KR100582588B1 - Electro-photographic photosensitive member - Google Patents

Abstract

It provides a highly sensitive electrophotographic photosensitive member with extremely small changes in electrical characteristics. A conductive base, an intermediate layer formed on the conductive base, a charge generating layer, and a charge transfer layer, the intermediate layer having a conductive metal oxide powder and a binder having a dye disposed on a surface thereof, the conductive metal oxide powder having an average In the case of acicular needles, the diameter is 0.13 to 0.27 μm, the length is 1.68 to 5.15 μm, and the light absorption of the dye is between 450 and 950 nm. A highly sensitive electrophotographic photosensitive member is obtained with a very small change in electrical characteristics.

Description

Electrophotographic photosensitive member

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, and more particularly to an electroconductive metal oxide powder of an intermediate layer applied to an electrophotographic photosensitive member. It is about.

The electrophotographic photosensitive member generally used includes a conductive base, an intermediate layer covering the conductive base, a charge generating layer and a charge transfer layer. The intermediate layer includes a binder and a conductive metal oxide powder. The conductive metal oxide powder mainly has a dual effect of lowering the resistance of the intermediate layer and increasing the surface roughness. If the resistance of the intermediate layer is too high, the electrons become difficult to move and the residual potential becomes high. The unevenness of the surface of the intermediate layer scatters incident light and prevents moire on the surface of the electrophotographic photosensitive member.

This intermediate | middle layer can be obtained by apply | coating to the electroconductive base the resin paint (including the conductive metal oxide compound and resin as a provider) which becomes 50% or more of a solid component. Paints with a lot of solids are easy to form precipitates and shorten the life of the paints. Since the conductive metal oxide powder has low dispersibility to the paint, it is difficult to form a uniform coating film on the surface of the intermediate layer, and it is difficult to control the electrical characteristics and the image quality of the photosensitive layer. In addition, the bonding strength between the conductive metal oxide powder and the binder resin is poor, the coating film is easy to dry, and it is difficult to control the thickness of the intermediate layer formed after the cross-link reaction. For this reason, applications are declining for printing in high temperature and high humidity conditions.

The prior art regarding an electrophotographic photosensitive member is as follows.

Patent document 1 (U.S. Patent No. 4475605) relates to a photosensitive material which can be reused, and discloses an electrophotographic photosensitive member including a photosensitive layer and an intermediate layer. The intermediate layer is located between the conductive substrate and the photosensitive layer, and contains a conductive polymer and an inorganic white pigment. Examples of the inorganic white pigment include titanium oxide, zinc oxide, zinc zinc, and white lead. (白 鉛), lithopone and similar compounds thereof are listed.

Patent document 2 (U.S. Patent No. 4906545) relates to an electrophotographic photosensitive member including a conductive base and a coating layer applied to the surface of such a conductive layer. The coating layer includes at least one metal oxide, and examples of the metal oxide include zirconium oxide, magnesium oxide, calcium oxide, barium oxide, and lanthanum oxide. The photosensitive member includes a charge generating layer and a charge transfer layer. These oxides are mixed with various thermoplastic plastics and thermosetting plastics and applied to the coating layer.

Patent document 3 (the specification of U.S. Pat.No.5488461) relates to an electrophotographic photosensitive member and a predetermined device. The intermediate layer is a coating layer having a powder, that is, a coating layer containing barium lactate and barium oxide.

Patent document 4 (U.S. Patent No. 5468584) relates to an electrophotographic photosensitive member and an apparatus used therein, wherein the electrophotographic photosensitive member contains an intermediate layer, and the intermediate layer contains zirconium dioxide having a phosphide.

Patent document 5 (the US patent 6177219 specification) relates to the intermediate | middle layer which has needle granules. The intermediate layer includes granular granules of the n-type semiconductor and acicular granules of the n-type semiconductor, and the granular granules have a higher concentration than the acicular granules.

Patent document 6 (US Pat. No. 6,616,683) relates to an intermediate layer having a rough surface made of granules that scatter light, and the layer is formed by dispersing light scattering granules having different refractive indices in a resin, The average value of the granule diameter is 0.8 mu m or more, and the total surface of the granules is larger than 50 m 2 / g.

Patent document 7 (U.S. Patent No. 5660961) relates to an electrophotographic photosensitive member having better adhesion and interference wave prevention function. The intermediate layer has light-scattering inorganic granules having an average diameter of 0.3 to 0.7 µm, which is formed by a polymer crystal chemical reaction of amorphous silica.

Patent document 8 (Japanese Patent No. 2506694) relates to an intermediate layer in which a white pigment (light scattering granules) and a resin are dispersed in an intermediate layer, and an average surface roughness of 0.4 µm or less. These white pigments are titanium oxide (refractive index 2.76), zinc oxide (refractive index 2.02), emulsified zinc (refractive index 2.37), tin oxide (refractive index 1.94-2.09), lithopone (refractive index 1.84), and the like.

Patent document 9 (U.S. Pat.No.4308334 specification) is a method of apply | coating zinc oxide of the photosensitive dye on the surface, and the manufacturing method of the photosensitive member which has zinc oxide.

Patent document 10 (U.S. Pat.No.4043813 specification) relates to a method for applying zinc oxide of a photosensitive dye, the surface of which is a uniform coating layer composed of 12 selenide compounds of the telluride group and a resin (Iii). The selenium compound and the tellurium compound are chemically dispersed on the surface of the zinc oxide powder.

The main object of the present invention is to provide a conductive metal oxide powder having a dye on its surface. That is, the dye dispersed in the resin is disposed on the surface of the conductive metal oxide powder to provide a conductive metal oxide having a dye on the surface. The said electroconductive metal oxide powder which has the said dye on the surface, and a binder are contained in resin. This resin coating material exhibits better dispersibility than the conductive metal oxide powder not containing the dye, and has the feature of increasing the bonding strength of the binder.

Another object of the present invention is to provide a method for producing a conductive metal oxide powder having a dye on its surface. The method of this invention includes the method of arrange | positioning a dye to the surface of a powder by the crosslinking reaction of a temporary crosslinking resin.

It is still another object of the present invention to provide a highly sensitive electrophotographic photosensitive member, in which the electrophotographic photosensitive member has very little change in electrical characteristics such as residual potential after overlapping photosensitive charging and fatigue test prints.

One aspect of the present invention for achieving the above technical problem relates to an electrophotographic photosensitive member. (1) The electrophotographic photosensitive member of the present invention includes a conductive base, an intermediate layer formed on the conductive base, a charge generating layer and a charge transfer layer, wherein the intermediate layer has a conductive metal oxide powder and a binder having a dye disposed on the surface thereof. The conductive metal oxide powder has an average diameter of 0.01 to 0.5 µm, and in the case of needles, the thickness is 0.13 to 0.27 µm and the length is 1.68 to 5.15 µm, and the light absorption of the dye is between 450 and 950 nm. It is characterized by that.

(2) Preferably, the said dye of (1) contains a diazo metal complex, organometallic, or photosensitive dye, It is characterized by the above-mentioned.

(3) Preferably, the dye described in (2) is a diazo metal complex.

(4) Preferably, the said conductive metal oxide powder which arrange | positioned the said dye in any one of (1)-(3) on the surface contains the adhesive agent which fixes the said dye to the surface of conductive metal oxide powder. It features.

(5) Preferably, the adhesive and the binder described in (4) are prepared by a crosslinking reaction of a thermosetting resin, a crosslinked thermoplastic resin, or a mixture thereof.

(6) Preferably, the said adhesive agent and said binder as described in (5) are prepared by the crosslinking reaction of mutually same resin, It is characterized by the above-mentioned.

(7) Preferably, the adhesive according to (5) or (6) is a polyamide resin, a polyamic acid resin, a polyamide resin and an alkylated melamine-formaldehyde. Mixtures of resins, polyamide resins, resol type phenolic resins, alkylated melamine-formaldehyde resins, or polyrinyl butyrate resins prepared by crosslinking reactions. Characterized in that made.

(8) Preferably, the said crosslinking reaction as described in (7) is performed in presence of an acidic catalyst, It is characterized by the above-mentioned.

(9) Preferably, the conductive metal oxide according to any one of (1) to (8) is aluminum oxide, titanium oxide, zinc oxide, cerium oxide, iron oxide or magnesium oxide.

(10) Preferably, the average diameter of the said conductive metal oxide powder in any one of (1)-(9) is 0.03-0.3 micrometer, It is characterized by the above-mentioned.

(11) Preferably, the said conductive metal oxide powder which arrange | positioned the said dye of (4) on the surface is 0.5-2 mass% adhesive agent and 0.5-2 mass% dye with respect to the said conductive metal oxide powder. It is characterized by including.

The electrophotographic photosensitive member of the present invention comprises an intermediate layer, a charge generating layer, and a charge transfer layer, and includes the conductive metal oxide powder, which is an inorganic solid powder for light scattering, in the intermediate layer. Each layer is formed on a conductive base. The thickness, order and the like of the layers constituting the photoconductor are not particularly limited in the present invention. The size and specific use of the photoreceptor can be properly determined. The improvement which applied the well-known technique suitably may be added. For example, the photoreceptor which newly contains another layer may be sufficient. First, the structure of the intermediate | middle layer which is a characteristic of this invention is demonstrated in detail.

<Conductive Metal Oxide Powder with Dye Placed on Surface>

The intermediate layer has a conductive metal oxide powder and a binder in which the dye is disposed on the surface. The refractive index of electroconductive metal oxide powder is different from resin used as a binder. The intermediate layer in which the conductive metal oxide powder is uniformly dispersed on the surface can effectively scatter incident light and prevent interference (moir) caused by reflected light from the photosensitive layer. Dye is arrange | positioned at the surface of the electroconductive metal oxide powder of this invention. By such dye, the refractive index of electroconductive metal oxide powder changes. In addition, the dye increases the bonding strength between the conductive metal oxide powder and the binder in the intermediate layer.

The conductive metal oxide powder preferably has an average diameter of 0.01 to 0.5 µm, more preferably 0.03 to 0.25 µm, still more preferably 0.03 to 0.3 µm, particularly preferably 0.1 to 0.3 µm, Most preferably about 0.1 μm.

Examples of the conductive metal oxides include aluminum oxide, titanium oxide, zinc oxide, cerium oxide, iron oxide or magnesium oxide. Among them, titanium oxide or zinc oxide is preferable.

The conductive metal oxide powder may be produced by itself and a commercially available product may be purchased. Specific examples of commercially available conductive metal oxides include 23-K, 23-K (A), and 23-K (C) n-type zinc oxide (manufactured by Haksui Tech.) And extremely thin conductive SnO ₂ / Sb on the surface. ET-500W, ET-600W, and ET-300W spherical rutile titanium oxide (manufactured by Ishihara Sangyo), WK-500, TM-100, TM coated with tin oxide on the surface The application of -200 potassium titanate (manufactured by Otsuka Chemical Co., Ltd.) and extremely thin conductive lead, cadmium and zinc oxide (manufactured by Sakai Chemical Co., Ltd.) on the surface can be discussed.

Needle-shaped metal oxides can also be applied to the present invention. In the case where the conductive metal oxide powder is needle-shaped, the conductive metal oxide powder preferably has an average diameter of 0.13 to 0.27 µm and an average length of 1.68 to 5.15 µm. For example, acicular titanium dioxide may be mentioned on the surface of FT-1000, FT-2000, and FT-3000 conductive SnO ₂ / Sb (manufactured by Ishihara Sangyo).

The conductive metal oxide powder has a refractive index different from that of the resin. To illustrate the main metal oxides and other compounds thereof, aluminum oxide (Al ₂ O ₃ : refractive index 1.77), silica oxide (SiO ₂ : refractive index 1.54), titanium oxide (TiO ₂ : refractive index 2.7), zinc oxide (ZnO: refractive index 2.03) ), Cerium oxide (CeO ₂ : refractive index 2.6), iron chloride (Fe ₂ O ₃ : refractive index 2.94), zinc emulsion (ZnS: refractive index 2.37), potassium iodide (KI: refractive index 1.67), magnesium oxide (Mg ₂ O: refractive index 1.74) ) And cadmium emulsion (CdS: refractive index 2.51).

In some cases, a metal may be used together with or instead of the conductive metal oxide powder. In the case of using a metal, the metal may be dispersed in the intermediate layer. Preferably, it is uniformly dispersed in the intermediate layer.

As mentioned above, dye is arrange | positioned on the surface of electroconductive metal tetrachloride powder. As the dye disposed on the surface of the conductive metal oxide powder, a diazo metal complex, an organometallic acid, an acid dye or a photosensitive dye may be used. Of these, diazo metal complexes are preferable. The structure of the diazo metal complex is shown in US Pat. No. 6,153,735 and US Pat. No. 5,843,611. Commercially available diazo metal complexes which can be used in the present invention include Valifast colors Yellow 1101, Yellow 1105, orange 3209, orange 3210, red 1308, red 3304, red 3306 (manufactured by Orient Chemical Industries), and " Orgalon color Yellow 102, Yellow 120, red 304, red 306 (product of Kelly Chemical Corporation) etc. As said acid dye, Everacid Yellow A-4R, Yellow N-5GW, Yellow M-2R, Yellow ANFG (Everlight Chemical Corporation) Company) and "Solar Acid Yellow MR, Yellow NFG, Yellow N5G (manufactured by Solar Fine Chemical).

The light absorption of the dye is 450 ~ 950 nm. In addition, in this specification, "light absorption 450-950 nm" means that there exists an absorption peak in the said range.

An adhesive may be used for the reason of disposing the dye on the surface of the conductive metal oxide powder. As the adhesive, thermosetting resins, crosslinkable thermoplastic resins, and mixtures thereof can be used. For example, polyamide resin, polyamic acid resin, resol type phenolic resin, melamine-formaldehyde resin, alkylated melamine-formaldehyde melamine-formaldehyde resins, polyvinylbutane acid ester resins, epoxy resins and mixtures thereof may be used.

In order to catalyze the crosslinking reaction, an acid catalyst and a crosslinking agent may be added to the thermoplastic resin capable of crosslinking with the thermosetting resin. By performing in the presence of an acid catalyst, a better photosensitive member can be manufactured. The acid catalyst and the crosslinking agent are not particularly limited. You may use a suitable compound suitably in the range which does not impair the effect of this invention. For example, US Pat. No. 6,197,462 describes polyamide resins, melamine-formaldehyde resins and alkylated melamine-formaldehyde resins as crosslinking agents, and acid catalysts, as applied to the present invention.

In the conductive metal oxide powder of the present invention, when the adhesive can be used, the metal or conductive metal compound powder having a dye disposed on the surface thereof is 0.5 to 2% by mass of the adhesive and It is preferable to contain 0.5-2 mass% of dye.

<Solvent>

The solvent used in the adhesive is capable of dissolving the resin acting as the adhesive, and it is necessary to be able to fix the resin on the surface of the conductive metal oxide powder after the light is polished. For example, methanol, buthanol, tetrahydrofuran (THF) or similar organic solvents may be used, but is not particularly limited.

<Crosslinking reaction>

Crosslinking reaction is performed by drying using oven (for example, 120 degreeC, 30 minutes). The dye is applied by crosslinking the thermosetting resin, the crosslinkable thermoplastic resin, and a mixture thereof to the surface of the conductive metal oxide powder.

Advantages of Metal Oxides with Dye Placed on Surfaces

An advantage of disposing a dye such as a diazo metal complex on the surface of the conductive metal oxide powder is to reduce the thickness of the intermediate layer and to have stable electrical properties and more preferable print quality even in an environment of low temperature, low humidity, or high temperature and high humidity.

<Middle floor>

In this invention, the paint used for manufacture of an intermediate | middle layer contains the electroconductive metal oxide powder, the binder, and the solvent which arrange | positioned the dye on the surface. As the binder, a thermosetting resin, a crosslinkable thermoplastic resin, or a mixture thereof may be used. This binder can also be used for the reason that the dye can be fixed to the surface of the conductive metal oxide powder. The polyamide resin as the adhesive is preferable because the formed intermediate layer can prevent expansion and dissolution similar to the solvent of the charge generating layer of the second layer and is excellent in adhesion to the aluminum substrate. Among these, polyamide resins having an N-methoxymethyl group disclosed in the specification of US Pat. No. 6,197,462 are more preferable. US Patent No. 6,197,462 also discloses a melamine-formaldehyde resin crosslinking agent suitable for crosslinking of polyamide resins, a high and partially alkylated melamine-formaldehyde resin crosslinking agent. When the highly alkylated melamine-formaldehyde resin is used as a crosslinking agent, an acid catalyst may be added as a catalyst. Preferred acid catalysts include p-toluenesulfonic acid, methanesulfonic acid, maleic acid, phosphoric acid, hexamic acid, mixtures thereof, and the like. to be. It is preferable that pH of the coating material after adding an acidic catalyst shall be 5 or less, and more preferably 3 or less. When the melamine-formaldehyde resin and the partially alkylated melamine-formaldehyde resin are used as the crosslinking agent, it is possible to omit the acid catalyst.

In a preferred embodiment of the present invention, a resol type phenolic resin is added, but the alkylated melamine-formaldehyde resin acts on the polyamide resin and the resol type phenolic resin, respectively, and is a polyamide-melamine-poly compound which is a three-component compound. Amide, polyamide-melamine-phenolic, phenolic-melamine-phenolic, or phenolic-phenolic.

<Resistance>

It is preferable that the resistance of the intermediate layer is between 10 ³ and 10 ¹² Ωcm. If the resistance is smaller than 10 ³ Ωcm, a short circuit occurs, and if it is larger than 10 ¹² Ωcm, electron transfer becomes a problem. If the photosensitive layer is subjected to the next photosensitive charging, a high residual potential of ghost appears during printing. There is concern. More preferably, the resistance value is between 10 ⁷ and 10 ¹⁰ Ωcm (US Pat. No. 5,660,961).

<Thickness and Surface Roughness>

Generally speaking, the degree of the size of the powder that can be used in the intermediate layer, the difference in refractive index with the surrounding resin, the solid content and the thickness after drying determine the amount of incident light and the surface roughness of the intermediate layer. Gives. If the surface of the intermediate layer contains sufficient conductive metal oxide powder, it is possible to lower the reflected light and reduce the moire (US Pat. No. 5,660,961 and US Pat. No. 5,460,911). What is necessary is just to apply | coat a metal oxide, an additive, and resin uniformly to thickness 3micrometer or more. Too thin can scatter light on the surface to reduce the moiré of the print, moreover it completely covers the substrate and does not break, causing non-uniformity in insulation and staining of the print. In order to obtain better electrical characteristics and a complete surface shielding effect, the thickness may be between 8 and 12 µm. Content of the conductive metal oxide apply | coated to the intermediate | middle layer contained in the photosensitive layer of this invention is 16 to 83% with respect to the mass of the film after drying, More preferably, it is 50 to 70%.

<Charge Generation Layer>

The charge generating layer includes a charge generating material and an adhesive. Known polishing techniques such as ball mills, roller mills, and sand mills disperse the charge generating material in a solution containing an adhesive. The uniform dispersion of the charge generating material in the resin solution generally takes 1 to 3 days, and is applied to the intermediate layer by spraying, immersion, roller, or the like, and then oven and infrared light. Dry it by air drying. What is necessary is just to determine a charge generating substance, a compounding quantity, etc. with reference to a well-known technique suitably, and it does not specifically limit in this invention.

<Charge moving floor>

The charge transfer layer is made of a material that moves holes (specified in US Patent No. 5,489,496). For example, a hydrazone compound, a pyazoline compound, a triphenylamine compound, and beads- Triarylamines, poly-triarylamines, triphenylmethane compounds, stilbene compounds, oxdiazole compounds and the like. Preferred hole-moving materials include N, N'-beads (alkylphenyl)-[1,1'-biphenyl] -4,4-diamine (TPD), beads ( N-alkylphenyl-N'alkylnaphthyl)-[1,1'-biphenyl)]-4,4-diamine (NBP), a benzidine derivative, and the like, wherein the alkyl group is methyl, Ethyl, propyl, n-butyl and the like are preferred (US Pat. No. 5,958,637).

The structure of TDP is the following kind.

As the charge transfer layer, one or two or more kinds of hole transport materials may be used in some cases. The binder used for the charge transfer layer contains a resin having a good insulating property, for example, a polycarbonate ester, a polycarbonate copolymer, a polycarbonate ester copolymer, Polyvinyl butyl ester resin, polyvinyacetal resin, polyacrylic resin, silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone (polyketone) resins, styrene-acrylic resin copolymers, polystyrene resins, melamine resins, polymethylmethacrylate resins, polyvinychloride, ethylene-vinyl acetate copolymers, Vinyl chloride-vinyl acetate copolymers, polyacrylamide resins, and the like. Such resins may be used alone or in combination (US Pat. No. 5,958,637). More preferable resins are polycarbonate esters and crosslinked polycarbonate ester copolymers. Other resins such as binders used in the charge generating layer may also be used in combination with the polycarbonate esters. The mass ratio of the substance which moves a hole and polycarbonate ester is between 20:80 and 80:20, More preferably, it is 30:70 to 70:30.

The coating method of the charge transfer layer is the same as that of the above-described intermediate layer, and the thickness of the charge transfer layer is 5 to 50 µm, more preferably 10 to 30 µm. If the thickness is thinner than 5 μm, the initial voltage of the charge is too low, and an electric leakage is worse.

The thickness of the photosensitive layer is measured with a coating thickness tester LZ-3000C, and the surface roughness is performed using Surfcom 1400 (manufactured by Tokyo Seimisu).

<OPC test>

The electrical property test of the photosensitive layer is performed using a photosensitive layer test system (product number PDT-2000LAP, manufactured by Quality Engineering Associates, Inc.). Before testing, first fix the test OPC tube to the clamp of the PDT-2000LAP, and place the corona charging end and the measuring end against the test tube and place it vertically. At this time, the vertical distance is 0.032 inch (inch). The distance between the corona filling stage and the measuring stage is 25 mm and measured simultaneously with the filling (the moving speed of the corona filling stage and the measuring stage is 100 mm / sec).

a) Charge voltage: It is the energy required to charge the surface of the OPC tube to 700V, and it is about -4.92 ~ -5.67㎸.

b) Exposure energy: Exposure intensity that discharges the energy charged up to -700V on the surface of the OPC standard tube by exposure, and makes the voltage after instant discharge to a certain value (about 100V), about 0.25 ~ 0.3uj / cm 2.

c) Charge voltage (Vc, Vi): The corona charging end and the measuring end are perpendicular to the test tube, charged at a voltage of -700 volts along the tube axis, and The average value of the voltage is measured, rotated in steps of 90 degrees, and the average value of four times is Vc. When charging 700 volts at a time, the value of a specific voltage (for example, the position of 100 mm) is Vi.

d) Instantaneous discharge voltage (Vd): Immediately after charging, the residual potential measured after exposing to 25 micrometer second by the light of wavelength 780nm is instantaneous discharge voltage (Vd).

e) Dark decay (D.K): After charging by corona charging method, it is the change of tube surface voltage for 10 seconds without exposure and the change of voltage of 1-3 seconds.

f) Residual potential (V _f ): As described in c), immediately after charging with a corona charging stage, the surface is discharged by exposure to a constant energy of light, and the residual potential after discharge is related to the exposure energy. As this exposure energy increases, the residual potential is lowered. If the exposure energy exceeds a certain value, the residual potential does not decrease, and the residual potential V _f therein is the surface residual voltage after the exposure discharge energy is made to the maximum value (uj / cm 2).

g) Photosensitivity (E _1/2 ): Immediately after charging, exposure is made with light of wavelength 780 nm, and the exposure energy is increased by dividing 22 times from 0 to 2uj / cm 2, from the curve of surface voltage versus exposure energy. The exposure energy required when the surface residual potential is 1/2 of one charge voltage is the light sensitivity.

h) Life test: The life test is the change of Vc and Vd after 200 consecutive charges and exposure discharges of the test OPC tube according to the above c) and d) methods.

OPC print testing is performed using the IAS-1000G Image Analysis ystem and in accordance with ISO / IEC 13660.

Hereinafter, the embodiment of the present invention will be described in detail. Again, the present invention is not limited to the following examples.

Example 1 Preparation of Zinc Oxide Applying Diazo Metal Complex to Surface

200 g of zinc oxide (n-type, average powder diameter of 0.1 to 0.25 µm, trade name 23-K, manufactured by Haksui Tech.), 1 g of diazo metal complex (trade name Valifast Y1101, manufactured by Oriental Chemical), 6.25 g of Sol type phenolic resin (trade name PF-3150, manufactured by Chang Chun Petrochemical), 3 g high methylated melamine-formaldehyde resin (trade name Cymel 303, manufactured by Cytec Industries), and 1.5 g p-toluenesulfonic acid (toluenesulfonic) acid) (added 0.3% to the mass of the phenolic resin) was mixed with 200 g of methanol, heated to reflux for 0.5 hour while stirring with a machine, and concentrated under reduced pressure. In addition, the crosslinking reaction was completely carried out in an oven (120 ° C., 3 hours). After grinding | polishing with the ultrafine powder by the ball mill, it put into the container, added methanol, and vibrated for 0.5 hour by ultrasonic waves, stirring. The mixture was washed with methanol under reduced pressure filtration, and washed five times until the color of the solution became very light. Furthermore, when it dried under reduced pressure filtration, the zinc oxide in which the diazo metal complex was apply | coated to the surface was obtained. That is, the conductive metal compound in which the dye was arrange | positioned at the surface was obtained. It was confirmed that zinc oxide was applied from the change of the infrared spectrum and the refractive index.

(Preparation of the middle layer)

400 g of zinc oxide coated with a diazo metal complex on the surface, 333 g of methoxymethylpolyamide (trade name FR-104, manufactured by Nippon Shizai), 100 g of Cyme 1303 (mass ratio is ZnO / FR104 / Cymel = 1.2 / 1 / 0.3), 1953 g of methanol and 500 g of butanol were mixed with a sand grinder for 24 hours, and 10 g of PF-3150 resol-type phenolic resin, 17 g (0.3 mass%) of diazo metal complex (Valifast) Y1101) and the mixture obtained by adding 10 g of p-toluenesulfonic acid were stirred at 22 ° C. for 72 hours, and the clay was about 100 cps. And the intermediate | middle layer was produced according to the following.

The intermediate | middle layer was produced by the immersion coating method in the aluminum tube (surface roughness Rmax is 1.2 micrometers) of diameter 24mm and length 246mm, and it hardened | cured at 120 degreeC for 20 minutes, and surface roughness Rmax was 1.17. It was -1.6 micrometers.

(Preparation of charge generating layer)

The paint of the charge generating layer was mixed with 3 g of titanium oxyphthalocyanine, 1 g of polyvinyl butyral (trade name BX-1, manufactured by Sekisui Chemical), and 43 g of cyclohexanol. And it grind | polished for 24 hours with the sand grinder, Furthermore, 53 g of methyl ethyl ketones were added, it stirred, and the dye was disperse | distributed. When the film is dried at 70 ° C. for 15 minutes in the same manner as in the subsequent immersion coating method of the intermediate layer, a film having a thickness of about 0.2 μm is obtained.

(Preparation of charge transfer layer)

10 g of TPD (N, N'-diphenyl-N, N 'beads (3 "-methylphenyl)-(1,1'-biphenyl) -4,4-di Amine, 15 g of polycarbonate ester (trade name Iupilon Z-300, manufactured by Mitsubishi Gas Chemical Industries), 56 g of tetrahydrofuran (THF), and a monobenzine with a mass of 19. Similarly applied to the surface and dried at 120 ° C. for 60 minutes, a film having a thickness of about 20 μm is obtained.

(Fatigue Test on OPC Features)

In the present invention, OPC was evaluated by measuring the electrical properties of OPC at room temperature (25 ° C. and 40% relative humidity) in PDT-2000LAP. Table 1 shows the results.

Table 1: Electrical Characteristics Test Results Vc Vd D.K Vi V _f E _1/2 716 92 12/2 713 53 0.114

Environmental testing of the print was conducted with a commercially available laser printer. The results are shown in Table 2.

Table 2: Print Environment Test Set temperature 0 5 10 15 20 35 45 Temperature / relative humidity 1.4 / 54 6.3 / 50 11.4 / 69 16.4 / 54 21.5 / 34.6 35.8 / 40 44.4 / 54 Ghost Nil Nil Nil Nil Nil Nil Nil Fog Nil Nil Nil Nil Nil Nil Nil

The electrical fatigue test of the print can be reused by one-time filling after testing with a commercially available laser printer and not using carbon. Table 3 shows the results of printing up to 9370 sheets with a HP5000 type fritter at room temperature (25 ° C.) and 40% relative humidity, printing a test page every 500 sheets, and using 540 g of carbon in all.

Table 2: Electrical characteristics before printing and after printing 9000 pages Vc Vd D.K Vi V _f E _1/2 Average blackness Printer i 699 111 15/2 707 51 0.117 1.45 After printer 698 105 17/2 694 49 0.122 1.41

Comparative Example 1

It is the same as that of Example 1 except not applying a diazo metal complex to the surface of zinc oxide. Table 4 and Table 5 are the test results.

Table 4: Electrical properties with a charge energy of -5.67㎸ and an exposure energy of 0.25㎸ Vc Vd D.K Vi V _f E _1/2 714 137 12/2 714 88 0.124

Table 5: Environmental Testing of Prints Set temperature 0 5 10 15 20 35 45 Temperature / relative humidity 1.4 / 54 6.3 / 50 11.4 / 69 16.4 / 54 21.5 / 34.6 35.8 / 40 44.4 / 54 Ghost Nil Nil Nil Nil Nil Nil Nil Fog Nil Nil Nil lightness lightness Severe Severe

Example 2

The other process is the same as that of Example 1 except surface roughness Rz apply | coating to an aluminum tube of 0.8 micrometer. Table 6 shows the change in the electrical properties of the OPC tube once and seven days and the stability of the OPC tube.

Table 6: Changes in electrical properties when charging energy is -5.67 ㎸ and exposure energy is 0.25 ㎸ Vc Vd D.K Vi V _f E _1/2 1 day 702 146 14/2 708 120 0.126 7 days 704 142 15/2 717 127 0.131

Example 3

The binder used for the intermediate layer was the same as in Example 1 except that FR-104 (Cymel 303 and PF-3150 were added) but the content of the diazo metal complex was increased to 0.5%. Table 7 shows the electrical properties of the OPC tube.

Table 7: Electrical Characteristics Vc Vd D.K Vi V _f E _1/2 706 74 14/2 704 58 0.106

Example 4

The binder used for the intermediate layer was increased to 0.45% of the diazo metal complex as well as to the polyamic acid CM-8000 (manufactured by Toray Industries Co., Ltd.) having the following structural formula. The same procedure as in Example 1 was performed except that BHT (Butylated hydroxy toluene) of a phenolic antioxidant was added.

The clay of the interlayer paint is 154 cps (21 ° C). In the OPC tube of this example, black spots and virtual images did not occur after the print test. Its electrical properties are shown in Table 8.

Table 8: Electrical properties at -5.73 kW of charging energy and 0.32 kW of exposure energy Vc Vd D.K Vi V _f E _1/2 685 82 18/2 689 51 0.102

In the OPC tube made according to this example, an electrical property change test was conducted for 1 to 12 days. The results are shown in Table 9. From Table 9, the variation of Vd and V _f is found that the stability of the electrical properties of the pipe were available OPC in the present embodiment from extremely small to examples.

Table 9: Electrical Property Test Results Test time Vc Vd Dark decay Vi V _f E _1/2 1 day 690 97 21/2 690 56 0.107 12 days 687 107 19/2 688 58 0.109 Average 682 92 22/2 684 51 0.106

Comparative Example 2

It is the same as that of Example 4 except not applying a diazo metal complex to the surface of zinc oxide. Environmental testing of the print was conducted with a commercially available laser printer. Table 10 shows the test results of the present Comparative Example 2 and Example 4, among the Comparative Example 2, when printing in an environment of high temperature and high humidity, more severe fog occurs.

Table 10: Print Environment Test Zinc oxide surface 15 ℃ / 50% 10 ℃ / 50% 5 ℃ / 50% 0 ℃ / 50% 35 ℃ / 50% 45 ℃ / 50% Example 4 Diazo metal adhesive Nil Nil Nil Nil Nil Nil Example 2 No diazo metal complex Nil lightness lightness lightness Severe Severe
Table 11 shows the results of electrical property tests for 1 to 12 days in the OPC tube made by this comparative example. As can be seen from Table 11, since the value of Vd decreases, but the dark decay increases, it was found that the electrical characteristics of the OPC tube produced in this comparative example were stable.

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Table 11: Electrical Characteristics Changes Test time Vc Vd Dark decay Vi V _f E _1/2 1 day 696 83 10/2 692 24 0.119 12 days 676 58 17/2 677 24 0.106 Average 691 71 16/2 687 21 0.112

Example 5

The same procedure as in Example 1 was carried out except that the amount of Cymel 303 used was from 0% to 50% (relative to the mass of methoxymethylpolyamide (FR104)) without using a resol type phenolic resin for the binder of the intermediate layer. Electrical properties are shown in Table 12. The Vd of the prepared OPC tube increased with the increase in the amount of the crosslinking agent Cymel 303, except for these, the OPC tube produced in this example was not able to see black spots and virtual images after the print test.

Table 12: Electrical Characteristics Clay in paint Cymel 303% Vc Vd D.K Vi V _f E _1/2 151 0 703 90 16/2 699 76 0.111 76 10 725 103 12.8 / 2 723 80 0.118 82 20 712 105 12/2 713 94 0.122 83 30 712 146 12/2 714 105 0.118 95 40 707 140 12/2 711 67 0.129 121 50 711 159 12/2 714 116 0.110

The electrophotographic photosensitive member of the present invention is a highly sensitive electrophotographic photosensitive member in which the change in electrical characteristics such as after overlapping photosensitive charging and fatigue test prints is extremely small.

Claims (11)

A conductive base, an intermediate layer formed on the conductive base, a charge generating layer, and a charge transfer layer, the intermediate layer having a conductive metal oxide powder and a binder having a dye disposed on a surface thereof, the conductive metal oxide powder having an average An electrophotographic photosensitive member having a diameter of 0.01 to 0.5 µm, a needle shape of 0.13 to 0.27 µm in thickness and 1.68 to 5.15 µm in length, and a light absorption of the dye between 450 and 950 nm. The method of claim 1, wherein the dye, An electrophotographic photosensitive member comprising a diazo metal complex, an organometallic or a photosensitive dye. The method of claim 2, wherein the dye, An electrophotographic photosensitive member, which is a diazo metal complex. The method according to any one of claims 1 to 3, The conductive metal oxide powder in which the dye is disposed on the surface is An electrophotographic photoconductor comprising an adhesive for fixing the dye to the surface of the conductive metal oxide powder. The method of claim 4, wherein The conductive metal oxide powder having the dye disposed on the surface thereof, An electrophotographic photosensitive member comprising 0.5 to 2% by mass of an adhesive and 0.5 to 2% by mass of a dye based on the conductive metal oxide powder. The method of claim 4, wherein The adhesive and the binder, An electrophotographic photosensitive member, which is prepared by a crosslinking reaction of a thermosetting resin, a crosslinked thermoplastic resin, or a mixture thereof. The method of claim 6, The adhesive and the binder, An electrophotographic photosensitive member, which is prepared by a crosslinking reaction of the same resin. The method of claim 6 or 7, wherein the adhesive Polyamide resins, polyamic acid resins, mixtures of polyamide resins and alkylated melamine-formaldehyde resins, polyamide resins and resol type phenolic resins An electrophotographic photoconductor comprising a mixture of an alkylated melamine-formaldehyde resin or a crosslinking reaction of a polyrinyl butyrate resin. The method of claim 8, The crosslinking reaction is An electrophotographic photosensitive member, which is carried out in the presence of an acidic catalyst. According to claim 1, The conductive metal oxide An electrophotographic photosensitive member, which is aluminum oxide, titanium oxide, zinc oxide, cerium oxide, iron oxide or magnesium oxide. According to claim 1, The electrophotographic photosensitive member, characterized in that the average diameter of the conductive metal oxide powder is 0.03 ~ 0.3㎛.