JPH10175167A - Honing processing method and manufacture of electronic photosentitizer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a honing processing method and a method to manufacture an electronic photosentitizer by utilizing the honing processing method. SOLUTION: A honing processing liquid including a polishing material is discharged from a gun 3 to the surface of a conductive base body 1 by a wet type honing processing, so as to make the surface of the conductive base body 1 in a coarse surface. The honing processing liquid is circulated through a pump 2. To the honing processing liquid, an antifoaming agent is added, and as an antifoaming agent, a fatty acid esters antifoaming agent, an alcohols antifoaming agent, and a silicone-based antifoaming agent are suitable in particular. Those antifoaming agents exercise a high antifoaming effect, when polymer particles with a low density, and a low affinity with the water, such as a PMMA resin, for example, is used as the polishing material in the honing processing liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a honing method for roughening the surface of a substrate by performing wet honing on the surface of the substrate, and a method for producing an electrophotographic photosensitive member using the honing method.

[0002]

2. Description of the Related Art An electrophotographic apparatus has high speed and high printing quality, and is used in fields such as a copying machine and a laser beam printer. As a photoconductor used in an electrophotographic apparatus, an organic photoconductor (OPC) using an organic photoconductive material has been developed and spread. In addition, the structure of the photoconductor is changed from a single-layer photoconductor in which a charge transfer complex structure or charge generation material is dispersed in a binder resin to a function separation type photoconductor in which the charge generation layer and charge transport layer are separated The performance has improved. At present, the mainstream structure of the function-separated type photoreceptor is such that an undercoat layer is formed on an aluminum base material, and then a charge generation layer and a charge transport layer are formed.

Further, with the progress of the electrophotographic apparatus, a higher quality image has been required in the performance of the photosensitive member. For improvement of photoreceptor repetition stability and environmental stability, the charge generation layer, charge transport layer, and undercoat layer all have important effects on electrophotographic properties such as sensitivity, image quality, and repetition stability. ing. Furthermore, various types of substrates such as extrusion tubes, ED tubes, and EI tubes have been used for the purpose of cost reduction and improvement of image quality defects.

[0004]

In an exposure system using a coherent light such as a laser light source such as a laser printer or a digital copier, incident light reflected inside the photoconductor interferes inside the photoconductor by reflection. , A grain of light and shade corresponding to the interference pattern occurs on the print. In order to reduce the interference fringes, a method of roughening the surface of the substrate has been studied.

Hitherto, for example, the following treatment methods have been studied as methods for roughening the surface of a photoreceptor substrate. Japanese Unexamined Patent Publication (Kokai) No. 63-264760 discloses a method for roughening a substrate by jetting only high-pressure water from a nozzle.
No. 4, JP-A-2-191963, JP-A-3-19963.
Japanese Patent Application Laid-Open No. 64762 and Japanese Patent Application Laid-Open No. 5-216261 disclose a method of using honing for the surface roughening treatment.
Japanese Patent Application Laid-Open No. 6-67441 discloses a method for roughening non-cut aluminum using two or more guns.

In the wet honing method, a stable rough surface can be easily obtained with a short processing time, a desired roughness can be accurately obtained, and abnormal irregularities which cause coating film defects are extremely small. It is excellent from the viewpoint of production such as obtaining a rough surface having roughness. Further, the wet honing method is superior to the anodic oxidation method and the buff polishing method in terms of image quality stability against black spots and interference fringe patterns on the photoreceptor.

However, depending on the type of the abrasive, foaming may occur when the suspension with water is stirred, and the honing treatment may be difficult due to the foam. When foaming occurs despite the excellent surface properties of the base material honed using such abrasives, the foaming can occur in the liquid supply system of the honing gun in a very short time from the beginning of use or in continuous use. Was mixed, so that the honing polishing liquid could not be discharged. The cause of such a foaming phenomenon is that the honing is largely affected by the surfactant remaining during the synthesis of the abrasive, or the abrasive is easily raised in a liquid because the specific gravity of the abrasive is relatively small, and furthermore, the water is mixed with water. It is also conceivable that the abrasive fine particles having poor affinity tend to be easily aggregated in the liquid surface layer and tend to remain as bubbles at the interface with the gas phase. Alternatively, it is conceivable that the remaining amount of the surfactant used in the production of the organic fine particles for an abrasive is stirred in water to generate bubbles.

Normally, the roughness of the honing surface is generally controlled by the blowing pressure. However, once the bubbles are entrapped as described above, even if the blowing pressure of the honing gun is increased, the pressure is controlled by the elasticity of the bubbles. The power is lost and the polishing liquid cannot be discharged satisfactorily.

[0009]

In view of these circumstances, the present inventor has found a polishing liquid that does not cause foaming for any abrasive. In other words, the treatment liquid resulted in stable honing without foaming even when using a soft, light specific gravity, and poorly hydrophilic abrasive. That is,
The honing treatment method of the present invention is a honing treatment method in which a honing treatment liquid is sprayed onto a substrate surface to roughen the substrate surface, wherein the honing treatment liquid contains an abrasive and contains an antifoaming agent. And Further, in the method for producing an electrophotographic photoreceptor of the present invention, a honing treatment liquid is sprayed on a conductive substrate to roughen the surface of the conductive substrate, and a photosensitive layer is formed on the roughened conductive substrate. Wherein the honing solution contains an abrasive and an antifoaming agent. According to the honing treatment method of the present invention, it is possible to obtain a polishing liquid without foaming while maintaining the excellent polishing effect of the abrasive, and to form a controlled light scattering surface without abnormal irregularities. Will be able to do it. Further, according to the method of manufacturing an electrophotographic photoreceptor of the present invention, the surface of the conductive substrate can be a controlled light scattering surface without abnormal irregularities, and an excellent image without interference fringes can be formed. Can be.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The wet honing method is a method of treating a substrate surface in which an abrasive is suspended in water and sprayed at a high speed as described above. The abrasive used in the wet honing method has a particle size of 10 to 100 μm, a hardness of 800 to 5000 kg / mm ² in Knoop hardness, and a specific gravity of 0.5 to 10
And the shape is not particularly limited, but a spherical powder is preferably used. As the material of the abrasive, iron, glass, alumina, ferrite, zirconia, chromium oxide, silicon carbide, boron carbide, inorganic fine powder such as boron nitride, epoxy resin, PMMA resin, polyvinylidene fluoride, polyurethane particles, Organic fine powder such as melamine resin particles may be used. Among these abrasives,
In particular, when a spherical organic fine powder is used, it collides with the substrate softer than the case of the inorganic fine powder, and since there is no abnormal projection shape of the abrasive, a stable rough surface without abnormal irregularities of the substrate is obtained. Therefore, there is an advantage that deterioration of the honing apparatus due to abrasion of the piping can be prevented.

[0011] The foaming phenomenon due to the abrasive is likely to occur particularly when polymer particles having characteristics such as low density and low affinity with water are used as the abrasive. In particular, when epoxy resin, PMMA resin, polyvinylidene fluoride, polyurethane particles, melamine resin particles and the like are used, the effect of adding the defoaming agent shown in the present invention is extremely large.

The antifoaming agents which can be used in the honing solution of the present invention include oil-based antifoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; stearic acid, oleic acid, palmitic acid, etc. Fatty acid-based defoaming agents; fatty acid ester-based defoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, butyl stearate, natural wax, and monoglyceride Polyoxyalkylene glycols and derivatives thereof, polyoxyalkylene monohydric alcohols, alcohol antifoaming agents such as di-t-amylphenoxyethanol, 3-heptanol and 2-ethylhexanol; di-t-aminophenoxyethanol 3 Ether-based antifoaming agents such as heptylcellosolve 3-heptylcellosolve 3-heptylcarbitol; phosphate-based antifoaming agents such as tributyl phosphate, Na-octyl phosphate and tris (butoxyethyl) phosphate; amine-based anti-foaming agents such as diamylamine Antifoaming agents; amide antifoaming agents such as polyalkylamide, acylate polyamine, dioctadecanoylpiperazine; metal soap antifoaming agents such as aluminum stearate, calcium stearate, potassium oleate, and calcium salt of wool oleic acid A sulfate ester antifoaming agent such as sodium lauryl sulfate; dimethylpolysiloxane, silicone paste, silicone emulsion, silicone-treated powder, organically modified polysiloxane,
Silicone defoamers such as fluorosilicone; other
Ferric sulfate, bauxite, propane trichloride, and the like.

Among these antifoaming agents, fatty acid ester-based antifoaming agents, alcohol-based antifoaming agents, and silicone-based antifoaming agents are particularly preferable from the viewpoint of the defoaming effect. As a combination of an antifoaming agent and an abrasive, in particular, a fatty acid ester-based antifoaming agent, an alcohol-based antifoaming agent, a silicone-based antifoaming agent, an epoxy resin, a PMMA resin, a polyvinylidene fluoride, and a polyurethane-based, which easily cause a foaming phenomenon. Particles and resin fine particles such as melamine resin particles, in particular, a combination with PMMA resin is preferred.

The above-mentioned antifoaming agent can obtain the effect by adding 1 to 10000 ppm to the suspension containing the abrasive, and particularly preferably 100 to 1000 ppm. When the added amount of the defoaming agent is 1 ppm, the defoaming effect is insufficient and
If it exceeds 0000 ppm, there is a concern that residual components may affect the electrical characteristics of the electrophotographic photoreceptor if the cleaning of the substrate is insufficient.

Some antifoaming agents are difficult to dissolve in water. In this case, the suspension containing water or the abrasive is heated, and the defoaming agent is dissolved therein by dropping and stirring. It becomes possible. Alternatively, a method in which the antifoaming agent is once dissolved in a water-soluble solvent and then diluted with water is also possible.

As the conductive substrate obtained by the honing solution of the present invention, the surface of the conductive substrate has a center line average roughness Ra of 0.1 from the viewpoint of suppressing the coherence of the electrophotographic photosensitive member and preventing image quality defects. It is preferable to process to a range of 0.5 μm. The roughness of the substrate by the honing treatment can be appropriately controlled by the shape, size, hardness, specific gravity, spray pressure, spray moving speed, spray amount, suspension concentration, etc. of the abrasive. The honing-treated substrate is usually washed with water to remove abrasives, cutting powder, and the like adhering to the substrate, and then subjected to a draining process to form a photosensitive layer.

An example of the structure of a photoreceptor formed of a substrate subjected to the honing treatment according to the present invention will be described below. On the conductive substrate formed by the honing method of the present invention, an undercoat layer is formed if necessary, and further a photosensitive layer is formed. Although the photosensitive layer is effective in any photoreceptor configuration, a laminated photoreceptor having a charge transport layer as a surface layer is excellent in performance such as repeated stability and environmental fluctuation. The configuration of the laminated photoreceptor serving as the surface layer will be mainly described.

As the conductive substrate, a metal substrate such as copper, aluminum, nickel, and iron is effective. The surface of the base material may be left as it is, or may be subjected to processing such as mirror cutting, etching, anodic oxidation, rough cutting, centerless grinding, etc. in advance. Thereafter, the substrate is roughened by washing and honing. In addition, a conductive layer can be formed on the base material as needed. This conductive layer is obtained by forming a film in which a conductive material such as a metal oxide such as tin oxide, antimony oxide, and titanium oxide, or a fine metal powder such as gold, iron, aluminum, and copper is dispersed in a resin. .

The undercoat layer is made of an acetal resin such as polyvinyl butyral, a polyvinyl alcohol resin, casein,
Polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol- In addition to high molecular weight resin compounds such as formaldehyde resins and melamine resins, there are organometallic compounds containing zirconium, titanium, aluminum, manganese, silicon atoms and the like. These compounds can be used alone or as a mixture or a polycondensate of a plurality of compounds. Among these compounds, when an organometallic compound containing zirconium or titanyl or a silane compound is contained, the residual potential is low, the potential change due to the environment is small, and the potential change due to repeated use is small.

Examples of the silane compound include, for example, vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl)- γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-
Aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane and the like. Among these, particularly preferred silicon compounds are vinyltriethoxysilane, vinyltris (2-methoxyethoxysilane), 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, N-2-
(Aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3- Silane coupling agents such as mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and the like can be mentioned.

Examples of the organic zirconium compound include zirconium butoxide, ethyl zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium butoxide acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, octane Zirconium phosphate, zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate,
Examples include methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide, and the like.

Examples of the organic titanium compound include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium Lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium triethanol aminate, polyhydroxytitanium stearate and the like.

Examples of the organic aluminum compound include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, and aluminum tris (ethyl acetoacetate).

Various organic or inorganic fine powders can be mixed in the undercoat layer for the purpose of improving electric characteristics and light scattering. In particular, white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white, and lithopone; inorganic pigments such as alumina, calcium carbonate, and barium sulfate; and Teflon resin particles, benzoguanamine resin particles, and styrene resin particles Etc. are effective. The fine powder to be added has a particle size of 0.01 to 2 μm. The fine powder is added as necessary, but if added, the weight ratio is 10 to the solid content of the undercoat layer.
80% by weight or more preferably 30 to 70% by weight is added. Further, the thickness of the undercoat layer is preferably in the range of 0.1 to 10 μm.

When the fine powder is mixed in the formation of the undercoat layer coating liquid, the fine powder is added to a solution in which the resin component is dissolved, and a dispersion treatment is performed. As a method of dispersing the fine powder in the resin, a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill,
A method such as a paint shaker can be used.

The photosensitive layer formed on the undercoat layer may have a basically single-layer structure or a laminated structure in which a charge generation layer and a charge transport layer are functionally separated. In the case of a laminated structure, the order of lamination of the charge generation layer and the charge transport layer may be any of the upper layers. Further, a surface protective layer can be formed as necessary.

The charge generation layer is formed by forming a charge generation substance by vacuum evaporation or by dispersing and applying the charge generation substance together with an organic solvent and a binder resin. As the charge generating substance,
Amorphous selenium, crystalline selenium, selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and alloys, inorganic photoconductors such as zinc oxide and titanium oxide, metal-free phthalocyanine, titanyl phthalocyanine, copper phthalocyanine, tin phthalocyanine, Various organic pigments and dyes such as gallium chloride phthalocyanine, hydroxygallium phthalocyanine, various phthalocyanine pigments such as indium phthalocyanine, squarium, anthantrone, perylene, azo, anthraquinone, pyrene, pyrylium salts, and thiapyrylium salts. Used. In addition, these organic pigments generally have several types of crystal forms, and in particular, phthalocyanine pigments are known to have various crystal types such as α, β, etc. , Any of these crystal forms can be used.

The following can be exemplified as the binder resin in the charge generation layer. That is, polycarbonate resin such as bisphenol A type or bisphenol Z type, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer Use of a coalescing resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicon resin, silicon-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, or a copolymer thereof. Can be. These binder resins can be used alone or in combination of two or more.

The compounding ratio (weight ratio) of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10. Also,
The thickness of the charge generation layer is generally set in the range of 0.01 to 5 μm, preferably 0.05 to 2.0 μm. As a method for dispersing the charge generating material in the resin, a method such as a roll mill, a ball mill, a vibration ball mill, an attritor, a dyno mill, a sand mill, and a colloid mill can be used.

Examples of the charge transporting material used in the charge transporting layer include the following. 2,5-bis (p
Oxadiazole derivatives such as -diethylaminophenyl) -1,3,4-oxadiazole; 1,3,5-triphenyl-pyrazoline, 1- [pyridyl- (2)]-
Pyrazoline derivatives such as 3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline; triphenylamine, tri (P-methyl) phenylamine, N, N-bis (3,4-dimethylphenyl) biphenyl Aromatic tertiary amino compounds such as -4-amine and dibenzylaniline; N, N'-diphenyl-N, N
Aromatic tertiary diamino compounds such as' -bis (3-methylphenyl)-[1,1-biphenyl] -4,4'-diamine; 3- (4'dimethylaminophenyl) -5,6
1,2-, 4-triazine derivatives such as -di- (4'-methoxyphenyl) -1,2,4-triazine; hydrazone derivatives such as 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone; 2-phenyl-4 Quinazoline derivatives such as -styryl-quinazoline, benzofuran derivatives such as 6-hydroxy-2,3-di (p-methoxyphenyl) -benzofuran, p- (2,2-diphenylvinyl) -N, N-diphenylaniline and the like α
-Stilbene derivatives; enamine derivatives; carbazole derivatives such as N-ethylcarbazole; hole transport substances such as poly-N-vinylcarbazole and derivatives thereof. Quinone compounds such as chloranil, bromoanil and anthraquinone; tetracyanoquinodimethane compounds;
Fluorenone compounds such as 7-trinitrofluorenone and 2,4,5,7-tetranitro-9-fluorenone; xanthone compounds; thiophene compounds; and electron transport materials such as diphenoquinone compounds. Alternatively, a polymer having a group consisting of the compounds shown above in a main chain or a side chain may be used. These charge transport materials can be used alone or in combination of two or more.

Examples of the binder resin used for the charge transport layer include acrylic resin, polyarylate, polyester resin, bisphenol A type and bisphenol Z.
Type, bisphenol C type, bisphenol AP
Insulating resin such as various polycarbonate resins such as types, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber or polyvinyl carbazole, polyvinyl anthracene, polyvinyl pyrene, etc. Organic photoconductive polymers or copolymers thereof.

The charge transport layer can be formed by applying a solution obtained by dissolving the above-described charge transport material and binder resin in a suitable solvent, followed by drying. As the solvent used for forming the charge transport layer, for example, benzene,
Aromatic hydrocarbons such as toluene and chlorobenzene, ketones such as acetone and 2-butanone, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and ethylene chloride, tetrahydrofuran, dioxane, ethylene glycol, diethyl ether and the like A cyclic or linear ether, a mixed solvent thereof, or the like can be used. The compounding ratio of the charge transport material and the binder resin is 10: 1.
１ ： 1: 5 is preferred. The thickness of the charge transport layer is generally 5
５０50 μm, preferably 10-40 μm.

In order to prevent the deterioration of the photoreceptor due to ozone or oxidizing gas generated in the electrophotographic apparatus, or light or heat, additives such as antioxidants, light stabilizers and heat stabilizers are added to the photosensitive layer. Can be added. For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, organic phosphorus compounds and the like.

Examples of light stabilizers include benzophenone,
Derivatives such as benzotriazole, dithiocarbamate, and tetramethylpiperidine are included.

Further, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue when repeatedly used. Examples of the electron-accepting substance that can be used in the photoreceptor of the present invention include, for example, succinic anhydride, maleic anhydride, dibromomaleic anhydride,
Phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitro Benzoic acid and phthalic acid can be mentioned. Of these, fluorenone-based, quinone-based, and benzene derivatives having an electron-withdrawing substituent such as Cl, CN, and NO ₂ are particularly preferable.

The coating can be performed by a coating method such as a dip coating method, a spray coating method, a bead coating method, a blade coating method, and a roller coating method. In the case where the humidification treatment method described in the present invention is not used, drying is preferably performed by touch drying at room temperature and then heating and drying. Heat drying at 30 ° C
It is desirable to carry out at a temperature of from about 200 ° C. to a time of from 5 minutes to 2 hours.

A surface protective layer can be formed on the photosensitive layer if necessary. As the surface protective layer, there is an insulating resin protective layer or a low resistance protective layer in which a resistance adjuster is added to the insulating resin. In the case of a low resistance protective layer, for example, a layer in which conductive fine particles are dispersed in an insulating resin can be used. The average particle diameter of white, gray or bluish white with an electric resistance of 10 ⁹ Ω · cm or less as conductive fine particles is 0.3.
μm or less, preferably 0.1 μm or less fine particles are suitable, for example, molybdenum oxide, tungsten oxide, antimony oxide, tin oxide, titanium oxide, indium oxide,
A solid solution carrier of tin oxide and antimony or antimony oxide or a mixture thereof, or a mixture of these metal oxides in a single particle or a coating thereof is given. Above all, tin oxide or a solid solution of tin oxide and antimony or antimony oxide is preferably used because it can appropriately adjust electric resistance and can make the protective layer substantially transparent. (JP-A-57-30847, JP-A-57-12834)
No. 4)

Examples of the insulating resin include condensation resins such as polyamide, polyurethane, polyester, epoxy resin, polyketone and polycarbonate, and vinyl polymers such as polyvinyl ketone, polystyrene and polyacrylamide.

The photoreceptor having a substrate obtained by the method of the present invention can be used as a light lens type copier, a laser beam printer for emitting near-infrared light or visible light, a digital copier, an LED printer, a laser facsimile, etc. It can be used for photographic devices. The photoreceptor can be used in combination with a one-component or two-component regular developer or a reversal developer. Further, the photoreceptor having a substrate obtained by the method of the present invention can obtain good characteristics with less occurrence of current leak even in a contact charging system using a charging roller or a charging brush.

[0040]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Comparative Example 1 An abrasive suspension for surface roughening treatment was charged into the honing apparatus shown in FIG. In FIG. 1, 1 is a substrate, 2 is a pump, 3 is a gun, 4 is an air introduction pipe, and 5 is a processing vessel.
30 liters of ion-exchanged water is charged into the processing vessel 5 as a honing suspension, and then PMM is used as an abrasive.
3.4 kg of A (polymethyl methacrylate) spherical fine particles (manufactured by Soken Chemical Co., Ltd., MR-60G d50 = 60 μm)
Was introduced. When the water in the processing vessel 5 was stirred through the stirrer 6 to mix the water and the abrasive composed of PMMA fine particles, bubbles were generated, and the height of the bubbles rose to a position of 20 cm above the water surface. When the foam was collected and observed, a large amount of PMMA fine particles of the abrasive was contained in the foam.

In order to perform a honing treatment, 8
A4mmφ A1050 material mirror-cut aluminum pipe 1 is attached, and while pumping the suspension for honing treatment to the gun 3 at a flow rate of 6 liter / min, 1.9 kgf / c
Compressed air of m ² was sprayed from the gun 3 together with the abrasive-containing suspension, and the gun 3 was moved at 500 mm / min in the axial direction of the aluminum pipe while rotating the aluminum pipe. The substrate was taken out and washed with ion-exchanged water to obtain a substrate for photoconductor production. The center line average roughness (Ra) of this substrate was 0.19 μm. The substrate obtained here is referred to as a comparative treated substrate 1-1.

This process was repeated and the surface roughening treatment of 50 base materials was performed.
In the 0-th line, the roughness of the substrate was reduced to Ra 0.08 μm. The substrate obtained here is referred to as a comparative treated substrate 1-2. A photosensitive layer was formed on the honing-treated base material thus obtained. Mixture of 170 parts by weight of n-butyl alcohol in which 4 parts by weight of polyvinyl butyral resin (Slec BM-S manufactured by Sekisui Chemical) is dissolved, 20 parts by weight of an organic zirconium compound (acetylacetone zirconium butyrate) and an organic silane compound (γ-aminopropyl) Trimethoxysilane) (10 parts by weight) was additionally mixed and stirred to obtain an undercoat layer coating solution.

On the substrate honed by using this coating solution, the substrate was coated and air-dried at room temperature for 5 minutes, then heated at 50 ° C. for 10 minutes and then heated to 50 ° C. for 8 minutes.
It was placed in a 5% RH constant temperature / humidity bath, subjected to a humidification and curing acceleration treatment for 20 minutes, and then placed in a hot air dryer at 150 ° C. for 10 minutes.

A mixture comprising 15 parts by weight of gallium chloride phthalocyanine as a charge generating material, 10 parts by weight of vinyl chloride vinyl acetate copolymer resin (Nippon Unicar VMCH), and 300 parts by weight of n-butyl alcohol was mixed with a sand mill.
Time dispersed. This liquid was applied onto the undercoat layer by dip coating and dried to form a charge generation layer having a thickness of 0.2 μm.

Next, N, N'-diphenyl-N, N'-
Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine 4 parts by weight and bisphenol Z
6 parts by weight of a polycarbonate resin (molecular weight: 40,000) and 80 parts by weight of chlorobenzene were added and dissolved. This liquid was applied and dried using a dip coating apparatus to obtain a film thickness of 25 μm.
Was formed and dried at 110 ° C. for 40 minutes to produce an electrophotographic photosensitive member having three layers.

The obtained electrophotographic photosensitive member was mounted on a color copier A-color 635 manufactured by Fuji Xerox Co., Ltd., and a print operation was performed to check the image quality. Table 1 shows the results. In the substrate after the repeated production, the roughness of the substrate was low, and the occurrence of interference fringes in the print was observed.

Example 1 A heater was thrown into a container containing 10 liters of ion-exchanged water, and the water temperature was raised to 60 ° C. As a defoamer in this warm water, Pluronic TR-701 manufactured by Asahi Denka Co., Ltd.
(Polyoxyalkylene condensate of ethylenediamine)
3.34 g was charged and dissolved by stirring. This solution was put into the honing vessel 5, and 20 liters of ion-exchanged water was further added, followed by stirring and mixing. PMMA spherical microparticles (MR-60G, Soken Chemical Co., d50 = 60) were added to this aqueous solution.
(μm), 3.4 kg was charged, and the water was stirred. As a result, generation of bubbles was extremely small, and the height of the bubbles was stopped at a position of 1 cm above the water surface. In the same manner as in Comparative Example 1, using this suspension, an A1050 material mirror-cut aluminum pipe 1 having a diameter of 84 mm was attached to perform honing treatment, and the pump 2 was used for 6 liters / hour.
1.9 kgf / cm
The compressed air of No. 2 was sprayed from the gun 3 together with the abrasive-containing suspension, and the gun 3 was moved at 500 mm / min in the axial direction of the aluminum pipe while rotating the aluminum pipe. This substrate was brush-washed with ion-exchanged water to obtain a substrate for producing a photoreceptor. Center line average roughness of this substrate (Ra)
Was 0.17 μm. The base material obtained here is referred to as a practically processed base material 1-1.

This process was repeated and the surface roughening treatment of 50 base materials was performed. However, no air bubbles were caught in the gun 3 and the 50th base material had a roughness of 0.19 μm Ra. was gotten. This is referred to as an execution substrate 1-2. A photosensitive layer was formed on the honing substrate thus obtained under the same conditions as in Comparative Example 1. The obtained electrophotographic photosensitive member was mounted on a color copying machine A-color 635 manufactured by Fuji Xerox Co., Ltd., and a printing operation was performed in the same manner as in Comparative Example 1. Table 1 shows the results
Shown in The photoreceptor using the base material manufactured in Example 1 was able to obtain an extremely clear image without image quality defects even with the base material after continuous manufacture.

Example 2 Example 1 was different from Example 1 in that Pluronic L-61 (polyoxyethylene-polyoxypropylene condensate) manufactured by Asahi Denka Co., Ltd. was used as an antifoaming agent, and the amount of addition was changed to 5.1 g. A treated substrate was produced with the same formulation as in Example 1 to obtain a treated substrate 2-1 and a treated substrate 2-2. At this time, the height of bubbles generated during the treatment was stopped at a position 1 cm above the water surface. Table 1 shows the results.

[0050]

[Table 1]

Example 3 A container containing 10 liters of ion-exchanged water was thrown into the container, and a heater was charged to raise the water temperature to 60 ° C. As a defoamer in this warm water, Pluronic TR-701 manufactured by Asahi Denka Co., Ltd.
(Polyoxyalkylene condensate of ethylenediamine)
3.34 g was charged and dissolved by stirring. This solution was put into the honing vessel 5, and 20 liters of ion-exchanged water was further added, followed by stirring and mixing. PMMA spherical microparticles (MR-60G, Soken Chemical Co., d50 = 60) were added to this aqueous solution.
A mixture of 1.7 kg of 1.7 μm) and 1.7 kg of PMMA spherical microparticles (manufactured by Soken Chemical Co., Ltd., MR-30G, d50 = 30 μm) was added, and the water was stirred. It stopped at a position 1 cm above the water surface.
Using the suspension, a honing treatment apparatus shown in FIG. 1 was fitted with a mirror-cut aluminum pipe 1 of A6063 material having a diameter of 30 mm, and 2.6 kgf while being pumped at a flow rate of 6 liters / minute to a gun 3. / Cm ² of compressed air was sprayed from the gun 3 together with the abrasive-containing suspension through the air introduction pipe 4, and the gun 3 was moved at 700 mm / min in the axial direction of the aluminum pipe while rotating the aluminum pipe. This substrate was brush-washed with ion-exchanged water to obtain a substrate for producing a photoreceptor. The center line average roughness (R
a) was 0.18 μm. The base material obtained here is referred to as a practically processed base material 3-1.

This treatment was repeated and the surface roughening treatment of 50 base materials was performed. However, air bubbles were not entrapped in the gun, and the base material having a Ra 0.18 μm roughness was found even in the 50th base material. Obtained. This will be referred to as an execution processing base material 3-2. The same photosensitive layer as in Comparative Example 1 was formed on the honing substrate thus obtained. The electrophotographic photoreceptor thus obtained is used as an electrophotographic printer (PC-
PR1000 / 4R (manufactured by NEC Corporation) to perform a printing operation. Table 2 shows the results. Working treatment base material 3-
In each of Examples 1 and 3-2, no interference fringes were generated, no current leaked from the contact charging device, and an extremely clear image without image quality defects was obtained.

Comparative Example 2 An abrasive suspension for surface roughening treatment was introduced into the honing apparatus shown in FIG. As a suspension for honing treatment, 30 liters of ion-exchanged water is charged into the treatment vessel 5, and P
MMA spherical fine particles (manufactured by Soken Chemical Co., Ltd., MR-60G, d5
0 = 60 μm) 1.7 kg and PMMA spherical fine particles (manufactured by Soken Chemical Co., Ltd., MR-30G, d50 = 30 μm)
1.7 kg of the mixture were charged. When the water in the processing container 5 was stirred to mix the water and the PMMA abrasive, bubbles were generated, and the height of the bubbles rose to a position of about 30 cm above the water surface. The foam component was abrasive PMMA particles. In order to perform the honing process, a mirror-cut aluminum pipe 1 of A6063 material of 30 mmφ is mounted and 2.6 kgf / cm ₂ while pumping liquid to the gun 3 at a flow rate of 6 liter / min.
The compressed air was sprayed from the gun 3 together with the abrasive-containing suspension, but air bubbles were entrapped and the air pressure was deprived of the air bubbles, and the substrate could not be roughened. The first substrate obtained at this time is referred to as a comparative substrate 2-1. The same photosensitive layer as that of Comparative Example 1 was formed on the comparative base material 2-1. The same photosensitive layer was attached to the printer shown in Example 3 and a printing operation was performed. did.

Examples 4 to 8 Substrate treatment was carried out in the same manner as in Example 3 except that the defoaming agent and the amount added were changed to the compounds shown in Table 2, thereby forming a photoreceptor. The print quality was checked. Table 2 shows the results.

[Table 2]

[0055]

According to the honing treatment method of the present invention, even when an abrasive which easily causes foaming is used, foaming can be suppressed and honing can be performed. As a result, the choice of abrasives is expanded, and an abrasive having more excellent polishing performance can be used. Further, the electrophotographic photoreceptor obtained by the method for producing an electrophotographic photoreceptor of the present invention can obtain an excellent image without interference fringes or the like.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a wet honing apparatus applied to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate (aluminum tube) 2 Pump 3 Gun 4 Air introduction pipe 5 Processing container 6 Stirrer

 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Hiroshi Yamamoto 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd.

Claims (9)

[Claims] A honing treatment method for spraying a honing treatment liquid onto a substrate surface to roughen the substrate surface.
A honing treatment method, wherein the honing treatment liquid contains an abrasive and an antifoaming agent. 2. The honing treatment method according to claim 1, wherein the antifoaming agent is selected from a fatty acid ester-based antifoaming agent, an alcohol-based antifoaming agent, and a silicone-based antifoaming agent. 3. The honing method according to claim 1, wherein the abrasive comprises an organic fine powder. 4. The honing method according to claim 3, wherein the organic fine powder comprises resin fine particles. 5. A method for producing an electrophotographic photoreceptor in which a honing treatment liquid is sprayed on a conductive substrate to roughen the surface of the conductive substrate and form a photosensitive layer on the roughened conductive substrate. And a method for producing an electrophotographic photoreceptor, wherein the honing treatment solution contains an abrasive and an antifoaming agent. 6. The method according to claim 5, wherein the defoaming agent is selected from a fatty acid ester-based defoaming agent, an alcohol-based defoaming agent, and a silicone-based defoaming agent. . 7. The method according to claim 5, wherein the abrasive is made of an organic fine powder. 8. The method according to claim 7, wherein the organic fine powder comprises resin fine particles. 9. The spraying speed of the honing treatment liquid is 10
~150m / sec, the production method of the electrophotographic photosensitive member according to claims 5 to 8 spraying pressure is 0.1 to 10 / cm ² of the honing processing liquid.