TW200413867A - Electro-photographic photosensitive member - Google Patents

Abstract

There is provided an electro-photographic photosensitive member, which includes a conductive substrate and a charge block layer, a charge generation layer and a charge transmission layer formed on the electro-optic substrate. The charge block layer includes conductive metal oxide powders having surfaces coated with dye and a binder, wherein, when being formed to be granular, the conductive metal oxide powders have an average grain size of 0.01 to 0.5 micrometer, when being formed to be of needle shape, the conductive metal oxide powders have a short diameter of 0.13 to 0.27 micrometer, and a long diameter of 1.68 to 5.15 micrometers, and the dye absorbs light of wavelength between 450 to 950nm.

Description

200413867 (1) Description of the invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an electronic photoreceptor, and more particularly to a conductive powder suitable for a charge blocking layer of the electronic photoreceptor. An electronic photoreceptor currently used in the prior art includes a conductive substrate and a charge blocking layer, a charge generating layer, and a charge transfer layer formed on the photoelectric substrate. The charge blocking layer includes a binder. With conductive metal oxide powder. The conductive metal oxide powder mainly has two functions, one is to reduce the resistance of the charge blocking layer, and the other is to increase the roughness of the surface of the charge blocking layer. If the resistance of the charge blocking layer is too high, it will make it difficult for electrons to pass through and have a high residual potential. The roughness of the surface of the charge barrier layer will scatter the incident light and avoid interference fringes on the surface of the electronic photoreceptor. The charge barrier layer consists of a resin coating containing more than 50% solids (containing the conductive metal compound powder and A resin as a binder) is prepared by coating the conductive substrate. Coatings with a high solid content are prone to deposits and reduce the life of the coating. In addition, the galvanic metal oxide powder has a low dispersibility in the coating, which is not conducive to the formation of a coating film (charge barrier layer) with a uniform distribution of the conductive metal oxide powder, resulting in the control of the electrical characteristics and clear imaging characteristics of the photosensitive drum. Not good. Furthermore, the bonding force between the conductive metal oxide powder and the binder resin is not good, which makes the thickness of the charge blocking layer formed by the drying and bridging reaction of the coating film difficult to control, and it is not conducive to wetness at south temperature. Print under conditions. Several patents related to electronic photoreceptors are listed below. US Pat. No. 4775605 to Kenji Seki et al.? Issued Oct. 4, 1988 --- Reusable photosensitive materials in an electronic photoreceptor It includes a photosensitive layer and an intermediate layer. This intermediate layer is located between the conductive substrate and the photosensitive layer. It includes a conductive polymer and an inorganic white pigment. The inorganic white pigment includes titanium oxide, zinc oxide, zinc sulfide, white lead, Lithopone and the like. U.S. Pat. No. 4906545 to Toshio Fukagai et al.? Issued

March 6, 1990 ----- An electronic photoreceptor includes a conductive substrate and an undercoat layer on the conductive layer. The undercoat layer includes at least one metal oxide, namely zirconia, magnesium oxide, and oxide. Calcium, barium oxide, and lanthanum oxide. The photosensitive layer includes a charge generating layer and a charge conducting layer. These oxides can be mixed with various thermoplastic or thermosetting plastics and fixed on the undercoat layer. 0 U.S.Pat. No. 5488461 to Shintetsu Go et al.? Issued Jan. 30, 1996 --- electronic photosensitive film and equipment used. The intermediate layer includes a coating having powder, that is, a coating containing barium sulfate or barium oxide. US Pat. No. 5468584 to Shintetsu Go et al.? Issued Nov. 21, 1995 ... The electronic photosensitive film includes an intermediate layer containing titanium dioxide with a chemical compound and the equipment used for the electronic photosensitive film. 0 US Pat No. 6177219 to Huoy-Jen Yuh et al.? Issued 200413867 Needle-like particles. Η-type semiconducting needle-like particles in the charge blocking layer, granular

Jan. 23, 2001 --- The charge-blocking layer was shown to have particles having a η-type semiconducting granularity and particles having a greater concentration than the needle-like particles. U · S · P at · Ν 〇 · 615 6 4 6 S female aal 468 t0 Abuk ^ H. Wehelie et al issued Dec · 5, 2000… charge resistance ·, W layer /, formed by particles that scatter light This coating is formed by scattering light-scattering particles in resin. The refractive index of light-scattering particles is different from that of resin. The average particle size is above 0.8 microns and the total surface area of the particles is greater than 50m2 / gm. U.S. Pat. No. 5660961 to Robert C. U. Yu et al.? Issued

Aug. 26, 1997 ... The electronic photosensitive film has better adhesion and the ability to eliminate interference waves. The charge blocking layer has an inorganic particle that can scatter light with an average size of 0.3 to 0.7 micrometers. The materials include amorphous stone, stone blocking powder, and mixtures thereof, which are dispersed in a network structure. The network structure is composed of The combination of organic silicon and polymer crystal chemical reaction.

Japan Pat · No. Patent No. 2506694, issued Apr · 2, 1996 ... An electronic photoreceptor. A charge blocking layer contains a white pigment (light-scattering particles) and is dispersed in a resin. The value of the formed rough surface Ra needs to be less than 0.4. This white pigment includes titanium oxide (refractive index 2.76), oxidation index (refractive index 2.02), zinc sulfide (2.37), tin oxide (1.94-2.09), lithopone (1.84), and the like. U.S. Pat. No. 4308334 to Kinoshita et al. 3 issued Dec. 29, 1981 --- A method for manufacturing a surface having a photosensitive dye zinc oxide and a photosensitive layer containing a oxidized oxidant. U.S. Pat. No. 4043813 to Daniel R. Logue et al., Issued 200413867

Aug. 23, 1977 ... Methods for manufacturing zinc oxide with photosensitivity dyes. Table 8: Group IIB selenide of telluride and resin are both coated with selenide or telluride by chemical means. The knife works on the surface of the zinc oxide particles. SUMMARY OF THE INVENTION A main object of the present invention is to provide a conductive metal or metal oxide powder having a dye on its surface, the dye being dispersed on the surface of particles of the powder with a resin. The conductive metal or metal oxide powder having a dye on the surface has better dispersibility in a coating containing a binder resin than the conductive metal or metal oxide powder having no dye on the surface, and the conductive The metal or metal oxide powder has an improved bonding force with the binder. Another object of the present invention is to provide a method for producing a conductive metal or metal oxide powder containing a dye on its surface, including a method of fixing a dye to the surface of particles of the powder by a bridging reaction of a bridging resin. 'Another object of the invention is to provide an electronic photoreceptor with high sensitivity. After repeated printing and fatigue testing and printing, #Electrical properties are not substantially M'. That is, after repeated electrical distribution and photosensitive discharge, There is very little change in the residual potential. Embodiment A surface-coated metal oxide The electronic photosensitivity film of the present invention includes a charge blocking layer and an electric 200413867. The charge blocking layer includes a charge-generating layer that scatters light, and an inorganic solid powder of a charge-conducting layer. Disk coating metal oxide powder particles + not n ^ ^ ρ >; Emissivity and resin as a binder. J Electric He resistance ^ layer can effectively scatter the incident line first, eliminating the radiation to reduce the radiation. ^ ^ 、 Interfering shapes caused by reflected light on α first). The azo metal complex dye attached to the surface of the metal oxide powder in the present invention not only changes the refractive index of light, but also increases the binding force of the powder to the binder resin in the charge blocking layer. In addition to azo metal complex dyes, organometallic dyes, acidic dyes, and light-sensitive dyes can be used in the present invention to achieve the above-mentioned objectives. The structures of monoazo metal complex dyes have been revealed in usp6i53735 and uSP5843611. Commercially available monoazo metal complex dyes that can be used in the present invention include Valifast Yellow 1101, Yellow 1105, Orange 3209, Orange 3120, Red 1308, Red 3304, Red 3306 (available from rient chemical Industries,

Ltd., manufactured); Orgalon Yellow 102, Yellow 120, Red 300, Red 306 (manufactured by Kelly Chemical Corporation, Ltd.). Acid dyes include

Everacid Yellow A-4R, Yellow N-5GW, Yellow M-2R, Yellow ANFG (by

Everlight Chemical Industrial Corporation, Taipei, Taiwan); Solar Acid Yellow MR, Yellow NFG, Yellow N5G (manufactured by Solar Fine

Chemical Co., Ltd. (manufactured by Taipei, Taiwan) · Suitable conductive metal emulsion powders have a particle size of an average of 0.01 to 0.5 microns, more preferably 0.1 to 0.25 microns, preferably about 0.1 μm. For example, conductive metal oxides include η- 200413867 5L oxidation terms such as 23_K, 23-K (A) and 23-K (C) (manufactured by Haksui Tech · C ·· Ud ·,); the surface is coated with Spherical rutile crystal titanium oxide with extremely thin conductive Sn02 / Sb layer, such as ET-500W, ET-600W, ET-300W (manufactured by Ishihara SangyKaishaUd,); cinnamic acid bell coated with tin oxide , Such as WK-5〇〇, TM-100, TM-200 (manufactured by Otsuka Chemical Co., Ltd.); the surface is coated with extremely thin conductive faults and woven electrical zinc oxide (by Sakai chemicai c 〇 · LTd ·, manufactured). Needle-shaped metal oxides are also suitable for the present invention, and their average particle size is 0.13-0.27 microns: 1.68-5.15 microns (diameter: long), such as needle-shaped titanium dioxide, whose surface area has been coated with a layer of conductive SnO2 / Sb (trade name FT_i00〇〇, FT-2000 'FT-3000, manufactured by ishihara Sangyo Kaisha, Ltd.,). These light-scattering particles have a refractive index different from that of resins, such as aluminum oxide (Al2O3 ·· refractive index 1.77), silicon oxide (SiO2: refractive index 1.54), and titanium oxide (Ti2: refractive index 2.7) ), Oxidation index (Zn〇 •• refractive index 2.03), hafnium oxide (Ce02 refractive index: 2.6), iron oxide (Fe2O3 refractive index 2.94), sulfuration index (ZnS: refractive index ip) , Potassium iodide (κι: refractive index 1.67), magnesium oxide (Mg20: refractive index: 1.74), cadmium sulfide (Cds: refractive index 2.51). More suitable light-scattering metal oxides include titanium oxide and zinc oxide. Adhesive The coating resin usually used on the surface of metal oxide powder accounts for 0.1 to 5 percent by weight, and a more suitable ratio is about 2 percent. The adhesive for piano can be fixed on the surface of the metal oxide powder with thermosetting resin or bridging thermoplastic resin and its 200413867 compound. For example, polyamine resin, polyamic acid resin, resol type phenol resin, melamine-formaldehyde resin, alkylated melamine-formaldehyde resin, polybutyrate resin , Epoxy resins and their mixtures. An acid catalyst and / or a bridging agent must sometimes be added to the thermosetting resin and the bridging thermoplastic resin to catalyze their bridging reaction. U.S. Patent No. 6,197,462 B1 discloses a polyamine resin, a melamine-formaldehyde resin, an alkylated melamine-formaldehyde resin, and an acid catalyst, which can be suitably used as a bridging agent in the present invention. Solvents When using thermosetting resins, bridging thermoplastic resins or their mixtures as surface coating adhesives, the solvent chosen must be able to dissolve them and fix the resin to the surface of the metal oxide powder after volatilization. For example, methanol, butanol, tetramethylfuran (THF), and similar organic solvents. From the above, the dye used here is mixed with an adhesive and a solvent and is applied to the surface of the metal oxide particles together. It belongs to a type of physical adhesion.

Bl Μ Here, the bridging reaction is carried out in a drying process. When drying in an oven (12 (rc, 3 () minutes), thermosetting resin, bridging thermoplastic resin or a mixture thereof etc. will bridge the surface of the metal oxide. The dye is fixed on it. The advantages of the metal gaseous material of the material are that the coating of the azo metal salt dye on the surface of the metal oxide has the advantages of reducing the thickness of the charge blocking layer and being stable at low temperature and low humidity and high temperature and high humidity. 11 200413867 Electrical properties and better print quality. Charge barrier layer The coating used to make the charge barrier layer includes metal oxides, adhesives, and solvents that have been applied on the surface. The adhesive used can be a thermosetting resin or a bridgeable Thermoplastic resins and their mixtures can use the adhesive used for the metal oxide of the surface coating dye. Polyamide resin is a better choice because the charge blocking layer generated by this resin can resist the second layer (charge generation Layer), which swells or dissolves the solvent, and has excellent adhesion to aluminum substrates. Among them, N_A is disclosed in US patent No. 6,197,462 B1. Oxymethyl methyl polyamine resins are more preferred. US Patent No. 6,197 462 B1 also discloses a melamine · formaldehyde resin bridging agent suitable for bridging the polyamine resin, highly or partially alkylated melamine · 曱Aldehyde resin bridging agent. When a highly alkylated melamine-formaldehyde resin is used as a bridging agent, an acid catalyst must be added at the same time to catalyze the bridging reaction. A suitable acid catalyst such as p-toluenesulfonic acid , Methanesulfonicacid, maieicacid, phosphoric acid, hexarnic acid and a mixture of these acids. The pH of the coating after adding the acid catalyst needs to be Below $, preferably below 3. When using a melamine-formaldehyde resin or a partially alkylated melamine-methyl resin as a bridging agent, the acid catalyst can be omitted. In the present invention In a preferred embodiment, a fusible phenolic resin is further added. The alkylated melamine-formaldehyde resin can interact with the polyamine resin and the fusible phenolic resin to form three kinds of components. Copolymers of 200413867 and di-x compounds (polyamide-melamine-polyamide, polyamide-melamine-phenolic, phenolic-melamine-phenolic, " and phenolic-phenolic) ° Resistance In order to provide effective resistance to the charge barrier layer, In this invention, the resistance value ranges from 10 ohm-cm to 1012 hm-cm. If the resistance is less than 103 ohm-cm, it will leak electricity. If the resistance is greater than 1012 hm-cm, the insulation is too high to transfer electrons. , There will be a high residual potential when the photosensitive drum performs the next round of photosensitive cloth (white ghosting will occur when printing), so the best resistance value is best _ from 107ohm-cm to 1010ohm-cm between. (Usp 566〇96i) Thickness and rough surface In general, the amount of incident light scattering caused by particles used in the charge blocking layer depends on the average particle size, the refractive index value of the particles and the surrounding resin, the solid content, and the These thicknesses affect the roughness of the surface of the charge blocking layer. When the surface of the charge blocking layer has enough particles that can scatter light, the reflected light is reduced and interference waves are reduced (usp 566〇96i & usp 546〇911). The coated metal oxides, additives, and resins used in this invention need to be adjusted to a uniform coating film thickness of more than 3 microns, because when it is too thin, there are not enough particles on the surface to reduce light scattering and reduce printed interference waves. The insulating layer that completely covers the substrate causes uniformity and black spots in printing. To obtain better electrical properties and completely cover the surface of the substrate, the coating film thickness should be controlled between 3 and 16 microns. For the best electrical characteristics, the coating film thickness should be controlled between 8 and 12 microns. The electricity in the photosensitive film in this patent: The coated metal oxide used in the barrier layer has a usage range of "to 13 JOO / 83 weight percent (for dry film weight) weight percentage. The preferred range of use is 50 to 70 charge generation layer, the charge generation layer includes the charge generation material and an adhesive. Disperse the colorant of the charge generation material in a solvent-containing solution by a suitable technique = I such as ball milling, roller milling, sand milling, and the like Way, one L > until 3 days before the average dispersion of the charge-generating material in the resin solution, reed coating on the photosensitive drum, such as spraying, impregnation, roller method. Then use the appropriate method such as oven, infrared Drying in light, air, and similar methods. Charge transfer layer The charge transfer layer includes a material that conducts holes (usp 5489496), such as hydrazone compounds, pyrazoline compounds, Triphenylamine compounds (biphenyl- and poly (tdarylamines)), triphenylamine compounds triphenylmethane compounds), stilbene compounds, oxadiazole compounds, etc. Particularly excellent conductive hole materials include N, N'-dialkylphenyl-1,1, _ Diphenyl_4,4, -diamine (1 ^,] ^ '-1 ^ 8 (& 1] ^ 1911611 丫 1)-[1,1'-biphenyl] _4,4'-diamine), two (N'-methylphenyl-N'-naphthyldiphenyl) -4,4 diamine (Bis (N-alkylphenyl-N'alkyl naphthyl) 14 200413867-[l'l'-biphenyl]-4, 4'-diamine (NBP)), and benzidine derivatives, etc., in which the alkyl group is, for example, methyl, ethyl, propyl, n-butyl, etc. (USP 5958637). N, N , -Diphenyl N, N, di (3 ”tolyldiphenyl-44, -diamine

CH3 (N, N '-(ϋρ1 ^ ι ^ 1-N, N, -M (3,, · π ^ 1 ^ 1ρ1 ^ ηΥ1) · (1, ΐΉρ1 ^ η7ΐ) -4,4'-diamine, TPD The structure is as follows

The charge-transporting layer may use only one type of hole-transporting material or two or more 'depending on the actual situation. The adhesive used in the charge transfer layer includes some resins with good insulation properties. Commonly used resins include polycarbonate, polycarbonate copolymer, polycarbonate polyester copolymer, polyvinyl butyral resin, and polyvinyl alcohol resin. (Polyvinylacetal resins), polyacrylic resins, silicone resins, polyamide resins, polyurethane resins, polyester resins , Epoxy resins, poly ketone resins, styrene_acrylic copolymers, polystyrene resins, melamine resins, polyacrylic acid Polymethylmethacrylate resins, polyvinyl chloride, ethylene-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers 15 200413867 polymers (vinyl chloride-vinyl acetate copolymers) Polyacrylamide resins. These resins can be used singly or in combination (USP 5958637). The preferred resin in this invention is a polycarbonate, bridgeable polycarbonate copolymer. Other resins, such as the binder used in the charge-generating layer, can be mixed with polycarbonate. The weight percentage of the material of the hole and the polycarbonate is 20:80 to 80:20, and the preferred ratio is from 30:70 to 70:30. The coating method of the charge transfer layer is similar to the above-mentioned charge barrier layer. Its thickness ranges from 5 microns to 50 microns, and the preferred thickness is 10 to 30 microns. If the thickness is less than 5 microns, the voltage at which the charge is started is too low (leakage ), Electrical characteristics greater than 100 microns will deteriorate. The film thickness of the photosensitive film was measured with a film thickness tester (Coating thickness tester LZ-300C), and its surface roughness was tested with Surfcomm 400 (manufactured by Tokyo Seimtsu). OPC test procedure The electrical characteristics of the photosensitive film were tested with a photosensitive drum test system (manufactured by Quality Engineering Assocites, Inc., model PDT-2000LAP). During the test, the test tube was fixed on the clamp of PDT-2000LAP. The corona (cron) distribution head and detection head were perpendicular to the test officer, and the vertical distance was 032 inches. . The distance between the corona cloth head and the detection head is 25 mm, and the detection is performed at the same time when the power is turned on (the movement speed of the corona cloth head and the detection head is 100mm / sec). 16 200413867

a) Charge Voltage (b) (Charge Voltage) · The energy when the surface of the qpc tube can be charged to -700V is about _4 · 92 ~ -5 · 67 KV b) Exposure (ExP〇sure energy) ·· The energy when the surface of the 〇PC standard tube is electrically charged to _700 volts is exposed and discharged, and the voltage after the instantaneous discharge can reach a certain value (about 100V). The exposure intensity is about 0.25 ~ 0.3. # J / em2 c) Distribution voltage (Vc, Vi): Corona distribution head and detection head are perpendicular to the test tube, and forward the voltage of -700 volts along the tube axis. Detect the average voltage of this line, press Rotate the tube 90 degrees each time and make an average of Vc 4 times. If only one fixed-point voltage (for example, 100 mm) is detected when the first 700 volts are applied, the value is Vi. d) Instantaneous discharge voltage (vd): The residual voltage measured after 25 microseconds of exposure to light with a wavelength of 780 nm after each power-on is the instantaneous discharge voltage (Vd). e) Dark decay (DK ·): each time the battery is charged with a corona cloth, the surface voltage of the tube is detected for 10 seconds under unlit light, and the voltage of the first and third seconds of unexposed discharge is measured. value. f) Residual potential (Vf) · As explained in item c), after charging with a corona cloth head, the surface is then exposed with a certain amount of light to discharge the surface. The residual voltage after discharge is related to the exposure energy. When increasing, the residual voltage will gradually decrease. When the exposure energy exceeds a certain value, the residual voltage will no longer decrease. Here Vf is the surface residual voltage after the energy of the exposure discharge is adjusted to the maximum value (2 # j / cm2). g) Photosensitivity (Em): Immediately after the application of electricity, the light with a wavelength of 78nm is added to the exposure. The month b of the mother-human exposure ranges from small to large, from 2 to j / cm2, and from 0 to 2 17 200413867. # j / cm2 is divided into 22 times, then the curve of surface voltage vs. exposure energy can be obtained after measuring the 22nd time, and the residual voltage of the surface of the 0pc tube after exposure is found to be 1 / of the voltage of the first time. The required exposure energy at 2 is called the light sensitivity. h) Life test: Measure the changes in Vc and vd after continuously testing the 0pc tube according to the methods (c) and (d) above and then exposing and discharging for 200 times. This is called the life test. 〇pc's print test uses IAS_1000G image analysis system (image

Analysis System) instruments are performed in accordance with ISO / IEC 13660. Example 1 Preparation of Zinc Oxide Coated with Azo Metal Complex Dyes 200 g of zinc oxide (n-type, with an average particle size of 0-0.25 μm, 23-K, trade name, taken from ] ^ 1117 ^ 11. (: 〇., 1 ^ (1., "Made by 1 ^ 11), 1 g of azo metal complex dye (trade name Valifast γη〇1, by Oriented Chemical Co., Ltd., (Manufactured), 6.25 grams of fusible acid resin (trade name PF_3150, manufactured by Chang Chun Petrochemical Co., Ltd "Taiwan), 3 grams of highly methylated melamine- Formaldehyde resin (highly methylated melamine-formaldehyde resin) (trade name Cymel 3〇3, by Cytec

Industries Inc. Ltd., USA), and 5 g of p-toluene sulfonic acid (0.3% by weight relative to phenolic resin) 'are mixed in 200 g of methanol solvent, The above mixture is mechanically stirred and heated to reflux the solvent for about 0.5 hours, and then decompressed using a rotary evaporator. 18 200413867 Evaporate the solvent and place it in the oven at 120 ° C for 3 hours to promote the completion of the reaction. The ball mill grinds the finished product into a very fine powder, puts it in a container, adds methanol while stirring for 0.5 hours with ultrasonic vibration, and then filters it with the same% and rinses with methanol. Repeated washing 5 times until the color of the solution changes: Then, it was evacuated and dried, and then zinc oxide was coated on the surface of the azo metal a wood. The oxidation spectrum of the coated zinc oxide was compared with the uncoated zinc oxide infrared spectrum, and the change in the refractive index of the zinc oxide was verified. Preparation of Charge Barrier Layer 400 parts by weight of zinc oxide containing an azo metal complex dye on the surface, 333 parts by weight of methoxymethyl substituted polyamide (trade name FR-i〇4 ,by

Nippon Shizai Co., Ltd., manufactured by Japan), 100 parts by weight of Cymel 3〇3 (weight i ratio is ZnO / FR104 / Cymel = 1.2 / l / 0.3), 1953 parts by weight of methanol 'and 500 parts by weight The solution consisting of butanol was ground with a sand mill for 24 hours, 10 parts by weight of PF-3150 fusible phenol resin was added, and 17 parts by weight (0.3%, based on the total weight of the coating) of azo metal Compound dye (Valifast Y1101) and 10 parts by weight of p-toluenesulfonic acid. This mixture was mechanically stirred at 22 ° C for 72 hours. The viscosity was measured at about 100 cpS. Then apply the following techniques to form a charge blocking layer. An aluminum tube with a diameter of 24 mm and a length of 246 mm (surface roughness Rmax 1.2 microns) was prepared by impregnation coating method, and then dried at 120 C for 20 minutes to cure the layer. The surface roughness was Rmax 1.17-1.6 microns. Preparation of Charge Generation Layer 19 200413867 The coating of the charge generation layer is 3 parts by weight of titanyl OXyphthalocyanine and 1 part by weight of polyvinyl butyral. (Trade name Βχ), by 由 c〇,

Ltd., manufactured by Japan) and 43 parts by weight of cyclohexanone are mixed with a sand mill for 24 hours, then 53 parts by weight of methyl ethyl ketone are added, and the dye is stirred and dispersed, as in the impregnation coating preparation method of the charge blocking layer, 70 cc drying for 15 minutes, film thickness is about 0.2 microns. Preparation of the charge-conducting layer The coating of the charge-conducting layer is based on parts by weight of TpD and 15 parts by weight of poly_carbonic acid vinegar (trade name Iupilon Z_300, by Hall—㈣Gas Chemical

Industries Ltd. Japan) and 56 parts of tetrahydrofuran (thf) and 19 parts of monochlorobenzene. The impregnated coating preparation method similar to the charge blocking layer is applied to the surface of the charge generating layer, and then dried at 1200c for 60 minutes, and the film thickness is about 20 microns. OPC Characteristics and Fatigue Test The evaluation of the OPC method in the present invention is to measure the electrical characteristics of OPC using pDT_2OO00LAp at room temperature (at 25 C and 40% relative humidity), as shown in Table 1. Table 1: Electrical characteristics test results

Vc Vd D.K. Vi Vf El / 2 716 92 12/2 713 53 0.114 The environmental test for printing was printed with a laser printer 20 200413867 which is commonly used in the market. The test results are shown in Table 2 and Table 2. Printed environmental 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 The electrical fatigue test of the non-no-no-no-no-no-no-no-bottom-ash-no-no-no-no-no-no-no-printing is printed with a laser printer commonly used in the general market. After the toner is used up once, you can fill it again and continue printing. At room temperature (25 ° (3 and 45% humidity), print with 1 ^ 5000, so that the total number of pages reaches 9370, each 500. A test page was printed with a total of 540 grams of toner. The test results are shown in Table 3 and Table 3. Electrical characteristics before printing and after printing 9,000 pages.

Vc Vd DK Vi vf Ei / 2 Average blackness 9000 pages before printing 699 111 15/2 707 51 0.117 1.45 9000 pages after printing 698 105 17/2 694 49 0.122 1.41 Comparative Example 1 Except for the nitrogen metal complex dye, other preparation methods were the same as in Example 1. The test results are listed in Tables 4 and 5 below. 21 200413867 Table 4: Electrical properties, its distribution energy is -5.67KV, exposure energy is 0.25

Vc Vd DK Vi Vf Ei / 2 714 137 12/2 714 88 0.124 Table 5: Printed environmental 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 image None None None None

Example 2 The steps were the same as those of Example 1 except that coating was performed on a tube having a surface roughness Rz of 0.8 μm. Table 6 lists the electrical properties of the OPC tube after the first and seventh days. The results show that the change is very small, showing that the OPC tube has stable electrical characteristics. Table 6: Tracking results of electrical properties, the distribution energy is -5.67KV, and the exposure energy is 0.25 _

Vc Vd DK Vi vf Ei / 2 Day 1 702 146 14/2 708 120 0.126 Day 7 704 142 15/2 717 127 0.131 Example 3 The adhesive used in addition to the charge blocking layer was changed to a single FR-104 (without Cymel 303 and PF-3150 were added, and the content of the azo metal complex dye 22 200413867 (Valifast YllOl) was increased to 0.5%. The other preparation steps were the same as in Example 1. Table 7 lists the electrical properties of the OPC tube of this embodiment. Table 7: Electrical properties

Vc Vd DK Vi vf Ei / 2 706 74 14/2 704 58 0.106 Example 4 The adhesive used in addition to the charge blocking layer was replaced with a single polyamic acid (trade name CM-8000 with the following chemical structural formula) by Toray Industries Inc., made by Japan), the content of azo metal complex dye (valifast Y1101) was increased by 0.45%, and 1.5% of hindered anti-oxidant βητ (Butylated hydroxy toluene) was added to the charge conductive layer coating (based on the weight of TPD as Except for the benchmark), the other preparation steps are the same as in Example i:

. The viscosity of the coating of the charge-blocking layer is 154 cps (21.0). After the OPC tube of this example is printed, there are no black spots and ghosts. The electrical properties are listed in Table 8. 23 200413867

The tracking test of the lightning properties of the OPC camp pusher f made in this embodiment from the first day to the twelfth day, the following table shows the average value and the average value. It can be seen from the data that the Vd and vf change poles-the OPC tube made by the embodiment does not have stable electrical characteristics. ® ~ Table 9 ·· Electrical property tracking results Test time Vc Vd Day 1 690 97 Day 12 687 107 Average 682 92 D.K. 21/2 19/2 22/2

Vi Vf 690 56 688 58 684 51 It is 1/2 0.107 0.109 0.106 Comparative Example 2 Except that the gasification surface is not coated, its preparation steps are the same as those of Example 4 Laser printer commonly used on the market Printing Example 4 The test result is π, which is more severe than the India. In addition to nitrogen metal complex dye #, the environmental test for its printing is general. Table 10 lists the comparative example 2 and the actual & < column 2 under the high temperature and high humidity environment.

24 200413867 Table 10: Environmental test for printing 50 ° C / 50% Zinc oxide surface 15 ° C / 50% 100 ° C / 50% 50 ° C / 50% 0 ° C / 50% 35 ° C / 50% 45 ° C / 50% (24 hours) Example 4 with azo metal No. No No No No No No No No Azo Metal Comparative Example 2 No complex slight dye The OPC tube is tested for electrical properties from the first day to the twelfth day. It can be seen from the data in Table 11 that the value of Vd decreases but the dark attenuation increases, indicating that the OPC tube made in this comparative example shows unstable electrical characteristics. Table 11: Tracking results of electrical properties Test time Vc Vd DK Vi vf Ei / 2 Day 1 696 83 10/2 692 24 0.119 Day 12 676 58 17/2 677 24 0.106 Average 691 71 16/2 687 21 0.112 Example 5 Adhesives other than the charge-blocking layer do not use a fusible phenolic resin and Cymel 303 in an amount of 0% to 50% (methoxy-methyl substituted polyamide (FR104) Except for the weight), other preparation steps are the same as in Example 1. Electrical properties are shown in Table 12. The Vd of the prepared OPC tube increased with the increase of the percentage of the cross-linking agent Cymel 25 200413867 303. In addition, the OPC tube prepared in this example was free from black spots and ghost images after the printing test. Table 12: Electrical Properties Coating Viscosity (cps) Cymel 303% Vc Vd DK Vi vf El / 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 Because the present invention only lists some specific examples for illustration, familiar with this Those skilled in the art can make changes without departing from the scope of patent application in this case after understanding the concept of this invention. 26

Claims (1)

200413867 Scope of patent application: 1. An electronic photoreceptor including a conductive substrate and a charge blocking layer, a charge generating layer, and a charge transfer layer formed on the photoelectric substrate, which are characterized by the charge blocking layer The conductive metal oxide powder is coated with a dye on the surface and a binder, wherein the conductive metal oxide powder has an average particle size between 0.01 and 0.5 microns when it is granular, and When it is needle-shaped, it has short tethers between 013 and 027 microns; | Long diameter between 1.68 and 5.15 microns, and the dye has an absorption wavelength between 450 and 950 nm. 2. An electronic photoreceptor according to item i of the application, wherein the dye is an azo metal complex dye, an organometallic dye or a light-sensitive dye. 3. The electronic photoreceptor according to item 2 of the patent application scope, wherein the dye is an azo metal complex dye. 4. The electronic photoreceptor according to item i, 2 or 3 of the scope of patent application, wherein the conductive metal oxide powder coated with a dye on the surface includes a dye for fixing the dye on the surface of the conductive metal oxide powder. Adhesive. 5. The electronic photoreceptor according to item 4 of the application, wherein the adhesive and the adhesive are prepared from a thermosetting resin, a bridging thermoplastic resin, or a mixture thereof through a bridging reaction. 6. The electronic photoreceptor according to item 5 of the application, wherein the adhesive and the adhesive are prepared by the same resin through a bridging reaction. 7. The electronic photoreceptor according to item 5 or 6 of the patent application scope, wherein the adhesive is made of polyamide resin; polyacrylic acid (polyamic acid); Mixture of alkylated melamine-formaldehyde resin 27 200413867 (Polymerized 4 amine resin, a mixture of resol type phenolic resin and alkylated melamine · · Formaldehyde resin; or polyvinyl butyrate An ester (polyvinyl butyrate) resin is prepared by a bridging reaction. 8. The electronic photoreceptor according to item 7 of the application, wherein the bridging reaction is performed in the presence of an acid catalyst. 9. The electronic photoreceptor according to item i of the application, wherein the conductive metal oxide is aluminum oxide, titanium oxide, oxide, hafnium oxide, iron oxide (Fe203), or magnesium oxide. _10. The electronic photoreceptor according to item 1 of the scope of the patent application, wherein the average particle size of the conductive metal oxide is between 0.3 and 0.3 micrometers. 11. The electronic photoreceptor according to item 4 of the patent application, wherein the conductive metal oxide powder coated with a dye on the surface contains 05% to 2% of a binder and 0.5% to 2% of a dye, and the conductive metal is oxidized. The weight of the powder is used as a reference. . 28 200413867 (1) Designated representative map: (1) The designated representative map in this case is: (). (2) A brief description of the component symbols in this representative map: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: