JP5309848B2 - Manufacturing method of laminate - Google Patents

Description

  The present invention relates to a method for producing a laminate that can efficiently fill the pores of a porous substrate with a metal oxide and can form a metal oxide film having excellent surface smoothness and denseness.

  Conventionally, it has been known that metal oxide films exhibit various excellent physical properties. Taking advantage of these properties, metal oxide films have been used in a wide range of fields such as transparent conductive films, optical thin films, and fuel cell electrolytes. As a method for producing such a metal oxide film, for example, a sol-gel method, a sputtering method, a CVD method, a PVD method, a printing method, a laser ablation method and the like are known (for example, Patent Documents 1 to 3).

  On the other hand, a spray pyrolysis method has been proposed as another method for obtaining such a metal oxide film. The spray pyrolysis method is a method in which a metal oxide film is obtained by spraying a solution containing a metal source constituting the metal oxide film onto a high temperature substrate, and a substrate heated to about 500 ° C. is usually used. Since it is used, the solvent instantly evaporates and the metal source undergoes a thermal decomposition reaction, so that the metal oxide film can be obtained in a short and simplified process.

As a study of such spray pyrolysis method, for example, in Patent Document 4, a raw material solution is prepared by adding hydrogen peroxide or aluminum acetylacetonate to a solution containing a TiO ₂ precursor, and the temperature is as high as about 500 ° C. A method is disclosed in which a TiO ₂ precursor is thermally decomposed into TiO ₂ by intermittently spraying the raw material solution onto a held substrate to obtain a porous TiO ₂ thin film on the substrate.

JP 2002-348665 A JP-A-4-361239 JP-A-2005-213105 JP 2002-145615 A

  Conventionally, in the spray pyrolysis method, a method of injecting a metal oxide film perpendicularly to a substrate has been common. However, in such a method, when a porous base material is used, it may be difficult to fill the pores of the porous base material with a metal oxide, and a metal excellent in surface smoothness, denseness, etc. In some cases, an oxide film could not be obtained.

  The present invention has been made in view of the above problems, and can provide a metal oxide film that can efficiently fill the pores of a porous base material with a metal oxide and has excellent surface smoothness and denseness. The main object is to provide a method for manufacturing a laminate that can be formed.

  In order to solve the above-described problems, in the present invention, a porous substrate obtained by heating a metal oxide film forming solution in which a metal salt or an organometallic compound is dissolved as a metal source to a temperature equal to or higher than the metal oxide film forming temperature. The laminate is a method for producing a laminate in which a metal oxide film is formed on the porous substrate, and the injection direction of the metal oxide film forming solution is directed toward the porous substrate. And the manufacturing method of the laminated body characterized by inclining with respect to the normal line direction of the said porous base material surface is provided.

  According to the present invention, by inclining the injection direction of the metal oxide film forming solution to a predetermined angle, the pores of the porous substrate can be efficiently filled with the metal oxide, and surface smoothness and denseness can be achieved. A metal oxide film excellent in the above can be formed.

  In the said invention, it is preferable to incline the spray direction of the said metal oxide film formation solution 10 degrees or more with respect to the normal line direction of the said porous base material surface. This is because the pores of the porous substrate can be filled with the metal oxide more efficiently.

  In the said invention, it is preferable to inject the said metal oxide film formation solution in fan shape. This is because the pores of the porous substrate can be filled with the metal oxide more efficiently.

  In the present invention, the supporting means for supporting the porous substrate, the heating means for heating the porous substrate, and the metal oxide at a predetermined angle with respect to the normal direction of the surface of the porous substrate. There is provided an apparatus for manufacturing a laminate, characterized by having an injection unit for injecting a solution for forming a film.

  According to the present invention, by injecting the metal oxide film forming solution at a predetermined angle, the pores of the porous substrate can be efficiently filled with the metal oxide, and the surface smoothness and denseness can be improved. An excellent metal oxide film can be formed.

  In the present invention, the pores of the porous base material can be efficiently filled with the metal oxide, and the metal oxide film excellent in surface smoothness and denseness can be formed.

  Hereafter, the manufacturing method of the laminated body of this invention and the manufacturing apparatus of a laminated body are demonstrated in detail.

A. First, the manufacturing method of the laminated body of this invention is demonstrated. In the method for producing a laminate of the present invention, a metal oxide film forming solution in which a metal salt or an organometallic compound is dissolved as a metal source is sprayed onto a porous substrate heated to a temperature equal to or higher than the metal oxide film forming temperature. By this, it is a manufacturing method of the layered product which forms a metal oxide film on the above-mentioned porous substrate, and it is directed to the above-mentioned porous substrate side for the injection direction of the above-mentioned metal oxide film formation solution, and It is inclined with respect to the normal direction of the porous substrate surface.

  According to the present invention, by inclining the injection direction of the metal oxide film forming solution to a predetermined angle, the pores of the porous substrate can be efficiently filled with the metal oxide, and surface smoothness and denseness can be achieved. A metal oxide film excellent in the above can be formed. In particular, according to the present invention, a dense metal oxide film can be formed on a porous substrate. Therefore, for example, when an ITO film useful as a transparent electrode of a dye-sensitized solar cell is formed, the total light transmittance is improved by reducing the thickness of the transparent electrode layer and the adhesion to the substrate by smoothing the surface Improvements can be made. In addition, when a YSZ film useful as an electrolyte of a solid oxide fuel cell is formed, the thickness of the electrolyte can be reduced, and there is an advantage that the output of the battery can be increased.

Next, the manufacturing method of the laminated body of this invention is demonstrated using drawing. FIG. 1 is a schematic cross-sectional view showing an example of a method for producing a laminate according to the present invention. In the method for producing a laminate shown in FIG. 1, first, the porous substrate 1 is heated to a temperature equal to or higher than the metal oxide film formation temperature. Next, a metal oxide film forming solution (not shown) containing a metal source is sprayed onto the heated porous substrate 1 using the spray nozzle 2. At this time, the jetting direction D _a metal oxide film forming solution sprayed from the spray nozzle 2, toward the porous substrate 1 side, and, with respect to the normal direction D _b of the porous surface of the substrate 1 Tilt at an angle θ.

In the present invention, the injection direction of the metal oxide film forming solution is directed to the porous substrate side. Therefore, as shown in FIG. 1, the injection direction D _a of the metal oxide film-forming solution is usually directed to the lower side in the drawing with a porous substrate 1. On the other hand, when the injection direction of the metal oxide film forming solution is directed not to the porous substrate side but to the opposite side (the upper side of the drawing in FIG. 1), the metal oxide film forming solution is made into a mist. Thus, it is possible to form a metal oxide film, but such a case is usually not included in the present invention. This is because the injection directionality of the metal oxide film forming solution is lost, and the pores of the porous substrate cannot be filled efficiently.

Further, as will be described later, in the present invention, the metal oxide film forming solution may be sprayed in a fan shape using, for example, a flat spray nozzle. When a flat spray nozzle is used, as shown in FIG. 2, the metal oxide film forming solution 3 is sprayed in a fan shape with a predetermined angular spread. In this case, the direction of the injection axis D _c of the flat spray nozzle 2a, and the injection direction D _a of the metal oxide film-forming solution 3. Therefore, as shown in FIG. 3, a metal oxide film and the injection direction D _a of the forming solution 3, if the normal direction D _b of the porous substrate 1 is parallel, for example, a metal oxide in the region A even if it is injected in a state where the film-forming solution 3 is inclined with respect to the normal direction D _b of the porous substrate 1, not included in the present invention. In this invention, it is preferable that the injection direction of the solution for forming a metal oxide film is inclined with respect to the normal direction of the surface of the porous substrate in all directional components.

Further, in the present invention, the mechanism by which the pores of the porous substrate can be efficiently filled with the metal oxide is not yet known, but the surface of the porous substrate 1 as shown in FIG. hole 1a formed in the order it is expected that the diameter of the inner has a larger structure than the outermost surface, the jet direction D _a of the metal oxide film-forming solution, the porous substrate 1 by tilting with respect to the normal direction D _b of the surface, believed to be because the metal oxide 4a efficiently formed on the side surface of the hole 1a. As a result, as shown in FIG. 4 (b), the pores of the porous substrate 1b can be efficiently filled with the metal oxide, and the metal oxide film 4 excellent in surface smoothness and denseness is formed. I think it can be done. Note that the hole in FIG. 4 is greatly exaggerated and may differ from the actual one.
Hereinafter, the manufacturing method of the laminated body of this invention is demonstrated in detail for every structure.

1. Metal Oxide Film Forming Solution First, the metal oxide film forming solution used in the present invention will be described. The metal oxide film forming solution used in the present invention contains at least a metal source. Furthermore, a boron compound, an oxidizing agent, a reducing agent, an additive, and the like may be contained as necessary.

(1) Metal source First, the metal source used in the present invention will be described. The metal source used in the present invention is usually a metal salt or an organometallic compound. In the present invention, two or more kinds of metal sources may be used in combination.

  The metal element constituting the metal source is not particularly limited as long as a metal oxide film can be formed. For example, Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Ag, In, Sn, Ce, Sm, Pb, La, Hf, Sc, Gd, Ca, Cr, Ga, Sr, Nb, Mo, Pd, Sb, Te, Ba, Mention may be made of at least one metal element selected from the group consisting of W and Ta, among which Al, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, In, Sn, Ce and At least one metal element selected from the group consisting of La is preferred.

  The metal salt is not particularly limited as long as it can form a metal oxide film. For example, chlorides, nitrates, sulfates, perchlorates, acetates containing the above metal elements, A phosphate, a bromate, etc. can be mentioned. Among these, in the present invention, it is preferable to use chloride, nitrate, and acetate. This is because these compounds are easily available as general-purpose products. Specific examples of the metal salt include magnesium chloride, aluminum nitrate, aluminum chloride, calcium chloride, scandium acetate, titanium tetrachloride, vanadium oxosulfate, ammonium chromate, chromium chloride, ammonium dichromate, chromium acetate, chromium nitrate. , Chromium sulfate, manganese acetate, manganese nitrate, manganese sulfate, iron chloride (I), iron chloride (III), iron acetate (II), iron nitrate (III), iron sulfate (II), ammonium iron sulfate (III), chloride Cobalt, cobalt nitrate, cobalt acetate, nickel chloride, nickel nitrate, nickel acetate, copper chloride, copper nitrate, zinc chloride, zinc acetate, zinc chloride, yttrium nitrate, yttrium chloride, zirconium chloride, zirconium nitrate, zirconium tetrachloride, Silver chloride, silver acetate, indium chloride, indium acetate, chloride Tin, tin acetate, tin sulfate, cerium chloride, cerium acetate, cerium nitrate, cerium oxalate, diammonium cerium nitrate, cerium sulfate, samarium chloride, samarium nitrate, lead chloride, lead acetate, lead nitrate, lead iodide, phosphoric acid Lead, lead sulfate, lanthanum chloride, lanthanum acetate, lanthanum nitrate, gadolinium nitrate, strontium chloride, strontium acetate, strontium nitrate, niobium pentachloride, ammonium molybdate phosphate, molybdenum sulfide, palladium chloride, palladium acetate, palladium nitrate, pentachloride Antimony, antimony trichloride, antimony trifluoride, telluric acid, barium sulfite, barium chloride, barium chlorate, barium perchlorate, barium acetate, barium nitrate, tungstic acid, ammonium tungstate, tungsten hexachloride, five Tantalum, hafnium chloride, can be exemplified sulfuric hafnium.

  The organometallic compound is not particularly limited as long as it can form a metal oxide film, and specific examples include acetylacetonate complexes. Examples of the acetylacetonate-based complex include aluminum acetylacetonate, iron (III) acetylacetonate, nickel (II) acetylacetonate dihydrate, copper (II) acetylacetonate, zinc acetylacetonate, zirconium Tetraacetylacetonate, zirconium monoacetylacetonate, chromium (III) acetylacetonate, cobalt acetylacetonate, tris (acetylacetonato) indium (III), cerium acetylacetonate, lanthanum acetylacetonate, titanium acetylacetonate, Examples thereof include calcium acetylacetonate, molybdenyl acetylacetonate, and palladium acetylacetonate.

  Examples of organometallic compounds other than acetylacetonate complexes include magnesium diethoxide, calcium di (methoxyethoxide), calcium gluconate monohydrate, calcium citrate tetrahydrate, and calcium salicylate dihydrate. , Titanium lactate, tetraisopropyl titanate, tetranormal butyl titanate, tetra (2-ethylhexyl) titanate, butyl titanate dimer, titanium bis (ethylhexoxy) bis (2-ethyl-3-hydroxyhexoxide), diisopropoxy titanium bis (tri Ethanolaminate), dihydroxybis (ammonium lactate) titanium, diisopropoxytitanium bis (ethylacetoacetate), ammonium peroxocitrate tetrahydrate, dicyclopentadi Nyl iron (II), iron (II) lactate trihydrate, copper (II) dipivaloylmethanate, copper (II) ethyl acetoacetate, zinc lactate trihydrate, zinc salicylate trihydrate, stearic acid Zinc, strontium dipivaloylmethanate, yttrium dipivaloylmethanate, zirconium tetra-n-butoxide, zirconium (IV) ethoxide, zirconium normal propylate, zirconium normal butyrate, zirconium acetylacetonate bisethylacetoacetate, Zirconium acetate, zirconium monostearate, penta-n-butoxy niobium, pentaethoxy niobium, pentaisopropoxy niobium, indium (III) 2-ethylhexanoate, tetraethyl tin, dibutyl tin oxide (IV), tricyclohexyl tin (IV) Hydroxide, Li (methoxyethoxy) lanthanum, pentaisopropoxytantalum, pentaethoxytantalum, tantalum (V) ethoxide, lead (II) citrate trihydrate, lead cyclohexanebutyrate, gallium (III) trifluoromethanesulfonate, strontium dipivalo Ilmethanate and the like can be mentioned.

  The concentration of the metal source in the metal oxide film forming solution is not particularly limited, but for example, within the range of 0.001 to 1 mol / l, particularly within the range of 0.01 to 0.5 mol / l. Preferably there is. This is because if the concentration is within the above range, the metal oxide film can be formed in a relatively short time.

  In the present invention, it is also possible to add a doping metal source for the purpose of doping the metal oxide film. A functional metal oxide film can be obtained by using a doping metal source.

  The kind of the doping metal source is preferably selected as appropriate according to the kind of the target metal oxide film. For example, when obtaining a yttria-stabilized zirconia film (YSZ film) useful as an electrolyte of a solid oxide fuel cell, a metal source having a yttrium element is used as a doping metal source in addition to a metal source having a zirconium element. Specific examples of the metal source having an yttrium element include yttrium nitrate hexahydrate. That is, in the present invention, the metal source is preferably a combination of a zirconium-containing metal source containing a zirconium element and an yttrium-containing metal source containing an yttrium element. This is because a desired YSZ film can be obtained. As described above, the zirconium-containing metal source may be a metal salt containing a zirconium element or an organometallic compound containing a zirconium element, and among them, an organic metal containing a zirconium element. A compound is preferred. Particularly in the present invention, the zirconium-containing metal source is preferably zirconium tetraacetylacetonate. The yttrium-containing metal source is not particularly limited as long as it contains an yttrium element. As described above, it may be a metal salt containing an yttrium element, or an organic metal containing an yttrium element. A compound may be used, but among them, a metal salt containing an yttrium element is preferable. Particularly in the present invention, the yttrium-containing metal source is preferably yttrium nitrate. The ratio of the zirconium-containing metal source and the yttrium-containing metal source contained in the metal oxide film forming solution is not particularly limited as long as a desired YSZ can be obtained. In this case, the yttrium-containing metal source is preferably in the range of 3 to 30, more preferably in the range of 5 to 20, in terms of mole.

  In the present invention, the metal source is preferably a combination of an indium-containing metal source containing an indium element and a tin-containing metal source containing a tin element. The indium-containing metal source is not particularly limited as long as it contains an indium element. As described above, the indium-containing metal source may be a metal salt containing an indium element, or an organic metal containing an indium element. A compound may be used, but among them, a metal salt containing an indium element is preferable. In particular, in the present invention, the indium-containing metal source is preferably indium nitrate. On the other hand, the tin-containing metal source is not particularly limited as long as it contains a tin element, and as described above, it may be a metal salt containing a tin element, and contains a tin element. An organic metal compound may be used, but among them, a metal salt containing a tin element is preferable. In particular, in the present invention, the tin-containing metal source is preferably tin chloride.

(2) Solvent The solvent used in the present invention is not particularly limited as long as it can dissolve the above-described metal source. For example, water; methanol, ethanol, isopropyl alcohol, propanol, butanol, etc. Lower alcohols having a total carbon number of 5 or less; toluene; diketones such as acetylacetone, diacetyl, and benzoylacetone; ketoesters such as ethyl acetoacetate, ethyl pyruvate, ethyl benzoylacetate, and ethyl benzoylformate; and mixed solvents thereof Can be mentioned. Among these, water, methanol, ethanol, acetone, toluene, acetylacetone or a mixed solvent thereof is preferable. In the present invention, it is preferable to use at least one of the diketones and the ketoesters as all or part of the solvent. This is because the film forming property is improved.

(3) Boron compound Next, the boron compound used for this invention is demonstrated. In the present invention, the metal oxide film forming solution may contain a boron compound. By adding a boron compound, the crystallinity of the resulting metal oxide film can be reduced. As a result, the generation of grain boundaries can be suppressed, and a metal oxide film excellent in adhesion and unevenness followability can be obtained.

  The boron compound is not particularly limited as long as it can reduce the crystallinity of the metal oxide film, but it is preferable that the boron compound has no metal element. This is because the metal element derived from the boron compound can be prevented from being taken into the metal oxide film. Specific examples of the boron compound include boric acid, boron trifluoride-diethyl ether, lithium tetraborate, potassium borohydride, sodium borohydride, lithium tetrafluoroborate, tris (dimethylamino) boron, Examples thereof include triisopropyl borate, sodium peroxoborate tetrahydrate, and tetrafluoroboric acid. Among them, boric acid, boron trifluoride-diethyl ether, tris (dimethyl) are used from the viewpoint of having no metal element. Amino) boron, triisopropyl borate, and tetrafluoroboric acid are preferable, and boric acid is particularly preferable. This is because the crystallinity of the metal oxide film can be reduced more effectively.

It is known that boric acid (H ₃ BO ₃ ) becomes boron oxide (B ₂ O ₃ ) when heated to about 300 ° C. Although the detailed principle is not clear, from some experiments, this boron oxide may be an important factor for reducing the crystallinity of the metal oxide film. From such a viewpoint, the boron compound is preferably a compound that generates boron oxide when it comes into contact with a heated porous substrate.

  The concentration of the boron compound contained in the metal oxide film forming solution is not particularly limited as long as it is a concentration that can reduce the crystallinity of the metal oxide film. For example, 0.01 mol / l or more In particular, it is preferably in the range of 0.05 to 1 mol / l, particularly preferably in the range of 0.1 to 0.5 mol / l.

(4) Additive The solution for forming a metal oxide film used in the present invention may contain an additive such as a surfactant. The surfactant acts on the interface between the metal oxide film forming solution and the porous substrate. By using the surfactant, the contact area between the metal oxide film forming solution and the porous substrate can be improved, and a uniform metal oxide film can be obtained. In addition, it is preferable to select and use the usage-amount of the said surfactant suitably according to the metal source etc. to be used.

  Examples of the surfactant include Surfinol 485, Surfinol SE, Surfinol SE-F, Surfinol 504, Surfinol GA, Surfinol 104A, Surfinol 104BC, Surfinol 104PPM, Surfinol 104E, Surfinol. Examples include Surfinol series such as Nord 104PA (all manufactured by Nissin Chemical Industry Co., Ltd.), NIKKOL AM301, NIKKOL AM313ON (all manufactured by Nikko Chemical Co., Ltd.), and the like.

2. Next, the porous substrate used in the present invention will be described. The material of the porous substrate used in the present invention is not particularly limited as long as it has heat resistance to the above heating temperature. For example, glass, SUS, metal, ceramics, heat resistant plastic, etc. Among them, glass, SUS, metal, and ceramic are preferable. This is because it is versatile and has sufficient heat resistance.

The average pore diameter of the porous substrate is, for example, preferably in the range of 1 nm to 500 μm, and more preferably in the range of 10 nm to 100 μm. The average pore diameter of the porous substrate is measured by using a fully automatic gas adsorption amount measuring device (AUTOSORB-1-AG, manufactured by Yuasa Ionics Co., Ltd.), using N ₂ gas as a carrier gas, and measuring at 77K. Can be sought. Moreover, when the average pore diameter of a porous member exceeds 200 nm, it can measure with a mercury porosimeter (PoreMaster, Yuasa Ionics).

  Moreover, the film thickness of a porous base material is not specifically limited, It is preferable to select suitably according to the use of a laminated body.

3. Method for forming metal oxide film In the present invention, a metal oxide film forming solution is sprayed onto a porous base material heated to a temperature equal to or higher than the metal oxide film forming temperature, whereby a metal is formed on the porous base material. An oxide film is formed.

  In the present invention, the “metal oxide film forming temperature” refers to a temperature at which a metal element contained in a metal source can combine with oxygen and form a metal oxide film on a porous substrate. It depends on the composition of the metal oxide film forming solution such as the source and the solvent. In the present invention, such “metal oxide film formation temperature” can be measured by the following method. That is, a solution for forming a metal oxide film actually containing a desired metal source is prepared, and this metal oxide film forming solution is brought into contact with the porous substrate while changing the heating temperature. Measure the lowest heating temperature that can be formed. This minimum heating temperature can be used as the “metal oxide film forming temperature” in the present invention. At this time, whether or not the metal oxide film is formed is usually judged from the result obtained from an X-ray diffraction apparatus (Rigaku, RINT-1500). In the case of an amorphous film having no crystallinity, photoelectron spectroscopy is performed. It shall judge from the result obtained from the analyzer (the product made by VG Scientific, ESCALAB 200i-XL).

  As described above, the metal oxide film formation temperature varies depending on the type of the metal source used, but is usually in the range of 200 to 600 ° C. In the present invention, the heating temperature of the porous substrate is not particularly limited as long as it is a temperature equal to or higher than the metal oxide film formation temperature. For example, the metal oxide film formation temperature + 300 ° C. or lower, especially metal It is preferable that the oxide film formation temperature + 200 ° C. or lower, particularly the metal oxide film formation temperature + 100 ° C. or lower. The heating temperature of the porous substrate is usually in the range of 300 to 600 ° C.

  Examples of the method for heating the porous substrate include a method using a hot plate, an oven, a baking furnace, an infrared lamp, a hot air blower, etc., among which a method capable of maintaining the temperature of the porous substrate is preferable. Specifically, a method using a hot plate is preferable.

Next, a method for spraying the metal oxide film forming solution will be described. In the present invention, as shown in FIG. 1 described above, the injection direction D _a of the metal oxide film-forming solution, toward the porous substrate 1 side, and the normal direction D of the porous surface of the substrate 1 Tilt to _b . In the present invention, the injection direction of the metal oxide film forming solution is preferably inclined by 10 ° or more, more preferably by 20 ° or more, more preferably by 30 ° or more with respect to the normal direction of the surface of the porous substrate. It is more preferable to tilt. On the other hand, in the present invention, the injection direction of the metal oxide film forming solution is preferably inclined at 90 ° or less and more preferably at 80 ° or less with respect to the normal direction of the porous substrate surface. . This is because the pores of the porous substrate can be more efficiently filled with the metal oxide within the above range.

  In the present invention, the metal oxide film forming solution is usually sprayed using a spray device. The type of spray nozzle provided in the spray device is not particularly limited as long as it can spray the metal oxide film forming solution at a predetermined angle. For example, a flat spray nozzle, a slit nozzle, etc. Can be mentioned.

  In the present invention, the metal oxide film forming solution sprayed from the spray nozzle preferably has a smaller droplet diameter. This is because if the diameter of the droplet is small, the solvent of the metal oxide film forming solution is instantly evaporated, and the temperature drop of the porous substrate can be suppressed. The diameter of the droplet is, for example, preferably in the range of 0.01 μm to 1000 μm, and more preferably in the range of 0.1 μm to 300 μm.

  Moreover, the spray device may inject the solution with pressure, or may inject the solution with an injection gas. The propellant gas is not particularly limited as long as it does not hinder the formation of the metal oxide film, and examples thereof include air, nitrogen, argon, helium, oxygen, etc. Among them, nitrogen, which is an inert gas, Argon and helium are preferred. Further, the injection amount of the metal oxide film forming solution is, for example, preferably in the range of 0.01 to 50 L / min, and more preferably in the range of 0.05 to 1 L / min.

  In the present invention, it is preferable to relatively move at least one of the spray nozzle and the porous substrate when injecting the metal oxide film forming solution. This is because a metal oxide film having a more uniform thickness can be formed. Specifically, the spray nozzle may be fixed and the porous substrate may be moved, or the spray nozzle may be moved and the porous substrate may be fixed. Both the spray nozzle and the porous substrate are different from each other. It may be moved by movement.

4). Others In the method for producing a laminate of the present invention, the obtained metal oxide film may be washed. By cleaning the metal oxide film, impurities present on the surface of the metal oxide film can be removed. Specific examples include a method of washing using a solvent used in the metal oxide film forming solution.

B. Next, the manufacturing apparatus of the laminated body of this invention is demonstrated. The laminate manufacturing apparatus of the present invention includes a supporting means for supporting a porous substrate, a heating means for heating the porous substrate, and a predetermined angle with respect to a normal direction of the surface of the porous substrate. And a spraying means for spraying the metal oxide film forming solution.

  According to the present invention, by injecting the metal oxide film forming solution at a predetermined angle, the pores of the porous substrate can be efficiently filled with the metal oxide, and the surface smoothness and denseness can be improved. An excellent metal oxide film can be formed.

FIG. 5 is a schematic cross-sectional view showing an example of the laminate manufacturing apparatus of the present invention. Apparatus for producing a laminate shown in FIG. 5 and the support means 11 for supporting the porous substrate 1, a heating means 12 for heating the porous substrate 1, the normal direction D _b of the porous surface of the substrate 1 On the other hand, it has an injection means 13 having a spray nozzle 2 for injecting a metal oxide film forming solution (not shown) at a predetermined angle θ.

  The support means in the present invention is not particularly limited as long as it is a means capable of supporting the porous substrate. Moreover, the support means may have a function of a heating means described later. Further, the support means may have a movement means that can move freely.

  The heating means in the present invention is not particularly limited as long as it can heat the porous substrate. About a heating means, since it is the same as the means used with the heating method of the porous base material described in said "A. Manufacturing method of a laminated body", description here is abbreviate | omitted.

  The spraying means in the present invention usually has a spray nozzle for spraying a metal oxide film forming solution. The spraying unit may include an angle adjusting unit that adjusts the angle of the spray nozzle, an angle changing unit that continuously changes the angle of the spray nozzle, and a movable unit that can move freely.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be specifically described with reference to examples.

[Example 1-1]
(Preparation of porous substrate)
First, TiO ₂ fine particles having a primary particle diameter of 50 nm (P25 manufactured by Nippon Aerosil Co., Ltd.), acetylacetone and polyethylene glycol (average molecular weight 3000) were prepared. Next, these were dissolved and dispersed in water and isopropyl alcohol by a homogenizer to prepare a slurry of 37.5 wt% TiO ₂ fine particles, 1.25 wt% acetylacetone, and 1.88 wt% polyethylene glycol. Next, the slurry was applied onto a glass substrate with a doctor blade and allowed to stand at room temperature for 20 minutes, and then the slurry was dried at 100 ° C. for 30 minutes. Next, the dried slurry application member was placed in an electric muffle furnace (P90 manufactured by Denken) and baked at 500 ° C. for 30 minutes in an atmospheric pressure atmosphere. This obtained the porous base material. When the surface roughness of the porous substrate was measured using an atomic force microscope (AFM, Nanopics (manufactured by SII)), Ra = 1 μm.

(Production of laminate)
Indium nitrate (manufactured by Kanto Chemical Co., Inc.) and tin chloride (manufactured by Kanto Chemical Co., Ltd.) are dissolved in an ethanol solvent to form metal oxide films so that the respective concentrations are 0.1 mol / liter and 0.0052 mol / liter. A solution was prepared. Next, an airless spray (A74 airless auto gun, cross cut nozzle (flat spray nozzle) 1/15, spray liquid pressure) on a porous substrate heated to 500 ° C. is applied to a metal oxide forming solution (500 ml). 2 MPa, manufactured by Nordson). At this time, the angle θ between the spraying direction of the metal oxide film forming solution and the normal direction of the porous substrate surface was 10 °. This obtained the laminated body which has a porous base material and a metal oxide film.

[Example 1-2]
A laminated body was obtained in the same manner as in Example 1-1 except that the angle θ was 30 °.

[Example 1-3]
A laminate was obtained in the same manner as in Example 1-1, except that the angle θ was 45 °.

[Example 1-4]
A laminated body was obtained in the same manner as in Example 1-1 except that the angle θ was 60 °.

[Example 1-5]
A laminate was obtained in the same manner as Example 1-1 except that the angle θ was 90 °.

[Comparative Example 1]
A laminated body was obtained in the same manner as in Example 1-1 except that the angle θ was set to 0 °.

[Evaluation 1]
The surface roughness (Ra) of the laminates obtained in Example 1-1 to Example 1-6 and Comparative Example 1 and the film thickness of the metal oxide film were measured. The surface roughness (Ra) of the laminate was measured using an atomic force microscope (AFM, Nanopics (manufactured by SII)). The thickness of the metal oxide film was measured by observing a cross-sectional photograph with a scanning electron microscope (SEM). The results are shown in Table 1.

  As shown in Table 1, Example 1-1 to Example 1-6 obtain a metal oxide film having a smaller surface roughness and superior surface smoothness, denseness, and the like compared to Comparative Example 1. I was able to.

[Example 2]
Zirconium tetraacetylacetonate (manufactured by Kanto Chemical Co., Inc.), yttrium nitrate (manufactured by Kanto Chemical Co., Ltd.) and boric acid (manufactured by Kanto Chemical Co., Ltd.) were added at respective concentrations of 0.2 mol / liter, 0.061 mol / liter and 0.001. A metal oxide film forming solution was prepared by dissolving in a mixed solvent of toluene: ethanol: acetylacetone = 50: 25: 25 so as to be 1 mol / liter. And metal on the porous substrate (fuel cell fuel electrode, manufactured by Nippon Fine Ceramics Co., Ltd., samarium-doped ceria & nickel oxide porous member, average pore diameter 1 μm, thickness 800 μm, average particle diameter 1 μm) heated to 500 ° C. Using an airless spray (A74 airless auto gun, cross-cut nozzle (flat spray nozzle) 1/12, injection fluid pressure 2 MPa, manufactured by Nordson), the oxide film forming solution (1000 ml) was applied to the surface of the porous substrate. Injected at an angle of 45 ° with respect to the normal direction. Thereby, the laminated body which has the metal oxide electrolyte membrane (thickness on a porous base material: 3 micrometers) which consists of YSZ on a porous base material was obtained.

[Comparative Example 2]
A laminate was obtained in the same manner as in Example 2 except that the spray angle of the airless spray was not tilted (vertically downward) with respect to the normal direction of the porous substrate surface.

[Evaluation 2]
The YSZ film surfaces of the laminates obtained in Example 2 and Comparative Example 2 were observed using a scanning electron microscope (SEM). The result is shown in FIG. As shown in FIG. 6, the YSZ film obtained in Example 2 has a reduced grain boundary and excellent surface smoothness and denseness compared to the YSZ film obtained in Comparative Example 2. It was a membrane. This is considered to be because the film growth in the planar direction was promoted by spraying the metal oxide film forming solution from an oblique direction. In addition, by injecting the metal oxide film forming solution obliquely, the pores of the porous substrate could be filled efficiently, and a YSZ film having a small film thickness and high density could be formed. .

It is a schematic sectional drawing which shows an example of the manufacturing method of the laminated body of this invention. It is a perspective view explaining the manufacturing method of the laminated body of this invention. It is a perspective view explaining the manufacturing method of the conventional laminated body. It is a schematic sectional drawing explaining the laminated body obtained by this invention. It is a schematic sectional drawing which shows an example of the manufacturing apparatus of the laminated body of this invention. It is a SEM photograph of the metal oxide film obtained by the Example and the comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Porous base material 1a ... Hole 2 ... Spray nozzle 2a ... Flat spray nozzle 3 ... Metal oxide formation solution 4 ... Metal oxide film 4a ... Metal oxide 11 ... Support means 12 ... Heating means 13 ... Injection means

Claims (3)

By spraying a metal oxide film forming solution in which a metal salt or an organometallic compound is dissolved as a metal source onto a porous substrate heated to a temperature equal to or higher than the metal oxide film forming temperature, A method for producing a laminate for forming a metal oxide film,
A method for producing a laminate, wherein the metal oxide film-forming solution spray direction is inclined toward the porous substrate side and with respect to the normal direction of the porous substrate surface.   The method for producing a laminate according to claim 1, wherein the injection direction of the metal oxide film forming solution is tilted by 10 ° or more with respect to the normal direction of the surface of the porous substrate.   The method for producing a laminate according to claim 1 or 2, wherein the metal oxide film forming solution is sprayed in a fan shape.