JPH07313915A - Coating method and apparatus - Google Patents

Abstract

PURPOSE:To ensure a hydrolysis state more enhanced in reliability and to keep the stability of a coating soln. CONSTITUTION:In a coating method drawing up a cylindrical substrate with respect to a coating jig to form a film on the surface of the substrate, a coating soln. prepared by mixing a coating soln. main agent with a moisture-containing soln. is supplied to the coating soln. storage part formed by the surface of the substrate and the coating jig to coat the substrate. A coating apparatus is equipped with a coating soln. feeder 7 storing the coating soln. main agent, a moisture feeder 8 storing the moisture-containing soln., a mixer 9 mixing the coating soln. main agent supplied from the coating soln. feeder and the moisture-containing soln. supplied from the moisture feeder to prepare the coating soln. and the coating jig 3 and the coating soln. storage part 10 storing the coating soln. supplied from the mixer is formed by the coating jig and the cylindrical substrate. This coating apparatus is used to produce an electrophotographic photosensitive member enhanced in sensitivity and stability and excellent in the stability of production quality.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating method and a coating apparatus, and more particularly to a coating method for producing an electrophotographic photosensitive member having higher sensitivity, higher stability and excellent production quality stability. And a coating device.

[0002]

2. Description of the Related Art Electrophotographic devices are used in the fields of copiers, laser beam printers, etc. because of their high speed and high printing quality. As an electrophotographic photosensitive member used in an electrophotographic apparatus, an organic photosensitive member (OPC) using an organic photoconductive material has been developed and is becoming widespread. The structure of the electrophotographic photoreceptor is a single-layer type photoreceptor in which a charge transfer complex structure or a charge generating material is dispersed in a binder resin, and a function separation type photoreceptor in which a charge generating layer and a charge transport layer are separated. It has changed to the body and has improved performance. At present, the mainstream of this function-separated type photoconductor is a structure in which an undercoat layer is formed on an aluminum substrate, and a charge generation layer and a charge transport layer are formed thereon. With the progress of electrophotographic devices, the performance of the photoconductor is required to have higher quality image quality, and
For example, in order to improve the repetitive stability and environmental stability of the photoconductor, all the functional layers such as the charge generation layer, the charge transport layer and the undercoating layer have different electrophotographic properties such as sensitivity, image quality and repetitive stability It is known to have a significant impact.

The present inventors have investigated a functional layer having higher sensitivity and excellent image quality and repeated stability, and found that a film obtained by drying and curing a hydrolytic condensation-polymerizable compound such as a zirconium alkoxide or a silane coupling agent is They have found that they have excellent electrophotographic characteristics as a subbing layer, and have already commercialized a photoconductor having the subbing layer. Here, the hydrolytic condensation-polymerizable compound means a hydrolyzable reactive substituent such as an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, an acetate group, etc., centering on elements such as zirconium, titanium, aluminum, and silicon. It means a compound having a structure in which one or more is added. These hydrolytic condensation-polymerizable compounds require an appropriate amount of water during the curing reaction, and the hydrolysis reaction causes elimination of alkoxy groups such as methoxy group, ethoxy group, butoxy group and acetate groups, and the polycondensation reaction proceeds. It takes the form of reaction. Therefore, the presence of water is indispensable for efficiently curing the layer containing these compounds. However, when water is mixed in the coating solution, the polymerization reaction of the hydrolysis-polycondensable compound in the coating solution proceeds, the viscosity of the coating solution increases after a long time, and in some cases, gelation occurs. May change. In the case of the dip coating method which has been generally used as the coating method, it is necessary to store the coating liquid in the dipping tank for a long period of time. In addition, due to the progress of the polymerization reaction of the coating liquid, the coating film thickness varies, which causes an increase in residual potential, an increase in image quality defects, and the like, making it impossible to obtain sufficient electrophotographic characteristics. Further, depending on the coating liquid component, black spots may frequently occur in the image quality due to the residual substituent group component. Further, as the viscosity increases, the coating speed for obtaining an appropriate film thickness decreases, which may lead to a significant decrease in productivity. Furthermore, in the case of a coating liquid having a high hydrolysis reactivity, the coating liquid may cause gelation within one day. When such a coating liquid is used, the polymerization reaction proceeds rapidly and the coating liquid becomes The situation of gelation occurs.

Further, JP-A-53-22544 discloses a method of forming a coating film by contacting a surface of a cylindrical substrate with a liquid pool generated by a coating jig, and JP-A-63-172159. The gazette and the like disclose a method of supplying the coating liquid from the coating liquid supply unit to the coating liquid storage unit and applying the coating liquid using a ring-shaped coating jig. However, these methods also have the above-mentioned problems with respect to the coating liquid to be used, and the coating operation cannot be stably performed, and improvement thereof is demanded.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a coating method that secures a more reliable hydrolysis state and maintains the stability of a coating solution, and a coating apparatus used therefor. Another object of the present invention is to provide a coating method and a coating apparatus for manufacturing an electrophotographic photosensitive member having high sensitivity, high stability, and excellent manufacturing quality stability.

[0006]

The coating method of the present invention is a coating method in which a cylindrical substrate is pulled up to a coating jig to form a coating film on the surface of the cylindrical substrate. Is mixed to obtain a coating liquid, and then the coating liquid is supplied to a coating liquid storage portion formed by the surface of the cylindrical substrate and the coating jig to apply the coating liquid. The coating apparatus of the present invention is
In a coating device for pulling a cylindrical substrate onto a coating jig to form a coating film on the surface of the cylindrical substrate, a coating liquid supply device for supplying the coating liquid main component and a water supply for supplying a water-containing liquid. A coating device, a mixer for preparing a coating liquid by mixing a main component of the coating liquid supplied from the coating liquid supply part and a water-containing liquid supplied from the water supply part, and a coating jig. It is characterized in that the tool and the cylindrical substrate form a coating liquid storage part for storing the coating liquid supplied from the mixer.

FIG. 1 shows an example of a coating apparatus according to the present invention, which is for manufacturing an electrophotographic photosensitive member.
The coating device includes a coating liquid supply device 7 for supplying a coating liquid main component such as a photosensitive layer coating liquid, a water supply device 8 for supplying a water-containing liquid composed of a mixed liquid of water and a solvent, and the above coating liquid supply. It has a mixer 9 for preparing a coating liquid by mixing the coating liquid main agent supplied from the container with the water-containing liquid supplied from the moisture supply device 8, and a coating jig 3. The coating jig 3 is provided with a coating liquid leakage prevention member, which is composed of a doughnut-shaped elastic plate 6 slidably contacting the outer peripheral surface 2 of the cylindrical conductive substrate, on the inner peripheral side of the bottom surface. The coating liquid reservoir 10 is formed between the conductive substrate and the coating jig, and the coating liquid supplied from the mixer is stored in the coating liquid reservoir. The cylindrical conductive substrate 1 is fitted with a support 4 having the same outer diameter on the upper part and a support 5 having the same outer diameter on the lower part, and can be pulled up in the arrow direction by a well-known appropriate means not shown. Has become. When performing the coating operation, the coating liquid base material and the water-containing liquid are supplied to the mixer 9 from the coating liquid supply device 7 and the water supply device 8, respectively, and mixed to prepare a coating liquid. It is efficient to attach a stirring device to the mixer 9. The obtained coating liquid is supplied to the coating liquid storage unit 10, and the supply amount is adjusted by the liquid amount adjusting valve 12. When the cylindrical conductive substrate 1 that is the object to be coated is raised in the direction of the arrow, the outer peripheral surface 2 of the cylindrical conductive substrate 1 is coated with the coating liquid, and the coating film surface 11 is formed. When the upper part of the outer peripheral surface of the support 5 reaches the liquid surface of the coating liquid storage portion, the coating on the cylindrical conductive substrate is completed. After the coating film formation is completed, the cylindrical conductive substrate 1 fitted with the support 4 is removed by the coating device.

Next, a case of producing an electrophotographic photosensitive member by using the above coating apparatus and coating method will be described. As the cylindrical conductive substrate, in addition to metals such as copper, aluminum, nickel and iron, a metal is vapor-deposited on the surface,
It is possible to use a cylindrical, belt-shaped, or sheet-shaped substrate made of plastic, paper, or the like that has been made conductive by forming a coating film in which conductive powder is dispersed. In order to prevent interference fringes, the surface of the cylindrical conductive substrate may be subjected to surface roughening treatment by a method such as etching, anodic oxidation, wet blasting method, sand blasting method, rough cutting and centerless grinding. it can.

An example of the constitution of the coating liquid used in the present invention is illustrated by using the coating liquid for the undercoat layer. The following water-polymerizable compounds are listed as the main components of the coating liquid in the coating liquid for the undercoat layer. That is, it contains an element such as silicon, zirconium, titanium, aluminum, manganese, iron, tin, cobalt, nickel, lead, molybdenum in the molecule, and methoxy group, ethoxy group, butoxy group, etc. or acetate group with the element as the center. And a compound having a structure in which one or more hydrolyzable substituents are added. Above all,
Hydrolytic condensation-polymerizable compounds containing silicon, zirconium, titanium, or aluminum have high film-forming properties, low residual potential, little change due to environment, and little change in potential due to repeated use. It is preferable because it is excellent.

Examples of hydrolytic condensation-polymerizable compounds containing silicon include vinyltrimethoxysilane, γ-methacryloyloxypropyl-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 can be mentioned. Among these, silane compounds that are particularly preferably used are vinyltriethoxysilane, vinyltris (2-methoxyethoxysilane), 3-methacryloyloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 2- (3. 4-epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane,
3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and the like.

Examples of hydrolytic condensation-polymerizable compounds containing zirconium include zirconium methoxide, zirconium ethoxide, zirconium propoxide, zirconium butoxide, acetylacetonate zirconium butoxide, ethyl acetoacetate zirconium butoxide, zirconium acetate, Examples thereof include methacrylate zirconium butoxide and zirconium butoxide dimer. Examples of the hydrolytic condensation-polymerizable compound containing titanium include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, titanium octylene glycolate and titanium lactate. Examples of the hydrolytic condensation-polymerizable compound containing aluminum include aluminum triisopropylate, monobutoxyaluminum diisopropylate, aluminum tributyrate, diethyl acetoacetate aluminum diisopropylate and the like.

For the purpose of improving the film-forming property of the undercoat layer and improving the mechanical strength, it is possible to further mix a binder resin in the undercoat layer. As the binder resin, acetal resin such as polyvinyl butyral, 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. Polymeric resin compounds such as vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin and melamine resin can be used. Moisture-containing liquid for coating the undercoat layer is methanol, ethanol,
Alcohols such as butanol, toluene, xylene,
A small amount of water can be mixed with a solvent having a high compatibility with a coating liquid for forming an undercoat layer such as an aromatic hydrocarbon such as chlorobenzene or a mixed liquid of a resin and a solvent. The amount of water is preferably in the range of 0.001 to 5 parts by weight with respect to 1 part by weight of the solvent. If the water content is too high, the hydrolysis reaction with the hydrolyzable polymerizable compound may proceed rapidly, and the hydrolysis reaction product may be precipitated. Further, when the water content is small, a sufficient hydrolysis effect cannot be obtained.

In the undercoat layer, various organic or inorganic fine powders can be mixed for the purpose of preventing the generation of interference fringes, improving the electrical characteristics, and the like. In particular, titanium oxide, zinc oxide, zinc white, zinc sulfide, white lead, white pigments such as lithopone, inorganic pigments as extender pigments such as alumina, calcium carbonate, barium sulfate, Teflon resin particles,
It is effective to mix benzoguanamine resin particles, styrene resin particles and the like. These organic or inorganic fine powders are
Those having a particle size in the range of 0.01 μm to 2 μm are used.
If the particle size is too large, the undercoat layer becomes highly uneven, and electrical nonuniformity becomes large, so that image quality defects are likely to occur. Further, if the particle size is too small, a sufficient light scattering effect cannot be obtained. The above-mentioned organic or inorganic fine powder is added as necessary, but when added, it is contained in an amount of 10 to 80% by weight, more preferably 30 to 70% by weight, based on the solid content of the undercoat layer. An addition amount in the range is adopted.
When preparing the coating liquid for forming the undercoat layer, the organic or inorganic fine powder is added to the solution in which the resin component is dissolved, and the dispersion treatment is performed. To disperse the organic or inorganic fine powder in the resin, a roll mill, ball mill, vibrating ball mill, attritor, sand mill, colloid mill, paint shaker or the like can be used. The obtained coating liquid is applied using the coating device shown in FIG. When the thickness of the undercoat layer is increased, the concealment of the irregularities of the base material is improved, and therefore, by increasing the thickness of the undercoat layer, image quality defects are generally reduced. On the other hand, on the other hand, the electrical repeatability becomes poor, so it is desirable to set the film thickness within the range of 0.1 to 5 μm.

A photosensitive layer is formed on the undercoat layer formed as described above. Even if the photosensitive layer is basically a single layer structure, the charge generation layer and the charge transport layer are formed. It may have a laminated structure in which the functions are separated. In the case of a laminated structure, the charge generation layer and the charge transport layer may be laminated in either order. Further, it is possible to form a surface protective layer if necessary. The charge generation layer is formed by forming a charge generation material by vacuum vapor deposition or by applying a coating liquid obtained by dispersing the charge generation material together with an organic solvent and a binder resin. As the charge generation material, amorphous selenium, crystalline selenium, selenium-tellurium alloy, selenium-arsenic alloy, other selenium compounds and selenium alloys, zinc oxide, inorganic photoconductors such as titanium oxide, metal-free phthalocyanine, Various phthalocyanine pigments such as titanyl phthalocyanine, copper phthalocyanine, tin phthalocyanine, gallium phthalocyanine, etc., various organic pigments and dyes such as squarylium type, anthanthrone type, perylene type, azo type, anthraquinone type, pyrene type, pyrylium salt and thiapyrylium salt Is used. In addition, these organic pigments generally have several crystal types, and particularly phthalocyanine pigments have α and β
Various crystal forms are known, including the above, and any of these crystal forms can be used as long as it is a pigment that can provide characteristics such as sensitivity according to the purpose. A silane coupling agent or an organic metal alkoxide can be used for various purposes such as prevention of aggregation of the charge generating material, improvement of dispersion, improvement of electric characteristics, and the like. When using a coating solution containing a silane coupling agent or an organic metal alkoxide,
A coating film is preferably formed by the coating apparatus and coating method of the present invention.

Examples of the binder resin in the charge generation layer include the following. That is, polycarbonate resin such as bisphenol A type or bisphenol Z type, polyester resin, methacrylic resin, acrylic resin, vinyl chloride resin, styrene resin, vinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymerization Examples thereof include a combination, a vinyl chloride-vinyl acetate-maleic anhydride copolymer, a silicone resin, a silicone-alkyd resin, a phenol-formaldehyde resin, a styrene-alkyd resin, and a poly-N-vinylcarbazole. 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 10: 1 to
A range of 1:10 is desirable. The thickness of the charge generation layer is generally 0.01 to 5 μm, preferably 0.05 to
It is set in the range of 2.0 μm. To disperse the charge generating material in the resin, a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill or the like can be used.

Examples of the charge transport material used in the charge transport layer include those shown below. Oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-
Triphenyl-pyrazolin, 1- [pyridyl- (2)]
A pyrazoline derivative such as -3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline, an aromatic tertiary amino compound such as triphenylamine, tri (p-methyl) phenylamine and dibenzylaniline, N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1-biphenyl] -4,4'-
Aromatic tertiary diamine compounds such as diamine, 3- (4 '
-Dimethylaminophenyl) -5,6-di- (4'-methoxyphenyl) -1,2,4-triazine and the like 1,
2,4-triazine derivative, hydrazone derivative such as 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, quinazoline derivative such as 2-phenyl-4-styryl-quinazoline, 6-hydroxy-2,3-di (p-methoxy) Benzofuran derivatives such as phenyl) -benzofuran, p- (2,2-diphenylvinyl) -N,
Α-stilbene derivatives such as N′-diphenylaniline,
Hole-transporting substances such as enamine derivatives, carbazole derivatives such as N-ethylcarbazole, poly-N-vinylcarbazole and its derivatives; chloranil, bromoanil,
Quinone compounds such as anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9-fluorenone, xanthone compounds, thiophene compounds, etc. The electron-transporting substance (1); or a polymer having a group consisting of the compounds shown above in the main chain or side chain. These charge transport materials can be used alone or in combination of two or more.

Examples of the binder resin used in the charge transport layer include acrylic resin, polyarylate, polyester resin, polycarbonate resin such as bisphenol A type or bisphenol Z type, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene. Examples thereof include copolymers, polyvinyl butyral, polyvinyl formal, polysulfones, polyacrylamides, polyamides, insulating resins such as chlorinated rubber, and organic photoconductive polymers such as polyvinylcarbazole, polyvinylanthracene, and polyvinylpyrene. The charge transport layer can be formed by applying a solution prepared by dissolving the charge transport material and the binder resin shown above in a suitable solvent and drying the solution. Examples of the solvent used for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene and chlorobenzene, ketones such as acetone and 2-butanone, halogenated methylene chloride, chloroform and ethylene chloride. Aliphatic hydrocarbons, tetrahydrofuran, dioxane, ethylene glycol, diethyl ether and other cyclic or linear ethers, or mixed solvents thereof can be used. The compounding ratio of the charge transport material and the binder resin is preferably 10: 1 to 1: 5. The thickness of the charge transport layer is generally set in the range of 5 to 50 μm, preferably 10 to 40 μm.

Additives such as antioxidants, light stabilizers, and heat stabilizers in the photosensitive layer for the purpose of preventing deterioration of the photoreceptor due to ozone or oxidizing gas generated in the electrophotographic apparatus, or light and heat. Can be added. Examples of antioxidants include hindered phenols, hindered amines, paraphenylenediamines, aryl alkanes, hydroquinones, spirochromans, spiroindanones and their derivatives, organic sulfur compounds and organic phosphorus compounds. Examples of the light stabilizer include benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine derivatives. Further, at least one electron-accepting substance may be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use. Examples of the electron accepting substance that can be used in the electrophotographic photoreceptor of the present invention include succinic anhydride, maleic anhydride, and
Dibromo maleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid Acid, p
Examples thereof include nitrobenzoic acid and phthalic acid.
Of these, fluorenone type, quinone type, Cl, C
A benzene derivative having an electron-withdrawing substituent such as N or NO ₂ is particularly preferable. The coating can be performed using a coating method such as a dip coating method, a spray coating method, a bead coating method, a blade coating method, a roller coating method, etc., but the coating method of the present invention can also be used. Drying is preferably drying by touching at room temperature and then drying by heating. Heat drying
It is desirable to carry out at a temperature of 30 ° C. to 200 ° C. for a time in the range of 5 minutes to 2 hours.

If necessary, a surface protective layer can be formed on the photosensitive layer. Examples of the surface protective layer include an insulating resin protective layer and a low resistance protective layer obtained by adding a resistance adjusting agent to an 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. Electrically conductive particles have an electrical resistance of 10 ⁹ Ω.
Fine particles having an average particle size of 0.3 μm or less, preferably 0.1 μm or less, having a color of cm or less and exhibiting white, gray or bluish white, for example, molybdenum oxide, tungsten oxide, antimony oxide, tin oxide, titanium oxide are suitable. , Indium oxide, a solid solution 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 coated material. Among them, tin oxide and a solid solution of tin oxide and antimony or antimony oxide are preferably used because they can appropriately adjust the electric resistance and can make the protective layer substantially transparent. (JP-A-57-30847, JP-A-57-128)
344). 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.

A silane coupling agent or an organic metal alkoxide can be used for various purposes such as prevention of aggregation of conductive fine particles, improvement of dispersibility, and improvement of electric characteristics. These may be subjected to a surface treatment with the conductive fine particles in advance and then subjected to a dispersion preparation treatment, or may be subjected to a coating and drying treatment by adding a silane coupling agent or an organic metal alkoxide during coating. It is possible. The coating method of the present invention is preferably applied to the coating of the coating solution when using a silane coupling agent or an organic metal alkoxide.

[0021]

When a coating liquid containing a hydrolytic polycondensable compound is used, it is essential that water content is efficiently contained in the coating film before the curing treatment in order to sufficiently carry out the reaction of the coating film. . However, when water is added to the coating liquid, the coating liquid is significantly deteriorated and is not suitable for the dip coating method which requires long-term storage. However, according to the coating method and the coating apparatus of the present invention, the coating liquid main component and the water-containing liquid are mixed by the mixer, and the coating liquid is supplied to the coating liquid storage portion after the hydrolysis reaction is likely to occur. It Since the amount of coating liquid in the coating liquid storage part is small and it is not necessary to store the liquid in the coating liquid storage part for a long period of time, the quality of the coating liquid that has become susceptible to a hydrolysis reaction will deteriorate. Can be used without. Further, since the coating liquid is immediately supplied to the coating liquid storage unit after the hydrolyzable compound and water are mixed in the mixer of the supply unit for supplying the coating liquid, it is possible to always keep the state of the coating liquid constant. You can
It is possible to perform the coating operation stably with any coating liquid.

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 4 parts by weight of polyvinyl butyral resin (S-REC BM
-S, manufactured by Sekisui Chemical Co., Ltd.) and 150 parts by weight of n-butyl alcohol and 36 parts by weight of an organic zirconium compound (acetylacetonate zirconium butyrate) were mixed and stirred. This mixed liquid was put into the coating liquid supply device 7 of the apparatus shown in FIG. 1 as a main component of the photosensitive layer coating liquid. In addition, a 5 wt% propanol aqueous solution was placed in the water supplier 8. The liquids are supplied from the coating liquid supply device 7 and the water supply device 8 to the mixer 9 at a weight ratio of 10: 1, and after mixing, the coating liquid storage unit 10 is provided.
Was continuously fed to. At this time, the coating liquid was supplied from the inside of the mixer to the coating liquid storage portion at a rate of 0.14 cc / min.
About 15 cc of liquid was stored in the coating liquid storage part. Using a 40 mmφ aluminum substrate as the cylindrical substrate,
The above coating solution was applied thereon, air-dried at room temperature for 10 minutes, and then heat-cured at 170 ° C. for 10 minutes.

15 parts by weight of chlorogallium metal phthalocyanine as a charge generating material, 10 parts by weight of polyvinyl butyral resin (S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.), n
A mixture of 300 parts by weight of butyl alcohol was dispersed in a sand mill for 4 hours. The obtained dispersion was applied onto the undercoat layer by a dip coating method and dried to form a charge generation layer having a thickness of 0.2 μm. Then N, N '
-Diphenyl-N, N'-bis (3-methylphenyl)
4 parts by weight of-[1,1'-biphenyl] -4,4'-diamine and 6 parts by weight of a bisphenol Z polycarbonate resin (molecular weight 40,000) were dissolved by adding 80 parts by weight of chlorobenzene. The obtained solution is applied onto the charge generation layer by a dip coating method and dried to obtain a film thickness of 20 μm.
A charge transporting layer of m was formed to prepare an electrophotographic photoreceptor having three layers. The obtained electrophotographic photosensitive member was mounted on a laser beam printer XP-11 manufactured by Fuji Xerox Co., Ltd.
After charging at -700V, the exposure is performed with a predetermined amount of light to measure the potential, and 1000 at low temperature and low humidity.
The copying operation was performed 0 times, and the image quality after the running test was examined. The results are shown in Table 1 below. The number of black dots in the image quality column indicates the number of black dots in one B4 sheet.

Comparative Example 1 An electrophotographic photosensitive member was produced by the same method as in Example 1 except that the same amount of the coating liquid was supplied to the coating liquid storage portion without supplying the water from the moisture supply device. It evaluated similarly. The results are shown in Table 1 below.

Example 2 3 parts by weight of polyvinyl butyral resin (S-REC BX
1, Sekisui Chemical Co., Ltd.) dissolved ethyl alcohol 17
30 parts by weight of an organic zirconium compound (zirconium tetrabutyrate) was mixed and stirred in a solution of 0 parts by weight to obtain a coating liquid for the undercoat layer. This coating liquid was put into the coating liquid supply device 7 of the coating apparatus shown in FIG. Further, a 7 wt% propanol aqueous solution was put into the water supplier 8. The coating liquid was supplied to the mixer at a weight ratio of 10: 1 from the coating liquid supply unit and the water supply unit, respectively, and mixed, and then the obtained coating liquid was continuously supplied to the coating liquid storage unit. This coating solution was applied onto a 40 mmφ aluminum substrate so that the film thickness after drying was 1 μm, and dried and cured at 170 ° C. for 10 minutes to form an undercoat layer. As a charge generating material, a mixture of 15 parts by weight of titanyl phthalocyanine, 10 parts by weight of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nippon Unicar Co., Ltd.), and 300 parts by weight of n-butyl alcohol was dispersed in a sand mill for 4 hours. The obtained dispersion is applied onto the undercoat layer by a dip coating method and dried,
A charge generation layer having a thickness of 0.2 μm was formed. Subsequently, charge transport material: tri (p-methylphenyl) amine 90 parts by weight, polycarbonate resin (C-1400, Teijin Chemicals Co., Ltd.) 100 parts by weight, silicone oil (KF-54, Shin-Etsu Chemical Co., Ltd.) 0.002 Parts by weight, tetrahydrofuran 8
A coating solution for forming a charge transport layer consisting of 70 parts by weight was prepared, coated on the charge generation layer by a dip coating method, and dried to form a charge transport layer having a film thickness of 24 μm. It was made. The electrophotographic photosensitive member thus obtained was mounted on a laser beam printer (XP-11, manufactured by Fuji Xerox Co., Ltd.), charged at -700 V, and then exposed at a predetermined light intensity to obtain a potential. The measurement was performed.
The results are shown in Table 1.

[0026]

[Table 1]

Comparative Example 2 3 parts by weight of polyvinyl butyral resin (S-REC BX
1, Sekisui Chemical Co., Ltd.) dissolved ethyl alcohol 17
30 parts by weight of an organic zirconium compound (zirconium tetrabutyrate) was mixed and stirred with a solution of 0 parts by weight to obtain a coating liquid for forming an undercoat layer. This coating liquid was put into the coating liquid supply device 7 of the coating apparatus shown in FIG. Also, 7
A weight% aqueous propanol solution was placed in the water supplier 8.
From the coating liquid supply device and the water supply device, each liquid is 10: 1.
Was mixed in a mixer. When the obtained coating liquid was introduced into a dip coating device equipped with a continuous circulation device and circulated, the liquid started gelation after 2 days, so the circulation was stopped and the coating liquid was discarded.

Example 3 100 parts by weight of butyl alcohol and 30 parts by weight of a silane coupling agent (γ-aminopropyltrimethoxysilane) were mixed and stirred. The obtained coating liquid was put into the coating liquid supply device 7 of the coating apparatus shown in FIG. In addition, a 5 wt% propanol aqueous solution was placed in the water supplier 8. Coating liquid feeder 7
The liquids were respectively supplied from the water supply device 8 and the water supply device 8 to the mixer 9 at a weight ratio of 10: 1 and mixed, and then the obtained coating liquid was continuously supplied to the coating liquid storage section 10. At that time, the coating liquid was supplied from the mixer to the coating reservoir at a rate of 0.04 cc / min. About 14 cc of liquid was stored in the mixed liquid storage part. Using a 40 mmφ aluminum substrate, applying this coating solution on it, air-drying at room temperature for 10 minutes, and then heat-curing treatment at 170 ° C. for 10 minutes to obtain a film having a film thickness of 0.15 μm. Layers were formed. continue,
A charge generation layer and a charge transport layer were formed under the conditions of Example 2 to obtain an electrophotographic photoreceptor having three layers. The electrophotographic photosensitive member thus obtained was measured for potential under the conditions of Example 1, and was subjected to 10,000 copying operations under low temperature and low humidity to examine the image quality after the running test. As a result, the residual potential is -18.
The value was as low as V and the number of black spots was as small as 8 and the level was good.

Comparative Example 3 An electrophotographic photosensitive member was prepared in the same manner as in Example 3 except that the same amount of the coating liquid was supplied to the coating liquid storage section without supplying the moisture from the moisture supply device. did. As a result, the residual potential was about the same as -21V, but there were 250 black spots.

[0030]

According to the coating method and coating apparatus of the present invention, the main component of the coating liquid and the water-containing liquid are mixed by the mixer and supplied to the coating liquid storage section, so that the hydrolysis reaction is likely to occur. The coating liquid is provided for coating without being stored in the coating liquid storage section for a long period of time. Therefore, even a hydrolysis-reactive coating liquid can be used without degrading the quality. In addition, since the coating liquid is supplied to the coating liquid storage portion immediately after the hydrolyzable compound and the water are mixed in the mixer, the state of the coating liquid can be always kept constant, and any coating liquid can be used. However, the coating operation can be stably performed. Therefore, when an electrophotographic photoreceptor is formed using the coating method and coating apparatus of the present invention,
It is possible to obtain a film having a hydrolyzable compound in which curing of the coating film is accelerated, more stable electric characteristics are formed, and a copied image having excellent image quality is formed.

[Brief description of drawings]

FIG. 1 is a configuration diagram of an embodiment of a coating apparatus of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Cylindrical conductive substrate, 2 ... Outer peripheral surface, 3 ... Coating jig, 4
... Support body, 5 ... Support body, 6 ... Elastic plate, 7 ... Coating liquid supply device, 8 ... Moisture supply device, 9 ... Mixer, 10 ... Coating liquid storage part, 11 ... Coating film surface, 12 ... Liquid amount adjustment valve.

Claims (2)

[Claims] 1. A cylindrical substrate is pulled up to a coating jig,
In a coating method for forming a coating film on the cylindrical surface of the substrate,
After obtaining the coating liquid by mixing the coating liquid main component and the water-containing liquid,
A coating method, characterized in that the coating liquid is supplied to a coating liquid reservoir formed by a surface of a substrate and a coating jig to perform coating. 2. The cylindrical substrate is pulled up with respect to the coating jig,
In a coating device that forms a coating film on the surface of the cylindrical substrate,
A coating liquid supply device for supplying the coating liquid main component, a moisture supply device for supplying a water-containing liquid, a coating liquid main component supplied from the coating liquid supply part, and a water-containing liquid supplied from the moisture supply part. A coating liquid storage section for storing the coating liquid supplied from the mixer is provided, which comprises a mixer for mixing to prepare a coating liquid and a coating jig, and the coating jig and the cylindrical substrate. A coating device characterized by.