JP2006072046A - Manufacturing method for electrophotographic photoreceptor support, and electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an electrophotographic photoreceptor support, and an electrophotographic photoreceptor capable of obtaining superior images, while hardly producing defects on the anode oxidation coating. <P>SOLUTION: In the 1st step, strong acid liquid etching is carried out, after cleaning the surface of a conductive substrate consisting of an aluminum material. In the 2nd step, an under coating layer of the anode oxidation coatings is formed by anode oxidizing the surface of the conductive substrate. The strong acid liquid consists of a sulfuric acid solution of 3 % or higher but 70 % or lower in weight, and the etching is conducted at 50-90°C for 1-15 minutes. In the 2nd step, a sulfuric acid solution of 1 % or higher but 30 % or lower in weight is used as the electrolytic solution, and the anode oxidation coating is conducted with 3-12 μm thickness, with electric current density of 0.2-1.2 A/dm<SP>2</SP>at 0-15°C for electrolyzation. In the 3rd step, sealing is made on the fine holes 600 μS or larger, but 3000 μS or smaller by the nickel acetate method. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a support for an electrophotographic photoreceptor using a conductive substrate made of an aluminum-based material, and an electrophotographic photoreceptor using the support for an electrophotographic photoreceptor.

  Electrophotographic photosensitive members are used in laser printers and the like in addition to copying machines. The electrophotographic photosensitive member is formed by forming a photosensitive layer on an undercoat layer of an electrophotographic photosensitive member support. The electrophotographic photoreceptor support is formed by forming an undercoat layer on the surface of a conductive substrate. The conductive substrate is made of an aluminum-based material such as aluminum or an aluminum alloy. The undercoat layer is formed by forming an aluminum anodized film on the surface of the conductive substrate by anodizing. The photosensitive layer is formed by laminating a charge generation layer and a charge transport layer. The charge generation layer is formed by applying a coating solution containing an organic charge generation material on a support. The charge transport layer is formed by applying a coating solution containing an organic charge transport material on the charge generation layer.

  As a conventional electrophotographic photoreceptor and a method for producing the same, after cleaning the surface of an aluminum-based conductive substrate with an iron content of 0.05% by weight or less, and performing degreasing cleaning by etching with a weak acid, The surface is anodized to form an undercoat layer of an anodized film as a support, and a photosensitive layer on which a charge generation layer and a charge transport layer are laminated is formed as an electrophotographic photoreceptor. There are some (see, for example, Patent Document 1). The purpose of this method is to prevent the occurrence of etch pits by degreasing and cleaning by etching with a weak acid, and to prevent the occurrence of defects such as black spots and ground fog in an image using the manufactured photoreceptor. It is said.

Japanese Patent Laid-Open No. 07-261439

  However, in the conventional electrophotographic photosensitive member and the manufacturing method thereof disclosed in Patent Document 1, etch pits are generated by etching with an alkaline solution depending on the aluminum material, and liquid spots, flows, and defects are easily generated on the surface of the substrate. As a result, defects occur in the anodized film, and a photoconductor produced using such a defective support has a problem that defects such as “black spots” and “ground fog” occur in the image.

  The present invention has been made paying attention to such problems, and is formed by supporting an electrophotographic photosensitive member using a conductive substrate made of an aluminum-based material and anodizing the surface of the conductive substrate. A support for an electrophotographic photosensitive member having an undercoat layer of an aluminum anodic oxide film, wherein the anodized film is less prone to defects and can provide a good image. It is an object to provide a method and an electrophotographic photoreceptor.

  In order to achieve the above object, the method for producing a support for an electrophotographic photosensitive member according to the present invention includes a first step of cleaning an electroconductive substrate surface made of an aluminum-based material and then performing an etching treatment with a strong acid solution. And a second step of forming an undercoat layer of the anodized film on the surface of the conductive substrate by anodizing after the first step.

  In the method for producing a support for an electrophotographic photosensitive member according to the present invention, in the second step, water generated when the conductive substrate after the first step is washed with water and washed on the surface of the conductive substrate. It may be characterized by comprising a step of forming an undercoat layer of the anodized film by anodizing while holding the film.

  In the method for producing a support for an electrophotographic photosensitive member according to the present invention, the strongly acidic solution is composed of a sulfuric acid aqueous solution having a concentration of 3 wt% to 70 wt%, and the etching treatment is performed at 50 ° C. to 90 ° C. for 1 minute to It is preferable to carry out for 15 minutes.

  In the method for producing a support for an electrophotographic photosensitive member according to the present invention, the strong acid solution is composed of a phosphoric acid aqueous solution having a concentration of 70 wt% or more and 98 wt% or less, and the etching treatment is performed at 90 ° C. to 99 ° C. It may be characterized by being performed for 15 seconds to 4 minutes.

Furthermore, in the method for producing a support for an electrophotographic photosensitive member according to the present invention, an aqueous sulfuric acid solution having a concentration of 1% by weight to 30% by weight is used as the electrolytic solution in the second step, and an electrolysis temperature of 0 ° C. to 15 ° C. The anodized film may be formed to a thickness of 3 μm to 12 μm at a current density of 0.2 A / dm ^{2 to} 1.2 A / dm ² .

  Further, in the method for producing a support for an electrophotographic photosensitive member according to the present invention, after the second step, a third step of performing a fine sealing treatment of 600 μS or more and 3000 μS or less by a nickel acetate method, and after the third step, And a fourth step of removing the residual Ni compound by nitric acid cleaning.

  The electrophotographic photosensitive member according to the present invention is obtained by forming a photosensitive layer on the undercoat layer of the support for an electrophotographic photosensitive member produced by any one of the above-described methods for producing a support for an electrophotographic photosensitive member. It is characterized by comprising.

  In the present invention, the conductive substrate is made of an aluminum-based material, that is, aluminum or an aluminum alloy. The conductive substrate is preferably subjected to predetermined dimensional processing and surface processing. The etching treatment is preferably performed in a solution containing sulfuric acid or phosphoric acid as a main component.

A commercially available cleaning agent can be used for cleaning the substrate. When a solution containing sulfuric acid as a main component is used for etching, a sulfuric acid solution having a concentration of 10% by weight to 60% by weight is more preferable, and a solution having a concentration of 15% by weight to 30% by weight is more preferable. It is preferable to repeat washing with water at least twice after etching. When the water film generated when washed with water is dried during the transition to the next process, water marks remain on the surface of the conductive substrate, affecting the image quality of the photoreceptor, so after washing with water, It is desirable to move to the next step while keeping the water film. If there is time after washing, it is preferable to submerge the entire conductive substrate in a container filled with water. When the surface of the conductive substrate is anodized, a sulfuric acid solution having a concentration of 1% by weight to 30% by weight kept in the temperature range of 0 ° C. to 15 ° C. is used as the electrolyte, and the current density is about 0.5 A. / Dm ² is preferably performed for 15 to 60 minutes, and the concentration of the sulfuric acid solution is more preferably 5% by weight or more and 15% by weight or less. At this time, the amount of dissolved aluminum in the sulfuric acid solution is preferably 10 g / liter or less, more preferably 3 g / liter to 7 g / liter.

  In the case where the fine sealing treatment is performed by the nickel acetate method in the third step, a treatment time within 10 minutes is more preferable at a liquid temperature of 30 ° C. to 60 ° C. with a nickel acetate solution having a concentration of 1 wt% to 10 wt%. Is preferably performed within 2 minutes. Further, after the sealing treatment, it is very preferable that the surface is washed with water, then with nitric acid, and further with pure water so that the nickel acetate solution as a sealing agent does not remain on the surface.

  In the method for producing a support for an electrophotographic photosensitive member and the electrophotographic photosensitive member according to the present invention, a large etch pit is obtained by cleaning an electrically conductive substrate surface made of an aluminum-based material and then performing an etching treatment with a strong acid solution. Generation of anodized pits, spots, and flow can be prevented. As a result, the electrophotographic photosensitive member using the support for the electrophotographic photosensitive member according to the present invention does not cause defects such as “black spots” and “ground fog” even in a high humidity environment and other poor environments. Therefore, a good image with high image quality can be obtained stably.

  According to the present invention, an electrophotographic photoreceptor support using an electroconductive substrate made of an aluminum-based material, and an undercoat layer of an aluminum anodized film formed on the surface of the electroconductive substrate by anodizing treatment are provided. There can be provided a method for producing a support for an electrophotographic photosensitive member and an electrophotographic photosensitive member, which are electrophotographic photosensitive member supports that are less likely to cause defects in the anodized film and can provide a good image.

  Examples of the present invention will be described below. However, the technical scope of the present invention is not limited to the examples.

[Example 1]
First, a conductive substrate made of an aluminum-based material is degreased and washed at a liquid temperature of 50 ° C. using a degreasing cleaner (manufactured by Nippon Shib Chemical Co., Ltd .; trade name “Chem Cleaner 3505”). The degreasing detergent was removed by washing with water. Next, the conductive substrate was sufficiently washed with water, and 18 types of etching substrates were produced under the 18 types of etching conditions shown in Table 1. Further, washing with water was carried out 2 to 3 times, and an anodized film was formed on the surface of the substrate while keeping the water film generated when washed with water or wet (undried state). The anodized film is formed by using a sulfuric acid solution having a concentration of 150 g / liter as an electrolytic solution, maintaining the amount of dissolved aluminum in the electrolytic solution at a concentration of 3 g / liter to 7 g / liter, a liquid temperature of 11 ° C., and a current density. Was about 0.5 A / dm ² and anodizing was performed for 44 minutes. In this way, a 7 μm anodic oxide film layer was formed, and then washed with pure water.

  After washing, a nickel acetate sealing agent (Okuno Seiyaku Co., Ltd .; trade name “Top Seal H-298”) with a concentration of 15 g / liter was used, and the liquid temperature was 40 ° C. for 50 seconds. Sealing treatment was performed. After the treatment, the nitric acid was washed, and then washed with pure water to remove and clean the residual Ni. After cleaning, it was dried to produce an electrophotographic photoreceptor support.

  A charge generation layer was formed on each of the 18 types of electrophotographic photoreceptor supports thus prepared. The charge generation layer was formed by applying a coating solution in which a phthalocyanine pigment and a vinyl chloride vinyl acetate copolymer were dispersed and dissolved in a ratio of 1: 1 on the support. As a result, a charge generation layer having a thickness of 0.2 μm was formed. Next, a charge transport layer was formed on the charge generation layer of each support. The charge transport layer was formed by applying a coating solution in which Z polycarbonate resin and stilbene-based material were dissolved at a ratio of 10: 7 on the charge generation layer. Thereby, a charge transport layer having a thickness of 25 μm was formed. In this way, 18 types of electrophotographic photosensitive members shown in Table 1 were produced. Among these, (1) to (12), (17), and (18) are electrophotographic photoreceptors of examples of the present invention, and (13) to (16) are comparative examples.

  In order to see the effect of the electrophotographic photoreceptor thus obtained, each was mounted on a commercially available semiconductor laser printer, and the image quality was evaluated. The results are shown in Table 1.

  As shown in Table 1, in the electrophotographic photosensitive member of the example using 3 wt% to 70 wt% sulfuric acid solution (1 to 12) or phosphoric acid-nitric acid solution (17, 18) as an etchant, “Roughness”, “Photoreceptor coatability”, and “Image characteristics” were better than those of the comparative example using the system etching agent.

[Example 2]
To see the effect of changing the sulfuric acid concentration of the anodizing treatment, the sulfuric acid concentration in the anodizing step on the surface of the conductive substrate and the temperature of the sulfuric acid solution were changed. An electrophotographic photosensitive member was produced. Each of the electrophotographic photoreceptors prepared was evaluated for image quality in the same manner as shown in Table 1. The results are shown in Table 2.

As shown in Table 2, the concentration of the sulfuric acid solution for the anodizing treatment is preferably 5% by weight or more and 15% by weight or less, and “electrical characteristics” and “durability” are better than those of 30% by weight. It was.

Claims (7)

  A first step of cleaning the surface of the conductive substrate made of an aluminum-based material and then performing an etching process with a strong acid solution; and after the first step, the surface of the conductive substrate is subjected to an anodic oxidation coating on the surface of the conductive substrate. And a second step of forming a layer. A method for producing a support for an electrophotographic photosensitive member.   In the second step, the conductive substrate after the first step is washed with water, and a subbing layer of the anodized film is formed by anodizing while retaining the water film formed on the surface of the conductive substrate. The method for producing a support for an electrophotographic photosensitive member according to claim 1, comprising the step of forming   3. The electron according to claim 1, wherein the strongly acidic solution is composed of a sulfuric acid aqueous solution having a concentration of 3 wt% or more and 70 wt% or less, and the etching treatment is performed at 50 ° C. to 90 ° C. for 1 to 15 minutes. A method for producing a support for a photographic photoreceptor.   3. The strong acid solution is composed of a phosphoric acid aqueous solution having a concentration of 70% by weight or more and 98% by weight or less, and the etching treatment is performed at 90 ° C. to 99 ° C. for 15 seconds to 4 minutes. A method for producing a support for an electrophotographic photoreceptor. In the second step, a sulfuric acid aqueous solution having a concentration of 1 wt% or more and 30 wt% or less is used as an electrolytic solution, and an electrolysis temperature of 0 ° C. to 15 ° C. and a current density of 0.2 A / dm ^{2 to} 1.2 A / dm ² . 5. The method for producing a support for an electrophotographic photosensitive member according to claim 1, wherein the anodized film is formed to a thickness of 3 μm to 12 μm.   After the second step, the method includes a third step of performing a fine sealing treatment of 600 μS or more and 3000 μS or less by a nickel acetate method, and a fourth step of removing a residual Ni compound by nitric acid cleaning after the third step. A process for producing a support for an electrophotographic photosensitive member according to claim 1, 2, 3, 4, or 5.   A photosensitive layer is formed on the undercoat layer of the support for an electrophotographic photosensitive member produced by the method for producing a support for an electrophotographic photosensitive member according to claim 1, 2, 3, 4, 5, or 6. An electrophotographic photosensitive member characterized by comprising: