阅读说明：本技术 光电转换元件、有机光电导体、图像形成方法、图像形成设备和有机el元件 (Photoelectric conversion element, organic photoconductor, image forming method, image forming apparatus, and organic EL element ) 是由 纸英利 浅野友晴 于 2020-01-31 设计创作，主要内容包括：提供了光电转换元件,其包括：支撑体；光电转换层；底涂层；和表面层,其中光电转换层、底涂层和表面层以此顺序设置在支撑体上或上方,其中表面层为陶瓷膜,并且其中底涂层包括硅氧烷树脂。(Provided is a photoelectric conversion element including: a support body; a photoelectric conversion layer; a primer layer; and a surface layer, wherein the photoelectric conversion layer, the undercoat layer, and the surface layer are disposed in this order on or above the support, wherein the surface layer is a ceramic film, and wherein the undercoat layer comprises a silicone resin.)

1. A photoelectric conversion element, comprising:

a support body;

a photoelectric conversion layer;

a primer layer; and

a surface layer, wherein the photoelectric conversion layer, the undercoat layer, and the surface layer are disposed in this order on or above the support,

wherein the surface layer is a ceramic film, and

wherein the primer layer comprises a silicone resin.

2. The photoelectric conversion element according to claim 1,

wherein the primer layer and the surface layer are in contact with each other.

3. The photoelectric conversion element according to claim 1 or 2,

wherein the primer layer has a thickness of 0.01 microns or more but 2.5 microns or less.

4. The photoelectric conversion element according to any one of claims 1 to 3,

wherein the ceramic film comprises a transparent conductive oxide.

5. The photoelectric conversion element according to claim 4,

wherein the transparent conductive oxide comprises hematite.

6. The photoelectric conversion element according to claim 5,

wherein the cuprite comprises copper aluminum oxide.

7. The photoelectric conversion element according to claim 6,

wherein the copper aluminum oxide is CuAlO₂。

8. An organic photoconductor, comprising:

the photoelectric conversion element according to any one of claims 1 to 7.

9. An image forming method, comprising:

charging a surface of a photoconductor;

exposing the charged surface of the photoconductor to light to form a latent electrostatic image;

developing the latent electrostatic image with a developer to form a visible image; and

transferring the visible image to a recording medium,

wherein the photoconductor is the organic photoconductor according to claim 8.

10. An image forming apparatus, comprising:

a photoconductor;

a charging unit configured to charge a surface of the photoconductor;

an exposure unit configured to expose the charged surface of the photoconductor to light to form a latent electrostatic image;

a developing unit configured to develop the electrostatic latent image with a developer to form a visible image; and

a transfer unit configured to transfer the visible image onto a recording medium,

wherein the photoconductor is the organic photoconductor according to claim 8.

11. An organic EL element, comprising:

the photoelectric conversion element according to any one of claims 1 to 7.

Technical Field

The present disclosure relates to a photoelectric conversion element, an organic photoconductor, an image forming method, an image forming apparatus, and an organic EL element.

Background

Conventionally, many documents have been printed by electrophotographic apparatuses, and electrophotographic apparatuses have been effectively used for various purposes. However, due to the current trend of paper reduction and cost reduction, the chances of printing documents on paper media decrease year by year. Meanwhile, it has been considered to expand the use of electrophotographic apparatuses from office-only printing to commercial printing. Since electrophotography does not include a master production step, such as in offset printing, electrophotography has the advantage of on-demand printing in which various types of documents can be printed in a very small number of batches but in a large amount.

As a photoconductor for an electrophotographic apparatus, an organic photoconductor using an organic material has been widely used. In general, an organic photoconductor includes a conductive support formed of aluminum or the like and a photoconductive layer including an organic compound, wherein the photoconductive layer is disposed on the conductive support. The organic photoconductor is more advantageous than the inorganic photoconductor in that the organic photoconductor has excellent charging ability, the materials corresponding to various exposure light sources ranging from visible light to infrared light are easily developed, the materials that do not pollute the environment can be selected for use, and the production cost thereof is low. However, the organic photoconductors also have disadvantages in that the organic photoconductors have low physical and chemical durability and thus are liable to form abrasion or scratch after long-term use.

At the same time, the uniformity of the print is very important for commercial printing. The printed matter printed by the conventional electrophotographic apparatus has a problem in that the uniformity is inferior to that obtained in offset printing.

Furthermore, productivity and profit margins are more important for commercial printing than for office printing. Therefore, it is important to keep the replacement frequency of the photoconductors low. At present, the service life of a photoconductor used in a high-end model of an electrophotographic apparatus is generally set to about 1,000,000 prints. Even such a service life is not sufficient to achieve the desired durability of commercial printing.

Patent document 1 aims to provide an electrophotographic photoconductor having high sensitivity to a light source of short-wavelength light, and discloses an electrophotographic photoconductor including a support and a charge generation layer composed of a metal oxide including nitrogen, in which the charge generation layer is provided on the support.

However, the electrophotographic photoconductor disclosed in patent document 1 has a problem in that durability that can withstand commercial printing cannot be obtained.

As an element using the same technique as photoelectric conversion in an electrophotographic photoconductor, an organic Electroluminescence (EL) element is known. The organic EL element is formed by laminating display elements such as an organic EL light emitting layer sandwiched between an anode and a cathode on a substrate. The organic EL display element has a wider viewing angle than the liquid crystal display device. In addition, the organic EL display element has a fast response speed, and is expected as a next-generation display element due to its diversity of luminance due to an organic substance.

However, the organic EL element has a problem in that it is easily deteriorated when exposed to heat, moisture, or gas such as oxygen, resulting in a shortened life of the organic EL element.

Reference list

Patent document

Patent document 1

Unexamined Japanese patent application laid-open No. 2008-180937

Disclosure of Invention

Technical problem

Therefore, an object of the present disclosure is to provide a photoelectric conversion element having durability sufficient to withstand application of commercial printing or display elements.

Technical scheme

According to one aspect of the present disclosure, a photoelectric conversion element includes: a support body; a photoelectric conversion layer; a primer layer; and a surface layer. The photoelectric conversion layer, the undercoat layer, and the surface layer are disposed in this order on or above the support. The surface layer is a ceramic film. The primer layer includes a silicone resin.

Advantageous effects of the invention

The present disclosure can provide a photoelectric conversion element having durability sufficient to withstand the application of commercial printing or display elements.

Drawings

[ FIG. 1]

Fig. 1 is a schematic cross-sectional view depicting an embodiment of a photoconductor of the present disclosure.

[ FIG. 2]

Fig. 2 is a schematic cross-sectional view depicting another embodiment of a photoconductor of the present disclosure.

[ FIG. 3]

Fig. 3 is a schematic cross-sectional view depicting another embodiment of a photoconductor of the present disclosure.

[ FIG. 4]

Fig. 4 is a schematic cross-sectional view depicting another embodiment of a photoconductor of the present disclosure.

[ FIG. 5]

Fig. 5 is a schematic cross-sectional view depicting another embodiment of a photoconductor of the present disclosure.

[ FIG. 6]

Fig. 6 is a schematic cross-sectional view depicting another embodiment of a photoconductor of the present disclosure.

[ FIG. 7]

Fig. 7 is a schematic diagram depicting an aerosol deposition device.

[ FIG. 8]

Fig. 8 is a schematic cross-sectional view describing an embodiment of the organic EL element of the present disclosure.

[ FIG. 9]

Fig. 9 is a view describing an embodiment of an image forming method and an image forming apparatus of the present disclosure.

Detailed Description

Hereinafter, embodiments of the present disclosure will be described in detail.

The photoelectric conversion element of the present disclosure includes a support, a photoelectric conversion layer, an undercoat layer, and a surface layer, wherein the photoelectric conversion layer, the undercoat layer, and the surface layer are disposed in this order on or above the support. The surface layer is a ceramic film and the primer layer comprises a silicone resin.

(photoconductor)

First, an example of a case where the photoelectric conversion element of the present disclosure is a photoconductor will be described. In the case of a photoconductor, it is preferable that the photoelectric conversion layer is configured as a photoconductive layer, and the support is configured as a conductive support. The photoconductor of the present disclosure is preferably an organic photoconductor.

Fig. 1 is a schematic cross-sectional view depicting one embodiment of a photoconductor of the present disclosure.

In fig. 1, the photoconductor 1 includes a conductive support 201, a photoconductive layer 202 disposed on the conductive support 201, and an undercoat layer 208 and a surface layer 209 sequentially disposed on the photoconductive layer 202. As described above, in the photoconductor 1 of the present disclosure, the surface layer 209 is a ceramic film, and the undercoat layer 208 includes a silicone resin.

Fig. 2 is a schematic cross-sectional view depicting another embodiment of a photoconductor of the present disclosure.

The photoconductor 1 of fig. 2 is a function-split photoconductor in which a photoconductive layer includes a Charge Generation Layer (CGL)203, and a Charge Transport Layer (CTL) 204.

Fig. 3 is a schematic cross-sectional view depicting another embodiment of a photoconductor of the present disclosure.

The photoconductor 1 of fig. 3 is an embodiment in which an underlayer 205 is provided between the support 201 and the charge generation layer in the function-separating photoconductor 1 shown in fig. 2.

Fig. 4 is a schematic cross-sectional view depicting another embodiment of a photoconductor of the present disclosure.

The photoconductor 1 of fig. 4 is an embodiment in which a protective layer 206 is provided on a Charge Transport Layer (CTL)204 in the function separation photoconductor 1 shown in fig. 3.

Fig. 5 is a schematic cross-sectional view depicting another embodiment of a photoconductor of the present disclosure.

The photoconductor 1 of fig. 5 is an embodiment in which an intermediate layer 207 is provided between the support 201 and the underlying layer 205 in the function-separating photoconductor 1 shown in fig. 4.

The photoconductor of the present disclosure is not limited to each of the above embodiments as long as the photoconductor includes at least a photoconductive layer on or over a support, a surface layer is a ceramic film, and an undercoat layer includes a silicone resin.

As shown in fig. 6, for example, the photoconductor may be a photoconductor 1 in which an intermediate layer 207, a charge generation layer 203, a charge transport layer 204, an undercoat layer 208, and a surface layer 209 formed of a ceramic semiconductor film are arranged in this order on a conductive support 201.

The photoconductor of the present disclosure has excellent charging ability possessed by an organic photoconductor. Since the surface layer is a ceramic film, the photoconductor of the present disclosure has excellent wear resistance comparable to that of an inorganic photoconductor. Since the undercoat layer includes siloxane, the photoconductor of the present disclosure has excellent gas barrier properties. Therefore, the photoconductor of the present disclosure has excellent durability, and can produce excellent image quality.

Since the photoconductor includes an undercoat layer containing a silicone resin, particularly a photoconductive layer, which has high gas permeability and low strength, it can be densely covered with an inorganic film to improve gas barrier properties. The undercoat layer in the present disclosure has extremely high mechanical strength as compared with an organic material, which significantly increases the abrasion resistance of the photoconductor.

< photoconductive layer >

The photoconductive layer may be a multilayer photoconductive layer or a single layer photoconductive layer.

< multilayer photoconductive layer >

As described above, the multilayer photoconductive layer includes at least the charge generation layer and the charge transport layer in this order, and may further include other layers as necessary.

Charge generation layer

The charge generating layer includes at least a charge generating material, further includes a binder resin, and may further include other components as necessary.

The charge generating material is not particularly limited and may be appropriately selected depending on the intended purpose. As the charge generating material, an inorganic material or an organic material can be used.

The inorganic material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include crystalline selenium, amorphous selenium, selenium-tellurium-halogen and selenium-arsenic compounds.

The organic material is not particularly limited and may be appropriately selected from materials known in the art according to the intended purpose. Examples thereof include phthalocyanine-based pigments (e.g., metal phthalocyanine and metal-free phthalocyanine), and azo pigments having a carbazole skeleton, a triphenylamine skeleton, a diphenylamine skeleton or a fluorenone skeleton. The above listed examples may be used alone or in combination.

The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a polyvinyl butyral resin and a polyvinyl formal resin. The above listed examples may be used alone or in combination.

Examples of the method of forming the charge generating layer include vacuum film formation and casting from a solution dispersion system.

Examples of the organic solvent used in the charge generating layer coating liquid include methyl ethyl ketone and tetrahydrofuran. The above listed examples may be used alone or in combination.

The thickness of the charge generation layer is generally preferably 0.01 to 5 micrometers, and more preferably 0.05 to 2 micrometers.

Charge transport layer

The charge transport layer is a layer configured to accommodate charged charges, and moves charges generated in the charge generation layer and separated therefrom by exposure to combine with the accommodated charged charges. For holes to charge, it is important that the charge transport layer has a high resistance. In order to achieve a high surface potential with the contained charged charges, it is important that the charge transport layer has a low dielectric constant and good charge mobility.

The charge transport layer includes at least a binder resin, and may further include other components as necessary.

Examples of charge transport materials include positive hole transport materials, electron transport materials, and polymeric charge transport materials.

Examples of the electron transporting material (electron accepting material) include 2,4, 7-trinitro-9-fluorenone and 1,3, 7-trinitrodibenzothiophene-5, 5-dioxide. The above listed examples may be used alone or in combination.

Examples of the positive hole transporting material (electron donating material) include triphenylamine derivatives and α -phenylstilbene (phenylstilbene) derivatives. The above listed examples may be used alone or in combination.

Examples of the polymer transport material include materials having the following structures. Examples thereof include a polysilylene (polysillylene) polymer disclosed in unexamined Japanese patent application laid-open No. 63-285552, and a polymer having a triarylamine structure disclosed in unexamined Japanese patent application laid-open No. 09-304956.

As the binder resin, for example, a polycarbonate resin or a polyester resin is used. The above listed examples may be used alone or in combination.

Note that the charge transport layer may include a copolymer of a crosslinkable binder resin and a crosslinkable charge transport material.

The charge transport layer may be formed by dissolving or dispersing any of the above-described charge transport materials and binder resins in a suitable solvent, and applying and drying the resulting solution or dispersion. In addition to the charge transport material and the binder resin, an appropriate amount of additives, plasticizers, antioxidants, and leveling agents may be added to the charge transport layer.

The thickness of the charge transport layer is preferably 5 to 100 micrometers. Attempts have been made to reduce the thickness of the charge transport layer to meet the current demand for high image quality. In order to achieve high image quality of 1,200dpi or more, the thickness thereof is more preferably 5 to 30 micrometers.

< Single layer photoconductive layer >)

The single photoconductive layer includes a charge generating material, a charge transporting material and a binder resin, and may further include other components as necessary.

As the charge generating material, the charge transporting material, and the binder resin, the same materials as those in the multilayer photoconductive layer can be used.

When the single-layer photoconductive layer is formed by casting, the single-layer photoconductive layer is formed in most cases by dissolving or dispersing the charge generating material, the low-molecular-weight and high-molecular-weight charge transporting materials in a suitable solvent, and applying and drying the resulting solution or dispersion. In addition, the single photoconductive layer may further include a plasticizer and a binder resin as necessary. As the binder resin, the same binder resin as that of the charge transport layer can be used. As another binder resin, a binder resin may be further mixed with the same binder resin as that of the charge generation layer.

The thickness of the single photoconductive layer is preferably 5 to 100 micrometers, and more preferably 5 to 50 micrometers. When the thickness thereof is less than 5 μm, the charging ability may be low. When the thickness thereof is more than 100 μm, the sensitivity may be low.

< support >

The support may be appropriately selected depending on the intended purpose, and those having conductivity may be used. Preferred examples of the support include a conductor and a conductive-treated insulator. Examples thereof include: a support formed of a metal (e.g., Al and Ni) or an alloy thereof; forming a metal (e.g., Al) or a conductive material (e.g., In) thereon₂O₃And SnO₂) Insulating substrates of the film of (e.g., polyester and polycarbonate); a resin substrate in which carbon black, graphite, metal powder (e.g., Al, Cu, and Ni), or conductive glass powder is uniformly dispersed in a resin to impart conductivity to the resin; and conductively treated paper.

The shape and size of the support body are not particularly limited. Any plate-shaped support, drum-shaped support, or belt-type support may be used.

An underlying layer may optionally be disposed between the support and the photoconductive layer. The underlying layer is provided for the purpose of improving adhesion, preventing moire (moire), improving coating properties of the upper layer, and reducing residual potential.

The underlying layer typically includes a resin as a major component. Examples of the resin include: alcohol-soluble resins such as polyvinyl alcohol, copolymer nylon, and methoxymethylated nylon; and curable resins that form three-dimensional network structures, such as polyurethanes, melamine resins, and alkyd melamine resins.

In addition, powders of metal oxides (e.g., titanium oxide, silicon dioxide, aluminum oxide, zirconium oxide, tin oxide, and indium oxide), metal sulfides, or metal nitrides may be added to the underlying layers. The underlying layer may be formed by a common coating method using an appropriate solvent.

The thickness of the underlying layer is not particularly limited and may be appropriately selected depending on the intended purpose. Its thickness is preferably 0.1 to 10 micrometers, and more preferably 1 to 5 micrometers.

In the photoconductor of the present disclosure, a protective layer may be provided on the photoconductive layer to protect the photoconductive layer. Examples of the material 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, polyallyl sulfone, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene ether, polysulfone, polystyrene, polyacrylate, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin.

As a method for forming the protective layer, a conventional method such as dip coating, spray coating, bead coating, nozzle coating, spin coating, or ring coating can be used.

In the photoconductor of the present disclosure, an intermediate layer may be optionally provided on the support, thereby improving adhesion, as well as charge blocking properties. The intermediate layer usually includes a resin as a main component. The resin is preferably a resin having high insolubility against a typical organic solvent because the photoconductive layer is applied thereon in the form of a solution containing a solvent.

Examples of the resin include water-soluble resins (e.g., polyvinyl alcohol, casein, and sodium polyacrylate), alcohol-soluble resins (e.g., copolymer nylon and methoxymethylated nylon), and curable resins forming a three-dimensional network structure (e.g., polyurethane resin, melamine resin, phenol resin, alkyd-melamine resin, and epoxy resin).

< undercoat layer >

The primer layer includes a silicone resin. The silicone resin may be a resin formed by crosslinking an organic silica compound containing a hydroxyl group or a hydrolyzable group.

The silicone resin can fix the surface layer, which is a ceramic film, on the surface of the photoconductor, can enhance the gas barrier properties of the photoconductor, and significantly enhance the abrasion resistance of the photoconductor.

Siloxane resins

The silicone resin is formed by crosslinking an organosilicon compound having a hydroxyl group or a hydrolyzable group. The silicone resin may further include a catalyst, a crosslinking agent, an organic silica sol, a silane coupling agent, a polymer (e.g., an acrylic polymer), and the like, as necessary.

The crosslinking is not particularly limited and may be appropriately selected depending on the intended purpose. The crosslinking is preferably thermal.

Examples of the organosilicon compound containing a hydroxyl group or a hydrolyzable group include alkoxysilyl group-containing compounds, partial hydrolysis condensates of alkoxysilyl group-containing compounds, and mixtures thereof.

Examples of the alkoxysilyl group-containing compound include: tetraalkoxysilanes such as tetraethoxysilane; alkyltrialkoxysilanes such as methyltriethoxysilane; and aryl trialkoxysilanes, such as phenyltriethoxysilane. Further, any of the above compounds into which an epoxy group, a methacryloyl group or a vinyl group is introduced may also be used.

The partial hydrolysis of the alkoxysilyl group-containing compound can be produced by a known method in which a certain amount of water, a certain amount of a catalyst, and the like are added to the alkoxysilyl group-containing compound to carry out the reaction.

As the raw material of the silicone resin, a commercially available product can be used. Specific examples thereof include GR-COAT (available from Daicel Corporation), Glass Resin (available from OWENS CORNING JAPAN LLC.), pyretic Glass (available from OHASHI CHEMICAL INDUSTRIES LTD.), NSC (available from NIPPON FINE CHEMICAL CO., LTD.), Glass solutions GO150SX and GO200CL (available from Fine Glass Technologies Co., Ltd.), and copolymers of alkoxysilyl compounds with acrylic or polyester resins, such as MKC silicate (available from Mitsubishi CHEMICAL Corporation) and silicate/acryl varnish XP-1030-1 (available from Aica Kogyo Company, Lied.).

The thickness of the undercoat layer is preferably 0.01 micrometers or more but 4.0 micrometers or less, more preferably 0.03 micrometers or more but 4.0 micrometers or less, still more preferably 0.05 micrometers or more but 2.5 micrometers or less. The thickness thereof is preferably 0.1 μm or more. Of these, the thickness thereof is particularly preferably 0.01 μm or more but 2.5 μm or less.

< surface layer >

The surface layer of the photoconductor of the present disclosure is a ceramic film.

The ceramic constituting the ceramic film is generally a metal compound obtained by firing a metal. The ceramic is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include metal oxides such as titanium oxide, silicon dioxide, aluminum oxide, zirconium oxide, tin oxide, and indium oxide. The ceramic preferably comprises a transparent conductive oxide. The transparent conductive oxide is preferably a ceramic semiconductor.

< ceramic semiconductor >)

The ceramic semiconductor is a ceramic having a partial defect in its typical electronic configuration due to oxygen deficiency or the like, and is a generic name of compounds that exhibit conductivity under certain conditions due to the defect in the electronic configuration. The surface layer used in the present disclosure is preferably a ceramic semiconductor film. The ceramic semiconductor film is defined as being composed ofA layer exhibiting conductivity under certain conditions due to defects in electronic configuration, a layer in which ceramic semiconductor components are densely arranged without much space, and a layer containing no organic compound. The ceramic semiconductor film preferably comprises cuprite. Further, in the present disclosure, the ceramic semiconductor film preferably has charge mobility of holes or electrons. At 2X 10^-4The charge mobility of the ceramic semiconductor film at a field strength of V/cm is preferably 1X 10^-6cm²a/Vsec or greater. In the present disclosure, higher charge mobility is more preferable. The measurement method of the charge mobility is not particularly limited and may be appropriately selected from general measurement methods according to the intended purpose. Examples thereof include a method of producing and measuring a sample by the method disclosed in unexamined Japanese patent application laid-open No. 2010-183072.

Further, the bulk resistance including the thickness of the ceramic semiconductor film is preferably less than 1 × 10¹³Ω。

Red copper iron ore-

The hematite (hereinafter, may be referred to as "p-type semiconductor" or "p-type metal compound semiconductor") is not particularly limited and may be appropriately selected depending on the intended purpose, as long as the hematite has a function as a p-type semiconductor. Examples thereof include p-type metal oxide semiconductors, p-type compound semiconductors including monovalent copper, and other p-type metal compound semiconductors. Examples of p-type metal oxide semiconductors include CoO, NiO, FeO, Bi₂O₃、MoO₂、MoS₂、Cr₂O₃、SrCu₂O₂And CaO-Al₂O₃. Examples of the p-type compound semiconductor including monovalent copper include CuI, CuInSe₂、Cu₂O、CuSCN、CuS、CuInS₂、CuAlO、CuAlO₂、CuAlSe₂、CuGaO₂、CuGaS₂And CuGaSe₂. Examples of other p-type compound semiconductors include GaP, GaAs, Si, Ge, and SiC.

In view of enhancing the effect obtained by the present disclosure, the cuprite is preferably copper aluminum oxide, and the copper aluminum oxide is more preferably CuAlO₂。

(production of ceramic film)

The production method (film forming method) of the ceramic film is not particularly limited and may be appropriately selected from film forming methods of inorganic materials generally used according to the intended purpose. Examples thereof include a vapor deposition method, a liquid deposition method, and a solid deposition method. Vapor deposition methods are classified into, for example, Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD). Examples of physical vapor deposition include vacuum vapor deposition, electron beam vapor deposition, laser abrasion MBE, MOMBE, reactive vapor deposition, ion plating, cluster ion beam irradiation, 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, optical CVD, and laser CVD. Examples of the liquid deposition method include LPE, electroplating, electroless plating, and coating. Examples of solid phase deposition include SPE, recrystallization, graphoepitaxy, LB techniques, sol-gel processes, and Aerosol Deposition (AD).

In the above examples, AD is preferable because a uniform film, such as an electrophotographic photoconductor, can be formed over a relatively large area, and AD does not adversely affect the properties of the electrophotographic photoconductor.

Aerosol Deposition (AD) -

Aerosol Deposition (AD) is a technique of mixing particles or microparticles with a gas to become an aerosol, and ejecting the aerosol from a nozzle to a target (substrate) on which a film is formed to form the film. AD can form a film under a room temperature environment, and can form a film in a state where the crystal structure of the raw material is substantially maintained as it is. Therefore, the AD is suitable for film formation on a photoelectric conversion device (particularly, an electrophotographic photoconductor).

A method of forming a ceramic film according to aerosol deposition will be described.

Fig. 7 is a schematic diagram depicting an aerosol deposition device.

The inert gas used to generate the aerosol is stored in a cylinder 111 shown in fig. 7. The cylinder 111 is coupled to the aerosol generator 113 by a conduit 112a, and the conduit 112a is pulled into the aerosol generator 113. Inside the aerosol generator 113 is placed a quantity of particles 120, which is the material used in the present disclosure to form the ceramic membrane. Another conduit 112b coupled to the aerosol generator 113 is connected to a spray nozzle 115 inside the film forming chamber 114.

Inside the film forming chamber 114, a substrate 116 is supported by a substrate holder 117 so as to face the spray nozzle 115. An aluminum foil (positive electrode current collector) was used as the substrate 116. The film forming chamber 114 is connected to an exhaust pump 118 for adjusting the degree of vacuum inside the film chamber 114 through a conduit 112 c.

Although not illustrated, a system for moving the substrate holder 117 in a lateral direction (lateral direction in a plane of the substrate holder 117 facing the spray nozzle 115) is provided so as to move the spray nozzle 115 in a longitudinal direction (longitudinal direction in a plane of the substrate holder 117 facing the spray nozzle 115) at a constant speed. By moving the substrate holder 117 in the transverse direction and moving the spray nozzles 115 in the longitudinal direction to perform film formation, a ceramic film having a desired area can be formed on the substrate 116.

In the step of forming the ceramic film, first, the compressed air valve 119 is closed, and the atmosphere from the film forming chamber 114 to the aerosol generator 113 is evacuated by the exhaust pump 118. Next, the gas and the particles 120 introduced into the cylinder 111 of the aerosol generator 113 through the conduit 112a by opening the compressed air valve 119 are sprayed into the container to generate an aerosol in which the particles 120 are dispersed in the gas. The generated aerosol is ejected at high speed from the ejection nozzle 115 to the substrate 116 via the tube 112 b. After 0.5 second with the compressed air valve 119 opened, the compressed air valve 119 is closed in the next 0.5 second. Then, the compressed air valve 119 is opened again, and the opening and closing of the compressed air valve 119 are repeated at a cycle of 0.5 second. The gas flow rate from the gas cylinder 111 was set to 2L/min, and the film formation duration was 7 hours. The degree of vacuum inside the film forming chamber 114 when the compressed air valve 119 was closed was set to about 10Pa, and the degree of vacuum inside the film forming chamber 114 when the compressed air valve 119 was closed was set to about 100 Pa.

The ejection speed of the aerosol is controlled by the shape of the ejection nozzle 115, the length of the inner diameter of the conduit 112b, the internal pressure of the gas cylinder 111, or the displacement volume of the exhaust pump 118 (the internal pressure of the film forming chamber 114). In the case where the internal pressure of the aerosol generator 113 is set to several tens of thousands Pa, the internal pressure of the film forming chamber 114 is set to several hundreds Pa, and the opening shape of the nozzle 115 is a ring shape having an inner diameter of 1mm, for example, the ejection speed of the aerosol can reach several hundreds m/sec due to the internal pressure difference between the aerosol generator 113 and the film forming chamber 114. When the internal pressure of the film forming chamber 114 is maintained at 5 to 100Pa and the internal pressure of the aerosol generator 113 is maintained at 50,000Pa, a ceramic film having a porosity of 5 to 30% can be formed. The average thickness of the ceramic membrane can be adjusted by adjusting the duration of aerosol supply under the above conditions.

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

The particles 120 accelerated in velocity to receive kinetic energy in the aerosol are pressed into the photoconductor, which is the substrate 116, to finely pulverize the particles using impact energy. Ceramic films are sequentially formed on the charge transport layer by abutting the pulverized particles to a substrate (photoconductor) 116 and abutting the pulverized particles to each other.

Film formation is performed in various line patterns and rotation of the photoconductor drum. A ceramic film having a desired area is formed by scanning the substrate holder 117 or the ejection nozzles 115 in the longitudinal direction and the lateral direction of the surface of the substrate (photoconductor) 116.

(organic EL element)

Hereinafter, one example of a case where the photoelectric conversion element of the present disclosure is an organic Electroluminescence (EL) element will be described. Note that the foregoing description can also be applied to the organic EL element of this embodiment mode. In describing the organic EL element of the present embodiment, the following description is given with priority,

the organic EL element of the present disclosure has a gas barrier function, particularly a moisture barrier function, and has excellent durability because the surface layer is a ceramic film. In addition, the inclusion of the silicone resin in the undercoat layer results in improved gas barrier properties and more excellent durability, and can improve the quality of a displayed image. In particular, when the organic EL element includes an undercoat layer containing a silicone resin, the organic EL layer having large gas permeability and weak strength can be covered with an inorganic film having denseness, and the gas barrier property can be enhanced.

Fig. 8 is a schematic cross-sectional view for describing an embodiment of the organic EL element of the present disclosure. The organic EL element 50C of the present embodiment has a laminated structure obtained by disposing a support 51, a cathode 52, an electron injection layer 53, an electron transport layer 54, a light emitting layer 55, a hole transport layer 56, an undercoat layer 57, a surface layer 58, and an anode 59 in this order. Note that in the present disclosure, the reverse layer structure of the organic EL element is favorably regarded as a standard element configuration in terms of light emission, but the present invention is not limited to this configuration.

< support >

When the photoelectric conversion element is used as an organic EL element, the support 51 may be configured as a substrate. The support is preferably formed of an insulating substrate. The support may be, for example, a plastic substrate or a film substrate.

A barrier film may be provided on the main surface 51a of the support 51. The barrier film may be, for example, a film formed of silicon, oxygen, and carbon, or a film formed of silicon, oxygen, carbon, and nitrogen. Examples of the material of the barrier film include silicon oxide, silicon nitride, and silicon oxynitride. The average thickness of the barrier film is preferably 100nm or more but 10 μm or less.

< organic EL layer >

When the photoelectric conversion element is used as an organic EL element, the photoelectric conversion layer may be configured as an organic EL layer.

The organic EL layer includes, for example, a light-emitting layer, and is a functional portion contributing to emission of the light-emitting layer, such as transfer of carriers and combination of carriers depending on voltages applied to the anode and the cathode. The organic EL layer may include, for example, an electron injection layer 53, an electron transport layer 54, a light emitting layer 55, and a hole transport layer 56. The organic EL layer including electrodes such as a cathode and an anode may be referred to as an organic EL layer according to circumstances.

< Electron injection layer >)

The electron injection layer 53 may be provided as a layer that reduces the obstacle to electron injection from the cathode 52 to the electron transport layer 54 formed of an organic material having a small electron affinity. Examples of the material for the electron injection layer 53 include: metal oxides including, for example, magnesium, aluminum, calcium, zirconium, silicon, titanium, and zinc; and polyphenylene vinylene (polyphenylenevinylene), hydroxyquinoline, and naphthalimide derivatives.

The average thickness of the electron injection layer 53 is preferably 5nm to 1000nm, more preferably 10nm to 30 nm. Thickness can be measured by spectroscopic ellipsometry, surface roughness tester, or microscopic image analysis.

< Electron transport layer >

Examples of low molecular weight compounds that can be used as the material of the electron transport layer 54 includeAn azole derivative,Oxadiazole derivatives, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, imidazole derivatives, tetracarboxylic anhydride, various metal complexes (exemplified by tris (8-hydroxyquinolinato) aluminum (Alq 3)), and silole derivatives. These may be used alone or in combination. Among them, metal complexes such as Alq3 and pyridine derivatives are preferable.

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

< light-emitting layer >

Examples of the high polymer material forming the light emitting layer 55 include a polyphenylene vinylene-based compound, a polyfluorene-based compound, and a polycarbazole-based compound.

Examples of the low-molecular material forming the light-emitting layer 55 include metal complexes (e.g., tris (8-hydroxyquinoline) aluminum (Alq)₃) Tris (4-methyl-8 quinolinate) aluminum (III) (Almq)₃) 8-hydroxyquinoline zinc (Znq)₂) Europium (III) (Eu (TTA))₃(phen)) and 2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-porphyrin platinum (II)), metal complexes (e.g., bis [2- (o-hydroxyphenyl benzothiazole)]Zinc (II) (ZnBTZ)₂) And bis [2- (2-hydroxyphenyl) -pyridine]Beryllium (Bepp)₂) Metal complexes (e.g., tris [ 3-methyl-2-phenylpyridine), (e.g., metal complexes with metal complexes)]Iridium (III) (Ir (mpy)₃) Stilbene benzene derivatives, phenanthrene derivatives, perylene compounds, carbazole compounds, benzimidazole compounds, benzothiazole compounds, coumarin compounds, pyrene ketone compounds,A diazole compound, a quinacridone compound, a pyridine compound and a spiro compound. These may be used alone or in combination.

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

< hole transport layer >)

Examples of the material used in the hole transport layer 56 includeAn azole derivative,Oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, butadiene derivatives, 9- (p-diethylaminostyrylanthracene), 1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazone, α -phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives and thiophene derivatives. Other examples thereof include polyarylamines, fluorene-arylamine copolymers, fluorene-bithiophene copolymers, poly (N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, polyalkylthiophene, polyhexylthiophene, poly (p-phenylene vinylene), polythiophene vinylene, pyrenecarboxaldehydeResins, ethyl carbazole-formaldehyde resins, and derivatives thereof. These hole transporting materials may be used alone or in the form of a mixture of two or more of the above hole transporting materials. Alternatively, the hole-transporting substance may be used in the form of a mixture with another compound.

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

< undercoat layer >

Primer layer 57 may be the same as described above.

Primer layer 57 comprises a silicone resin. The undercoat layer 57 in the present embodiment may be configured as a silicone hard coat layer.

< surface layer >

The surface layer 58 may be the same as described above. Even in the present embodiment, the surface layer 58 is a ceramic film. As shown herein, the surface layer 58 may be formed on one side of the organic EL element, but is not limited thereto.

The ceramic film in the organic EL device and the method for producing the same can be appropriately modified and applied in addition to the above ceramic film and the above production method. For example, an anode may be formed on the ceramic film. A ceramic film may be formed on the cathode to embed the organic EL layer. The ceramic film may be formed to cover, for example, one side of the organic EL layer. The provision of the ceramic film of the present embodiment can impart a gas barrier function, particularly a moisture barrier function, to the organic EL element.

< cathode >

As the cathode 52, for example, a single substance of a metal element (e.g., Li, Na, Mg, Ca, Sr, Al, Ag, In, Sn, Zn, or Zr) or an alloy thereof can be used. LiF as an electrode protective film can be formed on the cathode in the same manner as in the case of the cathode. In addition, ITO, IZO, FTO, and aluminum are preferably used.

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

< Anode >

As the anode 59, for example, gold, silver, aluminum, and ITO are preferably used. Thickness can be measured by spectroscopic ellipsometry, surface roughness tester, or microscopic image analysis. When formed by vacuum deposition, a crystal resonator film thickness meter may be used.

(image Forming method and image Forming apparatus)

The image forming method of the present disclosure includes at least: charging a surface of a photoconductor; exposing the charged surface of the photoconductor to light to form a latent electrostatic image; developing the electrostatic latent image with a developer to form a visible image; and transferring the visible image to a recording medium. The photoconductor is the photoconductor of the present disclosure.

The image forming apparatus of the present disclosure includes at least: a photoconductor; a charging unit configured to charge a surface of the photoconductor; an exposure unit configured to expose the charged surface of the photoconductor to light to form a latent electrostatic image; a developing unit configured to develop the electrostatic latent image with a developer to form a visible image; and a transfer unit configured to transfer the visible image onto a recording medium. The photoconductor is the photoconductor of the present disclosure.

The image forming method and the image forming apparatus of the present disclosure may further include other steps and other units as necessary. Note that the charging unit and the exposing unit may be collectively referred to as an electrostatic latent image forming unit.

Embodiments of the image forming method and the image forming apparatus of the present disclosure will be described below by way of examples thereof.

Fig. 9 is a schematic diagram describing an image forming apparatus of the present disclosure. A charging unit 3, an exposure unit 5, a developing unit 6, a transfer unit 10, and the like are provided on the periphery of the photoconductor 1. First, the photoconductor 1 is uniformly charged by the charging unit 3. As the charging unit 3, a corotron device, a wire electrode (scorotron) device, a solid discharge element, a multi-pin electrode device, a roller charging device, or a conductive brush device is used, and a system known in the art may be used.

Next, an electrostatic latent image is formed on the uniformly charged photoconductor 1 by the exposure unit 5. As the light source of the exposure unit 5, any general-purpose emitter, such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium vapor lamp, a Light Emitting Diode (LED), a semiconductor Laser Diode (LD), and an Electroluminescence (EL) element, may be used. In addition, in order to emit only light of a desired wavelength range, various filters such as a sharp-cut filter (sharp-cut filter), a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter may be used.

Next, the electrostatic latent image formed on the photoconductor 1 is visualized by the developing unit 6. Examples of the developing system used include a one-component developing method using dry toner, a two-component developing method using dry toner, and a wet developing method using wet toner. When the photoconductor 1 is charged positively (negatively) and image-exposed, a positive (negative) electrostatic latent image is formed on the surface of the photoconductor. When the positive (negative) electrostatic latent image is developed with toner (electrostatic particles) of negative (positive) polarity, a positive image is obtained. When the positive (negative) electrostatic latent image is developed with toner (electrostatic particles) of positive (negative) polarity, a negative image is obtained.

Next, the toner image visualized on the photoconductor 1 is transferred onto the recording medium 9 fed by the roller 8 by the transfer unit 10. Further, the pre-transfer charger 7 can be used to more smoothly perform transfer. As the transfer unit 10, an electrostatic transfer system using a transfer charger, a bias roller, or the like; mechanical transfer systems such as adhesive transfer methods, pressure transfer methods; or a magnetic transfer system.

As a unit for separating the recording medium 9 from the photoconductor 1, a separation charger 11 or a separation claw 12 may be optionally used. As other separation methods, electrostatic attraction induction separation, side-edge belt separation, top-edge grip separation, or curvature separation is used. As the separate charger 11, a charging unit may be used. Further, in order to clean toner remaining on the photoconductor after transfer, a cleaning unit such as a fur brush 14, a cleaning blade 15 may also be used. For more effective cleaning, a cleaning pre-charger 13 may be used. As other cleaning devices, there are a wet system and a magnetic brush system. The systems listed above may be used alone or in combination. Further, in order to remove the latent image on the photoconductor 1, a charge removing unit 2 may be used. As the charge eliminating unit 2, a charge eliminating lamp or a charge eliminating charger may be used. Any examples of the exposure light source and the charging unit may be used for the charge eliminating unit. As for other processes not performed near the photoconductor, such as paper feeding, fixing, and paper discharging, any process known in the art may be used.

Examples

The present disclosure will be described in more detail by way of examples and comparative examples. The present disclosure should not be construed as being limited to the embodiments. Note that "parts" described below means "parts by mass" unless otherwise specified.

Example 1

Preparation example of electrophotographic photoconductor

The electrophotographic photoconductor of example 1 is produced in such a manner as to include an intermediate layer 207, a charge generation layer 203, a charge transport layer 204, an undercoat layer 208, and a surface layer 209 formed of a ceramic semiconductor film, which are disposed on a conductive support in this order, as shown in fig. 6.

Formation of an intermediate layer

The following intermediate layer coating liquid was applied on a conductive support (outer diameter: 60mm) formed of aluminum by dip coating to form an intermediate layer. The average thickness of the middle layer after drying at 170 ℃ for 30 minutes was 5 microns.

(intermediate layer coating liquid)

Zinc oxide particles (MZ-300, available from TAYCACORPORATION): 350 parts of

3, 5-di-tert-butyl salicylate (TCI-D1947, available from Tokyo Chemical industry co., ltd.): 1.5 parts of

Blocked isocyanate (SUMIJULE (registered trademark) 3175, solid content: 75 mass%, available from Sumitomo Bayer Urethane co., ltd.): 60 portions of

A solution obtained by dissolving 20 mass% of a butyral resin in 2-butanone (BM-1, available from SEKISUI CHEMICAL co., ltd.): 225 parts by weight

2-butanone: 365 parts of

Formation of a charge generation layer

The following charge generation layer coating liquids were applied onto the obtained intermediate layer by dip coating to form a charge generation layer. The average thickness of the charge generation layer was 0.2 μm.

(Charge generation layer coating liquid)

Y-type titanyl phthalocyanine: 6 portions of

Butyraldehyde resin (S-LEC BX-1, available from SEKISUI CHEMICAL co., ltd.): 4 portions of

2-butanone (available from KANTO CHEMICAL co., inc.): 200 portions of

Formation of a charge transport layer

The following charge transport layer coating liquid 1 was applied onto the obtained charge generation layer by dip coating to form a charge transport layer.

The average thickness of the charge transport layer after drying at 135 c for 20 minutes was 22 microns.

(Charge transport layer coating liquid 1)

Bisphenol Z polycarbonate (PANLITE TS-2050, available from TEIJIN LIMITED): 10 portions of

A low molecular weight charge transport material represented by the following structural formula (6): 10 portions of

Chemical formula 1

Tetrahydrofuran: 80 portions

The following undercoat-layer coating liquid was applied onto the obtained charge transport layer by dip coating to form an undercoat layer.

The average thickness of the primer layer after drying at 135 c for 20 minutes was 2 microns.

(undercoat layer coating liquid)

A curable silicone resin (NSC-5506, available from NIPPON FINE CHEMICAL co., ltd.): 80 portions

Tetrahydrofuran: 20 portions of

Formation of the ceramic film 1

(copper aluminum oxide)

Copper (I) oxide (available from Wako Pure Chemical Industries, ltd.): 40.014g

Alumina (AA-03, available from SUMITOMO CHEMICAL COMPANY, LIMITED): 28.52g

Copper aluminum oxide was prepared in the following manner. Copper (I) oxide and alumina were weighed and transferred to a mayonnaise bottle (mayonnaise bottle). The bottles were fixed on the sample stage of a vibrating screen (VIBRAX-VXR Basic, available from IKA) and shaken at a shaking intensity of 1,500rpm for 1 hour to conduct mixing. The resultant was heated at 1,100 ℃ for 40 hours to obtain copper aluminum oxide. The obtained copper aluminum oxide was pulverized using DRYSTAR SDA1 (available from Ashizawa Fintech ltd.) to obtain a powder having a number average particle size of 1 micron.

Next, the ceramic film 1 was formed according to aerosol deposition using the apparatus shown in fig. 7.

As the film forming chamber, a modified apparatus of a commercially available vapor deposition apparatus (VPC-400, available from ULVAC) was used.

As the aerosol generator, a commercially available stirrer (T.K. AGI Homo MIXER 2M-03, PRIMIX Corporation) was used.

Note that as the aerosol generator, a commercially available pressure feed bottle (RBN-S, available from KSK) having a volume of 1L provided in an ultrasonic cleaner (SUS-103, available from Shimadzu Corporation) may be used.

A conduit having an internal diameter of 4mm was pulled from an aerosol generator into a film forming chamber, with a spray nozzle (YB1/8MSSP37, available from SPRAYING SYSTEMS co., JAPAN) provided at the tip of the conduit. The photoconductor was disposed at a position 2mm from the ejection nozzle. As the photoconductor holder, a holder movable in the lateral direction is used. The area where the film is to be formed can be determined by moving the photoconductor holder and the jetting nozzle. Meanwhile, an aerosol generator and a gas cylinder filled with nitrogen were coupled with a pipe having an inner diameter of 4 mm.

Using the above apparatus, a ceramic film 1 having an average thickness of 2.5 μm was produced in the following manner.

The aerosol generator was charged with 40g of copper aluminum oxide powder having a number average particle size of 1 micron. Next, the atmosphere from the film forming chamber to the aerosol generator was evacuated by an exhaust pump. Then, nitrogen gas was fed from a gas cylinder to the aerosol generator, and stirring was started to generate aerosol in which particles were dispersed in the nitrogen gas. The generated aerosol is ejected from the ejection nozzle to the photoconductor through the conduit. The flow rate of nitrogen was 13L/min to 20L/min. Further, the duration of film formation was 20 minutes, and the degree of vacuum inside the film forming chamber at the time of formation of the ceramic film 1 was set to about 50Pa to about 150 Pa. The predetermined area for film formation is achieved by moving the substrate holder and the spray nozzle.

As the number average particle diameter of the copper aluminum oxide, the median of the measured values was obtained by measuring 5 times using MICROTRAC UPA-EX150 (available from NIKKISO co., ltd.) using methanol as a dispersion medium for a measurement duration of 60 seconds.

Example 2

A photoconductor was obtained in the same manner as in example 1 except that the undercoat-layer coating liquid was changed to the following undercoat-layer coating liquid. The average thickness of the primer layer after drying at 135 c for 20 minutes was 0.5 microns.

(undercoat layer coating liquid)

A curable silicone resin (NSC-5506, available from NIPPON FINE CHEMICAL co., ltd.): 60 portions of

Tetrahydrofuran: 40 portions of

Example 3

A photoconductor was obtained in the same manner as in example 1 except that the undercoat-layer coating liquid was changed to the following undercoat-layer coating liquid. The average thickness of the primer layer after drying at 135 c for 20 minutes was 0.3 microns.

(undercoat layer coating liquid)

A curable silicone resin (NSC-5506, available from NIPPON FINE CHEMICAL co., ltd.): 50 portions of

Tetrahydrofuran: 50 portions of

Example 4

A photoconductor was obtained in the same manner as in example 1 except that the undercoat-layer coating liquid was changed to the following undercoat-layer coating liquid. The average thickness of the primer layer after drying at 135 c for 20 minutes was 2.5 microns.

(undercoat layer coating liquid)

A curable silicone resin (NSC-5506, available from NIPPON FINE CHEMICAL co., ltd.): 90 portions of

Tetrahydrofuran: 10 portions of

Example 5

A photoconductor was obtained in the same manner as in example 1 except that the undercoat-layer coating liquid was changed to the following undercoat-layer coating liquid. The average thickness of the primer layer after drying at 135 c for 20 minutes was 4 microns.

(undercoat layer coating liquid)

A curable silicone resin (NSC-5506, available from NIPPON FINE CHEMICAL co., ltd.): 100 portions of

Example 6

A photoconductor was obtained in the same manner as in example 1 except that the undercoat-layer coating liquid was changed to the following undercoat-layer coating liquid. The average thickness of the primer layer after drying at 135 c for 20 minutes was 0.2 microns.

(undercoat layer coating liquid)

A curable silicone resin (NSC-5506, available from NIPPON FINE CHEMICAL co., ltd.): 40 portions of

Tetrahydrofuran: 60 portions of

Example 7

A photoconductor was obtained in the same manner as in example 1 except that the undercoat-layer coating liquid was changed to the following undercoat-layer coating liquid 1 to perform coating, and an undercoat-layer coating liquid 2 was applied onto the undercoat-layer coating liquid 1. The average thickness of the primer layer after drying at 135 c for 20 minutes was 5 microns.

(undercoat layer coating liquid 1)

A curable silicone resin (NSC-5506, available from NIPPON FINE CHEMICAL co., ltd.): 75 portions of

Tetrahydrofuran: 25 portions of

(undercoat layer coating liquid 2)

A curable silicone resin (NSC-5506, available from NIPPON FINE CHEMICAL co., ltd.): 100 portions of

Comparative example 1

A photoconductor was obtained in the same manner as in example 1 except that the formation of the undercoat layer was omitted. The ceramic membrane after film formation is a powder compact which can be broken by being lightly scraped by a fingernail, and the ceramic membrane cannot be formed.

< evaluation of electrophotographic photoconductor >

The electrophotographic photoconductors in examples 1 to 7 and comparative example 1 produced in the above-described manner were evaluated as follows. The evaluation results in each electrophotographic photoconductor are presented in table 1.

<<NO₂Evaluation of images after Exposure>>

First, in NO₂Keeping the electrophotographic photoconductor standing in an atmosphere for a certain time to allow NO₂Adsorbed on the surface of the electrophotographic photoconductor. Use of various electrophotographic photoconductors to adsorb NO onto adsorption sites near the surface of the electrophotographic photoconductor₂Saturation was investigated and it was found that exposure to light in a chamber whose concentration was controlled at 40ppm for 24 hours was preferable. Thus, the exposure conditions were set to have NO of 40ppm₂Concentration, and exposure duration was 24 hours.

Further, NO was performed using a modification apparatus of Ricoh Pro C9110 (available from Ricoh Company Limited) using Protoner Black C9100, and using a3 size copy Paper (POD gloss coating, available from Oji Paper co., ltd.) as Paper sheets₂Post-exposure image evaluation, Ricoh Pro C9110 has been modified to eliminate the initial idle process at image output. Further, the amount of abrasion of the surface of the photoconductor after printing 5,000,000 sheets was measured.

As an output image, after an evaluation pattern of 0 sheet, 500,000 sheets, or 5,000,000 sheets was printed, a halftone image was continuously output on 3 sheets. The dot reproduction state of the output image on the 3 sheets of paper was observed with the naked eye and under a microscope. The results were evaluated based on the following evaluation criteria.

(evaluation criteria)

Good: the dot reproduction state of the output image on 3 sheets of paper was not changed and there was no problem.

The method comprises the following steps: the dot reproduction state of the output image on 3 sheets of paper slightly changed, but there was no problem in actual use.

Difference: the dot reproduction state of the output image on 3 sheets of paper has a significant density variation.

TABLE 1

From the results presented in table 1, it was found that the electrophotographic photoconductors obtained in examples 1 to 7 were even in NO₂Stable image quality can be obtained after exposure and excellent durability can be obtained. Further, it was found that the thickness of the undercoat layer affects the durability, and the film thicknesses of examples 1,2 and 4 are preferable.

Example 8

The organic EL element presented in fig. 8 was prepared in the following manner.

Using SiO₂The layer was used as an underlying layer, and a film of Indium Tin Oxide (ITO) was formed on a glass substrate (support 51) by a sputtering method so that the surface resistance thereof was 15 Ω/□ to form a cathode 52. Then, the substrate was cleaned using a neutral cleaner, an oxygen-based cleaner, and isopropyl alcohol in this order.

Then, at 1X 10^-4ITZO as a target was subjected to sputtering by introducing argon gas and oxygen gas under vacuum conditions of Pa to form an electron injection layer 53 having a thickness of 20 nm. Then ultrasonically cleaned with acetone and isopropanol for 10 minutes and spray dried with nitrogen. Then, the resultant was cleaned with UV ozone for 10 minutes.

Depositing tris (8-hydroxyquinoline) aluminum (Alq) in a vacuum deposition apparatus under vacuum₃) (20nm) as an electron transport layer 54 and the following structural formula (B) (15nm) as a light emitting layer 55.

Chemical formula 2

Then, a hole transport material as the following structural formula (C) was deposited thereon under vacuum, thereby forming a hole transport layer 56 having a thickness of 20 nm. As described above, the organic EL layer including the electron injection layer 53, the electron transport layer 54, the light emitting layer 55, and the hole transport layer 56 is formed.

Chemical formula 3

A film of a silicone hard coat layer (curable silicone resin, NSC-5506, available from NIPPON FINE CHEMICAL co., ltd.) having a thickness of 100nm was formed by an inkjet method, thereby forming the undercoat layer 57. Inkjet was performed using an inkjet head GEN3E2 (available from Ricoh Industry Company, ltd.). The plotting frequency was set to 310Hz, and the distance between the head and the substrate was set to 1 mm. The pulse voltage was set to 20V. After film formation, the film was subjected to a heat treatment at 80 ℃ for 5 minutes.

Formation of copper aluminum oxide (CuAlO) with a thickness of 40nm by aerosol deposition₂) Thereby forming the surface layer 58. Further, the anode 59 formed of an ITO film having a thickness of 150nm was formed by a sputtering method, thereby obtaining an organic EL element.

Comparative example 2

An organic EL element was obtained in the same manner as in example 8 except that the silicone hard coat layer (undercoat layer 57) was not formed.

The organic EL element obtained in example 8 was stored under the following conditions: NO₂An atmosphere having a concentration of 20 ppm; and an exposure time of 24 hours. Then, wires were coupled to the anode and cathode of the element, and the element was driven under the following conditions: the current density at the time of voltage application was 30mA/cm²(ii) a And a duty ratio of 50% so as to be repeatedly turned on/off at a period of 10 msec by the DC pulse power supply. As a result, the initial luminance was 200cd/m². The light emission luminance after 46 hours of continuous light emission was maintained at 50% or more of the initial luminance.

The organic EL element obtained in comparative example 2 was evaluated in the same manner as in example 8. As a result, the luminance after 46 hours was 10% or less of the initial luminance.

Therefore, it was found that the organic EL element obtained in example 8 had excellent durability.

List of reference numerals

1: photoconductor

2: charge eliminating unit

3: charging unit

5: exposure unit

6: developing unit

7: pre-transfer charger

8: roller

9: recording medium

10: transfer unit

11: separated charger

12: separation claw

13: cleaning pre-charger

14: brush with brush head

15: cleaning scraper

50C: organic EL element

51: support body

52: cathode electrode

53: electron injection layer

54: electron transport layer

55: luminescent layer

56: hole transport layer

57: base coat

58: surface layer

59: anode

111: gas cylinder

112 a: catheter tube

112 b: catheter tube

112 c: catheter tube

113: aerosol generator

114: film forming chamber

115: spray nozzle

116: substrate (photoconductor)

117: substrate support

118: exhaust pump

119: compressed air valve

120: granules

201: support body

202: photoconductive layer

203: charge generation layer

204: charge transport layer

205: underlying layers

206: protective layer

207: intermediate layer

208: base coat

209: surface layer