JP7815629B2 - Laminate and device using same - Google Patents

Description

The present invention relates to a laminate, a device using the laminate, and a method for manufacturing the same.

The aerosol deposition method (AD method) has been known as a method for forming a ceramic layer on the surface of a substrate at room temperature. In the AD method, the substrates to which the ceramic coating is applied are typically metal materials such as stainless steel or iron, or glass. However, in recent years, ceramic coating technology for resin materials has been developed (Patent Documents 1 and 2).

When ceramic coating resin materials is intended to be a hard coating for resin cases, window materials, etc., sufficient adhesion of the ceramic material to the resin substrate is required. Furthermore, the ceramic coating film must have toughness that matches the performance of bulk ceramic. When applying this ceramic coating technology to resin materials to industrial products, there remains a challenge of improving adhesion and the toughness of the coating surface.

When this resin material is used as the surface material for organic electronic devices such as OPC, OLED, and OPV, it is unacceptable for the functionality of the device to be lost when ceramic coating is applied to these substrates. Furthermore, it is also an unacceptable technical issue if the coated ceramic material is easily removed from the substrate.

OPCs are considered to be the most mature organic electronic devices. Thanks to their high degree of design freedom and simple manufacturing equipment, OPCs account for nearly 100% of all photoconductors. However, the durability of OPCs is significantly shorter than that of inorganic photoconductors such as amorphous silicon photoconductors. As a result, a large number of OPCs are discarded and produced.

Recently, climate change, such as once-in-a-decade disasters, has become the norm, and _CO2 emissions, which can be said to be the root cause of these, are a serious social issue that must be reduced. The _CO2 emissions caused by the production and disposal of huge quantities of devices due to their fragility can no longer be ignored, and it is necessary to apply high-durability and long-life technologies to other devices as well.

The object of the present invention is to provide a laminate comprising a layer containing an organic material, a layer containing a siloxane compound and a metal oxide, and a layer containing a metal oxide, in which the layer containing the metal oxide has high strength and excellent durability.

The above problem is solved by the following configuration 1).
1) a layer (1) containing an organic material;
a layer (2) containing a siloxane compound and a metal oxide in contact with the layer (1) containing an organic material;
a layer (3) containing the metal oxide in contact with the layer (2) containing the siloxane compound and the metal oxide;
A laminate for use in an electrophotographic photoreceptor or an organic EL element ,
the metal oxide includes one of delafossite and perovskite,
The laminate is obtained by crosslinking the siloxane compound with an organosilicon compound having either a hydroxyl group or a hydrolyzable group.

The present invention provides a laminate comprising a layer containing an organic material, a layer containing a siloxane compound and a metal oxide, and a layer containing a metal oxide, in which the layer containing the metal oxide has high strength and excellent durability.

1 is a schematic cross-sectional view illustrating an embodiment of a photoreceptor of the present invention. FIG. 2 is a schematic cross-sectional view illustrating another embodiment of the photoreceptor of the present invention. FIG. 2 is a schematic cross-sectional view illustrating another embodiment of the photoreceptor of the present invention. FIG. 2 is a schematic cross-sectional view illustrating another embodiment of the photoreceptor of the present invention. FIG. 2 is a schematic cross-sectional view illustrating another embodiment of the photoreceptor of the present invention. FIG. 2 is a schematic cross-sectional view illustrating another embodiment of the photoreceptor of the present invention. FIG. 1 is a schematic diagram illustrating an aerosol deposition device. 1 is a schematic cross-sectional view illustrating an embodiment of an organic EL element of the present invention. 1A and 1B are diagrams illustrating an embodiment of an image forming method and an image forming apparatus according to the present invention. 1 is an example of a cross-sectional photograph of a laminate of the present invention. 1 is an example showing the carbon distribution in a cross section of a laminate of the present invention. 1 is an example showing the distribution of silicon in a cross section of a laminate of the present invention. 1 is an example showing the distribution of aluminum in a cross section of a laminate of the present invention. 1 is an example showing the appearance of the undercoat layer in a cross section of a laminate.

Hereinafter, the embodiments of the present invention will be described in more detail.
The laminate of the present invention comprises a layer (1) containing an organic material, a layer (2) containing a siloxane compound and a metal oxide in contact with the layer (1) containing the organic material, and a layer (3) containing the metal oxide in contact with the layer (2) containing the siloxane compound and the metal oxide.

When applying ceramic coating to organic materials using the AD method, in addition to controlling the erosion of the organic material, the adhesion between the organic material and the ceramic material is important. Adhesion is often achieved by forming a wedge-like effect by the ceramic material penetrating the substrate, forming an uneven surface at the interface, a process known as anchoring. In this case, the strength of the ceramic can be affected by this adhesion.
If the AD method is applied directly to an organic material, erosion due to the collision of the aerosol powder will progress, so it is advisable to provide an undercoat layer that promotes the growth of the aerosol powder deposition.
The undercoat layer is preferably made of a siloxane compound, and the materials used in the embodiments of the present invention are advantageous in promoting this deposition.

Improving adhesion is a particularly important issue when commercializing devices. We discovered that forming slight irregularities, known as anchoring, throughout the entire undercoat layer is effective in addressing this issue, leading to the completion of the present invention. Figure 10 is a cross-sectional electron microscope photograph showing an example of this embodiment. An undercoat layer and a thin ceramic layer are formed on an organic device, the OPC. Figures 11 to 13 show the results of elemental analysis of Figure 10 using an energy dispersive X-ray analyzer (EDS). The distributions of carbon, silicon, and aluminum are shown in order in these figures. The carbon originates from the organic material on the OPC surface, the silicon originates from a siloxane compound contained in the paint in the undercoat layer, and the aluminum originates from copper aluminate, the material of the ceramic layer formed by the AD method. It can be seen that aluminum is distributed throughout the undercoat layer.
It is possible to observe these distributions by adjusting the observation conditions of the electron microscope photographs. Figure 14 shows an example, in which the ceramic layer material is observed to be localized at the interface between the primer layer and the organic material.

The laminate of the present invention is suitably applied to photoelectric conversion elements, organic photoconductors (OPCs), image forming methods, image forming apparatuses, organic EL elements (OLEDs), organic thin-film solar cells (OPVs), and the like.
As described above, the laminate of the present invention comprises a layer (1) containing an organic material, a layer (2) containing a siloxane compound and a metal oxide in contact with the layer (1) containing the organic material, and a layer (3) containing the metal oxide in contact with the layer (2) containing the siloxane compound and the metal oxide. For example, among the above elements, an OPC comprises a layer (1) containing an organic material as a photoelectric conversion layer on a support, a layer (2) containing a siloxane compound and a metal oxide as an undercoat layer, and a layer (3) containing a metal oxide as a ceramic film, and the undercoat layer contains a siloxane compound.
First, an application example of the laminate of the present invention will be described using an OPC (hereinafter, sometimes referred to as the photoreceptor of the present invention) as an example, but the present invention is not limited to the following embodiment.

(Photoreceptor)
In the photoreceptor, the photoelectric conversion layer is preferably configured as a photosensitive layer, and the support is preferably configured as a conductive support. The photoreceptor of the present invention is preferably an organic photoreceptor.

FIG. 1 is a schematic cross-sectional view illustrating one embodiment of the photoreceptor of the present invention.
1, the photoreceptor 1 comprises a photosensitive layer 202 (the above-mentioned layer (1)) provided on a conductive support 201, and an undercoat layer 208 (the above-mentioned layer (2)) and a surface layer 209 (the above-mentioned layer (3)) provided in this order. As described above, the photoreceptor 1 of the present invention is characterized in that the surface layer 209 is a ceramic film and the undercoat layer 208 contains a siloxane compound.

FIG. 2 is a schematic cross-sectional view illustrating another embodiment of the photoreceptor of the present invention.
The photoreceptor 1 in FIG. 2 is of a function-separated type in which the photosensitive layer is composed of a charge generation layer (CGL) 203 and a charge transport layer (CTL) 204 .

FIG. 3 is a schematic cross-sectional view illustrating another embodiment of the photoreceptor of the present invention.
The photoreceptor 1 in FIG. 3 is the same as the function-separated type photoreceptor shown in FIG. 2, except that an undercoat layer 205 is provided between the support 201 and the charge generating layer (CGL) 203 .

FIG. 4 is a schematic cross-sectional view illustrating another embodiment of the photoreceptor of the present invention.
The photoreceptor 1 in FIG. 4 is the same as the function-separated type photoreceptor shown in FIG. 3, except that a protective layer 206 is provided on the charge transport layer (CTL) 204.

FIG. 5 is a schematic cross-sectional view illustrating another embodiment of the photoreceptor of the present invention.
The photoreceptor 1 in FIG. 5 is the same as the function-separated type photoreceptor shown in FIG. 4, except that an intermediate layer 207 is provided between the support 201 and the undercoat layer 205 .

The photoreceptor of the present invention is not limited to the above-described embodiments. For example, as shown in Figure 6, the photoreceptor 1 may be formed by providing an intermediate layer 207, a charge generation layer 203, a charge transport layer 204, an undercoat layer 208, and a surface layer 209 in this order on a conductive support 201.

The photoreceptor of the present invention has the excellent charging properties of an organic photoreceptor, and because the surface layer is a ceramic film, it has excellent abrasion resistance comparable to that of an inorganic photoreceptor. Furthermore, because the undercoat layer contains a siloxane compound, it has excellent gas barrier properties, and therefore it has excellent durability and excellent image quality.
In particular, by providing a photoreceptor with an undercoat layer containing a siloxane compound, the photosensitive layer, which has high gas permeability and low strength, can be covered with a dense inorganic film, thereby improving gas barrier properties. Furthermore, the undercoat layer in the present invention has significantly higher mechanical strength than organic materials, and can significantly improve the abrasion resistance of the photoreceptor.

<Photosensitive layer>
The photosensitive layer may be a multi-layered photosensitive layer or a single-layered photosensitive layer.

<<Multi-layered photosensitive layer>>
As described above, the multi-layered photosensitive layer has at least a charge generating layer and a charge transporting layer in this order, and may further have other layers as required.

-Charge generation layer-
The charge generating layer contains at least a charge generating material, a binder resin, and, if necessary, other components.
The charge-generating material is not particularly limited and can be appropriately selected depending on the purpose, and either inorganic or organic materials can be used. Examples include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, and azo pigments having a carbazole skeleton, triphenylamine skeleton, diphenylamine skeleton, or fluorenone skeleton. These may be used alone or in combination of two or more. The binder resin is not particularly limited and can be appropriately selected depending on the purpose, and examples include polyvinyl butyral resin and polyvinyl formal resin. These may be used alone or in combination of two or more.

The charge generating layer can be formed by a vacuum thin film forming method, a casting method from a solution dispersion system, or the like.
Examples of organic solvents used in the charge generation layer coating liquid include methyl ethyl ketone and tetrahydrofuran. These may be used alone or in combination of two or more. The thickness of the charge generation layer is generally preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.

-Charge transport layer-
The charge transport layer is a layer whose purpose is to retain the charge and to transfer the charge generated and separated in the charge generating layer by exposure to combine with the retained charge. To achieve the purpose of retaining the charge, high electrical resistance is required. Furthermore, to achieve the purpose of obtaining a high surface potential with the retained charge, a small dielectric constant and good charge mobility are required.
The charge transport layer contains at least a charge transport material or a sensitizing dye, a binder resin, and, if necessary, other components.
Examples of the charge transport material include a hole transport material, an electron transport material, and a polymer charge transport material.
Examples of the electron transport substance (electron acceptor substance) include 2,4,7-trinitro-9-fluorenone, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, etc. These may be used alone or in combination of two or more.
Examples of the hole transport material (electron donating material) include triphenylamine derivatives and α-phenylstilbene derivatives. These may be used alone or in combination of two or more. Examples of the polymer charge transport material include those having the following structures. For example, polysilylene polymers and polymers having a triarylamine structure are exemplified.
As the binder resin, for example, polycarbonate resin, polyester resin, etc. are used.
These may be used alone or in combination of two or more.
The charge transport layer may also contain a copolymer of a crosslinkable binder resin and a crosslinkable charge transport material.
Examples of sensitizing dyes include known metal complex compounds, coumarin compounds, polyene compounds, indoline compounds, and thiophene compounds.

The charge transport layer can be formed by dissolving or dispersing the charge transport material or sensitizing dye and binder resin in a suitable solvent, applying the solution, and drying the solution. If necessary, the charge transport layer may further contain additives such as a plasticizer, an antioxidant, a leveling agent, etc. in appropriate amounts in addition to the charge transport material or sensitizing dye and binder resin.
The thickness of the charge transport layer is preferably 5 to 100 μm. In response to the recent demand for higher image quality, efforts are being made to make the charge transport layer thinner. To achieve high image quality of 1200 dpi or more, the thickness of the charge transport layer is more preferably 5 to 30 μm.

<<Single-layer photosensitive layer>>
The single-layer photosensitive layer contains a charge generating material, a charge transporting material, and a binder resin, and may further contain other components as required.
The charge generating material, charge transport material, and binder resin may be the same as those used in the laminated photosensitive layer.
When a single-layer photosensitive layer is formed by a casting method, the single-layer photosensitive layer can often be formed by dissolving or dispersing a charge generating material and a low-molecular-weight or high-molecular-weight charge transport material in an appropriate solvent, applying the solution, and drying the solution. The single-layer photosensitive layer may further contain a plasticizer and a binder resin, if necessary. The binder resin may be the same as that used in the charge transport layer, or may be a mixture of the same binder resin as that used in the charge generating layer.
The thickness of the single-layer photosensitive layer is preferably 5 to 100 μm, more preferably 5 to 50 μm. If the thickness is less than 5 μm, the charging property may decrease, and if it exceeds 100 μm, the sensitivity may decrease.

<Support>
The support can be appropriately selected depending on the purpose, and for example, a conductive material can be used. Suitable examples of the support include a conductor or an insulator that has been treated to be conductive, such as a metal such as Al or Ni, or an alloy thereof; an insulating substrate such as polyester or polycarbonate on which a thin film of a metal such as Al, or a conductive material such as In ₂ O ₃ or SnO ₂ is formed; a resin substrate in which carbon black, graphite, metal powder such as Al, Cu, or Ni, conductive glass powder, or the like is uniformly dispersed in a resin to impart conductivity to the resin; and conductive paper.
There are no particular restrictions on the shape and size of the support, and any of plate, drum, and belt shapes can be used.

An undercoat layer may be provided between the support and the photosensitive layer, if necessary, for the purposes of improving adhesion, preventing moire, improving the coatability of the upper layer, reducing residual potential, etc.
The undercoat layer generally contains a resin as a main component, and examples of such resins include alcohol-soluble resins such as polyvinyl alcohol, copolymer nylon, and methoxymethylated nylon, and curable resins that form a three-dimensional network structure, such as polyurethane, melamine resin, and alkyd-melamine resin.
Furthermore, fine powders of metal oxides such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, and indium oxide, or metal sulfides, metal nitrides, etc. may also be added. These undercoat layers can be formed by a conventional coating method using an appropriate solvent.
The thickness of the undercoat layer is not particularly limited and can be appropriately selected depending on the purpose, and is preferably 0.1 to 10 μm, more preferably 1 to 5 μm.

In the photoreceptor of the present invention, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. Materials used for the protective layer include resins such as ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, aryl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, polyarylate, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin.
The protective layer can be formed by a conventional method such as dip coating, spray coating, bead coating, nozzle coating, spinner coating, or ring coating.

In the photoreceptor of the present invention, an intermediate layer may be provided on the support, if necessary, to improve adhesion and charge blocking properties. The intermediate layer generally contains a resin as its main component, and considering that the photosensitive layer will be coated thereon using a solvent, it is desirable that the resin be a resin that has high solvent resistance to common organic solvents.
Examples of the resin include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate; alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon; and curable resins that form a three-dimensional network structure, such as polyurethane resin, melamine resin, phenol resin, alkyd-melamine resin, and epoxy resin.

<Undercoat layer>
The undercoat layer contains a siloxane compound, and the siloxane compound is obtained by crosslinking an organosilicon compound having either a hydroxyl group or a hydrolyzable group.
The siloxane compound can fix a surface layer made of a ceramic film to the surface of the photoreceptor, and can also improve gas barrier properties and significantly increase abrasion resistance.

-Siloxane compounds-
The siloxane compound is obtained by crosslinking an organosilicon compound having either a hydroxyl group or a hydrolyzable group, and may further contain a catalyst, a crosslinking agent, an organosilica sol, a silane coupling agent, a polymer such as an acrylic polymer, and the like, as necessary.

The crosslinking method is not particularly limited and can be selected appropriately depending on the purpose, but thermal crosslinking is preferred.

Examples of the organosilicon compound having either a hydroxyl group or a hydrolyzable group include a compound having an alkoxysilyl group, a partial hydrolysis condensate of a compound having an alkoxysilyl group, or a mixture thereof.
Examples of the compound having an alkoxysilyl group include tetraalkoxysilanes such as tetraethoxysilane, alkyltrialkoxysilanes such as methyltriethoxysilane, and aryltrialkoxysilanes such as phenyltriethoxysilane. These compounds may also be used with an epoxy group, a methacryloyl group, or a vinyl group introduced therein.
The partial hydrolysis condensate of the compound having an alkoxysilyl group can be produced by a known method in which a predetermined amount of water, a catalyst, etc. is added to the compound having an alkoxysilyl group and reacted.

Commercially available products can be used as raw materials for the siloxane compound. Specific examples include GR-COAT (manufactured by Daicel Chemical Industries, Ltd.), Glass Resin (manufactured by Owens Corning), Heatless Glass (manufactured by Ohashi Chemical Industry Co., Ltd.), NSC (manufactured by Nippon Fine Chemical Co., Ltd.), glass stock solutions GO150SX and GO200CL (manufactured by Fine Glass Technology Co., Ltd.), and examples of copolymers of alkoxysilyl compounds with acrylic resins or polyester resins include MKC Silicate (manufactured by Mitsubishi Chemical Corporation), silicate/acrylic varnish XP-1030-1 (manufactured by Dai Nippon Shikizai Kogyo Co., Ltd.), X-40-9250 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KR-401 (manufactured by Shin-Etsu Chemical Co., Ltd.). The raw material for the siloxane compound is sometimes referred to as a curable siloxane resin.

In particular, from the viewpoint of improving the effects of the present invention, it is preferable that the siloxane compound contains the following structure:

The thickness of the undercoat layer is preferably 0.01 μm or more and 4.0 μm or less, more preferably 0.03 μm or more and 4.0 μm or less, and even more preferably 0.05 μm or more and 2.5 μm or less. It is also preferable that the thickness be 0.1 μm or more. Of these, a thickness of 0.01 μm or more and 2.5 μm or less is particularly preferable.

The metal oxide contained in the undercoat layer is derived from the aerosol powder used in the AD method.

<Surface layer>
The surface layer of the photoreceptor of the present invention is made of a ceramic film.
The ceramics constituting the ceramic film are generally metal oxides obtained by firing metals. The ceramics are not particularly limited and can be appropriately selected depending on the purpose. Examples include metal oxides such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, and indium oxide. The ceramics preferably contain a transparent conductive oxide, and the transparent conductive oxide is preferably a ceramic semiconductor. Furthermore, the transparent conductive oxide preferably contains delafossite or perovskite, and the delafossite preferably contains copper aluminum oxide, copper chromium oxide, or copper gallium oxide. Perovskite is a composite material of an organic compound and an inorganic compound, and can be represented by the following general formula (1):
XαYβMγ ... General formula (1)
In the above general formula (1), the ratio of α:β:γ is 3:1:1, and β and γ represent integers greater than 1. Furthermore, for example, X can be a halogen ion, Y can be an alkylamine compound ion, and M can be a metal ion.

<Ceramic semiconductors>
The ceramic semiconductor refers to ceramics that have partial defects in their normal electron configuration due to oxygen vacancies or the like, and is a general term for compounds that exhibit conductivity under specific conditions due to the defects in the electron configuration. The surface layer in the present invention is preferably a metal oxide-containing layer. The metal oxide-containing layer is defined as a layer that exhibits conductivity under specific conditions due to the defects in the electron configuration, in which ceramic semiconductor components are densely arranged without any gaps, and does not contain any organic compounds. The metal oxide-containing layer preferably contains delafossite. Furthermore, in the present invention, it is preferable that the metal oxide-containing layer has charge mobility of either holes or electrons. The charge mobility of the metal oxide-containing layer at an electric field strength of 2×10 ⁻⁴ V/cm is preferably 1×10 ⁻⁶ cm ² /Vsec or more. In the present invention, the higher the charge mobility, the better. The method for measuring the charge mobility is not particularly limited, and a general measurement method can be appropriately selected depending on the purpose. For example, a method of preparing a sample and measuring it according to the procedure described in JP 2010-183072 A can be used. The bulk resistance including the thickness of the metal oxide-containing layer is preferably less than 1×10 ¹³ Ω.

-Delafosite-
The delafossite (hereinafter sometimes referred to as a "p-type semiconductor" or "p-type metal compound semiconductor") is not particularly limited as long as it functions as a p-type semiconductor and can be appropriately selected depending on the purpose, and examples thereof include p-type metal oxide semiconductors, p-type compound semiconductors containing monovalent copper, other p-type metal compound semiconductors, _etc. Examples of the p-type _metal oxide semiconductors include CoO, NiO, FeO, _Bi2O3 , _MoO2 , _MoS2 , _Cr2O3 , _SrCu2O2 , _{and CaO} - _Al2O3 . Examples of the p-type compound semiconductor containing monovalent copper include CuI, CuInSe ₂ , Cu ₂ O, CuSCN, CuS, CuInS ₂ , CuAlO, CuAlO ₂ , CuAlSe ₂ , CuGaO ₂ , CuGaS ₂ , and CuGaSe _2. Examples of the other p-type metal compound semiconductors include GaP, GaAs, Si, Ge, and SiC.
From the viewpoint of improving the effects of the present invention, the delafossite is preferably a copper aluminum oxide, and the copper aluminum oxide is more preferably _CuAlO2 .

[Ceramic film fabrication]
The method for producing the ceramic film (film formation method) is not particularly limited, and a commonly used film formation method for inorganic materials can be appropriately selected depending on the purpose. Examples of the method include vapor deposition, liquid deposition, and solid phase deposition. Vapor deposition methods are classified into physical vapor deposition (PVD) and chemical vapor deposition (CVD). Examples of the physical vapor deposition method include vacuum deposition, electron beam deposition, laser ablation, laser ablation MBE, MOMBE, reactive vapor deposition, ion plating, cluster ion beam deposition, glow discharge sputtering, ion beam sputtering, and reactive sputtering. Examples of the chemical vapor deposition method include thermal CVD, MOCVD, RF plasma CVD, ECR plasma CVD, photo-CVD, and laser CVD. Examples of the liquid phase deposition method include LPE, electroplating, electroless plating, and coating. Examples of the solid phase growth method include SPE, recrystallization, graphoepitaxy, LB method, sol-gel method, and aerosol deposition (AD) method.
Among these, the AD method is preferred in that it can form a uniform film over a relatively large area such as an electrophotographic photosensitive member and does not affect the properties of the electrophotographic photosensitive member.

- Aerosol Deposition (AD) Method -
The aerosol deposition (AD) method is a technology in which fine particles or ultrafine particles prepared in advance are mixed with a gas to form an aerosol, which is then sprayed through a nozzle onto an object (substrate) to be coated with a film. The AD method is characterized by its ability to form films in a room temperature environment and to perform film formation while maintaining the crystal structure of the raw materials, making it suitable for film formation on photoelectric conversion devices (especially electrophotographic photoreceptors).

A method for forming a ceramic film by the aerosol deposition method will now be described.
FIG. 7 is a schematic diagram for explaining an aerosol deposition device.
7 stores an inert gas for generating an aerosol. The gas cylinder 111 is connected to an aerosol generator 113 via a pipe 112a, which extends into the aerosol generator 113. A certain amount of particles 120, which are the material for forming the ceramic film of the present invention, are introduced into the aerosol generator 113. Another pipe 112b connected to the aerosol generator 113 is connected to an injection nozzle 115 inside a film formation chamber 114.
Inside the film formation chamber 114, a substrate 116 is held by a substrate holder 117 so as to face the spray nozzle 115. Here, an aluminum foil (positive electrode current collector) is used as the substrate 116. An exhaust pump 118 for adjusting the degree of vacuum within the film formation chamber 114 is connected to the film formation chamber 114 via a pipe 112c.

Although not shown, the system is equipped with a mechanism for moving the substrate holder 117 laterally (the horizontal direction in the plane of the substrate holder 117 facing the injection nozzle 115) and moving the injection nozzle 115 vertically (the vertical direction in the plane of the substrate holder 117 facing the injection nozzle 115) at a constant speed. By depositing the film while moving the substrate holder 117 laterally and the injection nozzle 115 vertically, a ceramic film of the desired area can be formed on the substrate 116.

In the process of forming a ceramic film, first, the compressed air valve 119 is closed, and an exhaust pump 118 is used to evacuate the area from the film formation chamber 114 to the aerosol generator 113. Next, the compressed air valve 119 is opened, introducing gas from the gas cylinder 111 into the aerosol generator 113 through the pipe 112a, scattering particles 120 into the container and generating an aerosol in which the particles 120 are dispersed in the gas. The generated aerosol is sprayed at high speed from the nozzle 115 through the pipe 112b toward the substrate 116. After 0.5 seconds have elapsed with the compressed air valve 119 open, the compressed air valve 119 is closed for the next 0.5 seconds. Thereafter, the compressed air valve 119 is opened again, and the opening and closing of the compressed air valve 119 is repeated in 0.5-second cycles. The gas flow rate from the gas cylinder 111 is 2 liters/minute, the film formation time is 7 hours, the degree of vacuum in the film formation chamber 114 is about 10 Pa when the compressed air valve 119 is closed, and the degree of vacuum in the film formation chamber 114 is about 100 Pa when the compressed air valve 119 is open.
The aerosol ejection speed is controlled by the shape of the nozzle 115, the length and inner diameter of the pipe 112b, the internal gas pressure of the gas cylinder 111, the exhaust volume of the exhaust pump 118 (the internal pressure of the film-forming chamber 114), and the like. For example, if the internal pressure of the aerosol generator 113 is set to tens of thousands of Pa, the internal pressure of the film-forming chamber 114 is set to several tens to several hundred Pa, and the opening of the nozzle 115 is circular with an internal diameter of 1 mm, the aerosol ejection speed can be set to several hundred meters per second due to the internal pressure difference between the aerosol generator 113 and the film-forming chamber 114. If the internal pressure of the film-forming chamber 114 is maintained at 5 Pa to 100 Pa and the internal pressure of the aerosol generator 113 is maintained at 50,000 Pa, a ceramic film with a porosity of 5% to 30% can be formed. By adjusting the aerosol supply time under these conditions, the average thickness of the ceramic film can be adjusted.

The thickness of the ceramic film is preferably 0.1 μm to 10 μm, and more preferably 0.5 μm to 5.0 μm.

The particles 120 in the aerosol that have been accelerated and gained kinetic energy collide with the photosensitive member, which is the substrate 116, and are broken down into small pieces by the impact energy. These broken particles are then bonded to the substrate (photosensitive member) 116 and to each other, thereby sequentially forming a ceramic film on the charge transport layer.
The film is formed by rotating the photosensitive drum in a line pattern multiple times. The drum holder 117 and the spray nozzle 115 are scanned vertically and horizontally on the surface of the substrate (photosensitive member) 116 to form a ceramic film of a desired area.

(Organic EL element)
Next, an example of an organic electroluminescence element (OLED) having a photoelectric conversion element of the present invention will be described. The above description is also applicable to the organic EL element of this embodiment. However, when there is a description below regarding the organic EL element of this embodiment, the description below takes precedence.

The organic EL element of the present invention has a ceramic surface layer, which provides gas barrier properties, particularly moisture barrier properties, and excellent durability. Furthermore, the undercoat layer contains a siloxane compound, which improves gas barrier properties, further improving durability and the quality of displayed images. In particular, by having an organic EL element with an undercoat layer containing a siloxane compound, the organic EL layer, which has high gas permeability and low strength, can be covered with a dense inorganic film, thereby enhancing gas barrier properties.

Figure 8 is a schematic cross-sectional view illustrating one embodiment of the organic EL element of the present invention. The organic EL element 50C of this embodiment has a layered structure in which a support 51, a cathode 52, an electron injection layer 53, an electron transport layer 54, an emitting layer 55, a hole transport layer 56, an undercoat layer 57, a surface layer 58, and an anode 59 are provided in this order. Note that, in the present invention, the reverse layer structure of an organic EL element, which is advantageous for durability, is considered the standard element structure, but is not limited to this structure.

<Support>
In the organic EL element of this embodiment, the support 51 may be configured as a substrate. The support is preferably an insulating substrate. The support may be, for example, a plastic or film-like substrate.
A barrier film may be disposed on the main surface 51a of the support 51. The barrier film may be, for example, a film made of silicon, oxygen, and carbon, or a film made of silicon, oxygen, carbon, and nitrogen. Examples of materials for the barrier film include silicon oxide, silicon nitride, and silicon oxynitride. The average thickness of the barrier film is preferably 100 nm or more and 10 μm or less.

<Organic EL layer>
In the organic EL element of this embodiment, the photoelectric conversion layer may be configured as an organic EL layer.
The organic EL layer is a functional part that includes, for example, a light-emitting layer and contributes to the light emission of the light-emitting layer by, for example, carrier migration and carrier binding in response to a voltage applied to the anode and cathode. The organic EL layer can be configured to include, for example, an electron injection layer 53, an electron transport layer 54, a light-emitting layer 55, a hole transport layer 56, etc. In some cases, the organic EL layer may also include electrodes such as a cathode and an anode.

<Electron injection layer>
The electron injection layer 53 can be provided as a layer that lowers the barrier for electron injection from the cathode 52 to the electron transport layer 54 formed of an organic material with low electron affinity. Examples of materials that can be used for the electron injection layer 53 include metal oxides containing magnesium, aluminum, calcium, zirconium, silicon, titanium, and zinc, polyphenylene vinylene, hydroxyquinoline, and naphthalimide derivatives.

The average thickness of the electron injection layer 53 is preferably 5 to 1,000 nm, and more preferably 10 to 30 nm. Thickness can be measured using spectroscopic ellipsometry, a surface roughness meter, or microscope image analysis.

<Electron transport layer>
Examples of low molecular weight compounds that can be used as materials for the electron transport layer 54 include oxazole derivatives, oxadiazole derivatives, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, imidazole derivatives, tetracarboxylic acid anhydrides, various metal complexes typified by tris(8-hydroxyquinolinato)aluminum (Alq3), and silole derivatives, and one or more of these can be used. Among these, metal complexes such as Alq3 and pyridine derivatives are preferred.

The average thickness of the electron transport layer 54 is preferably 10 to 200 nm, and more preferably 40 to 100 nm. Thickness can be measured using spectroscopic ellipsometry, a surface roughness meter, or microscopic image analysis.

<Light-emitting layer>
The light-emitting layer 55 is a layer that emits light after excitons are generated by recombination of holes and electrons injected from the anode and cathode, respectively. Examples of polymer materials that form the light-emitting layer 55 include polyparaphenylene vinylene compounds, polyfluorene compounds, and polycarbazole compounds.

Examples of low-molecular-weight materials that form the light-emitting layer 55 include tris(8-hydroxyquinolinato)aluminum (Alq3), tris(4-methyl-8-quinolinolato)aluminum(III) (Almq3), 8-hydroxyquinoline zinc (Znq2), (1,10-phenanthroline)-tris-(4,4,4-trifluoro-1-(2-thienyl)-butane-1,3-dionate) europium(III) (Eu(TTA)3(phen)), a metal complex of 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine platinum(II), and bis[2-(o-hydroxyphenylbenzo[ Examples include metal complexes such as bis[2-(2-hydroxyphenyl)-pyridine]zinc(II) (ZnBTZ2), bis[2-(2-hydroxyphenyl)-pyridine]beryllium (Bepp2), metal complexes such as tris[3-methyl-2-phenylpyridine]iridium(III) (Ir(mpy)3), distyrylbenzene derivatives, phenanthrene derivatives, perylene compounds, carbazole compounds, benzimidazole compounds, benzothiazole compounds, coumarin compounds, perinone compounds, oxadiazole compounds, quinacridone compounds, pyridine compounds, and spiro compounds. These compounds can be used alone or in combination.

The average thickness of the light-emitting layer 55 is not particularly limited, but is preferably 10 to 150 nm, and more preferably 20 to 100 nm. Thickness can be measured using spectroscopic ellipsometry, a surface roughness meter, or microscope image analysis.

<Hole transport layer>
Examples of materials that can be used for the hole transport layer 56 include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, butadiene derivatives, 9-(p-diethylaminostyrylanthracene), 1,1-bis-(4-dibenzylaminophenyl)propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. Other examples include polyarylamine, fluorene-arylamine copolymer, fluorene-bithiophene copolymer, poly(N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, polyalkylthiophene, polyhexylthiophene, poly(p-phenylenevinylene), polythinylenevinylene, pyrene formaldehyde resin, ethylcarbazole formaldehyde resin, and derivatives thereof. These hole transporting materials may be used alone or in combination with other compounds.

The average thickness of the hole transport layer 56 is preferably 10 to 150 nm, and more preferably 40 to 100 nm.

<Undercoat layer>
The undercoat layer 57 may be the same as that described above. The undercoat layer 57 contains a siloxane compound. Note that the undercoat layer 57 in this embodiment may be configured as a silicone hard coat.

<Surface layer>
The surface layer 58 may be the same as that described above. In this embodiment, the surface layer 58 is also a ceramic film. As shown in the drawing, the surface layer 58 may be formed on the side surface of the organic EL element, but is not limited to this.

The ceramic film and its manufacturing method for an organic EL element can be modified as appropriate and applied in addition to the above. For example, an anode may be formed on the ceramic film. Alternatively, the ceramic film may be formed on the cathode so as to bury the organic EL layer. Alternatively, the ceramic film may be formed so as to cover the side surfaces of the organic EL layer, etc. By providing the ceramic film of this embodiment, it is possible to impart a gas barrier function, particularly a moisture barrier function, to the organic EL element.

<Cathode>
The cathode 52 may be made of, for example, a metal element such as Li, Na, Mg, Ca, Sr, Al, Ag, In, Sn, Zn, or Zr, or an alloy thereof. Furthermore, an electrode protective film such as LiF may be formed on the cathode in the same manner as for the cathode. Other preferred materials include ITO, IZO, FTO, and aluminum. The sheet resistance of the cathode is preferably several hundred Ω/□ or less.

The average thickness of the cathode 52 is preferably 10 to 500 nm, and more preferably 100 to 200 nm. Thickness can be measured using spectroscopic ellipsometry, a surface roughness meter, or microscopic image analysis.

<Anode>
For example, gold, silver, aluminum, ITO, ZnO, etc. are preferably used as the anode 59. When light is extracted from the anode, the transmittance is preferably 10% or more. The sheet resistance of the anode is preferably several hundred Ω/□ or less. The thickness can be measured by spectroscopic ellipsometry, a surface roughness meter, or microscope image analysis. When forming the anode by vacuum deposition, a quartz crystal film thickness meter can be used. The average thickness of the anode 59 is preferably 10 to 1,000 nm, and more preferably 10 to 200 nm.

(Image forming method and image forming apparatus)
The image forming method of the present invention is an image forming method comprising at least a charging step of charging the surface of a photoreceptor, an exposure step of exposing the charged surface of the photoreceptor to light to form an electrostatic latent image, a development step of developing the electrostatic latent image with a developer to form a visible image, and a transfer step of transferring the visible image to a recording medium, wherein the photoreceptor is the photoreceptor of the present invention.
The image forming apparatus of the present invention is an image forming apparatus having at least a photosensitive member, a charging means for charging the surface of the photosensitive member, an exposure means for exposing the charged surface of the photosensitive member to light to form an electrostatic latent image, a developing means for developing the electrostatic latent image with a developer to form a visible image, and a transfer means for transferring the visible image to a recording medium, wherein the photosensitive member is the photosensitive member of the present invention.
The image forming method and apparatus of the present invention may further include other steps and means as necessary. The charging means and the exposure means may be collectively referred to as an electrostatic latent image forming means.

An embodiment of the image forming method and image forming apparatus of the present invention will be described below by taking an example thereof.
9 is a schematic diagram for explaining the image forming apparatus of the present invention, in which a charging unit 3, an exposure unit 5, a developing unit 6, a transfer unit 10, etc. are arranged around a photoreceptor 1. First, the photoreceptor 1 is evenly charged by the charging unit 3. As the charging unit 3, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, etc. may be used, and known methods can be used.

Next, an electrostatic latent image is formed on the uniformly charged photoreceptor 1 by the exposure means 5. The light source can be any light-emitting device, including fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LEDs), semiconductor lasers (LDs), and electroluminescence (EL). Various filters, such as sharp-cut filters, band-pass filters, near-infrared cut filters, dichroic filters, interference filters, and color temperature conversion filters, can also be used to irradiate only light in the desired wavelength range.

Next, the electrostatic latent image formed on the photoreceptor 1 is visualized by the developing means 6. Development methods include one-component development using dry toner, two-component development, and wet development using wet toner. When the photoreceptor 1 is positively (negatively) charged and exposed to light, a positive (negative) electrostatic latent image is formed on the surface of the photoreceptor. If this is developed with toner of negative (positive) polarity (electroscopic fine particles), a positive image is obtained, and if it is developed with toner of positive (negative) polarity, a negative image is obtained.

Next, the toner image visualized on the photoreceptor 1 is transferred by the transfer means 10 onto the recording medium 9 delivered by the roller 8. A pre-transfer charger 7 may also be used to improve transfer. The transfer means 10 can be an electrostatic transfer method using a transfer charger, bias roller, etc.; a mechanical transfer method such as adhesive transfer or pressure transfer; or a magnetic transfer method.

If necessary, a separation charger 11 and separation claws 12 may be used to separate the recording medium 9 from the photoreceptor 1. Other separation methods include electrostatic attraction-induced separation, side edge belt separation, tip grip transport, and curvature separation. The aforementioned charging device can be used as the separation charger 11. Cleaning devices such as a fur brush 14 and cleaning blade 15 are used to clean toner remaining on the photoreceptor after transfer, and a pre-cleaning charger 13 may be used for more efficient cleaning. Other cleaning methods include web methods and magnetic brush methods, and these may be used alone or in combination. A discharger 2 may also be used to remove the latent image on the photoreceptor 1. A discharge lamp, discharger, or other device may be used as the discharger 2, and the aforementioned exposure light source and charging device may be used, respectively. Other known processes, such as document reading, paper feeding, fixing, and paper discharge, that are not close to the photoreceptor, can be used.

The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that "parts" refers to parts by mass unless otherwise specified. Furthermore, Examples 1, 2, 5, 7, and 8 refer to Reference Examples 1, 2, 5, 7, and 8, which are not included in the present invention.

Example 1
The following primer layer coating solution was applied to a 100 μm polyester film (Teonex Q51-A4-100 μm, manufactured by Teijin Limited) using a doctor blade, and then dried for 5 minutes at 130° C. The average thickness of the primer layer at this stage was 1 μm.

(Undercoat layer coating liquid)
100 parts of siloxane compound-containing paint (NSC-3101, Nippon Fine Chemical Co., Ltd.) 3 parts of trimethylethoxysilane (Tokyo Chemical Industry Co., Ltd.)

Next, a surface layer was formed on the surface of this film by the AD method using an apparatus as shown in Figure 7. High-purity alumina particles (Taimicron TM-DAR, Taimei Chemical Industry Co., Ltd.) were used as the metal oxide for film formation.
The film formation conditions by the AD method are as follows.

(Film formation conditions)
Moisture content of alumina particles: 0.2% or less (measured using a Karl Fischer moisture meter)
Dew point temperature when powder is charged into the container: -50°C or lower Aerosol gas type: Nitrogen gas Aerosol gas flow rate: 12 L/min (total amount)
Vacuum level inside the film formation chamber: 200 Pa
Angle between nozzle and coating sample: 60 degrees Distance between nozzle and coating sample: 15 mm
Coating speed: 200 mm/min
・Number of coatings: 6 times (3 round trips)

Example 2
A film was produced in the same manner as in Example 1, except that the conditions for forming the surface layer by the AD method in Example 1 were changed as follows.
(Film formation conditions)
Moisture content of alumina particles: 0.2% or less (measured using a Karl Fischer moisture meter)
Dew point temperature when powder is charged into the container: -50°C or below Aerosol gas type: Nitrogen gas Aerosol gas flow rate: 5 L/min (total amount)
Vacuum level inside the film formation chamber: 50 Pa
Angle between nozzle and coating sample: 80 degrees Distance between nozzle and coating sample: 5 mm
Coating speed: 200 mm/min
・Number of coatings: 6 times (3 round trips)

(Comparative Example 1)
A protective film was produced in the same manner as in Example 1, except that trimethylethoxysilane was not used in the undercoat layer coating liquid in Example 1.

Example 3
-Example of manufacturing an electrophotographic photoreceptor-
An electrophotographic photoreceptor of Example 3 having, on a conductive support 201, an intermediate layer 207, a charge generating layer 203, a charge transport layer 204, an undercoat layer 208, and a surface layer 209 made of a metal oxide-containing layer, in this order, as shown in FIG. 6 was produced by the following procedure.

- Formation of the middle class -
The intermediate layer was formed by applying the following intermediate layer coating solution to an aluminum conductive support (outer diameter 100 mm) by a dip coating method. After drying at 170°C for 30 minutes, the average thickness of the intermediate layer was 3 µm.

(Coating liquid for intermediate layer)
Zinc oxide particles (MZ-300, manufactured by Teika Corporation): 350 parts 3,5-di-t-butylsalicylic acid: 1.5 parts (TCI-D1947, manufactured by Tokyo Chemical Industry Co., Ltd.)
Blocked isocyanate: 60 parts (Sumidur (registered trademark) 3175, solid content concentration 75% by mass, manufactured by Sumika Bayer Urethane Co., Ltd.)
Solution of 20% by mass of butyral resin dissolved in 2-butanone: 225 parts (BM-1, manufactured by Sekisui Chemical Co., Ltd.)
・2-butanone: 365 parts

- Formation of charge generation layer -
The following charge generating layer coating liquid was dip coated onto the resulting intermediate layer to form a charge generating layer.
The average thickness of the charge generating layer was 0.2 μm.

(Coating liquid for charge generating layer)
Y-type titanyl phthalocyanine: 6 parts Butyral resin (S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd.): 4 parts 2-butanone (manufactured by Kanto Chemical Co., Ltd.): 200 parts

- Formation of charge transport layer -
The resulting charge generating layer was dip-coated with the following charge transport layer coating liquid 1 to form a charge transport layer.
After drying at 135°C for 20 minutes, the average thickness of the charge transport layer was 22 µm.

(Coating liquid 1 for charge transport layer)
Bisphenol Z-type polycarbonate: 10 parts (Panlite TS-2050, manufactured by Teijin Limited)
10 parts of a low molecular weight charge transport material of the following structural formula:

- Tetrahydrofuran: 80 parts

- Formation of primer layer -
An undercoat layer was formed on the resulting charge transport layer by ring coating using the following undercoat layer coating liquid, and after drying at 120° C. for 20 minutes, the average thickness of the undercoat layer was 1 μm.

(Coating liquid for undercoat layer)
Siloxane compound-containing paint: NSC-5506 (manufactured by Nippon Fine Chemical Co., Ltd.) 180 parts, trimethylethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 6 parts, polysilane (OGSOL SI-10-10, manufactured by Osaka Gas Chemicals Co., Ltd.) 15 parts, tetrahydrofuran (manufactured by Mitsubishi Chemical Corporation) 180 parts

- Formation of metal oxide-containing layer -
(Production of metal oxide powder)
2 kg of copper(I) oxide (NC-803, manufactured by Nippon Chemical Industry Co., Ltd.) and 1.43 kg of alumina (AA-03, manufactured by Sumitomo Chemical Co., Ltd.) were mixed and heated at 1,100°C for 40 hours to obtain copper aluminum oxide. This was pulverized using a dry disperser (Drystar SDA1, manufactured by Ashizawa Finetech Co., Ltd.), and by changing the pulverization conditions, copper aluminum oxide powders with cumulative particle sizes D50 of 0.8 μm, 1.0 μm, 2.1 μm, 4.3 μm, and 6.6 μm were obtained. The powder particle size was measured in dry mode under a pressure of 0.2 MPa using a laser diffraction/scattering particle size distribution analyzer (MT-3300EX, manufactured by Microtrac Bell Co., Ltd.).

Next, a metal oxide-containing layer was formed on the surface of the undercoat layer by the AD method using the above copper aluminum oxide powder (cumulative particle size D50: 4.3 μm).
The metal oxide-containing layer was formed by the AD method under the following conditions.

(Film formation conditions)
Moisture content of copper aluminum oxide powder: 0.2% or less (measured using a Karl Fischer moisture meter)
・Dew point temperature when powder is put into the container: -50°C
Aerosol gas type: nitrogen gas Aerosol gas flow rate: 5 L/min (total amount)
Vacuum level inside the film formation chamber: 55 Pa
Angle between nozzle and photosensitive drum: 80 degrees Distance between nozzle and photosensitive drum: 30 mm
Coating speed: 20 mm/min
Drum rotation speed: 20 rpm
・Number of coatings: 6 times (3 round trips)

Example 4
An electrophotographic photoreceptor was produced in the same manner as in Example 3, except that the conditions for forming the undercoat layer coating liquid and the metal oxide-containing layer in Example 3 were changed as follows.

(Coating liquid for undercoat layer)
Siloxane compound-containing paint: 60 parts of NSC-5506 (manufactured by Nippon Fine Chemical Co., Ltd.), 3 parts of trimethylethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 5 parts of polysilane (OGSOL SI-10-10, manufactured by Osaka Gas Chemicals Co., Ltd.), and 60 parts of tetrahydrofuran (manufactured by Mitsubishi Chemical Corporation).

A metal oxide-containing layer was formed on the surface of the undercoat layer by the AD method using the above copper aluminum oxide powder (cumulative particle size D50: 2.1 μm).
The metal oxide-containing layer was formed by the AD method under the following conditions.

(Film formation conditions)
Moisture content of copper aluminum oxide powder: 0.2% or less (measured using a Karl Fischer moisture meter)
・Dew point temperature when powder is placed in the container: -55°C
Aerosol gas type: nitrogen gas Aerosol gas flow rate: 4 L/min (total amount)
Vacuum level inside the film formation chamber: 50 Pa
Angle between nozzle and photosensitive drum: 80 degrees Distance between nozzle and photosensitive drum: 30 mm
Coating speed: 20 mm/min
Drum rotation speed: 20 rpm
・Number of coatings: 6 times (3 round trips)

Example 5
An electrophotographic photoreceptor was produced in the same manner as in Example 4, except that the conditions for forming the metal oxide-containing layer in Example 4 were changed as follows.

- Formation of metal oxide-containing layer -
(Production of metal oxide powder)
500 g of high-purity alumina particles (Taimicron TM-DAR, manufactured by Taimei Chemical Industry Co., Ltd.) and 500 g of barium titanate (manufactured by Kanto Chemical Co., Ltd.) were mixed in a Turbula mixer and pulverized using a dry disperser (Drystar SDA1, manufactured by Ashizawa Finetech Co., Ltd.) to obtain a metal oxide mixed powder with a cumulative particle size D50 of 0.8 μm.

Next, a metal oxide-containing layer was formed on the surface of the undercoat layer by the AD method using the above mixed powder.
The metal oxide-containing layer was formed by the AD method under the following conditions.

(Film formation conditions)
Moisture content of metal oxide mixed powder: 0.2% or less (measured using a Karl Fischer moisture meter)
・Dew point temperature when powder is placed in the container: -55°C
Aerosol gas type: nitrogen gas Aerosol gas flow rate: 4 L/min (total amount)
Vacuum level inside the film formation chamber: 50 Pa
Angle between nozzle and photosensitive drum: 80 degrees Distance between nozzle and photosensitive drum: 5 mm
Coating speed: 20 mm/min
Drum rotation speed: 20 rpm
・Number of coatings: 6 times (3 round trips)

(Comparative Example 2)
An electrophotographic photoreceptor was produced in the same manner as in Example 3, except that the conditions for forming the undercoat layer coating liquid and the metal oxide-containing layer in Example 3 were changed as follows.

(Coating liquid for undercoat layer)
Siloxane compound-containing paint: NSC-5506 (manufactured by Nippon Fine Chemical Co., Ltd.) 60 parts, polysilane (OGSOL SI-10-10, manufactured by Osaka Gas Chemicals Co., Ltd.) 5 parts, tetrahydrofuran (manufactured by Mitsubishi Chemical Corporation) 60 parts

A metal oxide-containing layer was formed on the surface of the undercoat layer by the AD method using the above copper aluminum oxide powder (cumulative particle size D50: 0.8 μm).
The metal oxide-containing layer was formed by the AD method under the following conditions.

(Film formation conditions)
Moisture content of copper aluminum oxide powder: 0.2% or less (measured using a Karl Fischer moisture meter)
・Dew point temperature when powder is put into the container: -52°C
Aerosol gas type: nitrogen gas Aerosol gas flow rate: 12 L/min (total amount)
Vacuum level inside the film formation chamber: 200 Pa
Angle between nozzle and photosensitive drum: 60 degrees Distance between nozzle and photosensitive drum: 30 mm
Coating speed: 20 mm/min
Drum rotation speed: 20 rpm
・Number of coatings: 6 times (3 round trips)

Example 6
The organic EL element shown in Fig. 8 was fabricated by the following procedure. An _SiO2 layer was used as an undercoat layer on the resin surface of the polyester film used in Example 1, and an indium-tin oxide (ITO) film with a surface resistance of 15 Ω/□ was formed by sputtering to form a cathode 52. The substrate was then washed successively with a neutral detergent, an oxygen-based cleaning agent, and isopropyl alcohol.
Next, sputtering was performed using ITZO as a target under vacuum conditions of 1×10 ⁻⁴ Pa by introducing argon and oxygen to form a 20 nm electron injection layer 53. Next, ultrasonic cleaning was performed with acetone and isopropyl alcohol for 10 minutes, followed by drying by spraying nitrogen gas, and UV ozone cleaning for 10 minutes.
Next, tris(8-quinolinolato)aluminum (Alq3) was vacuum-deposited in a vacuum deposition apparatus to form an electron transport layer 54 of 20 nm, and a compound of the following structural formula (B) was vacuum-deposited in a vacuum deposition apparatus to form a light-emitting layer 55 of 15 nm.

Next, a hole transport material represented by the following structural formula (C) was vacuum-deposited on top of the layer to a thickness of 20 nm to form a hole transport layer 56. In this way, an organic EL layer having an electron injection layer 53, an electron transport layer 54, an emitting layer 55, and a hole transport layer 56 was formed.

Next, a coating liquid for undercoat layer having the following composition was applied by inkjet printing to form an undercoat layer 57 having a thickness of 100 nm.
(Coating liquid for undercoat layer)
Siloxane compound-containing paint: 180 parts of NSC-5506 (manufactured by Nippon Fine Chemicals Co., Ltd.), 6 parts of trimethylethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 15 parts of polysilane (OGSOL SI-10-10, manufactured by Osaka Gas Chemicals Co., Ltd.), 100 parts of tetrahydrofuran (manufactured by Mitsubishi Chemical Corporation), and 80 parts of cyclohexanone (manufactured by Kanto Chemical Co., Ltd.).

The inkjet head used was a GEN3E2 inkjet head manufactured by Ricoh Industry Co., Ltd. The drawing frequency was 310 Hz, and the distance between the head and the substrate was 1 mm. The pulse voltage was 20 V. After film formation, a vacuum drying process was performed at 120° C. for 1 hour.
Next, a copper aluminum oxide (CuAlO ₂ ) film was formed to a thickness of 50 nm by aerosol deposition to form a surface layer 58. Furthermore, an anode 59 made of an ITO film to a thickness of 150 nm was formed by sputtering to obtain an organic EL element.

A portion was cut from each of the articles of Examples 1 to 6 and Comparative Examples 1 and 2, and the samples were processed using a focused ion beam processing device (Quanta 3D, FEI) to create a smooth cross section. The cross sections were then observed using an electron microscope (Ultra-55, Carl Zeiss) and an energy dispersive X-ray analyzer (NORAN System Six, Thermo Fisher Scientific) for EDS mapping. The standard conditions for electron microscope observation were an accelerating voltage of 2.0 kV, a magnification of 10,000x, and observation using an in-lens detector. The distribution of metal oxides contained in the primer layer was evaluated from these observations.

A scratch test was conducted on the surface layers of the laminates of Examples 1 to 6 and Comparative Examples 1 and 2. The scratch test was conducted using a scratch tester (CSR-2000, manufactured by Rhesca Co., Ltd.) with a stylus diameter of 5 μm, a scratch speed of 10 μm/s, an excitation level of 50 μm, and a load setting of 10 mN to create a scratch with a width of 50 μm. The magnitude of the load at the bending point of the signal output, which corresponds to the frictional force obtained in the scratch test, was evaluated.
The results are shown in Table 1. In Table 1, the substrate refers to the layer immediately below the undercoat layer (the layer on the opposite side to the ceramic film).

Undercoat layers containing siloxane compounds with metal oxides distributed homogeneously or in large quantities at the substrate interface exhibit excellent scratch resistance.

<Evaluation of Electrophotographic Photoreceptors>
The following evaluations were carried out on the electrophotographic photoreceptors of Examples 3 to 5 and Comparative Example 2, which were prepared as described above. The evaluation results for each electrophotographic photoreceptor are shown in Table 2.

<Image evaluation after exposure to _NO2 >
First, the electrophotographic photosensitive member is left standing in an _NO atmosphere for a certain period of time to adsorb _NO on the surface of the electrophotographic photosensitive member. As a result of examining the conditions for saturating _NO adsorption at the adsorption sites in the vicinity of the surface of the electrophotographic photosensitive member using various electrophotographic photosensitive members, it was found that exposure for 24 hours in a chamber controlled to a concentration of 40 ppm was preferable, and therefore the exposure conditions were set to an _NO concentration of 40 ppm atmosphere and an exposure time of 24 hours.

In addition, for image evaluation after _NO2 exposure, a modified Ricoh Pro C9110 (manufactured by Ricoh Co., Ltd.) was used, which had been modified to eliminate the initial idle process during image output. Pro Toner Black C9100 was used, and A3-size copy paper (POD Gloss Coat, manufactured by Oji Paper Co., Ltd.) was used for image evaluation. As output images, a halftone output was performed on three sheets in succession, forming a dot image of a continuous black and white pattern at 1200 dpi every four dots vertically and horizontally, at the timing of printing 0 sheets, 500,000 sheets, and 5,000,000 sheets of the evaluation pattern. The dot reproduction state of the three output images was confirmed visually and with a microscope, and evaluated based on the following evaluation criteria.

[Evaluation criteria]
5: The dot reproduction state of the three output images is unchanged from the initial print quality and is not a problem. 4: The dot reproduction state of the three output images is slightly inferior to the initial print quality, but no change is visible to the naked eye and is not a problem. 3: There is a slight change in the dot reproduction state of the three output images, but it is not a problem in actual use. 2: Slight bleeding is observed in the dot reproduction state of the three output images. 1: A clear change in density is observed in the dot reproduction state of the three output images.

In the undercoat layer containing the siloxane compound, the metal oxide is distributed homogeneously or in a large amount at the interface with the substrate, and excellent image evaluation characteristics can be obtained.
Furthermore, when the metal oxide content near the interface between the plastic film or photosensitive layer and the primer layer is higher than the metal oxide content near the opposite surface to the interface, the ceramic film has excellent strength and durability. This morphology can be obtained by adjusting the AD conditions in various ways.

Example 7
The following primer layer coating solution was applied with a doctor blade to a 1.0 mm thick polycarbonate sheet (Technoloy C000 polycarbonate resin sheet, Sumika Acryl Co., Ltd.) using the following procedure, followed by drying at 80° C. for 20 minutes and then at 120° C. for 20 minutes, resulting in an average primer layer thickness of 3 μm.

(Undercoat layer coating liquid)
Silicone paint (X-40-9250, Shin-Etsu Chemical Co., Ltd.) 380 parts; catalyst (DX-9740, Shin-Etsu Chemical Co., Ltd.) 20 parts; cyclopentanone (Tokyo Chemical Industry Co., Ltd.) 444 parts; tetrahydrofuran (Mitsubishi Chemical Corporation) 1,556 parts

Next, a surface layer was formed on the surface of this sheet by the AD method using an apparatus as shown in FIG.
High-purity alumina particles (Taimicron TM-DAR, Taimei Chemical Industry Co., Ltd.) were used as the metal oxide for film formation.
The film formation conditions by the AD method are as follows.

(Film formation conditions)
Moisture content of alumina particles: 0.2% or less (measured using a Karl Fischer moisture meter)
Dew point temperature when powder is charged into the container: -50°C or below Aerosol gas type: Nitrogen gas Aerosol gas flow rate: 5 L/min (total amount)
Vacuum level inside the film formation chamber: 50 Pa
Angle between nozzle and coating sample: 60 degrees Distance between nozzle and coating sample: 15 mm
Coating speed: 200 mm/min
・Number of coatings: 6 times (3 round trips)

(Example 8)
Sheets were produced in the same manner as in Example 7, except that the undercoat layer coating liquid in Example 7 was changed as follows, and the conditions for forming the surface layer (metal oxide-containing layer) were changed as follows.
(Undercoat layer coating liquid)
Silicone paint (KR-401, Shin-Etsu Chemical Co., Ltd.) 400 parts Cyclopentanone (Tokyo Chemical Industry Co., Ltd.) 444 parts Tetrahydrofuran (Mitsubishi Chemical Corporation) 1,556 parts

(Film formation conditions)
Moisture content of alumina particles: 0.2% or less (measured using a Karl Fischer moisture meter)
・Dew point temperature when powder is placed in the container: -55°C
Aerosol gas type: nitrogen gas Aerosol gas flow rate: 12 L/min (total amount)
Vacuum level inside the film formation chamber: 200 Pa
Angle between nozzle and photosensitive drum: 60 degrees Distance between nozzle and photosensitive drum: 30 mm
Coating speed: 20 mm/min
Drum rotation speed: 20 rpm
・Number of coatings: 6 times (3 round trips)

Example 9
An electrophotographic photoreceptor was produced in the same manner as in Example 3, except that the conditions for forming the undercoat layer coating liquid and the metal oxide-containing layer in Example 3 were changed as follows.

(Undercoat layer coating liquid)
Silicone paint (X-40-9250, Shin-Etsu Chemical Co., Ltd.) 76 parts; catalyst (DX-9740, Shin-Etsu Chemical Co., Ltd.) 4 parts; polysilane (OGSOL SI-10-40, manufactured by Osaka Gas Chemicals Co., Ltd.) 20 parts; tetrahydrofuran (manufactured by Mitsubishi Chemical Corporation) 400 parts

A metal oxide-containing layer was formed on the surface of the undercoat layer by the AD method using the above copper aluminum oxide powder (cumulative particle size D50: 2.1 μm).
The metal oxide-containing layer was formed by the AD method under the following conditions.

(Film formation conditions)
Moisture content of copper aluminum oxide powder: 0.2% or less (measured using a Karl Fischer moisture meter)
・Dew point temperature when powder is put into the container: -50°C
Aerosol gas type: nitrogen gas Aerosol gas flow rate: 5 L/min (total amount)
Vacuum level inside the film formation chamber: 50 Pa
Angle between nozzle and photosensitive drum: 80 degrees Distance between nozzle and photosensitive drum: 30 mm
Coating speed: 20 mm/min
Drum rotation speed: 20 rpm
・Number of coatings: 6 times (3 round trips)

Example 10
An electrophotographic photoreceptor was produced in the same manner as in Example 9, except that the conditions for forming the undercoat layer coating liquid and the metal oxide-containing layer in Example 9 were changed as follows.

(Undercoat layer coating liquid)
Silicone paint (X-40-9250, Shin-Etsu Chemical Co., Ltd.) 76 parts Catalyst (DX-9740, Shin-Etsu Chemical Co., Ltd.) 4 parts Charge transporting material of the following structure 20 parts

- 400 parts tetrahydrofuran (Mitsubishi Chemical Corporation)

(Film formation conditions)
Moisture content of copper aluminum oxide powder: 0.2% or less (measured using a Karl Fischer moisture meter)
・Dew point temperature when powder is put into the container: -52°C
Aerosol gas type: nitrogen gas Aerosol gas flow rate: 12 L/min (total amount)
Vacuum level inside the film formation chamber: 200 Pa
Angle between nozzle and photosensitive drum: 60 degrees Distance between nozzle and photosensitive drum: 30 mm
Coating speed: 20 mm/min
Drum rotation speed: 20 rpm
・Number of coatings: 6 times (3 round trips)

A scratch test was carried out on the surface layers of the laminates of Examples 7 to 10. The scratch test was carried out using a scratch tester (CSR-2000, manufactured by Rhesca Co., Ltd.) with a stylus diameter of 5 μm, a scratch speed of 10 μm/s, an excitation level of 50 μm, and a set load of 10 mN to create a scratch with a width of 50 μm. The magnitude of the load at the bending point of the signal output, which corresponds to the frictional force obtained in the scratch test, was evaluated.
The results are shown in Table 3. In Table 3, the substrate refers to the layer immediately below the undercoat layer (the layer on the opposite side to the ceramic film).

Any primer layer containing a siloxane compound and in which metal oxides are uniformly distributed exhibits excellent scratch resistance.

<Evaluation of Electrophotographic Photoreceptors>
The electrophotographic photoreceptors of Examples 9 and 10 prepared as described above were subjected to the same evaluation as in Example 3. Table 4 shows the evaluation results for each electrophotographic photoreceptor.

In the undercoat layer containing the siloxane compound, the metal oxide is distributed homogeneously or in a large amount at the interface with the substrate, and excellent image evaluation characteristics can be obtained.
Furthermore, when the metal oxide content near the interface between the plastic film or photosensitive layer and the primer layer is higher than the metal oxide content near the opposite surface to the interface, the ceramic film has excellent strength and durability. This morphology can be obtained by adjusting the AD conditions in various ways.

1 Photoconductor 2 Discharger 3 Charging means 5 Exposure means 6 Developing means 7 Pre-transfer charger 8 Roller 9 Recording medium 10 Transfer means 11 Separation charger 12 Separation claw 13 Pre-cleaning charger 14 Fur brush 15 Cleaning blade 50C Organic EL element 51 Support 52 Cathode 53 Electron injection layer 54 Electron transport layer 55 Light-emitting layer 56 Hole transport layer 57 Undercoat layer 58 Surface layer 59 Anode 111 Gas cylinder 112a Pipe 112b Pipe 112c Pipe 113 Aerosol generator 114 Film-forming chamber 115 Spray nozzle 116 Substrate (photoconductor)
117 Substrate holder 118 Exhaust pump 119 Compressed air valve 120 Particles 201 Support 202 Photosensitive layer 203 Charge generation layer 204 Charge transport layer 205 Undercoat layer 206 Protective layer 207 Intermediate layer 208 Undercoat layer 209 Surface layer

International Publication No. WO2017/199968 Pamphlet International Publication No. WO2018/194064 Pamphlet

Claims (5)

a layer (1) containing an organic material;
a layer (2) containing a siloxane compound and a metal oxide in contact with the layer (1) containing an organic material;
a layer (3) containing the metal oxide in contact with the layer (2) containing the siloxane compound and the metal oxide;
A laminate for use in an electrophotographic photoreceptor or an organic EL element ,
the metal oxide contained in the layer (3) includes either delafossite or perovskite,
The laminate is obtained by crosslinking the siloxane compound with an organosilicon compound having either a hydroxyl group or a hydrolyzable group. the layer (1) containing the organic material and the layer (2) containing the siloxane compound and the metal oxide form an interface (12);
the layer (2) containing a siloxane compound and a metal oxide and the layer (3) containing a metal oxide form an interface (23);
2. The laminate according to claim 1, wherein the layer (2) containing the siloxane compound and the metal oxide has a higher content of the metal oxide in the vicinity of the interface (12) than in the vicinity of the interface (23). 3. The laminate according to claim 1 , wherein the organic material is a charge transport material or a sensitizing dye. 4. The laminate according to claim 1 , wherein the siloxane compound has the following structure:
A device comprising a support and the laminate according to any one of claims 1 to 4 on said support.