 4cm squares, in ion-exchange water at 25°C for 24 hours, remove the polymer electrolyte membrane and visually inspect its surface.

[0125] Water resistance is evaluated according to the following criteria.

[0126] No cracks were observed. Cracks were observed.

[0127] The polymer electrolyte membrane in Example 3 had no cracks and was rated as "good".

[0128] (Initial viscosity) The UV-curable resin composition of Example 3 was prepared at 25°C. The viscosity of the freshly prepared UV-curable resin composition was measured using an E-type viscometer (Toki Sangyo Co., Ltd., TV200). The obtained viscosity was evaluated according to the following criteria. This viscosity is referred to as the initial viscosity.

[0129] Good viscosity is below 10 Pa·s; The viscosity difference exceeds 10 Pa·s.

[0130] The UV-curable resin composition of Example 3 had an initial viscosity of less than 10 Pa·s and was rated as "good". This indicates that UV-curable resin compositions with an initial viscosity of less than 10 Pa·s can be coated onto the film surface without uneven application.

[0131] (Applicable period) The pot life test is a test to evaluate the period during which a polymer electrolyte membrane can be made from a UV-curable resin composition. Specifically, the UV-curable resin composition is placed in a sealed container. The sealed container is stored at 25°C in the dark for 3 days. Then, the viscosity of the UV-curable resin composition after storage is measured at 25°C. The obtained viscosity is evaluated according to the following criteria. A Type E viscometer (Toki Sangyo Co., Ltd., TV200) was used.

[0132] Good viscosity is below 10 Pa·s; The viscosity difference exceeds 10 Pa·s.

[0133] The UV-curable resin composition of Example 3 has a viscosity of less than 10 Pa·s and is rated as "good". It can be seen that the UV-curable resin composition with a viscosity of less than 10 Pa·s after the pot life test can be coated onto the film surface without uneven coating.

[0134] (Examples 1 to 11) The results of chemical resistance and water resistance of the polymer electrolyte membranes of each embodiment, the initial viscosity of the UV-curable resin compositions of each embodiment, and the pot life are shown in Table 5.

[0135] [Table 5] As shown in Table 5, the UV-curable resin compositions of Examples 3 to 11, which used adduct-based urethane (meth)acrylates and carbonate-based urethane (meth)acrylates, exhibited good initial viscosity and pot life, and excellent processability as resin compositions for manufacturing polymeric electrolyte membranes. Furthermore, the polymeric electrolyte membranes constructed from such UV-curable resin compositions showed excellent chemical resistance and water resistance. Solid-state polymeric fuel cells and solid-state polymeric water electrolysis devices equipped with such polymeric electrolyte membranes have longer lifespans because they use polymeric electrolyte membranes that are less prone to degradation.

[0136] This invention can be implemented and modified in various ways without departing from the broad spirit and scope of the invention. Furthermore, the above-described embodiments are illustrative of the invention and do not limit its scope. That is, the scope of the invention is defined not by the embodiments, but by the claims. Moreover, various modifications implemented within the scope of the claims and their equivalents are considered to be within the scope of the invention.

[0137] This application is based on Japanese Patent Application No. 2023-214210, filed on December 19, 2023. The description, claims, and drawings of Japanese Patent Application No. 2023-214210 are incorporated herein by reference.

[0138] (Postscript) The various methods disclosed herein are hereby recorded as appendices.

[0139] (Note 1) UV-curable resin composition comprising: Carbamate (meth) acrylates with a weight-average molecular weight of 1,500 to 20,000 and a double bond equivalent of 600 g / mol to 7,500 g / mol; (Meth)acrylate monomers with a molecular weight of 150 to 300; Vinyl monomers with acidic functional groups; and Photopolymerization initiator, The content of the urethane (meth)acrylate is between 20% and 45% by weight relative to the total of 100% by weight of the urethane (meth)acrylate, the (meth)acrylate monomer, and the vinyl monomer. The content of the (meth)acrylate monomer is between 15% by weight and 45% by weight relative to the total of 100% by weight of the urethane (meth)acrylate, the (meth)acrylate monomer, and the vinyl monomer. The content of the vinyl monomer is between 20% and 55% by weight relative to the total of 100% by weight of the urethane (meth)acrylate, the (meth)acrylate monomer, and the vinyl monomer.

[0140] (Note 2) According to the UV-curable resin composition described in Appendix 1, the acidic functional group is composed of at least one selected from the group consisting of carboxyl, phosphonic acid, sulfonic acid and phosphate groups.

[0141] (Note 3) The UV-curable resin composition as described in Appendix 1 or Appendix 2, wherein the number of acidic functional groups in the vinyl monomer is 1 or 2.

[0142] (Note 4) A polymeric electrolyte membrane, which is composed of a UV-curable resin composition as described in any one of Annex 1 to Annex 3 after curing.

[0143] (Note 5) Solid polymer fuel cells have the following characteristics: The polymer electrolyte membrane described in Appendix 4; An anode catalyst layer is formed on one side of the polymer electrolyte membrane; A cathode catalyst layer is formed on the other side of the polymer electrolyte membrane; The first gas diffusion layer is formed on the opposite side of the anode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The second gas diffusion layer is formed on the opposite side of the cathode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The first diaphragm is disposed on the opposite side of the first gas diffusion layer, i.e., the other side, relative to the side where the anode catalyst layer is formed; and The second diaphragm is disposed on the opposite side of the second gas diffusion layer relative to the side on which the cathode catalyst layer is formed, i.e., the other side.

[0144] (Note 6) Solid polymer water electrolysis device, with the following features: The polymer electrolyte membrane described in Appendix 4; An anode catalyst layer is formed on one side of the polymer electrolyte membrane; A cathode catalyst layer is formed on the other side of the polymer electrolyte membrane; The first gas diffusion layer is formed on the opposite side of the anode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The second gas diffusion layer is formed on the opposite side of the cathode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The first diaphragm is disposed on the opposite side of the first gas diffusion layer, i.e., the other side, relative to the side where the anode catalyst layer is formed; and The second diaphragm is disposed on the opposite side of the second gas diffusion layer relative to the side on which the cathode catalyst layer is formed, i.e., the other side.

[0145] (Note 7) Methods for manufacturing polymer electrolyte membranes include: The preparation process involves preparing the ultraviolet-curable resin composition described in any one of Appendix 1 to Appendix 3; The resin layer forming process involves forming a resin layer composed of the UV-curable resin composition on a release film. In the film preparation process, another release film is prepared on the opposite side of the resin layer, i.e., the other side, which is opposite to the side on which the first release film is prepared. In the curing process, the resin layer is irradiated with ultraviolet light through one or more release films to cure the resin layer; and The peeling process involves peeling one release film and the other release film from the cured resin layer.

[0146] Explanation of reference numerals in the attached figures 10 Proton exchange type solid polymer fuel cell; 100 Proton exchange type solid polymer water electrolysis device; 20, 120 Anode electrode; 30, 130 Cathode electrode; 40 Polymer electrolyte membrane; 41, 141 Anode catalyst layer; 42, 142 Cathode catalyst layer; 43, 44, 143, 144 Gas diffusion layer; 51, 52, 151, 152 Separator; 53, 54, 153, 154 Tank; 61, 162 Oxygen; 62, 163 Water; 63, 161 Hydrogen; 65, 67, 165 Supply path; 66, 68, 166, 168 Discharge path; 70 External circuit; 71, 171 Electrons; 72, 172 Protons; 170 Power supply.

Claims

1. A UV-curable resin composition comprising: Carbamate (meth) acrylates with a weight-average molecular weight of 1,500 to 20,000 and a double bond equivalent of 600 g / mol to 7,500 g / mol; (Meth)acrylate monomers with a molecular weight of 150 to 300; Vinyl monomers with acidic functional groups; and Photopolymerization initiator, The content of the urethane (meth)acrylate is between 20% and 45% by weight relative to the total of 100% by weight of the urethane (meth)acrylate, the (meth)acrylate monomer, and the vinyl monomer. The content of the (meth)acrylate monomer is between 15% by weight and 45% by weight relative to the total of 100% by weight of the urethane (meth)acrylate, the (meth)acrylate monomer, and the vinyl monomer. The content of the vinyl monomer is between 20% and 55% by weight relative to the total of 100% by weight of the urethane (meth)acrylate, the (meth)acrylate monomer, and the vinyl monomer.

2. The ultraviolet-curable resin composition according to claim 1, wherein The acidic functional group is composed of at least one selected from the group consisting of carboxyl, phosphonic acid, sulfonic acid and phosphate groups.

3. The ultraviolet-curable resin composition according to claim 1 or 2, wherein The number of acidic functional groups in the vinyl monomer is 1 or 2.

4. A polymeric electrolyte membrane, which is composed of a UV-curable resin composition according to any one of claims 1 to 3 that has been cured.

5. Solid polymer fuel cells, possessing: The polymer electrolyte membrane according to claim 4; An anode catalyst layer is formed on one side of the polymer electrolyte membrane; A cathode catalyst layer is formed on the other side of the polymer electrolyte membrane; The first gas diffusion layer is formed on the opposite side of the anode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The second gas diffusion layer is formed on the opposite side of the cathode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The first diaphragm is disposed on the opposite side of the first gas diffusion layer, i.e., the other side, relative to the side where the anode catalyst layer is formed; and The second diaphragm is disposed on the opposite side of the second gas diffusion layer relative to the side on which the cathode catalyst layer is formed, i.e., the other side.

6. Solid polymer water electrolysis device, equipped with: The polymer electrolyte membrane according to claim 4; An anode catalyst layer is formed on one side of the polymer electrolyte membrane; A cathode catalyst layer is formed on the other side of the polymer electrolyte membrane; The first gas diffusion layer is formed on the opposite side of the anode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The second gas diffusion layer is formed on the opposite side of the cathode catalyst layer relative to the side on which the polymer electrolyte membrane is formed, i.e., the other side. The first diaphragm is disposed on the opposite side of the first gas diffusion layer, i.e., the other side, relative to the side where the anode catalyst layer is formed; and A second separator is arranged on the other side of the second gas diffusion layer opposite to the side on which the cathode catalyst layer is formed.

7. A method for producing a polymer electrolyte membrane, comprising: a preparation step of preparing the ultraviolet-curable resin composition according to any one of claims 1 to 3; a resin layer formation step of forming a resin layer composed of the ultraviolet-curable resin composition on one release film; a film arrangement step of arranging another release film on the other side of the resin layer opposite to the side on which the one release film is arranged; a curing step of irradiating the resin layer with ultraviolet rays through the one release film or the other release film to cure the resin layer; and a peeling step of peeling the one release film and the other release film from the cured resin layer. ​