KR100469122B1 - Method for anodizing of aluminium drum - Google Patents

Abstract

PURPOSE: Provided are method for manufacturing aluminum drum and sealing composition with high sealing effect for the aluminum drum useful for electro-photography, thereby resulting in good oxide coating film and excellent durability and image property. CONSTITUTION: The method comprises steps of: (A) positively oxidizing surface of aluminum drum; (B) applying sealing composition including 0.001-0.5 wt.% compound selected from polyacrylic acid, poly(acrylamide-CO-acrylic acid) or poly(acrylic acid-CO-maleic acid) or mixture thereof, 0.001-0.5 wt.% of aminoalcohol, 0.1-2 wt.% of polyethyleneglycol and the balance of water to seal the oxide coating film; and (C) applying photoresist over the sealed oxide coating film and curing the film under heating.

Description

Manufacturing method of electrophotographic aluminum drum {Method for anodizing of aluminum drum}

The present invention relates to a method for producing an electrophotographic photosensitive aluminum drum and a sealing composition for producing an electrophotographic photosensitive aluminum drum.

Electrophotographic technology is being applied to a photocopier and is rapidly spreading and being used in the printer field due to the advantages of high speed and high factor image quality. These are very fast copying or printing speeds as they irradiate light on the regenerated photosensitive member, form a latent phenomenon, and obtain visualization and image by developing the toner.

The characteristics required for the photoconductor used in such an electrophotographic method are required to be reelectric, charge retaining, photoresponsive, charge transporting, repeatable stability, environmental resistance, refining fracture resistance, wear resistance, image sharpness, and the like.

The photosensitive material in which the photosensitive layer of the photosensitive member is formed uses organic photoconductive material (OPC) in terms of light weight, price, and stability, and the photosensitive substrate is used due to the advantages of light weight, corrosion resistance, and low price. The aluminum base material on which the surface was formed by anodizing is used.

In the film forming step by anodizing the aluminum substrate, the aluminum substrate is used as the anode in the electrolyte, and when the electricity is supplied, the surface of the aluminum is oxidized by oxygen generated in the anode to form an aluminum oxide film, followed by sealing the oxide film. The process of washing with water is performed.

On the other hand, in the process of applying a photosensitive paint to the anodized aluminum film and thermally curing, the crack of the oxide film is generated, and the cracked film causes the resolution of the image to drop, and the crack of the film may cause high electrolyte concentration or temperature. In this case, the film is often formed too thick, which depends on the type of electrolyte, concentration, voltage, current, current density, temperature, and electrolysis time. Can overcome,

On the other hand, aluminum film by anodization is porous and adsorptive, so the film is contaminated and residues such as sulfuric acid inside the hole are used as a cause of corrosion later, and sealing is performed by high pressure steam and high temperature. This is done by treating with pure water, high temperature solution of chemicals, etc. It is known that the sealing effect is best performed in pure water, but sealing treatment by pure water has a disadvantage in that sealing efficiency is low and time consuming. In terms of sealing efficiency, it is known to perform in sealing liquids containing nickel acetate or cobalt acetate, but this also causes various components in the sealing liquid used in the sealing process to adhere to the surface of the film and act as a foreign substance. There are disadvantages such as the occurrence of black spots in the burn image, and the expensive waste water treatment costs due to the toxicity of nickel salts.

In order to overcome this problem, International Patent Publication No. 1997-46738 discloses a sealing method using a solution containing a surfactant and phosphonic acid. Not only does not achieve sufficient sealing effect by immersion, but the sealing solution according to the present invention has a very different sealing effect depending on the concentration range of each component, pH adjustment, etc., which is not suitable for the actual large anodization process. There is this.

Accordingly, the present inventors endeavored to overcome the above problems, while shortening the sealing time, foreign matter does not adhere to the oxide film, sealing is suitable for the mass production process does not significantly change the sealing conditions in conditions such as the composition and pH of the sealing liquid The present invention provides a method for producing an electrophotographic photosensitive aluminum drum having excellent sealing efficiency and excellent properties of a sealed oxide film, and a sealing composition for preparing an electrophotographic photosensitive aluminum drum. It is.

The present invention relates to a method for producing an electrophotographic photosensitive aluminum drum and a sealing composition for producing an electrophotographic photosensitive aluminum drum excellent in the sealing efficiency in the sealing process and excellent in the properties of the sealed oxide film, in detail to the present invention Method for producing an electrophotographic photosensitive aluminum drum comprising the steps of: a) anodizing the surface of an aluminum drum; b) 0.001 to 0.5% by weight of a compound selected from a compound of polyacrylic acid, poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid) or a mixture thereof, 0.001 to 0.5% by weight amino alcohol, 0.1 to 2 polyethylene glycol Sealing the oxide film with a sealing solution composition consisting of water by weight and the remainder; c) coating and thermosetting a photosensitive paint on the sealed oxide film; Characterized in that it comprises a.

In addition, the sealing liquid composition for producing an electrophotographic photosensitive aluminum drum according to the present invention has a content of a compound selected from a compound of polyacrylic acid, poly (acrylamide-co-acrylic acid), or poly (acrylic acid-co-maleic acid) or a mixture thereof of 0.005 to 0.05. % By weight, amino alcohol of 0.005 to 0.05% by weight, polyethylene glycol 0.5 to 1% by weight and the remainder is characterized by consisting of water.

Hereinafter, the present invention will be described in detail.

The manufacturing step of the electrophotographic photosensitive aluminum drum according to the present invention is a conventional anodizing step

a) anodizing the surface of the aluminum drum;

b) sealing the oxide film;

c) Applying a photosensitive paint on the sealed oxide film and thermally curing.

First, the aluminum drum is degreased and washed with weak alkali prior to the anodization process to remove impurities that may have adhered to the surface of the drum. In this washing process, unlike general washing with conventional industrial water, pure water from which inorganic ions are removed by ion exchange is used.

After the cleaning step, the aluminum drum is subjected to anodization in the electrolyte. As described above, when the concentration and temperature of the anodizing electrolyte are high or the thickness of the coating is relatively high, there is a high probability of cracking in the oxide film. Therefore, the thickness of the oxide film is thinner than before, and Adjust For this purpose, the concentration of the sulfuric acid electrolyte is preferably 130 to 160 g / L, the temperature of the electrolyte is preferably maintained at 19 to 21 ° C, and the current density is preferably DC 0.7 to 1.3 A / dm 2. As such, lowering the concentration and temperature of the electrolyte solution and maintaining the current density at a conventional level is because lowering the current density together with the concentration and temperature of the electrolyte solution slows down the growth rate of the oxide film, thereby increasing the processing time and thus increasing the cost. to be. Preferably, the concentration of dissolved aluminum is maintained at 1.3 to 7 g / L under the above conditions, and a relatively thin oxide film having a thickness of about 5 to 6 μm may be obtained by treatment for about 20 minutes under such conditions.

After the oxide film is formed as described above, the oxide film is subjected to a sealing process.

Sealing treatment is 0.001 to 0.5% by weight of a compound selected from polyacrylic acid, poly (acrylamide-co-acrylic acid) or a compound of poly (acrylic acid-co-maleic acid) or mixtures thereof, 0.001 to 0.5% by weight of amino alcohol, and 0.1 to 0.5 polyethylene glycol. 2% by weight and the remainder in the sealing solution composition consisting of water.

If the content of the compound selected from polyacrylic acid, poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid) or a mixture thereof in the sealing solution composition is 0.001% by weight or less, the effect according to the present invention is expected. In the case of more than 0.5% by weight, it is not preferable because the polymers are likely to remain on the surface of the oxide film after sealing. The content of the polymer is more preferably 0.005 to 0.05% by weight, when the content is the most excellent sealing efficiency in the sealing process.

The polyacrylic acid, poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid) exhibits the desired effect as the present invention in any range of average molecular weight, but preferably has an average molecular weight of 500 to 10,000. In particular, when it is about 1000 to 6000, the sealing efficiency improvement effect can be sufficiently seen without contaminating the surface of the oxide film.

The sealing liquid composition according to the present invention may have a similar effect to any one of polyacrylic acid, poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid), but may contain 30 to 50% by weight of polyacrylic acid. The sealing property is best when the mixture is 50 to 70% by weight of poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid).

The sealing liquid composition according to the present invention contains 0.001 to 0.5% by weight of amino alcohol, and the amino alcohol has a hydrophilic and basic amine group and a hydroxyl group capable of hydrogen bonding at the same time, so that it is easily dissolved in water and functions with the polymer. It has a characteristic that does not suppress the effect to improve the sealing properties with the polymer, in particular the range of 0.005 to 0.05% by weight is preferred, when more than 0.5% by weight may exhibit a phenomenon that the sealing properties rather deteriorate. .

Amino alcohols include ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol and 1 It is preferable to select from the group which consists of -amino-pentanol, and low molecular weight ethanolamine, diethanolamine, and triethanolamine are more preferable.

In addition, the sealing liquid composition according to the present invention contains 0.1 to 2% by weight of polyethylene glycol, particularly preferably in the range of 0.5 to 1% by weight, it is appropriate that the average molecular weight of the polyethylene glycol is 200 to 1000, in particular low molecular weight It is preferable to improve the sealing efficiency.

The aqueous solution pH of the sealing solution is preferably 5 to 7, more preferably 5.5 to 6.5, and the temperature of the sealing solution in which the sealing is made is preferably about 90 to 97 ° C.

Sealing treatment is made by immersing the aluminum substrate on which the oxide film is formed by anodization in the sealing liquid for 2 to 20 minutes, the sealing is completed in about 3 to 5 minutes.

In particular, it is also within the scope of the present invention to prevent foreign matters from adsorbed on the oxide film and to prevent black spots on the image by further immersing in deionized water at 90 to 100 ℃ for 5 to 20 seconds after the above sealing process.

In this way, when the sealing is finished, the aluminum drum is washed with hot water and dried. The use of ultrasonic waves in the cleaning process may increase the cleaning effect.

In the case of drying the drum on which the oxide film is formed only once in the open, water adsorbed on the oxide film evaporates during the drying process of the photosensitive paint and thus bubbles are formed, resulting in uneven surface of the photosensitive paint, resulting in image defects. Therefore, the washed drum is firstly dried with purified air at room temperature, and then secondly dried in an oven to slowly and completely remove moisture adsorbed on the oxide film. In this way, the oxide film of the drum is dried, and then the photosensitive paint is applied thereon, followed by thermosetting to complete the product.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

Polyacrylic acid was used as a 50% aqueous solution with an average molecular weight of 2000, poly (acrylamide-co-acrylic acid) was used as an average molecular weight of 8000, poly (acrylic acid-co-maleic acid) a 50% aqueous solution with an average molecular weight of 3000. Polyethylene glycol was used as a compound having an average molecular weight of 600

Example 1

As the electrolyte solution, the sulfuric acid solution concentration was 130 to 160 g / L, while the temperature of the electrolyte solution was maintained at 19 to 21 ° C., while the current density was 0.7 to 1.3 A / dm ² , anodized for 20 minutes to give an oxide film of about 5 to 6 μm. Get

A sealing liquid is prepared by 0.01% by weight of polyacrylic acid, 0.01% by weight of ethanolamine, 0.5% by weight of polyethylene glycol, and the remainder of water. In this manufacturing process, the sealing solution is adjusted using an ammonium acetate buffer solution so that the pH is 5.5 to 6.5. After heating the prepared sealing solution so that the temperature of the sealing solution is about 95 to 97 ℃, after immersing the aluminum drum with anodized surface for 10 minutes the surface prepared in the above step, the aluminum drum is washed with hot water in a conventional manner To dry.

Example 2

Except that 0.01% by weight of polyacrylic acid, 0.1% by weight of poly (acrylic acid-co-maleic acid), 0.01% by weight of ethanolamine, 0.5% by weight of polyethylene glycol, and the rest were prepared with a sealing solution made of water. Proceeded.

Example 3

It proceeded in the same manner as in Example 1 except that the sealing time was set to 5 minutes and further immersed in deionized water at 90 to 100 ° C. for 5 to 20 seconds.

Example 4

It proceeded in the same manner as in Example 2 except that the sealing time was set to 5 minutes and further immersed in deionized water at 90 to 100 ° C. for 5 to 20 seconds.

Comparative Example 1

The same procedure as in Example 1 was carried out except that the sealing solution was immersed in deionized water at 90 to 100 ° C. for 10 minutes without using the sealing solution according to the present invention.

Comparative Example 2

The procedure was the same as in Example 1 except that 0.5 wt% of lauryl-dimethyl-benzylammonium chloride and 0.25 wt% of polyphosphinocarboxylic acid were dissolved in pure water as a sealing solution.

Example 5

Comparison of sealing effect

After dispersing metal phthalocyanine as a charge generating layer on the surface of the aluminum drums prepared in Examples 1 to 4 and Comparative Examples 1 and 2 by applying a weight ratio of 1 to 1 in a vinyl chloride vinyl acetate copolymer, After mixing polycarbonate and hydrazone-based materials as a charge transfer layer to complete an electrophotographic photosensitive aluminum drum, the surface potential of the photoreceptor was measured, and the charge potential difference between the first rotation and the second rotation after the initial time and 100,000 copies was measured. The measurements were made and the images were evaluated. The results are shown in Table 1.

Table 1

As can be seen from Table 1, when the sealing treatment with the sealing liquid according to the present invention can be seen that the first and second rotation potential difference is remarkably small after the initial and long-term use, there was no blurry image coupling in the image. On the other hand, the results of Comparative Examples 1 and 2 were not enough sealing time, it can be said that the sealing efficiency is also not satisfactory.

In addition, it was confirmed from the SEM photographs of the sealed aluminum drums of Examples 1 to 4 that the surface characteristics were superior to those of the oxide films of Comparative Examples 1 and 2.

As described above, the method for manufacturing an electrophotographic photosensitive aluminum drum and the sealing composition for manufacturing the electrophotographic photosensitive aluminum drum according to the present invention have excellent sealing efficiency in the sealing process and can be sealed in a short time. The excellent characteristics of the oxide film has the advantage of providing an electrophotographic photosensitive aluminum drum with excellent durability and image characteristics.

Claims (10)

a) anodizing the surface of the aluminum drum; b) 0.001 to 0.5% by weight of a compound selected from a compound of polyacrylic acid, poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid) or a mixture thereof, 0.001 to 0.5% by weight amino alcohol, 0.1 to 2 polyethylene glycol Sealing the oxide film with a sealing composition comprising wt% and the remainder of water; c) coating and thermosetting a photosensitive paint on the sealed oxide film; Method for producing an electrophotographic photosensitive aluminum drum comprising a. The method of claim 1, The sealing liquid composition has a content of a compound selected from polyacrylic acid, poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid) or a mixture thereof in an amount of 0.005 to 0.05% by weight, and amino alcohol 0.005 to 0.05% by weight. % And 0.5 to 1% by weight of polyethylene glycol and the remainder of the electrophotographic photosensitive aluminum drum, characterized in that made of water. The method of claim 2, The polyacrylic acid, poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid) in the sealing liquid composition has a mean molecular weight of 500 to 10,000. The method of claim 3, wherein Polyacrylic acid, poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid) in the sealing liquid composition has an average molecular weight of 1000 to 6000. The method of claim 1, Amino alcohols include ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol and 1 A method for producing an electrophotographic aluminum drum, characterized in that it is at least one compound selected from the group consisting of amino-pentanol. The method of claim 2, Method for producing an electrophotographic photosensitive aluminum drum, characterized in that the average molecular weight of polyethylene glycol in the sealing liquid composition is 200 to 1000. The method of claim 2, The temperature of the sealing liquid is a manufacturing method of the electrophotographic aluminum drum, characterized in that 90 ~ 97 ℃. The method of claim 1, Method of producing an electrophotographic photosensitive aluminum drum, characterized in that for 5 to 20 seconds further immersion in deionized water of 90 to 100 ℃ after sealing. The content of the compound selected from polyacrylic acid, poly (acrylamide-co-acrylic acid) or poly (acrylic acid-co-maleic acid) or a mixture thereof is 0.005 to 0.05% by weight, aminoalcohol 0.005 to 0.05% by weight, polyethylene glycol 0.5 Sealing liquid composition for producing an electrophotographic photosensitive aluminum drum, characterized in that consisting of 1 to 1% by weight and the rest. The method of claim 9, Amino alcohols include ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol and 1 Sealing composition for electrophotographic aluminum drum production, characterized in that at least one compound selected from the group consisting of -amino-pentanol.