JP2019064861A - Method for producing molding, and molding - Google Patents

Abstract

To provide a method for producing a molding whose surface can be formed with fine ruggedness by a ceramic, a metal or a metal oxide, and a molding.SOLUTION: Provided is a method for producing a molding 100 in which at least a part of the surface of an objective article 10 is provided with at least either a recessed part or a projecting part composed of at least one kind selected from a group consisting of a ceramic, a metal and a metallic compound, comprising: a step where a composition 20 containing a photocurable resin and particles of at least one kind selected from a group consisting of a ceramic, a metal and a metallic compound is applied to an objective article 10 or a mold 30 having at least either a recessed part or a projecting part on the surface; a step where the objective article 10 and the mold 30 are pressed via the composition 20; a step where the pressed composition 20 is photo-cured; and a step where the photo-cured composition 20 is sintered.SELECTED DRAWING: Figure 1

Description

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

  In recent years, with the development of inorganic materials such as ceramics, metals and metal oxide materials and the progress of their microfabrication techniques, the functions of inorganic materials are further evaluated, and their application to various products is advanced.

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

  In addition, there is a technique in which fine irregularities are formed on the surface of an inorganic material to impart water repellency or hydrophilicity to the surface. Furthermore, inorganic materials having fine irregularities on the surface are also useful as catalysts and capacitors.

  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 fine structure inexpensively and in a large area is desired.

  As one of such microfabrication methods of inorganic materials, there is a MIM (Metal Injection Molding) method of injection molding using metal powder as a raw material (see, for example, Non-Patent Documents 1 and 2). In the MIM method, a step of mixing components such as metal powder, thermoplastic resin, wax and the like, a step of injection molding, a step of degreasing the thermoplastic resin, and a step of sintering are carried out to obtain a metal molded article of three dimensional structure. . The MIM method can produce a product having a complicated shape as compared to the press sintering method.

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

Unexamined-Japanese-Patent No. 2010-52408

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

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

  Then, the subject of this invention is providing the manufacturing method and molded object of the molded object which can form fine unevenness | corrugation with ceramics, a metal, or a metal oxide on the surface of a molded object.

The present invention includes the following forms.
<1> A method for producing a molded article having at least one of a recess and a protrusion formed of at least one selected from the group consisting of ceramics, metals and metal compounds on at least a part of the surface of a target article,
A mold containing a photocurable resin and at least one particle selected from the group consisting of a ceramic, a metal and a metal compound on the surface of at least one of the target article or the concave and convex portions on a surface thereof The step of applying
Pressing the target article and the mold through the composition;
Photocuring the pressed composition;
Sintering the photocured composition;
A method for producing a molded article, comprising:
<2> The particles are gadolinium-doped ceria (GDC), ceria, samarium-doped ceria (SDC), yttria stabilized zirconia (YSZ), scandia stabilized zirconia (ScSZ), zirconia, lanthanum strontium cobalt ferrite (LSCF), lanthanum Strontium cobaltite (LSC), samarium strontium cobaltite (SSC), lanthanum strontium manganite (LSM), lanthanum strontium cobalt manganite (LSCM), manganese cobalt spinel oxide (MCO), lanthanum strontium chromite (LSCr), gallium nitride , silicon carbide, tungsten carbide, alumina, titania, and from the group consisting of lanthanum gallate (LaGaO ₃₎ Comprising at least one member-option method for producing a molded article according to <1>.
The manufacturing method of the molded article as described in <1> or <2> in which the <3> above-mentioned composition further contains a photoinitiator.
<4> The molded article according to <3>, wherein the photopolymerization initiator is selected such 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 consisting of a carbon atom, an oxygen atom and a hydrogen atom, and a radical polymerization initiator consisting of a carbon atom, a nitrogen atom, an oxygen atom and a hydrogen atom The manufacturing method of the molded article as described in <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-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, phenylglyoxylic acid group The manufacturing method of the molding as described in <5> containing at least 1 sort (s) selected from the group which consists of a chill ester, an acetophenone, p-anisyl, a benzyl, benzoin, and a benzophenone.
<7> The photocurable resin is at least one of a photocurable resin composed of carbon atom, oxygen atom and hydrogen atom, and a photocurable resin composed of carbon atom, nitrogen atom, oxygen atom and hydrogen atom, The manufacturing method of the molded object of any one of <1>-<6>.
The manufacturing method of the molded article of any one of <1>-<7> in which the <8> above-mentioned photocurable resin contains at least one of a (meth) acrylic resin and an epoxy resin.
The manufacturing method of the molded article of any one of <1>-<8> in which the <9> above-mentioned photocurable resin contains the compound represented by following General formula (1).

[In 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>, including a compound in which X is a divalent linear hydrocarbon group or a divalent group containing a (poly) alkyleneoxy group in the general formula (1) Manufacturing method.
The manufacturing method of the molded article of any one of <1>-<10> in which the <11> above-mentioned photocurable resin contains the polymerizable compound which consists of a monomer, an oligomer, or both a monomer and an oligomer.
The manufacturing method of the molded article of any one of <1>-<11> whose viscosity of the <12> above-mentioned photocurable resin is 1.5 mPa * s-100 mPa * s.
The manufacturing method of the molded article of any one of <1>-<12> whose diameter of the said recessed part of the <13> above-mentioned mold or the said convex part is 50 micrometers or less.
<14> The molded article according to any one of <1> to <13>, wherein the ratio (aspect ratio) of the depth or height to the diameter of the recess or the protrusion of the mold is 2 or more. Manufacturing method.
<15> The method for producing a molded article 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 a fuel cell electrode or electrolyte, 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 manufacturing method of the molded article of any one of>.
The manufacturing method of the molded article of any one of <1>-<16> which uses the composition from which a component differs by <17> said composition.
<18> The method for producing a molded article according to <17>, wherein the composition and the composition having different components differ in type of at least one particle selected from the group consisting of ceramics, metals and metal compounds. .
<19> A composition different from the component is applied to 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. And after light curing to obtain a second cured product,
The manufacturing method of the molded object as described in <17> or <18> which sinters the said 1st hardened | cured material and the said 2nd hardened | cured material collectively.
<20> At least a portion of the surface has at least one of a recess and a protrusion composed of at least one selected from the group consisting of ceramics, metals and metal compounds, and the depth to the diameter of the recess or protrusion is A molded product having a height or height ratio (aspect ratio) of 2 or more.

  According to the present invention, it is possible to provide a method for producing a molded article and a molded article capable of forming fine irregularities on the surface of the molded article with a ceramic, a 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 typically an example of the relationship between the absorption spectrum of a polymerization initiator, the absorption spectrum of particle | grains, and the wavelength of the irradiated light used for hardening. In Example 1, it is a plane | planar SEM image of the hardened | cured material in which the uneven | corrugated shaped pattern was formed only with the resin component. It is the planar SEM image which expanded FIG. It is a photograph which shows the result of having confirmed the hardenability of the composition. 3 is a plan SEM image of the calcined material obtained in Example 1. FIG. It is the planar SEM image which expanded FIG. It is a graph which shows the result of having measured the cross-sectional shape of the calcination thing obtained in Example 1 with the laser microscope. It is a plane optical microscope image of the replica mold produced in Example 2. (A) is a perspective photograph which shows the external appearance of the calcined material of Example 2 which formed the uneven | corrugated shaped pattern in the curved surface, (B) is a plane optical microscope image of the pattern in (A). 7 is a planar optical microscope image of the calcined material obtained in Example 2. 15 is a graph showing a temperature profile of a sintering process in Example 3. It is an external appearance photograph of the sinter obtained in Example 3. It is the planar laser-microscope image to which the sintered product obtained in Example 3 was expanded. It is a graph which shows the result of having measured the cross-sectional shape of the sintered material obtained in Example 3 by the laser microscope. It is the planar SEM image which expanded FIG. (A) is the planar SEM image which expanded FIG. 16, (B) is the planar SEM image which further expanded (A). It is the planar SEM image which expanded FIG. 17 (B). 7 is a flat laser microscope image of the sinter obtained in Example 4. It is a graph which shows the result of having measured the cross-sectional shape of the sinter obtained in Example 4 with the laser microscope. 7 is a planar SEM image of the sinter obtained in Example 4. (A) is the planar SEM image which expanded FIG. 21, (B) is the planar SEM image which further expanded (A). (A) is a perspective SEM image of FIG. 21, (B) is a perspective SEM image which expanded (A) further. It is a perspective SEM image which expanded FIG. 23 (B) further. It is a plane optical microscope image when a part of hardened | cured material obtained in Example 5 is removed and each layer is exposed. It is a cross-sectional optical microscope image of the sample which peeled the YSZ board from the hardened | cured material obtained in Example 5. FIG. It is a figure explaining the observation direction of FIG.25 and FIG.26. 7 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.
The numerical range shown using "-" in this specification shows the range which includes the numerical value described before and after "-" as minimum value and the maximum value, respectively.
In the drawings, the same or corresponding members are denoted by the same reference numerals.

<Method for producing molding>
Although an example of the manufacturing method of the molded object of this invention is shown in FIG. 1, the manufacturing method of the molded object of this invention is not limited to this. Further, the shape, size, and the like of the members in the drawings are not limited to this.

  The method for producing the molded article 100 is a molded article having at least one of a recess and a projection formed 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 10 100 is a manufacturing method, and a composition 20 containing a photocurable resin and at least one particle selected from the group consisting of ceramics, metals, and metal compounds is used as the target article 10 or the concave and convex portions. A step of applying to a mold 30 having at least one surface (hereinafter also referred to as “application step”.) A step of pressing the target article 10 and the mold 30 through the composition 20 (hereinafter, referred to as “application step”) It is also referred to as “pressing step.” A step of photo-curing the pressed composition 20 (hereinafter, also referred to as “photo-curing step”.) And a composition that is photo-cured. 20 (cured product 22) a step of sintering a (hereinafter, also referred to as "sintering step". FIG. 1 (E)), a. The present invention may further have other steps.

  In the method for producing the molded product 100, a 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. 1C) (FIG. 1D, curing is performed in a state where the mold 30 is removed) Even if the object 22 is sintered (FIG. 1 (E)), the uneven shape is maintained.

  The thermoplastic resin is generally a material having a large value of Young's modulus and being hard to deform. Therefore, as in Non-Patent Document 1 and Patent Documents 1 and 2, a thermoplastic resin is conventionally used as a resin. In these methods, it is possible to form an asperity shape on the order of 100 μm.

  However, when a thermoplastic resin is used as the resin, it can not withstand the heat at the time of the temperature rise of sintering, and the shape is dripped in the middle of the temperature rise, so the uneven shape transferred to the composition 20 is maintained. Hateful. Therefore, it was found that in the method using a thermoplastic resin, when the asperity shape is further refined, the transfer can not be performed accurately.

  On the other hand, since the photocurable resin has a higher decomposition temperature than the thermoplastic resin, the photocurable resin functions as a binder up to a high temperature. Thereby, when photocurable resin is used, the fine uneven | corrugated shape which can not be obtained when thermoplastic resin is used is realizable. Moreover, in the thermoplastic resin which is dripped by heating, the shape of the target article 10 is basically limited to a flat plate shape, whereas when a curable resin is used, the target article 10 having various shapes may be uneven. It can form a shape.

  Moreover, the recessed part and convex part comprised with the hardened | cured material of photocurable resin are strong compared with the recessed part and convex part comprised with the composition 20 containing a thermoplastic resin. Therefore, it becomes possible to store or transport for a long distance in the state of a cured product after the light curing step. That is, after performing up to the light curing step (FIG. 1 (C)), the sintering step (FIG. 1 (E)) may be performed again after a lapse of time. Therefore, since it is possible to sinter at once after producing a plurality of cured products, it is possible to achieve high throughput and to reduce the manufacturing cost.

In addition, when using a thermoplastic resin, since it becomes easy to foam by vacuum degassing | defoaming in order to use media, such as water and alcohol, an antifoamer may be required. In addition, since the medium is volatilized by vacuum degassing for a long time, addition of an antifoaming agent is desirable also for shortening the time of vacuum degassing.
On the other hand, in the case of the 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 medium is not used when using a photocurable resin, it is not necessary to use an antifoaming agent since foaming due to the medium does not occur. In addition, since the photocurable resin after curing has a large molecular weight, it is difficult to vaporize by vacuum degassing, and vacuum degassing can be performed for a long time. Thereby, the defect derived from the air bubble in the molded object which is a product can be decreased.

  In addition, when using a thermoplastic resin, a drying step is required before the sintering step because a medium is used, but when a medium is not used when a photocurable resin is used, the drying step is unnecessary. Become.

  And in the method of using a photocurable resin, manufacturing time can be shortened compared with the method of using curable resin which hardens | cures after appropriate time like patent document 1 (Japanese Patent Application Laid-Open No. 2008-101501). In addition, variation between lots can be suppressed. Furthermore, the unevenness of the cured state in one molded article can be suppressed, and a finer asperity shape can be formed.

In addition, in the case of 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. Also in the case of a thermoplastic resin, since it exists in the state of the composition until sintering, it is assumed 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 the photocurable resin, since curing is performed before sintering and the curing time is short, the time in the state of the composition is short, and the dispersant may not be used.

In addition, in the method of shape | molding uneven | corrugated shape with a metal mold | die, an uneven | corrugated | grooved part can only be integrally formed with a main-body part. On the other hand, in the method of the present invention, it is possible to add an uneven shape to the target article 10 by retrofitting. Therefore, with respect to various target articles 10, it is possible to provide a fine uneven shape on the surface.
Hereafter, the manufacturing method of a molded object is demonstrated for every process.

(Applying process)
In the application 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. For example, at least one of a photocurable resin composed of carbon atom, oxygen atom and hydrogen atom, and a photocurable resin composed of carbon atom, nitrogen atom, oxygen atom and hydrogen atom Can be mentioned.

  Specifically as a photocurable resin, (meth) acrylic resin and an epoxy resin are mentioned. Examples of the (meth) acrylic resin include mono (meth) acrylate resin having one (meth) acryloyl group and poly (meth) acrylate resin having two or more (meth) acryloyl groups, and 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. The following compounds can be mentioned as specific example compounds.

  As a di (meth) acrylate resin, the compound represented by following General formula (1) is mentioned.

  In formula (1), R each 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, carbon It is further preferable that it is a bivalent linear hydrocarbon group of several to six.
The divalent hydrocarbon group represented by X in Formula (1) may have a substituent. A hydroxyl group etc. can be mentioned as a substituent.

  The divalent group containing a (poly) alkyleneoxy group represented by X in the formula (1) is a polyalkyleneoxy group containing two or more even if it is a monoalkyleneoxy group containing one alkyleneoxy group, It is also 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 a (poly) alkyleneoxy group represented by X in the formula (1) may contain another group other than the (poly) alkyleneoxy group. Other groups include bisphenol group and the like.

  The divalent group containing a (poly) alkyleneoxy group represented by X in Formula (1) may have a substituent. A hydroxyl group etc. can be mentioned as a substituent.

  Among the compounds represented by the general formula (1), examples of the compound (epoxy ester) in which X is a divalent group containing an alkyleneoxy group include the following compounds.

  As a commercial item of epoxy ester, for example, trade name of Kyoeisha Chemical Co., Ltd .: epoxy ester M-600A, epoxy ester 40 EM, epoxy ester 70 PA, epoxy ester 200 PA, epoxy ester 80 MFA, epoxy ester 3002 M (N), epoxy ester 3002 A (N), epoxy ester 3000 MK, and epoxy ester 3000A.

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

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. Preferably, the viscosity is 6.5 mPa · s to 20 mPa · s.
The viscosity of the photocurable resin is a value as measured according to JIS Z8803: 2011.

Ceramics, metals and metal compounds are not particularly limited. For example, when applied to an SOFC electrode, gadolinium-doped ceria (GDC), ceria, samarium-doped ceria (SDC), yttria stabilized zirconia (YSZ), scandia Stabilized zirconia (ScSZ), zirconia, lanthanum strontium cobalt ferrite (LSCF), lanthanum strontium cobaltite (LSC), samarium strontium cobaltite (SSC), lanthanum strontium manganite (LSM), lanthanum strontium cobalt manganite (LSCM), Manganese cobalt spinel oxide (MCO), lanthanum strontium chromite (LSCr), gallium nitride, silicon carbide, tungsten car Id, alumina, titania, and may include at least one selected from the group consisting of lanthanum gallate (LaGaO _3).

The average particle diameter 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 10 nm to 300 nm More preferable.
The average particle size can be measured by a laser diffraction / scattering particle size distribution measuring apparatus, and a value obtained by calculating a median diameter from the obtained particle size distribution can be used as an average particle size. The average particle size can also be determined by observation using a SEM (scanning electron microscope).

  The contents of the ceramic particles, the metal particles and the metal compound particles in the composition 20 can be appropriately designed in accordance with the desired density of the molded product obtained after sintering. For example, the content is preferably 40% by mass to 65% by mass, more preferably 50% by mass to 60% by mass, and still more preferably 50% by mass to 56% by mass. When the content is 65% by mass or less, cracking at the time of 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. As other components, a photoinitiator, a sensitizer, a dispersing agent, an antifoamer, a plasticizer etc. are mentioned. In the composition 20 according to the present invention, a sensitizer, a dispersant, an antifoaming agent, and a plasticizer are not necessarily required.

  The photopolymerization initiator may be a radical polymerization initiator, a cationic polymerization initiator or an anionic polymerization initiator. The radical polymerization initiator includes at least one of a radical polymerization initiator consisting of a carbon atom, an oxygen atom and a hydrogen atom, and a radical polymerization initiator consisting 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- [2 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-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, phenylglyoxylic acid methyl ester, aceto Enon, p- anisyl, benzyl, at least one can be mentioned is selected from the group consisting of benzoin and benzophenone.

  Preferably, 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, in the case of using GDC as particles, GDC absorbs light having a wavelength of 400 nm or less. Therefore, as the photopolymerization initiator, it is preferable to select one having an absorption spectrum at a wavelength of more than 400 nm. 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (CAS No. 119313-12-1) is mentioned as what has an absorption spectrum over wavelength 400nm, and a commercial item is mentioned. Is available, for example, under the trade name IRGACURE 369 (BASF Japan Ltd.). Since 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 has an aminoacetophenone and a benzene ring, it has a wide absorption wavelength range and absorbs even light on the long wavelength side near 450 nm. Thus, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 enables polymerization even with particles that absorb light of 400 nm or less.

  In the case of using a photopolymerization initiator having an absorption spectrum at a wavelength of more than 400 nm, light having a wavelength of more than 400 nm is used for curing. An example of the relationship between the absorption spectrum of the photopolymerization initiator at this time, the absorption spectrum of the particles, and the wavelength of the irradiation light used for curing is shown as a schematic graph in FIG. 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 to be used.
For example, when using a compound represented by General Formula (1) as the photocurable resin and using a photopolymerization initiator having an absorption spectrum at a wavelength of more than 400 nm as the photopolymerization initiator, the content of the photopolymerization initiator is It is preferable that it is 2 mass% or more with respect to the total amount of photocurable resin and a photoinitiator. A polymerization reaction progresses sufficiently as it is 2 mass% or more, and it is excellent in a moldability.

  The composition 20 includes 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 as 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 stirrer, a kneader, or a mixer may be used. Also, after mixing, air bubbles may be removed from the composition 20 using an air bubble removing device.

  In the case where the photopolymerization initiator is difficult to mix with the photocurable resin, it is preferable to perform hot water boiling after the mixing and further to perform ultrasonic agitation. The boiling and ultrasonic agitation may be alternately repeated. The hot water temperature is appropriately set according to the types of the photopolymerization initiator and the photocurable resin.

  The particles of at least one selected from the group consisting of ceramics, metals and metal compounds may be subjected to a granulation treatment by a ball mill, bead mill or the like before mixing. By subjecting to the particle disaggregation treatment, it becomes possible to form a more uniform nano-sized concavo-convex 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. It is further preferred that
The viscosity of the composition is a value as measured according to JIS Z8803: 2011.

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

  The composition 20 described above is applied to a target article 10 or a mold 30. The mold 30 is not particularly limited as long as it has at least one of a recess and a protrusion on its surface.

  Examples of the target article 10 include an electrode or an electrolyte of a fuel cell, a dielectric or an electrode of a capacitor, a superconducting magnet, a superconducting electrode, a friction sliding surface, a tool, an actuator, a sensor, a catalyst, and the like. The surface of the target article 10 on which the unevenness is formed 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 composites of graphite and carbon nanotubes; single crystal silicon (Si), polysilicon (α-Si), silicon carbide (SiC), silicon nitride ( Semiconductor materials such as SiN); and metal materials such as nickel (Ni), aluminum (Al), tungsten (W), tantalum (Ta), copper (Cu) and the like. 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 a 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 comprising carbon atoms, oxygen atoms and hydrogen atoms is used as the photocurable resin, the replica mold is preferably also composed of a resin comprising carbon atoms, oxygen atoms and hydrogen atoms, and photocured In the case of using a photocurable resin composed of carbon atom, nitrogen atom, oxygen atom and hydrogen atom as the hydrophobic resin, it is preferable that the replica mold is also composed of resin composed of carbon atom, nitrogen atom, oxygen atom and hydrogen atom . A replica mold of such a material tends not to poison the fuel cell when the resulting molded product is used for the fuel cell.

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

  From the viewpoint of enhancing the flexibility of the replica mold to suppress the occurrence of mold release defects, the resin used for the replica mold may be epoxy ester. As an epoxy ester, the compound whose X in the above-mentioned General formula (1) is a bivalent group containing a (poly) alkylene oxy group can be mentioned.

  In the case where the composition 20 is cured by irradiating light from the mold 30 side in the subsequent photocuring step, the material of the mold 30 preferably transmits light of the wavelength used for curing.

  The diameter of the recess or protrusion of the mold 30 may be 50 μm or less. The manufacturing method of the present invention may be nano-order (1 to 99 nm) because it can be microfabricated, but it is not necessarily limited to this. Even if it is sub-micron order (100 to 999 nm), micron order (1 μm to 1 μm) 99 μm).

  The ratio (aspect ratio) of the height to the diameter of the concave or convex portion of the mold 30 may be any, and the production method of the present invention has an aspect ratio of 2 or more because the retentivity of the concavo-convex shape is high. Is also possible. The aspect ratio can be designed appropriately 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 applying the release treatment, the mold 30 can be easily peeled off from the cured product 22. As the releasing agent, those generally known can be used, and a fluorine compound, a silane coupling agent, a surfactant and the like can be mentioned.

  The method for 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, screen printing method, printing method such as gravure printing method, brush coating method, doctor blade method, roll coating method, etc. may be mentioned. From the viewpoint of increasing the area, it is preferable that the method 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 surface of both the mold 30 and the target article 10, and the concavo-convex pattern of the mold 30 is transferred to the composition 20.

  The pressing method is not particularly limited, and a method of simply pressing the target article 10 and the mold 30 to each other, a method of pressing by sandwiching two flat plates, and the like can be mentioned.

The pressing force is preferably 100 kPa to 50 MPa, and more preferably 1 MPa to 10 MPa.
When the pressing force is 100 kPa or more, the composition 20 can easily enter to the end of the unevenness of the mold 30, and when it is 50 MPa or less, breakage of the mold 30 can be easily suppressed.

The pressing time is preferably 10 seconds to 1 hour, and more preferably 3 minutes to 10 minutes.
If the pressing time is 10 seconds or more, the composition 20 easily enters the tips of the irregularities of the mold 30. If the pressing time is 1 hour or less, the composition 20 tends to be excessively dried to deteriorate the fluidity. It is in.

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

  The light to be irradiated is selected to have a wavelength that 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. Specifically, it is preferable to use light of a wavelength of more than 400 nm, and it is preferable to use light of 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 emitted 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 mold 30 is removed and then the light is irradiated.

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 light curing process (FIG. 1 (D)).
The removed mold 30 can be reused by removing the composition 20 if the composition 20 remains on the surface. The removal method of the composition 20 from the mold 30 includes a method of immersing in a solvent to dissolve the photocurable resin in the composition 20 and the like. The mold 30 after being immersed in a solvent is preferably dried to remove the solvent.

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

Further, after the mold 30 is removed, the composition 20 may be further applied before the next sintering step (FIG. 1 (E)). Furthermore, the composition 20 used at the time of application may be the same as or different from the composition 20 used at the first time. Examples of the different compositions 20 include those having different types and amounts of photocurable resins, and those having different types and amounts of at least one particle selected from the group consisting of ceramics, metals and metal compounds.
The use of compositions with different components enables application to the production of moldings of various technical fields, for example, a laminate of a ceramic electrolyte and an electrode in SOFC, a composite electrode of SOFC (for example, GDC and LSC) Molded articles in various technical fields such as electrodes) can be produced.

Furthermore, when the application position of the composition 20 to be applied is on the cured product 22, a cured product of the laminate can be obtained.
Further, when the application position of the composition 20 to be further applied is 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, if different compositions of components are used, it is possible to form different patterns of components on one surface.

  And when using two or more compositions, in the conventional method, it is necessary to perform sintering which sinters every time it applies a composition, but according to the method of the present invention, it bakes collectively. As it is possible to obtain a molded product, it is possible to produce it at low cost and with high throughput.

  In addition, since the method of the present invention can be prepared by batch sintering, the number of steps taken out from the sintering furnace is reduced as compared with the conventional method in which sintering is performed each time the composition is applied. The occurrence can be suppressed. Therefore, for example, according to the method of the present invention, since each layer in a molded article having a laminated structure can be thinned, a highly deformable piezoelectric actuator 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 etc. can be used for sintering.
The sintering temperature and the sintering time (holding time at the maximum temperature) are appropriately set according to the type of particles of the ceramic, metal and metal oxide to be used. For example, in the case of GDC particles, the temperature is preferably 1100 ° C. or more to 1700 ° C., and more preferably 1400 ° C. to 1550 ° C. from the viewpoint of the strength of the resulting molded article 100.
The sintering time may be, for example, 60 minutes to 5 hours, or 120 minutes to 3 hours.

  The atmosphere conditions in the sintering step are not particularly limited as long as the photocurable resin and the like burn and disappear. Sintering in air at normal pressure is preferable in terms of cost, but sintering may be performed in gas pressure such as hot isostatic pressing (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 or convex portion can be 50 μm or less, can be submicron order (100 to 999 nm), or can be nanoorder (1 to 99 nm).
Further, the ratio (aspect ratio) of the depth or height to the diameter of the recess or the protrusion can be 2 or more.
The diameters of the recesses and protrusions and the aspect ratio can be measured with an electron microscope.

<Molded item>
The molded product has, on at least a part of the surface, at least one of a recess and a protrusion formed of at least one selected from the group consisting of ceramics, metals and metal compounds. 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 (aspect ratio) of the depth or height to the diameter of the recess or the protrusion is 2 or more. Is possible. In addition, the diameter of the recess or the protrusion can be 50 μm or less, can be submicron order (100 to 999 nm), and can be nanoorder (1 to 99 nm).

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples.

Example 1
1. Preparation of resin component 4% by mass of IRGACURE 369 (BASF Japan Ltd.) is added to 96% by mass of 1,6-hexanediol diacrylate (viscosity: 7.0 mPa · s) and mixed, and then hot water roasting at 80 ° C. Ultrasonic agitation was performed. The water component and ultrasonic agitation were alternately repeated 5 times to prepare a resin component.

2. Confirmation of Resolution of Resin Component The prepared resin component does not contain particles. The resolution of this resin component was confirmed.
The resin component is applied to a mold having a plurality of concave portions with a diameter of 200 nm, and light of a wavelength of 300 nm to 450 nm is exposed at a dose of 4.5 J using a UV irradiation device (Lamp system SPOT type ultraviolet curing device manufactured by Panasonic Corporation, Aicure UP 50). Irradiated at / cm ² 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 FIG. 3 and FIG. 4, in the cured product of only the resin component to which no particle is added, a pattern with a diameter of 200 nm was transferred. This resin component was found to have sufficient resolution.

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

4. Confirmation of Curability of Composition With respect to the obtained composition, it was confirmed whether the composition was cured using a UV lamp of wavelength 300 nm to 450 nm. The irradiation time was 30 seconds, and the exposure was performed at an illuminance of 75 lx and an irradiation amount of 2.25 J / cm ² .
As shown in FIG. 5, the composition was sufficiently cured, and the shape did not change even when pressed and touched with a spatula, and the shape retention was excellent. This composition contains GDC particles having absorption in the ultraviolet wavelength range, but was found to cure sufficiently in a UV lamp.

5. Preparation of replica mold On the surface, 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 a release treatment with platinum and a fluorine compound. An epoxy resin-based negative photoresist SU-8 3025 (trade name, manufactured by Nippon Kayaku Co., Ltd.) was applied to the release-treated master mold. And the light of wavelength 300nm-400nm was exposed using UV irradiation apparatus (The Panasonic Corporation make, lamp system SPOT type | mold ultraviolet curing device Aicure UP50). The exposure time was 1 minute, the illuminance was 75 lx, 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. Release Process of Replica Mold The obtained replica mold was coated with platinum using a sputtering apparatus (ESC 101, manufactured by Elionix Co., Ltd.). On top of this, a mold release agent (manufactured by Daikin Industries, Ltd., product name OPTOOL, containing 1% by mass of a fluorine compound) was applied, heated at 85 ° C. for 2 hours, and then rinsed with water for 30 minutes.

7. Application and curing One drop of the composition prepared above was dropped onto the replica mold subjected to release treatment, and the glass plate was pressed from above. In this state, light with a wavelength of 300 nm to 450 nm was irradiated by a UV lamp. The irradiation time was 10 minutes, the illuminance was 75 lx, and the irradiation amount was 45 J / cm ² . After light irradiation, the replica mold was removed.

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

9. Observation FIGS. 6 and 7 show planar SEM images of the calcined material. As shown in FIGS. 6 and 7, a pattern with a diameter of 2 μm was confirmed. Since the interparticle distance is about several hundred nm, it is believed that crystal growth will sinter.

  FIG. 8 is a graph showing the results of measuring the cross-sectional shape of the calcined material 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 concavo-convex shape on the order of 10 μm required to increase the efficiency of SOFC can be formed.

Example 2
(Formation of uneven shape on curved surface)
A replica mold was produced in the same manner as in Example 1 except that a master mold having a pillar pattern with 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.
The planar optical microscope image of the replica mold produced in FIG. 9 is shown. As shown in FIG. 9, a pattern of recesses of 10 μm in diameter was formed on the replica mold.

  As shown in FIG. 10 (A), the composition prepared in Example 1 was applied to the curved surface arrow (→) on the outer surface of a cylinder with a diameter of 30 mm, and a pillar pattern was formed using the prepared replica mold. Transfer and cure in the same manner as Example 1.

  FIG. 10 (B) is a planar optical microscope image of a cured product formed on a cylinder. As shown in FIG. 10B, a pillar pattern with a diameter of 10 μm was formed on the curved surface.

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

[Example 3]
(Preparation of electrode sample)
A replica mold was produced in the same manner as in Example 1 except that a master mold having a pillar pattern with a diameter of 50 μm, a depth of 15 μm, and a pitch interval of 100 μm was used, and a mold release treatment was performed. One drop of the composition prepared in Example 1 was dropped onto the replica mold subjected to the release treatment, and the YSZ plate (manufactured by Tosoh Corp., diameter 24 mm, thickness 0.5 mm) was pressed thereon. In this state, light with a wavelength of 300 nm to 450 nm was irradiated by a UV lamp from the replica mold side. The irradiation time was 10 minutes, the illuminance was 75 lx, and the irradiation amount was 45 J / cm ² . After light irradiation, the replica mold was removed to obtain a cured product. Thereafter, calcination was performed at 300 ° C. for 60 minutes, and sintering was performed 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 appearance photograph of the obtained sintered product, and FIG. 14 shows its plane laser microscope image. The patterned part was sintered and integrated with the YSZ plate.
FIG. 15 is a graph showing the results of measuring the cross-sectional shape of the sinter with a laser microscope.
The height of the pattern was about 11 μm and the diameter was 50 μm. A large shrinkage of the pattern due to sintering was not confirmed, and a good shape was obtained.

  16 to 18 are planar SEM images in which FIG. 14 is enlarged. The image of FIG. 17 can confirm the crystal growth of GDC particles. In FIG. 18, it can be confirmed that the grown crystals are sticking to each other. From this result, it is understood 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 appearance of crystals was confirmed from the enlarged SEM image, it was found to be similar to the above sample and to be highly reproducible.

Example 4
A sinter was produced in the same manner as in Example 3 except that a master mold having a pillar pattern with a diameter of 10 μm, a depth of 15 μm and a pitch of about 25 μm was used.
FIG. 19 shows a planar laser microscope image of the obtained sinter. As shown in the image of FIG. 19, even in the pillar pattern having a diameter of 10 μm, a 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 sinter 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 expanded.

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 part is a GDC crystal, and the reproducibility of the sintered pattern is high.
FIG. 22 is a planar SEM image obtained by enlarging FIG. FIG. 23 is a perspective SEM image. FIG. 24 is a perspective SEM image obtained by further enlarging FIG. 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, in the same manner as in Example 3, a cured product (1) (hereinafter also referred to as a GDC pattern layer) having a pattern on its surface was produced on a YSZ plate.
Then, 60 mass% of LSCF particles and 40 mass% of the resin component prepared in Example 1 were mixed to obtain a slurry composition.
One drop of the composition obtained is dropped on the GDC pattern layer and pressed with a PET film, and then a wavelength of 300 nm to 450 nm is obtained using a UV irradiation device (Lamp system SPOT type UV curing device Aicure UP50 manufactured by Panasonic Corporation). Was irradiated at an exposure dose of 45 J / cm ² . Thereby, a layered product in which a layered cured product (2) (hereinafter also referred to as an LSCF layer) containing LSCF particles was formed on the GDC pattern layer was obtained.

FIG. 25 is a planar optical microscope image of the obtained laminate, in which a part of the LSCF layer is removed and a part of the GDC pattern layer therebelow is also removed to expose each layer. Moreover, FIG. 26 is a cross-sectional optical microscope image when the YSZ plate is peeled and observed for ease of observation. FIG. 27 is a view for explaining the observation direction of FIGS. 25 and 26. FIG.
As shown in FIGS. 25 and 26, the LSCF layer was formed on the GDC pattern layer.

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

[Reference Example 1]
In Example 5, by replacing the LSCF particles used for the cured product (2) with ceramic particles, it is possible to produce a formed product in which a ceramic electrolyte and an electrode having a pattern are laminated by batch sintering. .

10 target articles 20 compositions 30 molds 40 electric furnace 100 moldings

Claims (20)

A method for producing a molded article 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 a target article,
A mold containing a photocurable resin and at least one particle selected from the group consisting of a ceramic, a metal and a metal compound on the surface of at least one of the target article or the concave and convex portions on a surface thereof The step of applying
Pressing the target article and the mold through the composition;
Photocuring the pressed composition;
Sintering the photocured composition;
A method for producing a molded article, comprising: The particles may be gadolinium-doped ceria (GDC), ceria, samarium-doped ceria (SDC), yttria stabilized zirconia (YSZ), scandia stabilized zirconia (ScSZ), zirconia, lanthanum strontium cobalt ferrite (LSCF), lanthanum strontium cobaltite (LSC), samarium strontium cobaltite (SSC), lanthanum strontium manganite (LSM), lanthanum strontium cobalt manganite (LSCM), manganese cobalt spinel oxide (MCO), lanthanum strontium chromite (LSCr), gallium nitride, silicon carbide , tungsten carbide, alumina, titania, and selection than the group consisting of lanthanum gallate (LaGaO ₃₎ That comprises at least one method for producing a molded article according to claim 1.   The manufacturing method of the molded object of Claim 1 or Claim 2 in which the said composition further contains a photoinitiator.   The method for producing a molding according to claim 3, wherein the photopolymerization initiator is selected such that the absorption wavelength of the photopolymerization initiator does not overlap with the absorption wavelength of the particles contained in the composition.   The photopolymerization initiator is at least one of a radical polymerization initiator consisting of a carbon atom, an oxygen atom and a hydrogen atom, and a radical polymerization initiator consisting of a carbon atom, a nitrogen atom, an oxygen atom and a hydrogen atom. Or the manufacturing method of the molded object of 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-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, phenylglyoxylic acid methyl ester Ether, acetophenone, p- anisyl, benzyl, comprises at least one member selected from the group consisting of benzoin and benzophenone method for producing a molded article according to claim 5.   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 manufacturing method of the molded object of any one of-Claim 6.   The manufacturing method of the molded object of any one of Claims 1-7 in which the said photocurable resin contains at least one of a (meth) acrylic resin and an epoxy resin. The manufacturing method of the molded object of any one of Claims 1-8 in which the said photocurable resin contains the compound represented by following General formula (1).

[In 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 article according to claim 9, comprising a compound in which X is a divalent linear hydrocarbon group or a divalent group containing a (poly) alkyleneoxy group in the general formula (1). .   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 manufacturing method of the molded object of any one of Claims 1-11 whose viscosity of the said photocurable resin is 1.5 mPa * s-100 mPa * s.   The manufacturing method of the molded object of any one of Claims 1-12 whose diameter of the said recessed part of the said mold or the said convex part is 50 micrometers or less.   The manufacturing method of the molded article according to any one of claims 1 to 13, wherein a ratio (aspect ratio) of a depth or a height to a diameter of the recess or the protrusion of the mold is 2 or more. .   The method for producing a molded product according to any one of claims 1 to 14, wherein the mold is a replica mold copied from a master mold.   The target object is any one of an electrode or an electrolyte of a fuel cell, a dielectric or an electrode of a capacitor, a superconducting magnet, a superconducting electrode, a friction sliding surface, a tool, an actuator, a sensor, or a catalyst. The manufacturing method of the molding of any one of-.   The method for producing a molded article according to any one of claims 1 to 16, wherein a composition different from the component is further used as the composition.   The method for producing a formed article according to claim 17, wherein the composition having different components differs from the composition in type of at least one particle selected from the group consisting of ceramics, metals and metal compounds. Applying a composition different in the component to 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 curing to obtain a second cured product,
The manufacturing method of the molded object of Claim 17 or Claim 18 which sinters the said 1st hardened | cured material and the said 2nd hardened | cured material collectively.   At least a portion of the surface has at least one of a recess and a protrusion composed of at least one selected from the group consisting of ceramics, metals and metal compounds, and the depth or height relative to the diameter of the recess or protrusion A molded product having a aspect ratio (aspect ratio) of 2 or more.