Photocurable resin composition, method for producing the same, and method for producing a photocured product

Abstract

To provide a photocurable resin composition that can be adequately photocured even when comprising black inorganic particles.SOLUTION: A photocurable resin composition according to an embodiment comprises a matrix resin to be cured by light irradiation, and filling particles that are dispersed in the matrix resin and comprise black inorganic particles. The filling particles 4 each comprise a black inorganic particle 1 and white inorganic materials 3 provided to coat the surface of the black inorganic particle 1.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to a photocurable resin composition, a method for producing the same, and a method for producing a photocured product. [Background technology]

[0002] Stereolithography is a well-known technique for creating three-dimensional objects by irradiating light onto a slurry, which is a mixture of solid powders such as metal particles or ceramic particles and a liquid photocurable resin, to harden the mixture. In one typical configuration of this type of stereolithography, for example, slurry is dispensed from a syringe and deposited, smoothed and leveled with a squeegee, and then light is irradiated onto a predetermined area of ​​the smoothed slurry deposit to form a hardened layer. Further, slurry is supplied onto the hardened layer, smoothed and leveled with a squeegee, and light is irradiated onto a predetermined area of ​​the smoothed slurry deposit to form another hardened layer. By repeating the same process, a three-dimensional additive manufacturing object, which is an assembly of multiple hardened layers, is finally produced.

[0003] For example, in solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells (SOECs), efforts are being made to make them more compact by making electrodes such as the oxygen and hydrogen electrodes porous and integrating them into an electrode-channel structure in which the electrodes also function as gas channels. Lanthanum strontium cobalt iron oxide (LSCF) particles are used as the constituent material for the oxygen electrodes of such SOFCs and SOECs. When fabricating electrodes using LSCF particles using conventional ceramic manufacturing techniques, a layer-by-layer bonding method is used. While this method has the advantages of enabling mass production and firing of an integrated structure, it has been difficult to mold microstructures.

[0004] Furthermore, when applying stereolithography to the manufacture of electrodes using LSCF particles, a mixed slurry of a photocurable resin and LSCF particles is used. The aforementioned steps of discharging and depositing the slurry, smoothing the slurry deposit with a squeegee, and irradiating the slurry deposit with light are repeated multiple times to produce a three-dimensional additive manufacturing object, which is then fired to produce a porous electrode. Stereolithography has the advantage of easily forming microstructures. However, because LSCF particles are black, when they are mixed with a photocurable resin and stereolithography is performed, the light from the light source is absorbed by the black particles, preventing the light from reaching a certain depth. This presents a drawback: the entire object cannot be photocured uniformly. This drawback is not limited to the use of LSCF particles; it also occurs when, for example, conductive particles such as carbon and a photocurable resin are used to manufacture conductive components using stereolithography. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-257323 [Patent Document 2] Japanese Patent Application Publication No. 2019-064861 [Patent Document 3] Japanese Patent Application Publication No. 7-289873 Summary of the Invention [Problem to be solved by the invention]

[0006] The problem to be solved by the present invention is to provide a photocurable resin composition that can be photocured well even when black inorganic particles are blended therein, a method for producing the same, and a method for producing a photocured product. [Means for solving the problem]

[0007] In an embodiment Method for producing photocurable material teeth, The method includes the steps of preparing a slurry of a photocurable resin composition, molding the slurry of the photocurable resin composition, irradiating a desired region of the molded product of the slurry of the photocurable resin composition with light to form a first photocured product of the photocurable resin composition, molding the slurry of the photocurable resin composition on the first photocured product of the photocurable resin composition, and irradiating a desired region of the molded product of the slurry of the photocurable resin composition with light to form a second photocured product on the first photocured product of the photocurable resin composition, wherein the photocurable resin composition isThe composition comprises a matrix resin that is cured by irradiation with light, and filler particles that are dispersed in the matrix resin and contain black inorganic particles, the filler particles comprising the black inorganic particles and a white inorganic substance that is provided so as to cover the surfaces of the black inorganic particles. A laminate of the first photocured product and the second photocured product is obtained. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 2 is a cross-sectional view schematically showing a first example of a filler particle in the photocurable resin composition of the embodiment. [Figure 2] FIG. 3 is a cross-sectional view schematically showing a second example of a filler particle in a photocurable resin composition according to an embodiment. [Figure 3] 1A to 1C are cross-sectional views illustrating a method for producing a photocured product according to an embodiment. [Figure 4] FIG. 1 is a cross-sectional view showing an electrochemical cell produced according to an example. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, photocurable resin compositions according to embodiments, methods for producing the same, and methods for producing photocured products will be described with reference to the drawings. In each embodiment shown below, substantially identical components are designated by the same reference numerals, and some of their descriptions may be omitted. The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each part, etc. may differ from the actual ones. In the following description, the symbol "~" indicates a range between the respective upper and lower limit values. In this case, each range includes the upper and lower limit values.

[0010] (Photocurable resin composition and its manufacturing method) A photocurable resin composition according to an embodiment includes a matrix resin that is cured by irradiation with light and filler particles that are dispersed in the matrix resin and contain black inorganic particles. In the photocurable resin composition according to an embodiment, the filler particles include black inorganic particles and a white inorganic substance that is provided so as to cover the surfaces of the black inorganic particles. The photocurable resin composition according to the embodiment and a method for producing the same are described in detail below.

[0011] A matrix resin that hardens when irradiated with light (photocurable resin) is a resin that hardens (photocures) by increasing the molecular weight through chain polymerization of monomers using light. Photocuring refers to changing from a liquid to a solid through the action of light energy, and organic materials that harden are called photocurable resins. Ultraviolet light is generally and widely used as the light that causes the hardening action. Ultraviolet lasers are useful because they have a high energy density and can be focused to a small spot diameter. On the other hand, resins that harden with visible light are also widely used industrially.

[0012] Liquid photocurable resins cure in roughly the following steps: The photopolymerization initiator absorbs ultraviolet light, and after absorbing the ultraviolet light, the photopolymerization initiator becomes activated. The activated photopolymerization initiator then undergoes decomposition and reacts with resin components such as monomers and oligomers. These reaction products then react with other resin components, and the reaction proceeds in a chain reaction. Then, a three-dimensional crosslinking reaction progresses, increasing the molecular weight and solidifying the resin.

[0013] Photocurable resins are generally composed of monomers, oligomers, photopolymerization initiators, and various additives (stabilizers, fillers, pigments, etc.). Polymerization methods are broadly divided into cationic polymerization and radical polymerization.

[0014] Monomers are molecules with functional groups that become the repeating units of resins that harden when exposed to light. They become polymers when polymerized by light. Examples of monomers that undergo cationic polymerization include vinyl ether monomers. Examples of monomers that undergo radical polymerization include acrylate monomers and phthalate monomers. The names vinyl ether monomer, phthalate monomer, and acrylate monomer are general terms for compounds, and include all those to which various functional groups are attached.

[0015] An oligomer is a compound obtained by reacting several monomers in advance and, like monomers, polymerizes under light to form a polymer. Examples of oligomers that undergo cation polymerization include vinyl ether oligomers, alicyclic photocurable oligomers, and glycidyl ether photocurable oligomers. Examples of oligomers that undergo radical polymerization include urethane acrylate oligomers, polyester acrylate oligomers, photocurable acrylate oligomers, and acrylic acrylate oligomers. The names vinyl ether oligomers, alicyclic photocurable oligomers, glycidyl ether photocurable oligomers, urethane acrylate oligomers, polyester acrylate oligomers, photocurable acrylate oligomers, and acrylic acrylate oligomers are general terms for compounds and include all of these compounds to which various functional groups are attached.

[0016] In the photocurable resin of the embodiment, the resin component as the main component may be only a monomer or only an oligomer, or may be a mixture of both in any ratio.

[0017] Photopolymerization initiators are components that absorb light and become activated (excited), triggering reactions such as cleavage, hydrogen (proton) abstraction, and electron transfer. These reactions generate radical molecules in the case of acrylic photocurable resins, and hydrogen ions in the case of photocurable resins. These radical molecules and hydrogen ions attack monomer molecules and oligomers, causing three-dimensional polymerization and crosslinking reactions, leading to curing. When this reaction results in molecules of a certain size, the irradiated portion changes from a liquid state to a solid state. Photopolymerization initiators used in cationic polymerization include sulfonium and iodonium. Photopolymerization initiators used in radical polymerization include benzophenone, acetophenone, and thioxanthone. The names sulfonium, iodonium, benzophenone, acetophenone, and thioxanthone are generic terms for these compounds and include all of these with various functional groups attached.

[0018] To improve the spreadability (workability) of the photopolymerization initiator during squeegeeing, a diluent solvent for the photocurable resin (matrix resin) may be added to adjust the viscosity. Examples of diluent solvents for photocurable resins include Aronix (a low-viscosity photocurable resin product manufactured by Toagosei Co., Ltd.). Among Aronix products, suitable diluent solvents for photocurable resins include M-101A (phenol EO (ethylene oxide)-modified acrylate), M-117 (nonylphenol EO (ethylene oxide)-modified acrylate), M-220 (polypropylene glycol diacrylate), M-309 (trimethylolpropane acrylate), and M-350 (trimethylolpropane EO (ethylene oxide)-modified acrylate). In order to improve the workability described above, the dilution solvent for the photocurable resin is preferably added in an amount of 50 mass % or less, and more preferably in a range of 5 to 50 mass %, based on the total mass of the photocurable resin excluding the dilution solvent of the embodiment.

[0019] An antifoaming agent may be added to the photocurable resin (matrix resin) to prevent foaming or to eliminate foam that has formed. The antifoaming agent is not particularly limited, but a dimethyl silicone antifoaming agent (e.g., TSA720 (trade name, manufactured by Momentive Performance Materials Japan, LLC)) can be used, but is not limited thereto. Furthermore, the photocurable resin of the embodiment may contain additives other than the above-mentioned antifoaming agent.

[0020] Furthermore, a photopolymerization inhibitor may be blended to improve the storage stability of the photocurable resin. For example, a nitrosamine-based polymerization inhibitor may be used as the photopolymerization inhibitor. Examples of photopolymerization inhibitors that may be used include Q-1300 and Q-1301 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Furthermore, a thermal polymerization initiator may be used to adjust the curing speed of the photocurable resin. Examples of the thermal polymerization initiator that may be used include azo thermal polymerization initiators. Examples of the azo thermal polymerization initiator that may be used include AIBN, V-40, V-59, V-65, V-70, and V-601 (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0021] The filler particles dispersed in the photocurable resin described above comprise black inorganic particles and a white inorganic substance provided so as to cover the surfaces of the black inorganic particles, and are appropriately selected depending on the application of the photocured product (stereolithography product) produced using the photocurable resin composition of the embodiment. For example, when the photocurable resin composition is used as an oxygen electrode material for an electrochemical cell such as an SOFC or an SOEC, the black inorganic particles include LSCF particles. The LSCF particles are, for example, (La 1-x Sr x )(Co 1-y Fe y )O 3-δIt has a composition of (0 < x < 1, 0 < y < 1, 0 < δ < 1). When using the photocured product of the photocurable resin composition as a conductive member, examples of the black inorganic particles include carbon particles such as carbon, graphene, carbon nanotubes, fullerenes, ketjen black, and metal particles such as iron particles. In addition to these, various black inorganic particles can be used according to the intended use, and examples include manganese particles, boron carbide particles, and the like. The black inorganic particles may be one type of particle or a mixture of two or more types of particles.

[0022] Furthermore, the white inorganic substance coated on the surface of the black inorganic particles may be a film-like substance or a particulate substance applicable to coating, and can be appropriately selected according to the coating method to be applied. For example, when applying coating with an adhesive or powder plating as the coating method of the white inorganic substance, white inorganic particles are used. Examples of the white inorganic particles include ceria particles, gadolinium-doped ceria particles, aluminum oxide particles, zirconium oxide particles, aluminum nitride particles, barium titanate particles, and the like. These are appropriately selected according to the intended use of the photocured product (3D printed object) manufactured using the photocurable resin composition of the embodiment. For example, when using the photocurable resin composition as an oxygen electrode material of an electrochemical cell such as SOFC or SOEC, gadolinium-doped ceria particles used as part of the constituent material of the oxygen electrode are preferable as the white inorganic particles. Other white inorganic particles than gadolinium-doped ceria particles can also be appropriately used according to the intended use.

[0023] The white inorganic materials, such as black inorganic particles and white inorganic particles, used in the embodiments may be any materials that have relatively different light absorption characteristics. The white inorganic particles may be any materials that absorb less light than the black inorganic particles and are more likely to reflect light. The black inorganic particles are, for example, particles with a color tone ranging from black to dark gray, which are more likely to absorb light, and have an average light reflectance (reflectance when irradiated with light having a wavelength of 350 to 750 nm) of 10% or less. The white inorganic particles are, for example, particles with a color tone ranging from white to light gray, which are more likely to reflect light, and have an average light reflectance (reflectance when irradiated with light having a wavelength of 350 to 750 nm) of 40% or more. The reflectance can be measured using a colorimeter (Konica Minolta, CM-5) or the like.

[0024] The black inorganic particles preferably have an average particle size of, for example, about 0.8 to 10 μm. The average particle size of the black inorganic particles may be the primary particle size or the secondary particle size of aggregates or granules. If the average particle size of the black inorganic particles is less than 0.8 μm, it is difficult to cover the surface of the black inorganic particles with white inorganic particles. If the average particle size of the black inorganic particles exceeds 10 μm, their function as a filler dispersed in the photocurable resin is likely to be reduced. The white inorganic particles preferably have an average particle size of, for example, about 0.1 to 0.5 μm. If the average particle size of the white inorganic particles is less than 0.1 μm or exceeds 0.5 μm, the uniform adhesion of the black inorganic particles to the surface is likely to be reduced. The particle size distribution of the inorganic particles is not particularly limited. Here, the average particle size is defined by the median diameter (D50), and the particle size distribution is defined by the volume distribution and number distribution. The average particle size can be measured using a laser diffraction / scattering particle size distribution analyzer (HORIBA, LA-960V2) etc. In addition, even when white particles are attached so as to cover the aggregates of black particles, the above-mentioned effects can be similarly exhibited.

[0025] The surfaces of the black inorganic particles and the white inorganic particles may be subjected to a surface treatment such as a silane coupling treatment to enhance dispersibility. The silane coupling treatment can improve wettability with the photocurable resin. Examples of silane coupling agents used in the silane coupling treatment include epoxysilane, aminosilane, vinylsilane, methacrylsilane, mercaptosilane, methoxysilane, and ethoxysilane. The surface modification treatment using these silane coupling agents can also achieve the same effect even if they are added later.

[0026] In addition, the surfaces of black inorganic particles and white inorganic particles can be titanate-coupling-treated to improve wettability with photocurable resins. Examples of titanate coupling agents used in titanate-coupling treatment include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl-tris(dioctylpyrophosphate) titanate, tetraisopropyl-bis(dioctylphosphite) titanate, tetraoctyl-bis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)-bis(ditridecyl)phosphite titanate, and bis(dioctylpyrophosphate)oxyacetate titanate. Surface modification treatments using these titanate coupling agents can also achieve similar effects when added later.

[0027] Methods for coating the surfaces of black inorganic particles with white inorganic particles include coating with an adhesive or powder plating. When coating with an adhesive, examples of suitable adhesives include thermoplastic resins such as sodium silicate, vinyl acetate resin, polyvinyl resin, ethylene vinyl acetate resin, vinyl chloride resin, acrylic resin, polyamide resin, cellulose, polyvinylpyrrolidone, polystyrene resin, cyanoacrylate, and polyvinyl acetal, as well as thermosetting resins such as epoxy resin, urethane resin, polyaromatic resin, structural acrylic resin, urea resin, melamine resin, phenolic resin, and resorcinol resin. For example, as shown in Figure 1, adhesive 2 is applied to the surface of black inorganic particles or aggregated particles 1 formed by aggregating black inorganic particles to a certain size using a spray or other method. Before adhesive 2 hardens, white inorganic particles 3 are attached, and then adhesive 2 is fully hardened. In this manner, filled particles 4 are obtained, in which the surfaces of black inorganic particles 1 are coated with white inorganic particles 3.

[0028] Next, we will describe a method of using powder plating to coat the surface of black inorganic particles with white inorganic particles. Powder plating is a technique for plating a powder (here, white inorganic particles) onto the surface of a base material (here, black inorganic particles), or a technique for plating a material (here, white inorganic particles) onto the surface of a powder (here, black inorganic particles). First, we will describe a case where black inorganic particles are used as the substrate and Ag plating is used as the metal plating material. There are no particular limitations on the plating method, and electroplating, electroless plating, or displacement plating can be used.

[0029] Electroplating requires an electroplating bath. Electroplating bath components include metal salts, conductivity salts, anode dissolution accelerators, complexing agents, and additives to adjust the appearance and physical properties of the film. Electroless plating bath components include metal salts, as well as reducing agents, complexing agents, pH buffers, and stabilizers. Substitution plating uses a plating bath in which complexing agents and additives are added to metal salts.

[0030] For example, although most silver plating baths are alkaline silver cyanide plating baths, non-cyanide baths can also be used. A typical metal salt is one whose main ingredient is potassium silver cyanide. This is a complex salt of silver ions. It forms colorless, transparent crystals that dissolve well in water. In addition to this compound, a silver cyanide plating bath also contains free potassium cyanide or sodium cyanide, potassium carbonate, potassium hydroxide, brighteners, hardeners, etc. Black and white inorganic particles are dispersed in a plating bath composed of silver ions, and the surfaces of the black inorganic particles 1 are coated with white inorganic particles 3 via a plating film 5, as shown in Figure 2. In this way, filled particles 4 are obtained, in which the surfaces of the black inorganic particles 1 are coated with white inorganic particles 3.

[0031] Furthermore, when cobalt plating is applied to metal plating, most cobalt plating baths are composed of sulfur compounds such as potassium thiocyanate and sodium thiosulfate, and metallic cobalt compounds. Black inorganic particles and white inorganic particles are dispersed in a plating bath composed of cobalt metal ions, and the surfaces of the black inorganic particles 1 are coated with white inorganic particles 3 via a plating film 5, as shown in Figure 2. In this way, filled particles 4 are obtained in which the surfaces of the black inorganic particles 1 are coated with the white inorganic particles 3.

[0032] Metal plating can also be performed with manganese (Mn), iron (Fe), and nickel (Ni). For example, manganese phosphate can be used for manganese (Mn), iron chloride can be used for iron (Fe), and nickel sulfamate can be used for nickel (Ni). This results in filled particles 4 in which the surfaces of black inorganic particles 1 are coated with white inorganic particles 3 via a plating film 5.

[0033] The photocurable resin composition of the embodiment can be obtained by dispersing filler particles, which are black inorganic particles coated with white inorganic particles, into the photocurable resin described above. Various mixers can be used to disperse the filler particles into the photocurable resin. For example, a slurry of the photocurable resin composition can be prepared by stirring the photocurable resin and filler particles to be mixed using a planetary mixer or the like.

[0034] (Method of producing photocured product) The photocurable resin composition prepared as described above can be laminated by, for example, stereolithography to produce a laminated structure. Depending on the thickness of the photocured product (stereolithography), the desired photocured product may be obtained by a single stereolithography product without laminating the photocured products. The manufacturing process of the photocured product will be described with reference to FIG. 3.

[0035] First, as shown in FIG. 3(a), a photocurable resin composition slurry 12A is applied to a substrate 11. The photocurable resin composition slurry 12A is deposited on the substrate 11, for example, by ejecting it from a syringe. The substrate 11 may be a structural member that serves as the base for the photocured product, or it may simply be a material on which the slurry is applied. Next, the photocurable resin composition slurry 12 deposited on the substrate 11 is smoothed by using a squeegee 13. From the viewpoint of light penetration depth, the thickness of the deposited layer 12B of the smoothed slurry 12A is preferably set so that the cured thickness per layer is approximately 10 to 50 μm. The light penetration depth is an index indicating the thickness to which a photocurable resin will cure when filler particles, in which the surfaces of black inorganic particles are coated with white inorganic particles, are blended with the resin, and is preferably 10 μm or greater.

[0036] Next, as shown in FIG. 3(b), a curing light L such as ultraviolet light is irradiated onto a required region of the smoothed deposition layer 12B, photocuring the required region of the deposition layer 12B to form a first cured layer 14A. Subsequently, a photocurable resin composition slurry 12A is again deposited on the deposition layer 12B having the first cured layer 14A (FIG. 3(c)), and the slurry 12A is smoothed with a squeegee 13 to form a deposition layer 12C (FIG. 3(d)). Next, as shown in FIG. 3(e), a curing light is irradiated onto a required region of the deposition layer 12C, photocuring the required region of the deposition layer 12C to form a second cured layer 14B on the first cured layer 14A.

[0037] The steps of depositing the photocurable resin composition slurry 12A, smoothing the photocurable resin composition slurry 12A, and curing by irradiation with curing light L are repeated depending on the thickness of the photocured product to produce a photocured product 15 having a laminate of a first cured layer 14A, a second cured layer 14B, and optionally a third or more cured layers. In the photocured product production process of the embodiment, the surfaces of the black inorganic particles are coated with white inorganic particles, thereby suppressing absorption of the curing light L by the black inorganic particles. This allows the curing light L to reach the required depth of the deposited layers 12B and 12C of the photocurable resin composition slurry 12A, enabling successful photocuring of the deposited layers 12B and 12C. [Example]

[0038] Next, specific examples of the photocurable resin composition of the embodiment, a method for producing the same, and a method for producing a photocured product, and the evaluation results thereof will be described.

[0039] (Examples 1 to 5, Reference Example 1, Comparative Examples 1 and 2) First, LSCF particles coated with gadolinium-doped ceria (GDC) particles were prepared as filler particles. In Example 1, an adhesive was used to coat the GDC particles. In Example 2, Ag plating was used, in Example 3, Co plating was used, in Example 4, Mn plating was used, in Example 5, Fe plating was used, and in Reference Example 1, Ni plating was used. In Comparative Example 1, LSCF particles not coated with GDC particles were used.

[0040] The above-described filler particles were blended into a photocurable resin at a ratio of 50 to 70% by volume. A low-viscosity photocurable resin, TB1771E (product name, manufactured by ThreeBond Co., Ltd.), was used, and 10 to 50% by mass of M-350 (product name, manufactured by Toagosei Co., Ltd.) as a dilution solvent for the photocurable resin and 0.1 to 5% by mass of V-65 (product name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an azo thermal polymerization initiator were blended into the photocurable resin to prepare photocurable resin composition slurries for Examples 1 to 5 and Reference Example 1.

[0041] The photocuring depth of the above-described photocurable resin composition slurries was measured. Here, as a simple property evaluation, a shim ring (for example, 10 μm thick) was used as a spacer for film thickness control to squeeze the slurry, and then laser light (wavelength: 365 nm) was irradiated from above to cure the slurry, thereby measuring the photocuring depth. The results are shown in Table 1. As shown in Table 1, the photocuring depth of the photocurable resin composition slurries of Examples 1 to 5 and Reference Example 1 all achieved a photocuring depth of 10 μm or more, whereas the photocuring depth of the slurry of Comparative Example 1 was 1.0 μm or less. Therefore, it can be seen that by coating the surfaces of black inorganic particles with white inorganic particles, the photocuring properties of the photocurable resin composition slurries containing them can be improved.

[0042] Next, electrochemical cells were fabricated using oxygen electrodes fabricated using the photocurable resin composition slurries of Examples 1 to 5, Reference Example 1, and Comparative Example 1. As shown in FIG. 4, the electrochemical cell 21 includes a support layer 22, a hydrogen electrode 33, a solid oxide electrolyte layer 24, an intermediate layer 25, and an oxygen electrode 26. The oxygen electrode 26 of the electrochemical cell 21 was fabricated using the photocurable resin composition slurries of Examples 1 to 5, Reference Example 1, and Comparative Example 1. The oxygen electrode 26 was fabricated by baking a photocured product of the slurry. In the electrochemical cell of Comparative Example 2, the oxygen electrode was formed by screen-printing LSCF and then baking it.

[0043] The cell performance of the electrochemical cells of Examples 1 to 5, Reference Example 1, and Comparative Examples 1 and 2 was measured. The cell performance is shown as a relative value, with the output of an electrochemical cell in which an oxygen electrode was formed by a conventional method being set to 1.0. The electrochemical cell characteristics were comprehensively evaluated based on the photocuring depth and cell performance. For cases in which the photocuring depth was 10.0 μm or more and the cell characteristics exceeded 1.0, the overall evaluation was given as "Good." For cases in which only one of the above characteristics was satisfied, the evaluation was given as "Good." For cases in which none of the above characteristics were satisfied, the evaluation was given as "Poor." As shown in Table 1, all of Examples 1 to 5 exhibited favorable results. Although Reference Example 1 had inferior cell characteristics due to the use of Ni plating, the photocuring depth was good, and favorable characteristics were obtained in terms of the production of photocured products.

[0044] [Table 1]

[0045] The configurations of the above-described embodiments can be applied in combination with each other, and some of them can be replaced with other configurations. Although several embodiments of the present invention have been described herein, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, substitutions, modifications, etc. can be made without departing from the spirit of the invention. These embodiments and their modifications are intended to be included within the scope and spirit of the invention, as well as within the scope of the invention and its equivalents as set forth in the claims. [Explanation of symbols]

[0046] 1...black inorganic particles, 2...adhesive, 3...white inorganic particles, 4...filler particles, 5...plating film.

Claims

1. A method for producing a photocurable resin composition slurry, molding a slurry of the photocurable resin composition; irradiating a desired region of the molded product of the slurry of the photocurable resin composition with light to form a first photocured product of the photocurable resin composition; molding a slurry of the photocurable resin composition onto a first photocured product of the photocurable resin composition; and irradiating a desired region of the molded product of the slurry of the photocurable resin composition with light to form a second photocured product on the first photocured product of the photocurable resin composition, the photocurable resin composition comprises a matrix resin that is cured by light irradiation, and filler particles that are dispersed in the matrix resin and contain black inorganic particles, the filler particles comprising the black inorganic particles and a white inorganic substance that is provided so as to cover surfaces of the black inorganic particles; A method for producing a photocurable product, comprising obtaining a laminate of the first photocurable product and the second photocurable product.

2. 2. The method for producing a photocurable material according to claim 1, wherein the black inorganic particles contain at least one selected from the group consisting of lanthanum strontium cobalt iron oxide, iron, manganese, carbon, and boron carbide.

3. 3. The method for producing a photocurable material according to claim 1, wherein the white inorganic substance comprises at least one selected from the group consisting of ceria, gadolinium-doped ceria, aluminum oxide, zirconium oxide, aluminum nitride, and barium titanate.

4. 4. The method for producing a photocurable material according to claim 1, wherein the surfaces of the black inorganic particles are covered with white inorganic particles made of the white inorganic substance.

5. The method for producing a photocurable material according to claim 4 , wherein the surfaces of the black inorganic particles are covered with the white inorganic particles via an adhesive.

6. The method for producing a photocurable material according to claim 4 , wherein the surfaces of the black inorganic particles are coated with the white inorganic particles by powder plating.

7. The method for producing a photocurable material according to claim 4 , wherein the surfaces of the black inorganic particles are covered with the white inorganic particles via a metal plating film.

8. The method for producing a photocurable material according to claim 1 , wherein the first photocurable material or the laminate is an electrode material for an electrochemical cell.

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