Powder, laminate using the powder, and method of manufacturing a laminate

Abstract

A powder comprising a metal oxide, wherein the powder satisfies the following conditions (1) and (2): (1) has a peak top of particle size in a range of 0.1 to less than 5 μm and in a range of 5 to less than 50 μm in a frequency distribution curve based on a volume-based particle size distribution obtained by a laser diffraction method, (2) a difference between a tap density and an initial bulk density satisfies the following relationship: 0.88 g / cm 3 ≤ (tap density - initial bulk density) ≤ 0.94 g / cm 3 .

Description

TECHNICAL FIELD

[0001] The present invention relates to a powder, a laminate using the powder, and a method of manufacturing a laminate. BACKGROUND

[0002] There is a method called aerosol deposition (AD) method for forming a ceramic layer on a substrate surface at room temperature. In the AD method, a metal material such as stainless steel and iron or glass is generally used as a substrate to which a ceramic coating is applied. Currently, a ceramic coating technology for a resin material has been developed.

[0003] Such a ceramic coating requires that a ceramic material be sufficiently attached to a substrate. In addition, the ceramic coating film needs to be sufficiently strong and tough to match the performance of bulk ceramics. In applying such a resin material ceramic coating technology to industrial products, there are problems in improving adhesion and surface strength of the coating.

[0004] In the Japanese translation of PCT International Application Publication JP-T-2017 / 199968 (PTL 1), an organic-inorganic hybrid member in which primary inorganic particles and an organic polymer are covalently bonded is provided as an intermediate layer on a substrate of an organic material, and a secondary particle aggregate layer composed of an inorganic material is formed on the intermediate layer. The secondary particle aggregate layer can be understood as a ceramic layer. The intermediate layer is designed to: (1) reduce the bouncing of inorganic particles sprayed onto the resin substrate due to the elasticity of the resin substrate; (2) improve the explosion resistance of the substrate when a ceramic coating is performed by the AD method; and (3) improve the anchoring effect of the substrate. As an organic-inorganic hybrid material, a copolymer of alkoxysilane and polyamide acid, isocyanate compound, epoxy compound, or phenol is used.

[0005] In the Japanese translation of PCT International Application Publication JP-T-2018 / 194064 (PTL 2), a stress relaxation layer is formed, in which a stress relaxation layer, which can be called a primer layer, is formed between the above-mentioned substrate and the above-mentioned intermediate layer. When the inorganic layer is formed, if the film shrinks, the inorganic layer peels off from the substrate. The stress relaxation layer prevents this peeling by designing the viscoelasticity of the material that prevents the peeling, thereby preventing the peeling and cracking of the ceramic layer.

[0006] In addition to the improvement on the substrate, the ceramic coating on the resin material requires improvement on the ceramic material that forms the film.

[0007] In Japanese Unexamined Patent Application Publication 2020-180346 (PTL 3), a mixture of ceramic materials having different hardnesses is used. The mixture reduces the residual compressive stress generated during the film formation of the ceramic layer, and fills the gaps between the hard particles with easily deformable particles. The ceramic laminate manufactured using this material is difficult to peel off.

[0008] In Japanese Unexamined Patent Application Publication No. 2017-179421 (PTL 4), a collection of a crushed powder obtained by crushing a zirconia powder and a fine powder is proposed. By adjusting the ratio of the particle size distributions of the two powders, a thick and white zirconia film having a thickness of several tens of μm or more can be formed on a substrate.

[0009] In Japanese Unexamined Patent Application Publication No. 2008-056948 (PTL 5), a scheme of applying a thermal shock to a ceramic powder is proposed. By this coating, cracks and stress strains are imparted to the surface and inside of the fine particles of the ceramic powder. The so-called thermal shock is a treatment in which the ceramic powder is quenched after being kept at 500 to 1100°C for 10 minutes or more. After this shock, in the ceramic coating film of the AD method, the ceramic powder is easily crushed at the time of collision with the substrate, and the efficiency of forming a ceramic film on the substrate is improved.

[0010] List of Citations

[0011] Patent Literature

[0012] [PTL 1] Japanese translation of PCT International Application Publication JP-T-2017 / 199968

[0013] [PTL 2] Japanese translation of PCT International Application Publication JP-T-2018 / 194064

[0014] [PTL 3] Japanese Unexamined Patent Application Publication No. 2020-180346

[0015] [PTL 4] Japanese Unexamined Patent Application Publication No. 2017-179421

[0016] [PTL 5] Japanese Unexamined Patent Application Publication No. 2008-056948 SUMMARY

[0017] PROBLEMS

[0018] Since the toughness of the surface of a metal oxide produced by the AD method depends on the powder material for film formation, the substrate, and the film formation conditions, it is not possible to uniquely determine the means of toughening. The film formation conditions for improving the toughness should be determined depending on each material. Such condition determination becomes more difficult for a substrate of an organic substance, and thus a satisfactory condition can not be found. Therefore, for the powder material, the substrate, and the film formation conditions, it is required that the degree of freedom of the AD method be greater.

[0019] SOLUTION TO PROBLEM

[0020] The above problem can be solved by the following solution:

[0021] A powder comprising: a metal oxide,

[0022] wherein the powder satisfies the following conditions (1) and (2):

[0023] (1) has a peak top of particle size in a range of 0.1 to less than 5 μm and in a range of 5 to less than 50 μm in a frequency distribution curve based on a volume-based particle size distribution obtained by a laser diffraction method,

[0024] (2) a difference between a tap density and an initial bulk density satisfies the following relationship:

[0025] 0.88 g / cm 3 ≤ (tap density - initial bulk density) ≤ 0.94 g / cm 3 .

[0026] Effects of the Invention

[0027] According to the present invention, there is provided a powder, for a coating of a metal oxide, which can easily generate a tough metal oxide surface. BRIEF DESCRIPTION OF DRAWINGS

[0028] A more complete understanding of embodiments of the present disclosure and the many attendant advantages and features thereof will readily be had by reference to the following detailed description when considered in connection with the following drawings, in which:

[0029] [ Figure 1 ]

[0030] Figure 1 is a schematic diagram illustrating a mechanism of ceramic coating by the AD method.

[0031] [ Figure 2 ]

[0032] Figure 2 is a graph showing an example of a particle size distribution of a metal oxide powder.

[0033] [ Figure 3 ]

[0034] Figure 3 is a graph showing another example of a particle size distribution of a metal oxide powder.

[0035] [ Figure 4 ]

[0036] Figure 4 is a diagram showing a perovskite solar cell, a laminate according to an embodiment of the present disclosure.

[0037] The drawings are intended to illustrate exemplary embodiments of the present invention and should not be construed as limiting the scope thereof. Unless explicitly stated otherwise, the drawings should not be considered as drawn to scale. Likewise, in the multiple views, like or similar reference numerals refer to like or similar parts throughout the several views. DETAILED DESCRIPTION

[0038] In describing the embodiments illustrated in the drawings, specific terminology is employed for the sake of clarity. However, the disclosure of this specification is not intended to be limited to the specific terms so selected and it is to be understood that each specific element includes all technical equivalents that have a similar function, operate in a similar manner, and achieve a similar result.

[0039] Hereinafter, embodiments of the present application will be described with reference to the accompanying drawings. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0040] Hereinafter, embodiments of the present application will be described in detail.

[0041] As described above, the powder of the present application includes a metal oxide, and the powder satisfies the following conditions (1) and (2):

[0042] (1) in a frequency distribution curve based on a volume-based particle size distribution obtained by a laser diffraction method, has a peak top of particle size in a range of 0.1 to less than 5 μm and in a range of 5 to less than 50 μm,

[0043] (2) a difference between a tap density and an initial bulk density satisfies the following relationship:

[0044] 0.88 g / cm 3 ≤ (tap density - initial bulk density) ≤ 0.94 g / cm 3 .

[0045] According to the powder of the present application, for a coating of a metal oxide with an organic material as a base material which is significantly different from a material such as glass, metal, or ceramic in terms of softness and fragility, a strong and tough metal oxide surface can be simply generated.

[0046] The powder of the present application is applicable to ceramic coating by an AD method. The powder is particularly used as a material for firmly coating a metal oxide on an organic material base in the AD method.

[0047] Hereinafter, the mechanism of ceramic coating by the AD method will be described with reference to Figure 1 The ceramic particles 11 sprayed on a base material by the AD method cause cracks 12 (a) to (b) at the time of impact. Then, the particles are pulverized into fine fragments, and active fresh surfaces 13 (c) appear at the fractured surfaces of the pulverized particles. The fine crystalline pieces having such active fresh surfaces 13 move or rotate on the base plate due to the moment of inertia and impact pressure, and promote densification. Figure 1 Figure 1 Figure 1 ​​(d)). The active new surfaces recombine and solidify. Figure 1 (e)).

[0048] Figure 1 This is a conceptual diagram representing a simplified film-forming process for ceramic particles 1 using the AD method.

[0049] By pressing Figure 1 The changes are performed in the order of (a) to (e) to form a ceramic film. However, in reality, Figure 1 States (a) through (e) can be assumed to exist simultaneously. It is presumed that the ceramic coating exhibits various phases based on the probabilities of these states.

[0050] exist Figure 1 In the blasting stage (a), the focus is on the erosion of the substrate surface. If the collision state between ceramic particles 1 and the substrate is similar to sandblasting, the surface of the substrate will be eroded. Since the effect of sandblasting depends on the size of the medium, the particle size of the ceramic particles used in the raw material powder determines the extent of erosion.

[0051] This corrosion is particularly important to address when the substrate for ceramic coating is a brittle organic material other than glass or metal. Simply adhering raw material powder to the surface is insufficient to toughen the substrate through ceramic coating. Measures should be taken to achieve a balance between the erosion of the substrate by the AD method and the formation of a tough metal oxide surface.

[0052] By repeating the experiment to achieve this equilibrium, the powder of the present invention was obtained, which satisfies the above conditions (1) and (2). By satisfying condition (1), that is, having particle size peaks in the range of 0.1 to less than 5 μm and in the range of 5 to less than 50 μm in the frequency distribution curve based on the volume reference particle size distribution obtained by laser diffraction, not only can a surface layer with high mechanical strength be formed, which is different from the simple adhesion of powder to the substrate surface, but also the effect of excellent film-forming efficiency of ceramic coating can be obtained.

[0053] To further improve the effectiveness of the present invention, in condition (1) above, it is more preferable that the peak of the particle size is in the range of 1 to 2 μm and in the range of 10 to 12 μm. The adjustment of the particle size distribution in condition (1) above can be achieved by adjusting the particle size of the ceramic particles during feeding, or by feeding the ceramic particles into a dry disperser and adjusting the dispersion conditions of the dry disperser.

[0054] In this invention, the particle size distribution in condition (1) is measured under the following conditions.

[0055] Laser diffraction particle size distribution measuring device: Microtrac BEL, MT3300EX II.

[0056] Measurement method: dry method

[0057] Pressurized air for dispersing the sample during measurement: 0.15 MPa

[0058] Temperature and humidity environment during measurement: 23 ± 1°C, 50 ± 3% RH.

[0059] Figure 2 is a graph showing the particle size distribution of the powder obtained in Example 1 described later. In Figure 2 , the peak top mentioned in the above condition (1) exists at 1.8 μm and 11.6 μm. The "peak top" herein means the highest peak in each particle size range in condition (1). Figure 3 is a graph showing the particle size distribution of the ceramic coating in the prior art using the same powder as Figure 2 . This particle size distribution is not good. There is only one peak top under the above condition (1).

[0060] The strength and toughness of the metal oxide surface formed by the AD method depends on the bulk density of the raw material powder. Theoretically, the particle density of the aerosol sprayed by the AD method affects the film quality, however, the details are not clear. The bulk density is calculated according to Japanese Industrial Standard JIS R1628 1997 (Method for measuring the bulk density of fine ceramic powder).

[0061] The initial bulk density is related to the easiness of aerosol formation. The tap density affects the denseness of the film at the time of film formation. The inventors of the present application found that there is an optimum range of these density variations in order to produce a uniform and tough metal oxide surface. The powder of the present application was obtained by repeated experiments to determine this range. By using the difference between the tap density and the initial bulk density as in condition (2) satisfies the following relationship, a tough and uniform surface of the metal oxide can be more easily obtained.

[0062] 0.88 g / cm 3 ≤ (tap density - initial bulk density) ≤ 0.94 g / cm 3 .

[0063] In order to obtain a more tough surface, the initial bulk density of condition (2) is preferably 0.9 to 1.0 g / cm 3 . The difference (tap density - initial bulk density) is more preferably 0.89 to 0.94 g / cm 3 .

[0064] The bulk density can be easily adjusted by changing the particle diameter of the powder or by appropriately introducing a known additive. The bulk density is easily reduced by reducing the average particle diameter of the powder particles. Thus, a raw material powder having a small average particle diameter is suitable for reducing the bulk density. The average particle diameter of the recovered powder can be reduced by dispersing the powder particles placed in a dry disperser by increasing the dispersion time or increasing the electric power. As a preferred specific example of the additive, pyrogenic silica, pyrogenic alumina, pyrogenic titanium dioxide, and the like can be given, but are not limited to these.

[0065] The metal oxide contained in the powder of the present application is not particularly limited. Specifically, CoO, NiO, FeO, Bi2O3, MoO2, Cr2O3, SrCu2O2, CaO-Al2O3, Cu2O, CuAlO, CuAlO2, CuGaO2, and the like can be given, but are not limited to these. Among them, a metal oxide containing either or both of aluminum and copper elements is preferred.

[0066] The main component in the powder of the present application is the above metal oxide. The powder can optionally contain an additive such as for improving fluidization and anti-caking properties.

[0067] The laminate of the present application has a layer containing the powder of the present application.

[0068] Figure 4 is a view showing a perovskite solar cell as an example of the laminate of the present application.

[0069] As shown in Figure 4 , the perovskite solar cell module 100 has a photoelectric conversion element on the first substrate 1, the photoelectric conversion element having a first electrode 2a, 2b, a dense electron transport layer (dense layer) 3, a porous electron transport layer (porous layer) 4, a perovskite layer 5, a hole transport layer 6, a second electrode 7a, 7b.

[0070] Either of the first electrodes 2a and 2b and either of the second electrodes 7a and 7b has a through-hole 8 electrically connected to a terminal for leading out an electrode.

[0071] In the perovskite solar cell module 100, the second substrate 10 is disposed opposite to the first substrate 1 to sandwich the photoelectric conversion element therebetween, and a sealing member 9 is disposed between the first substrate 1 and the second substrate 10.

[0072] In the perovskite solar cell module 100, the first electrode 2a and the first electrode 2b are separated from each other by the hole transport layer 6 as an extended continuous layer. In Figure 4 , a and b represent a photoelectric converter.

[0073] Any one of the electron transport layer, the perovskite layer, and the hole transport layer can be formed using the powder of the present disclosure.

[0074] The laminate of the present disclosure can provide a layer containing the powder of the present disclosure on a layer containing an organic material. The layer containing the powder of the present disclosure can be provided by a known AD method.

[0075] The layer containing an organic material includes a plastic substrate.

[0076] The layer containing the powder of the present disclosure has a thickness of, for example, 0.1 to 100 μm, preferably 0.3 to 10 μm.

[0077] In one embodiment of the present disclosure, the laminate includes a layer containing an organic material, a layer containing an organic silicon compound adjacent to the layer containing an organic material, and a layer containing the powder of the present disclosure adjacent to the layer containing an organic silicon compound.

[0078] The layer containing an organic silicon compound is not particularly limited as long as it has a polysiloxane structure, and can be appropriately selected depending on the use. The layer containing an organic silicon compound having a polysiloxane structure prevents peeling of the layer containing the powder of the present disclosure.

[0079] As one method of forming the above-mentioned layer containing an organic silicon compound, an organic silicon compound having either a hydroxyl group or a hydrolysable group is crosslinked to form. If necessary, a catalyst, a crosslinking agent, a silicone sol, a silane coupling agent, and a polymer such as an acrylic polymer can be further included.

[0080] The crosslinking method is not particularly limited, and can be appropriately selected depending on the use. Heat crosslinking is preferred.

[0081] As the organic silicon compound having either a hydroxyl group or a hydrolysable group, there is no particular limitation, and a compound having an alkoxysilyl group, a partially hydrolyzed condensate of a compound having an alkoxysilyl group, and a mixture thereof, etc. can be exemplified.

[0082] As the above-mentioned compound having an alkoxysilyl group, tetraalkoxysilane such as tetraethoxysilane, alkyltrialkoxysilane such as methyltriethoxysilane, aryltrialkoxysilane such as phenyltriethoxysilane, etc. can be exemplified.

[0083] In addition, a compound in which an epoxy group, a methacryl group, or a vinyl group is introduced in these compounds having an alkoxysilyl group can also be used.

[0084] As a method of producing the above-mentioned partially hydrolyzed condensate of a compound having an alkoxysilyl group, a method in which a prescribed amount of water, a catalyst, or the like additive is added to the above-mentioned compound having an alkoxysilyl group and allowed to react can be exemplified.

[0085] As a raw material of the layer containing the organosilicon compound described above, there is no particular limitation, and commercially available products can be used, specific examples of which include, but are not limited to, GR-COAT (manufactured by Daicel Chemical Industry Co., Ltd.), Glass Resin (manufactured by Owens Corning), Heatless Glass (manufactured by Ohashi Chemical Industry Co., Ltd.), NSC (manufactured by Nippon Seiro Co., Ltd.), glass stock solution GO150SX, GO200CL (manufactured by Fine Glass Technology Co., Ltd.), MKC silicate (manufactured by Mitsubishi Chemical Corporation), silicate / acrylic varnish XP-1030-1 (manufactured by Dai-Nippon Ink and Chemicals, Incorporated), NSC-5506 (manufactured by Nippon Seiro Co., Ltd.).

[0086] The layer containing the organosilicon compound described above can contain a monoalkoxysilane as a constituent component to prevent cracking, and as the monoalkoxysilane, for example, trimethylethoxysilane, trimethylmethoxysilane, tripropylethoxysilane, trihexylethoxysilane can be cited.

[0087] Examples

[0088] Hereinafter, the present application will be described in detail by way of examples and comparative examples, but the present application is not limited to these examples. In the examples, parts refer to mass parts unless otherwise specified.

[0089] Example 1

[0090] The intermediate layer coating liquid was applied to the surface of the substrate with a doctor blade, and then heated and dried to form an intermediate layer having a thickness of 2 μm on the surface of the substrate. The powder of the metal oxide as a raw material was sprayed to the intermediate layer by an aerosol deposition method (AD method). A metal oxide-organic hybrid member provided with a surface layer formed of a metal oxide was obtained.

[0091] The film formation conditions and film formation materials of each layer were as follows:

[0092] Conditions for applying the intermediate layer

[0093] A coating was scraped with a doctor blade (YD type, manufactured by Mitutoyo Seiki Co., Ltd.) to form a film. During the scraping, the gap between the substrate and the doctor blade was set to 50 μm.

[0094] Heating and drying conditions of the intermediate layer

[0095] Subsequently, after heating and drying at 75°C for 20 minutes, heating and drying at 120°C for 20 minutes were performed.

[0096] Substrate

[0097] • Polyester film (Lumirror 75T60, manufactured by Toray Industries, Inc.)

[0098] Coating liquid for intermediate layer

[0099] The following materials were put into a container, and then mixed and stirred to obtain a uniform liquid mixture. PSZ balls having a diameter of φ 1 mm were put in at 40 vol% of the entire container, and the mixed liquid was subjected to a ball mill dispersion treatment at 120 revolutions per minute (rpm) for 18 hours.

[0100] Materials for coating liquid for intermediate layer

[0101] • Silicone oligomer (KR401, manufactured by Shin-Etsu Chemical Co., Ltd.): 333 parts

[0102] • Silica (AEROSIL NA50A, manufactured by Japan Aerosil Co., Ltd.): 167 parts

[0103] • Cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.): 444 parts

[0104] • Tetrahydrofuran (manufactured by Mitsubishi Chemical Co., Ltd.): 1,556 parts

[0105] Film formation conditions of AD method

[0106] • Water content of powder: 0.2% or less (measured value by Karl Fischer moisture meter)

[0107] • Dew point temperature at the time of putting the powder into the container: -50°C or less

[0108] • Type of aerosolization gas: dry air

[0109] • Flow rate of aerosolization gas: 5 L / min (total amount)

[0110] • Degree of vacuum in the film formation chamber: 50 Pa

[0111] • Angle between the nozzle and the coated sample: 90 degrees

[0112] • Distance between the nozzle and the coated sample: 15 mm

[0113] • Coating speed: 20 mm / min

[0114] • Number of coatings: 6 times (3 times of reciprocation)

[0115] Powder used in AD method

[0116] A mixture obtained by adding an additive to the particulate metal oxide 1 to be 0.2 mass% of the entire powder was used.

[0117] Raw material powder

[0118] • Metal oxide 1 (copper-aluminum oxide): 99.8 parts

[0119] • Additive (Reolosil ZD30S, manufactured by Tokuyama Corporation): 0.2 parts

[0120] The metal oxide 1 was prepared as follows:

[0121] Preparation of metal oxide powder 1

[0122] Copper (I) oxide (NC-803, manufactured by Nitto Chemical Industry Co., Ltd.) of 2 kg in total and aluminum oxide (AA-03, manufactured by Sumitomo Chemical Co., Ltd.) of 1.43 kg were mixed and heated at 1100°C for 40 hours to obtain copper-aluminum oxide.

[0123] The obtained oxide was pulverized with a dry disperser (Drystar SDA1, manufactured by Asada Seiki Co., Ltd.). The pulverization conditions were adjusted so that the particle size distribution described in the condition (1) of the present application had two peaks of the 1st peak (0.1 to less than 5 μm) and the 2nd peak (5 to less than 50 μm).

[0124] The particle size distribution described in the above condition (1) was measured under the following conditions:

[0125] Laser diffraction particle size distribution measuring device: MT3300EX II, manufactured by Microtrac BEL Co., Ltd.

[0126] Measurement method: dry method

[0127] Pressurized air for dispersing the sample during measurement: 0.15 MPa

[0128] Temperature and humidity environment at the time of measurement: 23 ± 1°C, 50 ± 3% RH.

[0129] The tap density and the initial bulk density in the condition (2) were determined according to JIS R1628 1997 (Method for measuring bulk density of fine ceramic powder).

[0130] Example 2

[0131] Except that the powder used for the AD method in Example 1 was changed to the powder described below, the same operation as in Example 1 was performed to obtain a metal oxide-organic substance mixed member.

[0132] Raw material powder

[0133] • Metal oxide 1 (copper-aluminum oxide): 99.5 parts

[0134] • Additive (Reolosil ZD30S, manufactured by Tokuyama Corporation): 0.5 parts

[0135] Example 3

[0136] The same operation as in Example 1 was performed except that the powder used for the AD method in Example 1 was changed to the powder described below, to obtain a metal oxide-organic substance hybrid member.

[0137] Raw material powder

[0138] • Metal oxide 1 (copper-aluminum oxide): 99.0 parts

[0139] • Additive (Reolosil ZD30S, manufactured by Tokuyama Corporation): 1.0 part

[0140] Comparative Example 1

[0141] The same operation as in Example 1 was performed except that the powder used for the AD method in Example 1 was changed to the powder described below, to obtain a metal oxide-organic substance hybrid member.

[0142] Raw material powder (dispersion material)

[0143] • Metal oxide 1 (copper-aluminum oxide): 100.0 parts

[0144] Comparative Example 2

[0145] The same operation as in Example 1 was performed except that the powder used for the AD method in Example 1 was changed to the powder described below, to obtain a metal oxide-organic substance hybrid member.

[0146] Raw material powder

[0147] • Metal oxide 1 (copper-aluminum oxide): 98.0 parts

[0148] • Additive (Reolosil ZD30S, manufactured by Tokuyama Corporation): 2.0 parts

[0149] Scratch tests were performed on the metal oxide-organic substance hybrid members of Examples 1 to 3 and Comparative Examples 1 and 2 described above. After the scratch tests, the scratch positions were observed with a confocal microscope to evaluate the depth of the groove of the scratch in the test.

[0150] The depth of the groove depends on the set load of the stylus in the scratch test. The rate of change of the groove depth with respect to the load is evaluated as a coefficient a from the approximate straight line below.

[0151] Groove depth = a x (load) + intercept (Equation 1)

[0152] Scratch test

[0153] • Tester: Ultra-thin film scratch tester CSR-2000 (manufactured by RHESCA Corporation)

[0154] • Scratch speed: 10 μm / s

[0155] • Spring constant: 100 g / mm

[0156] • Probe diameter: 5 μm R

[0157] • Excitation level: 100 μm

[0158] • Excitation frequency: 45 Hz

[0159] • Set load: 5, 7, 9, 11, 13, 15 (mN)

[0160] Observation of groove depth

[0161] • Tester: Confocal microscope OPTELICS H-1200 (manufactured by Lasertec Corporation)

[0162] • Lens magnification: 50 times

[0163] • Light source: White

[0164] The evaluation results are shown in the following tables. Table 1 shows the particle size distribution under the condition (1) of the present application. Table 2 shows the bulk density under the condition (2) of the present application. Table 3 shows the results of the scratch test of the laminates.

[0165] Table 1

[0166]

[0167] Table 2

[0168]

[0169] Table 3

[0170]

[0171] The metal oxide-organic hybrid member of Examples 1, 2 and 3 was more tenacious than the members of Comparative Examples 1 and 2.

[0172] From the results of the scratch test of these members, the metal oxide-organic hybrid member of Example 2 was the most tenacious. From the results of the examples and comparative examples, it was found that the difference between the tap density and the initial bulk density determined the tenacity of the metal oxide surface of the member obtained as the final product. In the present application, this difference was 0.88 to 0.94 g / cm 3 , which was an important factor determining the tenacity of the member. 3 , which was an important factor determining the tenacity of the member.

[0173] The above-described embodiments are illustrative and do not restrict the present application. Accordingly, many additional modifications and variations are possible in light of the above teachings. For example, elements and / or features of different illustrative embodiments can be combined with each other and / or substituted for each other within the scope of the application.

[0174] This patent application is based upon and claims priority to Japanese Patent Application No. 2021-150973 filed on September 16, 2021 with the Japan Patent Office, the disclosure of which is incorporated herein in its entirety by reference.

[0175] List of Reference Signs

[0176] 1 first substrate

[0177] 2, 2a, 2b first electrode

[0178] 3 dense electron transport layer (dense layer)

[0179] 4 porous electron transport layer (porous layer)

[0180] 5 perovskite layer

[0181] 6 hole transport layer

[0182] 7, 7a, 7b second electrode

[0183] 8 through portion

[0184] 9 sealing member

[0185] 10 second substrate

[0186] 100 photoelectric conversion module

[0187] a, b photoelectric conversion element

[0188] 11 ceramic particle

[0189] 12 crack

[0190] 13 active nascent surface

Claims

1. A powder comprising: Metal oxides in, The powder satisfies the following conditions (1) and (2): (1) In the frequency distribution curve based on the volume reference particle size distribution obtained by laser diffraction, there are particle size peaks in the range of 0.1 to less than 5 μm and in the range of 5 to less than 50 μm. (2) The difference between the tapped density and the initial bulk density satisfies the following relationship: 0.88g / cm 3 ≤(tap density - initial bulk density)≤0.94g / cm³ 3 , The initial bulk density is 0.9 to 1.0 g / cm³. 3 .

2. The powder according to claim 1, wherein, The peaks are in the range of 1 μm to 2 μm and in the range of 10 μm to 12 μm.

3. The powder according to any one of claims 1 to 2, wherein, The metal oxide contains at least one of aluminum and copper.

4. A laminated body, comprising: A layer containing the powder of any one of claims 1 to 3.

5. The laminated body according to claim 4, It further includes a layer containing organic materials. in, A layer containing the powder is disposed on the layer containing the organic material.

6. The laminated body according to claim 5, It further includes a layer containing organosilicon compounds. in, The layer containing the organosilicon compound is disposed adjacent to both the layer containing the organic material and the layer containing the powder.

7. A method for manufacturing a laminate, comprising: A layer containing the powder according to any one of claims 1 to 3 is prepared by aerosol deposition; and The layer containing the powder is stacked on top of the layer containing the organic material.

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