JP6975963B2 - Molded product manufacturing method and molded product - Google Patents

Description

The present invention relates to a method for producing a molded product and a molded product.

In recent years, with the development of inorganic materials such as ceramics, metals, and metal oxide materials and the progress of microfabrication technology thereof, the functions of the inorganic materials have been further evaluated, and their application to various products is progressing.

Applications of the inorganic material include, for example, a solid electrolyte material and an electrode of a solid oxide fuel cell (SOFC). Fuel cells operate at very high temperatures, but SOFCs use oxides such as ceramics, so they have excellent durability. In SOFC, cathode and anode electrodes are formed on both sides of a solid electrolyte composed of an inorganic material, respectively. It has been proposed to increase the surface area of the electrodes in order to improve the power generation efficiency of SOFCs.

Further, there is a technique of forming fine irregularities on the surface of an inorganic material to impart water repellency or hydrophilicity to the surface. Further, an inorganic material having fine irregularities on the surface is also useful as a catalyst or a capacitor.

As described above, since various functions are imparted by forming fine irregularities on the surface of the inorganic material, a processing technique capable of forming finer irregularities on the surface of the inorganic material is desired. .. In particular, a technique capable of forming a nano-sized microstructure at low cost and in a large area is desired.

As one of such microfabrication methods for inorganic materials, there is a MIM (Metal Injection Molding) method in which a metal powder is used as a raw material for injection molding (see, for example, Non-Patent Documents 1 and 2). In the MIM method, a metal molded product having a three-dimensional structure is obtained through a steps of mixing components such as metal powder, thermoplastic resin, and wax, an injection molding step, a step of degreasing the thermoplastic resin, and a step of sintering. .. The MIM method can produce a product having a complicated shape as compared with the press sintering method.

Further, as another example of the microfabrication method for an inorganic material, a method for applying the nanoimprint technology applied to an organic material to the microfabrication of ceramics has been proposed (see, for example, Patent Document 1). In the method described in Patent Document 1, a slurry-like composite in which ceramic powder and an organic material are mixed is applied to a pattern transfer mold having nano-sized irregularities on the surface, and the ceramic substrate is pressed (nanoimprint). After drying in this state, the mold is peeled off from the ceramic substrate and sintered.

Japanese Unexamined Patent Publication No. 2010-522808

http://www.ady-jp.jp/category/1213988.html http://www.castem.co.jp/mim/tech.html

By the manufacturing methods of Non-Patent Documents 1 and 2 and Patent Document 1, an inorganic molded product having a finer surface shape than before can be obtained, but a method capable of forming finer irregularities on the surface is desired. ..

Therefore, an object of the present invention is to provide a method for producing a molded product and a molded product capable of forming fine irregularities on the surface of the molded product with ceramics, metal, or a metal oxide.

〔式（１）中、Ｒは、水素原子又はメチル基を表し、Ｘは２価の炭化水素基、又は（ポリ）アルキレンオキシ基を含む２価の基を表す。〕
＜１０＞ 前記一般式（１）において、Ｘが２価の直鎖状炭化水素基、又は（ポリ）アルキレンオキシ基を含む２価の基である化合物を含む、＜９＞に記載の成形物の製造方法。
＜１１＞ 前記光硬化性樹脂は、モノマー、オリゴマー、又はモノマーとオリゴマーの両方からなる重合性化合物を含む、＜１＞〜＜１０＞のいずれか１項に記載の成形物の製造方法。
＜１２＞ 前記光硬化性樹脂の粘度が、１．５ｍＰａ・ｓ〜１００ｍＰａ・ｓである、＜１＞〜＜１１＞のいずれか１項に記載の成形物の製造方法。
＜１３＞ 前記モールドの前記凹部又は前記凸部の直径が、５０μｍ以下である、＜１＞〜＜１２＞のいずれか１項に記載の成形物の製造方法。
＜１４＞ 前記モールドの前記凹部又は前記凸部の直径に対する深さ又は高さの比（アスペクト比）が、２以上である、＜１＞〜＜１３＞のいずれか１項に記載の成形物の製造方法。
＜１５＞ 前記モールドは、マスターモールドから複写したレプリカモールドである、＜１＞〜＜１４＞のいずれか１項に記載の成形物の製造方法。
＜１６＞ 前記対象物品が、燃料電池の電極若しくは電解質、キャパシタの誘電体若しくは電極、超電導磁石、超電導電極、摩擦摺動面、工具、アクチュエータ、センサ、又は触媒である、＜１＞〜＜１５＞のいずれか１項に記載の成形物の製造方法。
＜１７＞ 前記組成物とは、成分が異なる組成物をさらに用いる、＜１＞〜＜１６＞のいずれか１項に記載の成形物の製造方法。
＜１８＞ 前記組成物と前記成分が異なる組成物とは、セラミックス、金属及び金属化合物からなる群より選択される少なくとも１種の粒子の種類が異なる、＜１７＞に記載の成形物の製造方法。
＜１９＞ 前記光硬化する工程で得られた第一の硬化物の上、及び前記第一の硬化物が形成された領域とは別の領域の少なくとも一方に、前記成分が異なる組成物を付与し、光硬化して第二の硬化物を得た後、
前記第一の硬化物と前記第二の硬化物とを一括して焼結する、＜１７＞又は＜１８＞に記載の成形物の製造方法。
＜２０＞ 表面の少なくとも一部に、セラミックス、金属及び金属化合物からなる群より選択される少なくとも１種で構成される凹部及び凸部の少なくとも一方を有し、前記凹部又は凸部の直径に対する深さ又は高さの比（アスペクト比）が、２以上である成形物。 The present invention includes the following forms.
<1> A method for producing a molded product having at least one of a concave portion and a convex portion composed of at least one selected from the group consisting of ceramics, metals and metal compounds on at least a part of the surface of the target article.
A composition containing a photocurable resin and at least one particle selected from the group consisting of ceramics, metals and metal compounds is placed on the target article or a mold having at least one of a concave portion and a convex portion on the surface thereof. The process of giving and
A step of pressing the target article and the mold through the composition, and
The step of photo-curing the pressed composition and
The step of sintering the photo-cured composition and
A method for manufacturing a molded product.
<2> The particles include gadrinium-doped ceria (GDC), ceria, samarium-doped ceria (SDC), yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), zirconia, lanthanum strontium cobalt ferrite (LSCF), and lantern. Strontium Strontium Cobaltite (LSC), Samarium Strontium Cobaltite (SSC), Lantern Strontium Manganite (LSM), Lantern Strontium Cobalt Manganite (LSCM), Manganese Cobalt Spinel Oxide (MCO), Lantern Strontium Chromite (LSCr), Gallium Nitride The method for producing a molded product according to <1>, which comprises at least one selected from the group consisting of silicon carbide, tungsten carbide, alumina, titania, and lanthangarate (LaGaO _3).
<3> The method for producing a molded product according to <1> or <2>, wherein the composition further contains a photopolymerization initiator.
<4> The molded product according to <3>, wherein the photopolymerization initiator is selected so that the absorption wavelength of the photopolymerization initiator does not overlap with the absorption wavelength of the particles contained in the composition. Production method.
<5> The photopolymerization initiator is at least one of a radical polymerization initiator composed of a carbon atom, an oxygen atom and a hydrogen atom, and a radical polymerization initiator composed of a carbon atom, a nitrogen atom, an oxygen atom and a hydrogen atom. The method for producing a molded product according to <3> or <4>.
<6> The radical polymerization initiator is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl. ] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2- Methyl-Propane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1 -On, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, phenylglycoxyacid methyl ester, acetophenone, p-anisyl, benzyl, The method for producing a molded product according to <5>, which comprises at least one selected from the group consisting of benzoin and benzophenone.
<7> The photocurable resin is at least one of a photocurable resin composed of a carbon atom, an oxygen atom and a hydrogen atom, and a photocurable resin composed of a carbon atom, a nitrogen atom, an oxygen atom and a hydrogen atom. The method for producing a molded product according to any one of <1> to <6>.
<8> The method for producing a molded product according to any one of <1> to <7>, wherein the photocurable resin contains at least one of a (meth) acrylic resin and an epoxy resin.
<9> The method for producing a molded product according to any one of <1> to <8>, wherein the photocurable resin contains a compound represented by the following general formula (1).

[In the formula (1), R represents a hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group or a divalent group containing a (poly) alkyleneoxy group. ]
<10> The molded product according to <9>, wherein X contains a compound which is a divalent linear hydrocarbon group containing a divalent linear hydrocarbon group or a (poly) alkyleneoxy group in the general formula (1). Manufacturing method.
<11> The method for producing a molded product according to any one of <1> to <10>, wherein the photocurable resin contains a monomer, an oligomer, or a polymerizable compound composed of both a monomer and an oligomer.
<12> The method for producing a molded product according to any one of <1> to <11>, wherein the photocurable resin has a viscosity of 1.5 mPa · s to 100 mPa · s.
<13> The method for producing a molded product according to any one of <1> to <12>, wherein the diameter of the concave portion or the convex portion of the mold is 50 μm or less.
<14> The molded product according to any one of <1> to <13>, wherein the ratio (aspect ratio) of the depth or height to the diameter of the concave portion or the convex portion of the mold is 2 or more. Manufacturing method.
<15> The method for manufacturing a molded product according to any one of <1> to <14>, wherein the mold is a replica mold copied from a master mold.
<16> The target article is an electrode or electrolyte of a fuel cell, a dielectric or electrode of a capacitor, a superconducting magnet, a superconducting electrode, a friction sliding surface, a tool, an actuator, a sensor, or a catalyst, <1> to <15. > The method for producing a molded product according to any one of the above items.
<17> The method for producing a molded product according to any one of <1> to <16>, wherein a composition having a different component from the composition is further used.
<18> The method for producing a molded product according to <17>, wherein the composition and the composition having different components differ in the type of at least one kind of particles selected from the group consisting of ceramics, metals and metal compounds. ..
<19> A composition having different components is imparted onto at least one of the first cured product obtained in the photocuring step and a region different from the region where the first cured product is formed. After photo-curing to obtain a second cured product,
The method for producing a molded product according to <17> or <18>, wherein the first cured product and the second cured product are sintered together.
<20> At least a part of the surface has at least one of a concave portion and a convex portion composed of at least one selected from the group consisting of ceramics, a metal and a metal compound, and the depth with respect to the diameter of the concave portion or the convex portion. A molded product having a height ratio (aspect ratio) of 2 or more.

According to the present invention, it is possible to provide a method for producing a molded product and a molded product capable of forming fine irregularities on the surface of the molded product with ceramics, metal, or a metal oxide.

It is a schematic sectional drawing which shows an example of the manufacturing method of the molded article of this invention. It is a graph which shows an example of the relationship between the absorption spectrum of a polymerization initiator, the absorption spectrum of a particle, and the wavelength of irradiation light used for curing. In Example 1, it is a plane SEM image of a cured product in which an uneven shape pattern is formed only by a resin component. FIG. 3 is an enlarged planar SEM image of FIG. It is a photograph which shows the result of having confirmed the curability of a composition. It is a plane SEM image of the calcined product obtained in Example 1. FIG. 6 is an enlarged planar SEM image of FIG. 6 is a graph showing the results of measuring the cross-sectional shape of the calcined product obtained in Example 1 with a laser microscope. It is a plane optical microscope image of the replica mold produced in Example 2. (A) is a perspective photograph showing the appearance of the calcined product of Example 2 in which a pattern having an uneven shape is formed on a curved surface, and (B) is a planar optical microscope image of the pattern in (A). It is a plane optical microscope image of the calcined product obtained in Example 2. It is a graph which shows the temperature profile of the sintering process in Example 3. FIG. It is an appearance photograph of the sintered body obtained in Example 3. 8 is an enlarged planar laser microscope image of the sintered product obtained in Example 3. It is a graph which shows the result of having measured the cross-sectional shape of the sintered compact obtained in Example 3 with a laser microscope. FIG. 14 is an enlarged planar SEM image of FIG. (A) is a plane SEM image obtained by enlarging FIG. 16, and (B) is a plane SEM image obtained by further magnifying (A). FIG. 17 (B) is an enlarged planar SEM image. 6 is a planar laser microscope image of the sintered product obtained in Example 4. It is a graph which shows the result of having measured the cross-sectional shape of the sintered compact obtained in Example 4 with a laser microscope. 6 is a planar SEM image of the sintered product obtained in Example 4. (A) is a plane SEM image obtained by enlarging FIG. 21, and (B) is a plane SEM image obtained by further magnifying (A). (A) is a perspective SEM image of FIG. 21, and (B) is a perspective SEM image obtained by further magnifying (A). It is a perspective SEM image which further enlarged FIG. 23 (B). It is a plane optical microscope image when a part of the cured product obtained in Example 5 was removed and each layer was exposed. 6 is a cross-sectional optical microscope image of a sample obtained by peeling a YSZ plate from the cured product obtained in Example 5. It is a figure explaining the observation direction of FIGS. 25 and 26. 6 is a cross-sectional optical microscope image of the calcined product obtained in Example 5.

Hereinafter, an example of the embodiment of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
In the present specification, the numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.
The same reference numerals are used for the same or corresponding members in each figure.

<Manufacturing method of molded product>
FIG. 1 shows an example of the method for producing a molded product of the present invention, but the method for producing a molded product of the present invention is not limited thereto. Further, the shape, size, etc. of the members in the drawing are not limited to this.

The method for producing a molded product 100 is a molded product having at least one of a concave portion and a convex portion composed of at least one selected from the group consisting of ceramics, a metal and a metal compound on at least a part of the surface of the target article 10. The composition 20 which is a manufacturing method of 100 and contains a photocurable resin and at least one particle selected from the group consisting of ceramics, metals and metal compounds is applied to the target article 10 or the concave portion and the convex portion. A step of applying to a mold 30 having at least one on the surface (hereinafter, also referred to as “applying step”; FIG. 1 (A)) and a step of pressing the target article 10 and the mold 30 via the composition 20 (hereinafter, referred to as “applying step”). Also referred to as a “pressing step” (FIG. 1 (B)), a step of photocuring the pressed composition 20 (hereinafter, also referred to as a “photocuring step”; FIG. 1 (C)), and a photocured composition. It has a step of sintering 20 (cured product 22) (hereinafter, also referred to as a “stituting step”; FIG. 1 (E)). The present invention may further have other steps.

In the method for producing the molded product 100, the composition 20 containing a photocurable resin together with at least one of ceramic particles, metal particles, and metal compound particles is used. By using a photocurable resin, even if the mold 30 is removed from the cured product 22 after the photocuring step (FIG. 1 (C)) (FIG. 1 (D), it is cured with the mold 30 removed). Even if the object 22 is sintered (FIG. 1 (E)), the uneven shape is maintained.

Thermoplastic resin is a material that generally has a large Young's modulus value and is not easily deformed. Therefore, as in Non-Patent Document 1 and Patent Documents 1 and 2, a thermoplastic resin has been used as a resin in the past. With these methods, it is possible to form uneven shapes on the order of 100 μm.

However, when a thermoplastic resin is used as the resin, it cannot withstand the heat generated during the temperature rise of sintering, and the shape is sagging during the temperature rise. Therefore, the uneven shape transferred to the composition 20 is maintained. Hateful. Therefore, it was found that the method using a thermoplastic resin cannot transfer accurately if the uneven shape becomes finer.

On the other hand, since the photocurable resin has a higher decomposition temperature than the thermoplastic resin, it functions as a binder up to a high temperature. As a result, when a photocurable resin is used, it is possible to realize a fine uneven shape that cannot be obtained when a thermoplastic resin is used. Further, in the case of a thermoplastic resin that sags due to heating, the shape of the target article 10 is basically limited to a flat plate shape, whereas if a curable resin is used, the target article 10 having various shapes has irregularities. The shape can be formed.

Further, the concave portions and the convex portions made of the cured product of the photocurable resin are stronger than the concave portions and the convex portions made of the composition 20 containing the thermoplastic resin. Therefore, it is possible to store or transport the cured product over a long distance in the state of the cured product after the photo-curing step. That is, after performing the photo-curing step (FIG. 1 (C)), the sintering step (FIG. 1 (E)) may be performed again after a while. Therefore, since a plurality of cured products can be produced and then sintered at once, the throughput can be increased and the manufacturing cost can be reduced.

When a thermoplastic resin is used, a medium such as water or alcohol is used, so that foaming is likely to occur due to vacuum defoaming, so a defoaming agent may be required. Further, since the medium is volatilized by vacuum defoaming for a long time, it is desirable to add a defoaming agent in order to shorten the vacuum defoaming time.
On the other hand, in the case of a photocurable resin, the composition 20 can be prepared with a low molecular weight compound such as a monomer or an oligomer as the photocurable resin, so that a mixture can be obtained without using a medium. Therefore, when a photocurable resin is used and no medium is used, it is not necessary to use a defoaming agent because foaming due to the medium does not occur. Further, since the photocurable resin after curing has a large molecular weight, it is difficult to volatilize by vacuum defoaming, and vacuum defoaming can be performed for a long time. This makes it possible to reduce defects derived from air bubbles in the molded product which is a product.

Further, when a thermoplastic resin is used, a drying step is required before the sintering step because a medium is used, but when a photocurable resin is used and a medium is not used, a drying step is not required. Become.

The method using a photocurable resin can shorten the production time as compared with the method using a curable resin that cures after an appropriate time as in Patent Document 1. In addition, variation between lots can be suppressed. Further, unevenness in the cured state in one molded product can be suppressed, and a finer uneven shape can be formed.

Further, in the curable resin described in Patent Document 1 having a long curing time, a dispersant is required so that the components are stably dispersed in the state of the composition. Even in the case of a thermoplastic resin, since it exists in the state of the composition until sintering, it is expected that the time in the state of the composition will be long, and a dispersant is required.
On the other hand, in the case of a photocurable resin, it is cured before sintering and the curing time is short, so that the time in the state of the composition is short and it is not necessary to use a dispersant.

In the method of forming the uneven shape by the mold, the uneven portion can be formed only integrally with the main body portion. On the other hand, in the method of the present invention, the uneven shape can be imparted to the target article 10 by retrofitting. Therefore, it is possible to impart a fine uneven shape to the surface of various target articles 10.
Hereinafter, the manufacturing method of the molded product will be described for each process.

(Granting process)
In the applying step, a composition 20 containing a photocurable resin and at least one particle selected from the group consisting of ceramics, metals and metal compounds is prepared.

The photocurable resin is not particularly limited, and for example, at least one of a photocurable resin composed of a carbon atom, an oxygen atom and a hydrogen atom, and a photocurable resin composed of a carbon atom, a nitrogen atom, an oxygen atom and a hydrogen atom. Can be mentioned.

Specific examples of the photocurable resin include (meth) acrylic resin and epoxy resin. Examples of the (meth) acrylic resin include a mono (meth) acrylate resin having one (meth) acryloyl group and a poly (meth) acrylate resin having two or more (meth) acryloyl groups, from the viewpoint of curability. It is preferable to use a poly (meth) acrylate resin, and it is more preferable to use a di (meth) acrylate resin from the viewpoint of handleability.

Examples of the mono (meth) acrylate resin include ethylene glycol monophenyl ether (meth) acrylate and 3-phenoxy-2-hydroxypropyl (meth) acrylate. Specific examples of the compound include the following compounds.

Examples of the di (meth) acrylate resin include compounds represented by the following general formula (1).

In the formula (1), R independently represents a hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group or a divalent group containing a (poly) alkyleneoxy group.

The divalent hydrocarbon group represented by X in the formula (1) is preferably linear, more preferably a divalent linear hydrocarbon group having 3 to 12 carbon atoms, and carbon. It is more preferably a divalent linear hydrocarbon group of number 4-6.
Divalent hydrocarbon group represented by X in the formula (1) may have a substituent. Examples of the substituent include a hydroxyl group and the like.

The divalent group containing a (poly) alkyleneoxy group represented by X in the formula (1) is a monoalkyleneoxy group containing one alkyleneoxy group or a polyalkyleneoxy group containing two or more. May be good. The number of alkyleneoxy groups in X is not limited. Examples of the (poly) alkyleneoxy group include a (poly) ethyleneoxy group and a (poly) propyleneoxy group.

The divalent group containing the (poly) alkyleneoxy group represented by X in the formula (1) may contain other groups other than the (poly) alkyleneoxy group. Examples of other groups include bisphenol groups.

Divalent group containing represented by (poly) alkyleneoxy group in X in Formula (1) may have a substituent. Examples of the substituent include a hydroxyl group and the like.

Among the compounds represented by the general formula (1), the following compounds can be mentioned as the compound (epoxy ester) in which X is a divalent group containing an alkyleneoxy group.

Commercially available products of epoxy ester include, for example, trade names of Kyoeisha Chemical Co., Ltd .: epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M (N), epoxy ester 3002A. (N), Ester Ester 3000MK, and Ester Ester 3000A are available.

The photocurable resin may contain a monomer, an oligomer, or a polymerizable compound consisting of both a monomer and an oligomer. When the monomer is contained, the viscosity of the composition 20 can be kept low. The inclusion of oligomers can increase the viscosity of composition 20. When both the monomer and the oligomer are contained, the viscosity of the composition 20 can be appropriately adjusted, and the mold 30 is excellent in impartability and handleability.

The viscosity of the photocurable resin is preferably 1.5 mPa · s to 100 mPa · s, and more preferably 5.0 mPa · s to 60 mPa · s, from the viewpoint of impartability to the mold 30 and handleability. It is preferably 6.5 mPa · s to 20 mPa · s, and more preferably 6.5 mPa · s.
The viscosity of the photocurable resin is a value measured according to JIS Z8803: 2011.

The ceramics, metals and metal compounds are not particularly limited, and for example, when applied to SOFC electrodes, gadrinium-doped ceria (GDC), ceria, strontium-doped ceria (SDC), yttria-stabilized zirconia (YSZ), scandia. Stabilized Zirconia (ScSZ), Zirconia, Lantern Strontium Cobalt Ferrite (LSCF), Lantern Strontium Cobaltite (LSC), Samalium Strontium Cobaltite (SSC), Lantern Strontium Manganite (LSM), Lantern Strontium Cobalt Manganite (LSCM), It may contain at least one selected from the group consisting of manganese cobalt spinel oxide (MCO), lanthantium strontium chromate (LSCr), gallium nitride, silicon carbide, tungsten carbide, alumina, titania, and lanthanum gallate (LaGaO _3). ..

The average particle size of at least one particle selected from the group consisting of ceramics, metals and metal compounds is preferably 10 nm to 3 μm, more preferably 10 nm to 1 μm, and more preferably 10 nm to 300 nm. More preferred.
The average particle size can be measured by a laser diffraction / scattering method particle size distribution measuring device, and a value obtained by calculating the median diameter from the obtained particle size distribution can be used as the average particle size. It is also possible to obtain the average particle size by observing using an SEM (scanning electron microscope).

The content of the ceramic particles, the metal particles and the metal compound particles in the composition 20 can be appropriately designed according to the desired density of the molded product obtained after sintering. For example, it is preferably 40% by mass to 65% by mass, more preferably 50% by mass to 60% by mass, and even more preferably 50% by mass to 56% by mass. When the content is 65% by mass or less, cracking during sintering tends to be suppressed.

The composition 20 may contain other components in addition to the photocurable resin, ceramic particles, metal particles and metal compound particles. Examples of other components include a photopolymerization initiator, a sensitizer, a dispersant, a defoaming agent, a plasticizer, and the like. The composition 20 according to the present invention does not necessarily require a sensitizer, a dispersant, an antifoaming agent, and a plasticizer.

The photopolymerization initiator may be a radical polymerization initiator, a cationic polymerization initiator, or an anionic polymerization initiator. Examples of the radical polymerization initiator include at least one of a radical polymerization initiator composed of a carbon atom, an oxygen atom and a hydrogen atom, and a radical polymerization initiator composed of a carbon atom, a nitrogen atom, an oxygen atom and a hydrogen atom. Specifically, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ 4- (4-morpholinyl) phenyl] -1-butanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1 -On, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, phenylglycoxyacid methyl ester, acetophenone, p-anisyl, benzyl, benzoin and benzophenone. At least one selected from the group is mentioned.

It is preferable that the absorption wavelength of the photopolymerization initiator does not overlap with the absorption wavelength of at least one particle selected from the group consisting of ceramics, metals and metal compounds contained in the composition 20.

For example, when GDC is used as a particle, the GDC absorbs light having a wavelength of 400 nm or less. Therefore, it is preferable to select a photopolymerization initiator having an absorption spectrum having a wavelength of more than 400 nm. Examples of those having an absorption spectrum over a wavelength of 400 nm include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (CAS No. 119133-12-1), which are commercially available products. Is available, for example, under the trade name IRGACURE369 (BASF Japan Ltd.). 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 has a wide absorption wavelength range because it has an aminoacetophenone and a benzene ring, and absorbs light on the long wavelength side near 450 nm. Therefore, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 enables polymerization even in the state of containing particles that absorb light of 400 nm or less.

When a photopolymerization initiator having an absorption spectrum over 400 nm is used, light having a wavelength over 400 nm is used for curing. FIG. 2 shows an example of the relationship between the absorption spectrum of the photopolymerization initiator, the absorption spectrum of the particles, and the wavelength of the irradiation light used for curing as a schematic graph. However, these relationships are not limited to FIG.

The content of the photopolymerization initiator can be appropriately designed according to the type and amount of the photocurable resin used.
For example, when a compound represented by the general formula (1) is used as the photocurable resin and a photopolymerization initiator having an absorption spectrum over a wavelength of 400 nm is used as the photopolymerization initiator, the content of the photopolymerization initiator is , 2% by mass or more is preferable with respect to the total amount of the photocurable resin and the photopolymerization initiator. When it is 2% by mass or more, the polymerization reaction proceeds sufficiently and the moldability is excellent.

The composition 20 comprises at least one particle selected from the group consisting of ceramics, metals and metal compounds, a photocurable resin (which may contain a monomer or an oligomer), a photopolymerization initiator which is an optional component, and the like. It is prepared by mixing with other ingredients.

The mixing method is not particularly limited, and an apparatus such as a propeller type stirrer, a kneader, or a mixer may be used. Further, after mixing, bubbles in the composition 20 may be removed by using a bubble removing device.

When it is difficult to mix the photopolymerization initiator with the photocurable resin, it is preferable to boil in hot water after mixing and further to stir with ultrasonic waves. The water bath and the ultrasonic agitation may be repeated alternately. The water bath temperature is appropriately set depending on the type of the photopolymerization initiator and the photocurable resin.

In addition, at least one kind of particles selected from the group consisting of ceramics, metals and metal compounds may be subjected to a pulverization treatment by a ball mill, a bead mill or the like before mixing. By performing the pulverization treatment, it is possible to form a more homogeneous nano-sized uneven shape.

The viscosity of the composition 20 is preferably 50 mPa · s to 100 mPa · s, more preferably 60 mPa · s to 80 mPa · s, and more preferably 60 mPa · s to 70 mPa · s from the viewpoint of impartability and handleability. Is more preferable.
The viscosity of the composition is a value measured according to JIS Z8803: 2011.

The curing time of the composition 20 (time from the start of irradiation with light to sufficient curing) is preferably 10 minutes or less, preferably 120 seconds or less, and further preferably 10 seconds or less. ..

The above composition 20 is applied to the target article 10 or the mold 30. The mold 30 is not particularly limited as long as it has at least one of a concave portion and a convex portion on the surface.

Examples of the target article 10 include electrodes or electrolytes of fuel cells, dielectrics or electrodes of capacitors, superconducting magnets, superconducting electrodes, friction sliding surfaces, tools, actuators, sensors, catalysts and the like. The surface on which the unevenness is formed in the target article 10 may be a flat surface or a curved surface. Further, the surface of the target article 10 may have irregularities.

Examples of the material of the mold 30 include carbon materials such as graphite (C) and a composite of graphite and carbon nanotubes; single crystal silicon (Si), polysilicon (α-Si), silicon carbide (SiC), and silicon nitride ( Semiconductor materials such as SiN); metal materials such as nickel (Ni), aluminum (Al), tungsten (W), tantalum (Ta), copper (Cu) and the like can be mentioned. Further, it may be a dielectric material such as ceramics, or an optical material such as quartz or soda glass.

The mold 30 may be a replica mold copied from the master mold. The replica mold may be made of the same material as the master mold or may be made of a different material.

When a photocurable resin composed of carbon atoms, oxygen atoms and hydrogen atoms is used as the photocurable resin, the replica mold is also preferably composed of a resin composed of carbon atoms, oxygen atoms and hydrogen atoms, and is photocurable. When a photocurable resin composed of carbon atom, nitrogen atom, oxygen atom and hydrogen atom is used as the sex resin, it is preferable that the replica mold is also composed of a resin composed of carbon atom, nitrogen atom, oxygen atom and hydrogen atom. .. Replica molds made of such materials tend not to poison the fuel cell when the resulting molded product is used in the fuel cell.

For example, a replica mold can be produced by transferring from a master mold by a UV-NIL (UV-nanoimprint lithiumography) method using a negative photoresist. The negative photoresist may be a (meth) acrylic resin or an epoxy resin.
Epoxy resin-based negative photoresists are commercially available products, such as, for example, trade names: SU-8 3005, SU-8 3010, SU-8 3025, SU-8 3035, SU-8 3050 (all of which are Nippon Kayaku). (Made by Co., Ltd.) is available.

From the viewpoint of increasing the flexibility of the replica mold and suppressing the occurrence of mold release defects, the resin used for the replica mold may be an epoxy ester. Examples of the epoxy ester include compounds in which X in the above-mentioned general formula (1) is a divalent group containing a (poly) alkyleneoxy group.

In the subsequent photo-curing step, when the composition 20 is cured by irradiating light from the mold 30 side, the material of the mold 30 is preferably one that transmits light having a wavelength used for curing.

The diameter of the concave portion or the convex portion of the mold 30 may be 50 μm or less. Since the production method of the present invention can be microfabricated, it may be in nano-order (1 to 99 nm), but is not necessarily limited to this, and even in submicron order (100 to 999 nm), it may be in micron order (1 μm to 1 μm). It may be 99 μm).

The height ratio (aspect ratio) to the diameter of the concave portion or the convex portion of the mold 30 may be any, and since the manufacturing method of the present invention has high retention of the uneven shape, the aspect ratio should be 2 or more. Is also possible. The aspect ratio can be appropriately designed according to the application of the molded product.

A mold release agent may be applied to the mold 30 to perform a mold release treatment. By performing the mold release treatment, the mold 30 can be easily peeled off from the cured product 22. As the release agent, generally known ones can be used, and examples thereof include a fluorine compound, a silane coupling agent, and a surfactant.

The method of applying the composition 20 to the target article 10 or the mold 30 is not particularly limited, and a commonly used method can be used. For example, a printing method such as a screen printing method and a gravure printing method, a brush coating method, a doctor blade method, a roll coating method and the like can be mentioned. From the viewpoint of increasing the area, it is preferable to use a method that can be continuously applied.

(Pressing process)
In the pressing step, the target article 10 and the mold 30 are pressed via the composition 20 (FIG. 1 (B)). By the pressing step, the composition 20 spreads on the surfaces of both the mold 30 and the target article 10, and the uneven pattern of the mold 30 is transferred to the composition 20.

The pressing method is not particularly limited, and examples thereof include a method of simply pressing the target article 10 and the mold 30 against each other, and a method of sandwiching and pressing between two flat plates.

The pressing force is preferably 100 kPa to 50 MPa, more preferably 1 MPa to 10 MPa.
When the pressing force is 100 kPa or more, the composition 20 easily penetrates to the tip of the unevenness of the mold 30, and when it is 50 MPa or less, the damage of the mold 30 is easily suppressed.

The pressing time is preferably 10 seconds to 1 hour, more preferably 3 minutes to 10 minutes.
When the pressing time is 10 seconds or more, the composition 20 easily penetrates to the tip of the unevenness of the mold 30, and when the pressing time is 1 hour or less, the composition 20 tends to be suppressed from being excessively dried and having poor fluidity. It is in.

(Photo-curing process)
In the photo-curing step, the pressed composition 20 is photo-cured (FIG. 1 (C)). By photo-curing, the composition 20 becomes a cured product 22.
The light irradiation conditions can be appropriately set according to the type and amount of the photocurable resin to be used, and when a photopolymerization initiator is used, the type and the like of the photopolymerization initiator.

As the light to be irradiated, a light having a wavelength that does not overlap with the absorption wavelength of at least one kind of particles selected from the group consisting of ceramics, metals and metal compounds contained in the composition 20 is selected. Specifically, it is preferable to use light having a wavelength of more than 400 nm, and it is preferable to use light having a wavelength of 420 nm or more.

When the mold 30 is made of a material that transmits the irradiation light, the light is irradiated through the mold 30. When the target article 10 is made of a material that transmits the irradiation light, the light is irradiated through the target article 10. When both the target article 10 and the mold 30 are made of a material that does not transmit the irradiation light, the light is irradiated after removing the mold 30.

When light is irradiated through the target article 10 or the mold 30, the mold 30 is removed from the cured product 22 after the photo-curing step (FIG. 1 (D)).
If the composition 20 remains on the surface, the removed mold 30 can be reused by removing the composition 20. Examples of the method for removing the composition 20 from the mold 30 include a method of immersing the composition 20 in a solvent to dissolve the photocurable resin in the composition 20. It is preferable that the mold 30 after being immersed in the solvent is dried to remove the solvent.

After removing the mold 30, a drying step may be provided, if necessary, before the next sintering step (FIG. 1 (E)).

Further, after removing the mold 30, the composition 20 may be further added before the next sintering step (FIG. 1 (E)). Further, the composition 20 used for the application may be the same as or different from the composition 20 used for the first time. Examples of the different composition 20 include those having different types and amounts of the photocurable resin, those having different types and amounts of at least one kind of particles selected from the group consisting of ceramics, metals and metal compounds, and the like.
The use of compositions with different components makes it possible to apply them to the production of molded products in various technical fields, for example, a laminate of a ceramic electrolyte and an electrode in SOFC, and a composite electrode of SOFC (for example, GDC and LSC). It is possible to produce molded products in various technical fields such as electrodes including electrodes).

Further, if the applied position of the composition 20 is set on the cured product 22, the cured product of the laminated body can be obtained.
Further, if the imparting position of the composition 20 to be further imparted is set to a region different from the region of the cured product 22 previously formed, a pattern of two or more compositions 20 can be formed. For example, by using compositions having different components, it is possible to form a pattern having different components on one surface.

When two or more compositions are used, in the conventional method, it is necessary to perform sintering by performing sintering each time the composition is applied, but according to the method of the present invention, it is baked all at once. Since it is possible to obtain a molded product by tying it, it is possible to produce it at low cost and with high throughput.

Further, since the method of the present invention can be produced by batch sintering, the number of steps to be taken out from the sintering furnace is reduced as compared with the conventional method of sintering each time a composition is applied, and the molded product is cracked. Occurrence can be suppressed. Therefore, for example, according to the method of the present invention, each layer in the molded product having a laminated structure can be made thin, so that a piezo actuator that can be greatly deformed can be manufactured.

(Sintering process)
In the sintering step, the cured composition 20 (cured product 22) is sintered (FIG. 1 (E)). An electric furnace 40 or the like can be used for sintering.
The sintering temperature and sintering time (holding time at the maximum temperature) are appropriately set depending on the types of ceramics, metals and metal oxide particles used. For example, in the case of GDC particles, the temperature is preferably 1100 ° C to 1700 ° C, more preferably 1400 ° C to 1550 ° C, from the viewpoint of the strength of the obtained molded product 100.
The sintering time may be, for example, 60 minutes to 5 hours or 120 minutes to 3 hours.

The atmospheric conditions of the sintering step are not particularly limited as long as the photocurable resin or the like burns and disappears. From the viewpoint of cost, it is preferable to sinter in air at normal pressure, but sintering may be performed in gas pressure such as hot isostatic pressing method (HIP).

According to the manufacturing method of the present invention, it is possible to form a fine uneven shape on the surface of the target article 10. For example, the diameter of the concave portion or the convex portion can be 50 μm or less, can be submicron order (100 to 999 nm), or can be nano order (1 to 99 nm).
Further, the ratio of the depth or height to the diameter of the concave portion or the convex portion (aspect ratio) can be set to 2 or more.
The diameters of the recesses and protrusions, as well as the aspect ratio, can be measured with an electron microscope.

<Molded product>
The molded product has at least one of a concave portion and a convex portion composed of at least one selected from the group consisting of ceramics, metals and metal compounds on at least a part of the surface. According to the above manufacturing method, since it is possible to form a fine uneven shape on the surface of the target article 10, the ratio of the depth or height to the diameter of the concave or convex portion (aspect ratio) is set to 2 or more. Is possible. Further, the diameter of the concave portion or the convex portion can be 50 μm or less, can be submicron order (100 to 999 nm), or can be nano order (1 to 99 nm).

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

[Example 1]
1. Preparation of resin components Add 4% by mass of IRGACURE369 (BASF Japan Ltd.) to 96% by mass of 1,6-hexanediol diacrylate (viscosity: 7.0 mPa · s), mix, and then boil at 80 ° C. The mixture was ultrasonically stirred. The resin component was prepared by alternately repeating hot water boiling and ultrasonic stirring 5 times.

2. Confirmation of the resolution of the resin component The prepared resin component does not contain particles. The resolution of this resin component was confirmed.
A resin component is applied to a mold having a plurality of recesses having a diameter of 200 nm, and light having a wavelength of 300 nm to 450 nm is exposed to an exposure amount of 4.5 J using a UV irradiation device (Panasonic Co., Ltd., lamp-type SPOT type ultraviolet curing device Aice UP50). Irradiation at / cm ² was performed to obtain a cured product. After curing, the mold was removed and the cured product was observed with a scanning electron microscope (SEM).

As shown in the planar SEM images of FIGS. 3 and 4, a pattern having a diameter of 200 nm was transferred to the cured product containing only the resin component to which no particles were added. This resin component was found to have sufficient resolution.

3. 3. Preparation of composition 60% by mass of GDC particles (average particle size 100 nm) were added to 40% by mass of the resin component and mixed on a petri dish with a spatula for about 5 minutes to obtain a slurry-like composition. The viscosity of the composition was 70 mPa · s.

4. Confirmation of curability of the composition It was confirmed whether the composition was cured by using a UV lamp having a wavelength of 300 nm to 450 nm with respect to the obtained composition. The irradiation time was 30 seconds, the illuminance was 75 lpx, and the irradiation amount was 2.25 J / cm ² .
As shown in FIG. 5, the composition was sufficiently cured, and the shape did not change even when pressed with a spatula and touched, and the shape retention was excellent. Although this composition contains GDC particles having absorption in the ultraviolet wavelength range, it was found to be sufficiently cured in a UV lamp.

5. Preparation of Replica Mold A master mold having a pillar pattern with a diameter of 2 μm, a depth of 8 μm, and a pitch interval of 2 μm was subjected to mold release treatment with platinum and a fluorine compound on the surface. An epoxy resin-based negative photoresist SU-8 3025 (trade name, manufactured by Nippon Kayaku Co., Ltd.) was applied to the mold-released master mold. Then, light having a wavelength of 300 nm to 400 nm was exposed using a UV irradiation device (a lamp type SPOT type ultraviolet curing device Acure UP50 manufactured by Panasonic Corporation). The exposure time was 1 minute, the illuminance was 75 lpx, and the irradiation amount was 4.5 J / cm ² . Then, it was baked at 85 ° C. for 3 minutes to obtain a replica mold.

6. Mold release treatment of replica mold The obtained replica mold was coated with platinum using a sputtering device (ESC101 manufactured by Elionix Inc.). A mold release agent (manufactured by Daikin Industries, Ltd., product name: Optool, containing 1% by mass of a fluorine compound) was applied thereto, heated at 85 ° C. for 2 hours, and then rinsed with water for 30 minutes.

7. A drop of the composition prepared above was dropped onto the replica mold that had been subjected to the application and the mold release treatment, and the glass plate was pressed from above. In this state, light having a wavelength of 300 nm to 450 nm was irradiated with a UV lamp. The irradiation time was 10 minutes, the illuminance was 75 lpx, and the irradiation amount was 45 J / cm ² . After irradiating with light, the replica mold was removed.

8. After curing, calcination was performed at 300 ° C. for 60 minutes.

9. Observation Figures 6 and 7 show the plan SEM images of the calcined material. As shown in FIGS. 6 and 7, a pattern having a diameter of 2 μm was confirmed. Since the distance between particles is about several hundred nm, it is thought that if the crystal grows, it will be sintered.

FIG. 8 is a graph showing the results of measuring the cross-sectional shape of the calcined product with a laser microscope. As shown in FIG. 8, it can be seen that a pillar pattern having a diameter of about 2 μm and a height of about 6.5 μm is formed. From this result, it was found that the uneven shape of 10 μm order required for high efficiency of SOFC can be formed.

[Example 2]
(Molding of uneven shape on curved surface)
A replica mold was prepared in the same manner as in Example 1 except that a master mold having a pillar pattern having a diameter of 10 μm, a depth of 15 μm, and a pitch interval of 25 μm was used, and a mold release treatment was performed.
FIG. 9 shows a planar optical microscope image of the replica mold produced. As shown in FIG. 9, the replica mold had a pattern of recesses having a diameter of 10 μm.

As shown in FIG. 10 (A), the composition prepared in Example 1 is applied to the curved surface arrow (→) portion of the outer surface of a cylinder having a diameter of 30 mm, and a pillar pattern is formed using the prepared replica mold. It was transferred and cured in the same manner as in Example 1.

FIG. 10B is a planar optical microscope image of a cured product formed on a cylindrical object. As shown in FIG. 10B, a pillar pattern having a diameter of 10 μm was formed on the curved surface.

The cured product was pre-baked at 300 ° C. for 1 hour. FIG. 11 shows a planar optical microscope image of the calcined product. The pillar pattern remained even after the temporary baking at 300 ° C.
From this result, it was found that a pattern on the order of 10 μm can be formed even on a curved surface having a relatively large curvature.

[Example 3]
(Preparation of electrode sample)
A replica mold was produced and subjected to a mold release treatment in the same manner as in Example 1 except that a master mold having a pillar pattern having a diameter of 50 μm, a depth of 15 μm, and a pitch interval of 100 μm was used. One drop of the composition prepared in Example 1 was dropped onto the replica mold subjected to the mold release treatment, and a YSZ plate (manufactured by Tosoh Corporation, diameter 24 mm, thickness 0.5 mm) was pressed from above. In this state, light having a wavelength of 300 nm to 450 nm was irradiated from the replica mold side by a UV lamp. The irradiation time was 10 minutes, the illuminance was 75 lpx, and the irradiation amount was 45 J / cm ² . After irradiation with light, the replica mold was removed to obtain a cured product. Then, it was calcined at 300 ° C. for 60 minutes, and further sintered using an electric furnace. FIG. 12 shows the temperature profile of the sintering process. Cooling from 1450 ° C. was natural cooling.

FIG. 13 shows an external photograph of the obtained sintered product, and FIG. 14 shows a planar laser microscope image thereof. The pattern molded portion was sintered and integrated with the YSZ plate.
FIG. 15 is a graph showing the results of measuring the cross-sectional shape of the sintered body with a laser microscope.
The height of the pattern was about 11 μm and the diameter was 50 μm. No large shrinkage of the pattern due to sintering was confirmed, and a good shape was obtained.

16 to 18 are plan SEM images obtained by enlarging FIG. 14. From the image of FIG. 17, the state of crystal growth of GDC particles can be confirmed. In FIG. 18, it can be confirmed that the grown crystals are attached to each other. From this result, it can be seen that the photocurable resin used acts as a binder and does not inhibit the crystal growth of GDC particles in the sintering step.

In order to confirm the reproducibility, another sample was prepared by the method of Example 3, and when the sample was observed by SEM, this sample was also sintered and became porous. When the state of the crystals was confirmed from the magnified SEM image, it was found that the crystals were similar to the above sample and had high reproducibility.

[Example 4]
A sintered product was prepared in the same manner as in Example 3 except that a master mold having a pillar pattern having a diameter of 10 μm, a depth of 15 μm, and a pitch interval of about 25 μm was used.
FIG. 19 shows a planar laser microscope image of the obtained sintered product. As shown in the image of FIG. 19, even in the pillar pattern having a diameter of 10 μm, the pillar pattern integrated with the YSZ plate was formed.

FIG. 20 is a graph showing the results of measuring the cross-sectional shape of the sintered body with a laser microscope. A pattern having a height of about 4 μm to 8 μm and a diameter of 13 μm (root portion) was formed. Since this sample is also porous, the surface area is significantly increased.

FIG. 21 shows a planar SEM image of the obtained sintered product. As shown in FIG. 21, it can be clearly seen that the molded portion is a crystal of GDC, and it can be seen that the reproducibility of the sintered pattern is high.
FIG. 22 is an enlarged planar SEM image of FIG. 21. FIG. 23 is a perspective SEM image. FIG. 24 is a perspective SEM image obtained by further magnifying FIG. 23. From the image of FIG. 24, it can be seen that the inside is sintered and the crystal is grown.

[Example 5]
(Preparation of electrode sample 2)
First, a cured product (1) (hereinafter, also referred to as a GDC pattern layer) having a pattern on the surface was produced on a YSZ plate by the same method as in Example 3.
Then, 60% by mass of the LSCF particles and 40% by mass of the resin component prepared in Example 1 were mixed to obtain a slurry-like composition.
One drop of the obtained composition is dropped onto the GDC pattern layer, pressed with a PET film, and then used with a UV irradiation device (Panasonic Co., Ltd., lamp type SPOT type ultraviolet curing device Aicure UP50) to have a wavelength of 300 nm to 450 nm. The light was irradiated with an exposure amount of 45 J / cm ^2. As a result, a laminated body in which a layered cured product (2) (hereinafter, also referred to as an LSCF layer) containing LSCF particles was further formed on the GDC pattern layer was obtained.

FIG. 25 is a planar optical microscope image when a part of the LSCF layer is removed and a part of the GDC pattern layer below the LSCF layer is also removed to expose each layer in the obtained laminate. Further, FIG. 26 is a cross-sectional optical microscope image when the YSZ plate is peeled off and observed for ease of observation. 27 is a diagram illustrating the observation directions of FIGS. 25 and 26.
As shown in FIGS. 25 and 26, an LSCF layer was formed on the GDC pattern layer.

The cured product was pre-baked at 300 ° C. for 1 hour. FIG. 28 shows a cross-sectional optical microscope image of the calcined product. The pillar pattern remained even after the temporary baking at 300 ° C. From this result, it was found that a molded product in which an SOFC electrolyte and an electrode having a pattern are laminated can be produced by batch sintering.

[Reference Example 1]
In Example 5, by substituting the LSCF particles used for the cured product (2) with ceramic particles, a molded product in which a ceramic electrolyte and an electrode having a pattern are laminated can be produced by batch sintering. ..

10 Target article 20 Composition 30 Mold 40 Electric furnace 100 Mold

Claims (20)

It is a method for manufacturing a molded product having at least one of a concave portion and a convex portion composed of at least one selected from the group consisting of ceramics, metals and metal compounds on at least a part of the surface of the target article.
A composition containing a photocurable resin and at least one particle selected from the group consisting of ceramics, metals and metal compounds is placed on the target article or a mold having at least one of a concave portion and a convex portion on the surface thereof. The process of giving and
A step of pressing the target article and the mold through the composition, and
The step of photo-curing the pressed composition and
A step of sintering the photo-cured composition at 1100 to 1700 ° C.
A method for manufacturing a molded product. The particles include gadrinium-doped ceria (GDC), ceria, samarium-doped ceria (SDC), yttria-stabilized zirconia (YSZ), scandia-stabilized zirconia (ScSZ), zirconia, lanthanum strontium cobalt ferrite (LSCF), and lanthanum strontium cobaltite. (LSC), Samarium Strontium Cobaltite (SSC), Lantern Strontium Manganite (LSM), Lantern Strontium Cobalt Manganite (LSCM), Manganese Cobalt Spinel Oxide (MCO), Lantern Strontium Chromite (LSCr), Gallium Nitride, Silicon Carbide The method for producing a molded product according to claim 1, which comprises at least one selected from the group consisting of tungsten carbide, alumina, titania, and lanthangarate (LaGaO _3). The method for producing a molded product according to claim 1 or 2, wherein the composition further contains a photopolymerization initiator. The method for producing a molded product according to claim 3, wherein the photopolymerization initiator is selected so that the absorption wavelength of the photopolymerization initiator does not overlap with the absorption wavelength of the particles contained in the composition. 3. The photopolymerization initiator is at least one of a radical polymerization initiator composed of a carbon atom, an oxygen atom and a hydrogen atom, and a radical polymerization initiator composed of a carbon atom, a nitrogen atom, an oxygen atom and a hydrogen atom. Or the method for producing a molded product according to claim 4. The radical polymerization initiator is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1. -[4- (4-morpholinyl) phenyl] -1-butanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane -1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, phenylglycylic acid methyl ester, acetophenone, p-anisyl, benzyl, benzoin and benzophenone The method for producing a molded product according to claim 5, which comprises at least one selected from the group consisting of. Claim 1 that the photocurable resin is at least one of a photocurable resin composed of a carbon atom, an oxygen atom and a hydrogen atom, and a photocurable resin composed of a carbon atom, a nitrogen atom, an oxygen atom and a hydrogen atom. The method for producing a molded product according to any one of claims 6. The method for producing a molded product according to any one of claims 1 to 7, wherein the photocurable resin contains at least one of a (meth) acrylic resin and an epoxy resin. The method for producing a molded product according to any one of claims 1 to 8, wherein the photocurable resin contains a compound represented by the following general formula (1).

[In the formula (1), R represents a hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group or a divalent group containing a (poly) alkyleneoxy group. ] The method for producing a molded product according to claim 9, wherein in the general formula (1), X contains a compound which is a divalent linear hydrocarbon group or a divalent group containing a (poly) alkyleneoxy group. .. The method for producing a molded product according to any one of claims 1 to 10, wherein the photocurable resin contains a monomer, an oligomer, or a polymerizable compound composed of both a monomer and an oligomer. The method for producing a molded product according to any one of claims 1 to 11, wherein the photocurable resin has a viscosity of 1.5 mPa · s to 100 mPa · s. The method for producing a molded product according to any one of claims 1 to 12, wherein the diameter of the concave portion or the convex portion of the mold is 50 μm or less. The method for producing a molded product according to any one of claims 1 to 13, wherein the ratio (aspect ratio) of the depth or height to the diameter of the concave portion or the convex portion of the mold is 2 or more. .. The method for manufacturing a molded product according to any one of claims 1 to 14, wherein the mold is a replica mold copied from a master mold. Any of claims 1 to 15, wherein the target article is an electrode or electrolyte of a fuel cell, a dielectric or electrode of a capacitor, a superconducting magnet, a superconducting electrode, a friction sliding surface, a tool, an actuator, a sensor, or a catalyst. The method for producing a molded product according to item 1. The method for producing a molded product according to any one of claims 1 to 16, further using a composition having a different component from the composition. The method for producing a molded product according to claim 17, wherein the composition having different components differs from the composition in the type of at least one particle selected from the group consisting of ceramics, metals and metal compounds. A composition having different components is applied to at least one of the first cured product obtained in the photo-curing step and a region different from the region where the first cured product is formed, and light is applied. After curing to obtain a second cured product
The method for producing a molded product according to claim 17 or 18, wherein the first cured product and the second cured product are sintered together. At least a part of the surface has at least one of a concave portion and a convex portion made of a ceramic or metal sintered product , and the ratio of the depth or the height to the diameter of the concave portion or the convex portion (aspect ratio) is determined. more der is, the diameter of the convex portion is molded Ru der below 999 nm.

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