JP2013057787A - Light irradiation device and method for manufacturing electrophotographic organophotoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light irradiation device, which can sufficiently cure an uncured film, thereby can form a protective film with high durability, which has high flexibility for designing the device and can be designed in a compact type, and which can continuously process a plurality of works, and to provide a method for manufacturing an electrophotographic organophotoreceptor.SOLUTION: The light irradiation device includes: a workpiece conveyance path space, which is vertically extending and in a circular column shape, for upwardly conveying a workpiece having an uncured film formed on an organic photosensitive layer on a cylindrical conductive support; a light radiating window for radiating light radially inward, disposed to surround the periphery of the workpiece conveyance path space; and a gas discharge port for discharging nitrogen gas radially inward, disposed to surround the periphery of the workpiece conveyance path space. The gas discharge port is disposed at a level position lower than a level position where the light radiating window is disposed. The nitrogen gas discharged from the gas discharge port flows upward.

Description

  The present invention relates to a light irradiation apparatus for forming a protective layer of an electrophotographic organic photoreceptor and a method for producing an electrophotographic organic photoreceptor (hereinafter also simply referred to as “organic photoreceptor”).

  In general, a photoreceptor used in an electrophotographic image forming apparatus is repeatedly subjected to a series of image forming processes including a charging process, an exposure process, a developing process, a transfer process, a cleaning process, and a charge eliminating process. Therefore, the organic photoreceptor is required to have little deterioration in electrical characteristics such as charging property and potential holding property even if the image forming process is repeatedly performed.

Conventionally, as a photoreceptor, for example, zinc oxide (ZnO), cadmium sulfide (CdS), cadmium selenide (CdSe), amorphous selenium-based (a-Se, a-Se-Te, a-As ₂ Se ₃ ), etc. Inorganic photoreceptors having the above compound in the photosensitive layer have been used, but in recent years, many of them are easy to manufacture, capable of high sensitivity design, low cost, non-polluting, etc. Because of its merit, organic photoreceptors having an organic compound in the photosensitive layer are the mainstream.

  However, organophotoreceptors are generally soft because the surface layer is mainly composed of a low molecular charge transport material and an inert polymer, and when repeatedly used in the image forming process, they are mechanically loaded by the development process and cleaning process. Wear easily. Such wear of the organic photoconductor causes a deterioration in electrical characteristics such as a deterioration in sensitivity and a decrease in chargeability, thereby causing a problem that a high-quality image cannot be formed over a long period of time.

In order to solve such a problem, a protective layer made of a cured resin is provided on the surface of the organic photoreceptor.
A protective layer made of a cured resin forms an uncured film that becomes a cured resin by applying a coating solution for forming a protective layer on an organic photosensitive layer on a cylindrical conductive support. It can be formed by irradiating with light.
As a light irradiation device used for irradiating a work with light, for example, a light emitting device that emits light radially inward to a cylindrical machine frame surrounding the periphery of a cylindrical work conveyance path space extending in the vertical direction There is a light irradiation device in which windows are formed over the entire circumference (see Patent Document 1).
Moreover, when irradiating light to a workpiece | work, oxygen gas in air | atmosphere is substituted with nitrogen gas, and light is irradiated to a workpiece | work in nitrogen gas atmosphere (refer patent document 2).
By irradiating the workpiece with light in a state where the oxygen gas is replaced with nitrogen gas, the inhibition of curing caused by the oxygen gas is suppressed, so that sufficient curing of the uncured film is obtained, and thus high durability is achieved. A protective layer can be formed.

JP 2008-083130 A JP 2008-304746 A

  However, in the technique disclosed in Patent Document 2, for example, the work is irradiated with light in a closed system filled with nitrogen gas, and thus replacing the inside of the closed system with nitrogen gas is necessary. There are disadvantages such as a large amount of nitrogen gas and a low degree of design freedom such as a large apparatus. Moreover, there is an industrial disadvantage that batch processing for individually processing a plurality of workpieces is performed.

The present invention has been made in consideration of the above-described circumstances, and the object thereof is to sufficiently cure an uncured film, and therefore, a protective layer having high durability can be formed. An object of the present invention is to provide a light irradiation apparatus and a method for producing an electrophotographic organic photoreceptor.
Another object of the present invention is to provide a light irradiating device that can be designed as a compact device with a high degree of design freedom.
Still another object of the present invention is to provide a light irradiation apparatus capable of continuously processing a plurality of workpieces.

The light irradiation apparatus of the present invention has a cylindrical conductive property in the manufacturing process of an electrophotographic organic photosensitive member in which an organic photosensitive layer and a protective layer made of a cured resin are laminated in this order on a cylindrical conductive support. A light irradiation device used for irradiating light to an uncured film formed on an organic photosensitive layer on a support to form a protective layer made of a cured resin,
In a state of surrounding the periphery of the work conveyance path space, the work in which an uncured film is formed on the organic photosensitive layer on the cylindrical conductive support in a columnar shape extending in the vertical direction is conveyed upward. A light exit window that emits light radially inward is provided,
A gas discharge port for discharging nitrogen gas radially inward is provided in a state surrounding the work transport path space.
The gas discharge port is provided at a level position lower than the level position where the light exit window is provided, and nitrogen gas discharged from the gas discharge port flows upward.

  In the light irradiation apparatus of this invention, it is preferable that it has a gas rising flow path extended to an up-down direction, and the upper part of the said gas rising flow path is connected to the said gas discharge port.

Further, in the light irradiation device of the present invention, the light exit window and the gas discharge port are commonly provided in a substantially cylindrical machine frame surrounding the periphery of the work transport path space,
It is preferable that the distance between the gas discharge port in the machine frame and the lowermost end of the machine frame is longer than the distance between the gas discharge port and the uppermost end of the machine frame.

  Moreover, in the light irradiation apparatus of this invention, it is preferable that the said gas discharge port is a cyclic | annular slit.

  Moreover, in the light irradiation apparatus of this invention, it has two or more said gas discharge ports, and each gas discharge port is arrange | positioned at equal intervals in the circumferential direction. The light irradiation apparatus in any one of.

The light irradiation device of the present invention includes a light source, a light guide member composed of a plurality of optical fibers, and a ring-shaped triangular prism.
It is preferable that each of the optical fibers is disposed in a state in which light from the light source is guided to one surface of the triangular prism, and a light exit window is configured by one surface orthogonal to the one surface of the triangular prism.

  Moreover, in the light irradiation apparatus of this invention, it is preferable that the said light source is a xenon lamp and the said optical fiber consists of quartz glass.

The method for producing an electrophotographic organic photoreceptor according to the present invention is a method for producing an electrophotographic organic photoreceptor using the light irradiation device described above,
While discharging nitrogen gas from the gas outlet and emitting light from the light exit window,
A workpiece in which an uncured film is formed on an organic photosensitive layer on a cylindrical conductive support,
The workpiece is conveyed upward in the work conveyance path space.

  In the method for producing an electrophotographic organic photoreceptor of the present invention, it is preferable that the uncured film contains metal oxide fine particles.

According to the light irradiation apparatus of the present invention, the gas discharge port for discharging nitrogen gas is provided at a level position below the light emission window from which light related to the curing of the uncured film is emitted, and is discharged from the gas discharge port. Since the nitrogen gas to be flowed upward, the nitrogen gas can be supplied to the portion of the uncured film that is irradiated with light. Therefore, it is possible to replace the periphery of the portion of the uncured film that is irradiated with light with a nitrogen gas atmosphere, and as a result, the uncured film is sufficiently cured, thus forming a highly durable protective layer. can do.
Further, according to the light irradiation apparatus of the present invention, since nitrogen gas is selectively supplied to the portion of the uncured film that is irradiated with light, the amount of nitrogen gas required for curing the uncured film is Compared with an apparatus configured to replace the inside of the closed system with nitrogen gas, a high degree of design freedom can be obtained, and the light irradiation apparatus can be designed to be small.
Furthermore, according to the light irradiation apparatus of the present invention, since the nitrogen gas can be supplied to the portion irradiated with light in the uncured film even when the work transport path space is an atmospheric atmosphere, With the configuration, a plurality of workpieces can be continuously processed.

  According to the method for producing an organic photoreceptor of the present invention, the gas discharge port for discharging nitrogen gas is provided at a level position below the light exit window from which light related to the curing of the uncured film is emitted. Since the uncured film is cured using a light irradiation device in which nitrogen gas discharged from the substrate flows upward, the uncured film is sufficiently cured, and thus a protective layer having high durability is formed. Can do.

It is an explanatory fragmentary sectional view which shows the structure of an example of the light irradiation apparatus of this invention. It is a bottom view of the light irradiation apparatus shown in FIG. It is sectional drawing for description which shows an example of a structure of the circular slide hopper coating device used for formation of the unhardened film | membrane for forming the protective layer in the manufacturing method of the electrophotographic organic photoreceptor of this invention. FIG. 4 is a perspective sectional view of the circular slide hopper coating device shown in FIG. 3. It is a schematic diagram for explanation showing a method for producing an organic photoreceptor of the present invention, in which (a) is a view in which a work is positioned below a work conveyance path space, (b) is a view in which light is applied to the work, (c) ) Is a diagram in which the workpiece is positioned above the workpiece conveyance path space.

  Hereinafter, the present invention will be specifically described.

(Light irradiation device)
FIG. 1 is a partial cross-sectional view for explaining the structure of an example of the light irradiation apparatus of the present invention, and FIG. 2 is a bottom view of the light irradiation apparatus shown in FIG.
The light irradiation device of the present invention includes a cylindrical conductive support in a manufacturing process of an organic photoreceptor in which an organic photosensitive layer and a protective layer made of a cured resin are laminated in this order on a cylindrical conductive support. It is an apparatus used to form a protective layer made of a cured resin by irradiating light to an uncured film formed on the upper organic photosensitive layer.
Specifically, a workpiece W (see FIG. 5) in which an uncured film is formed on an organic photosensitive layer on a cylindrical conductive support having a columnar shape extending in the vertical direction is conveyed upward. A light exit window 15 for emitting light radially inward is provided in a state surrounding the work transport path space S, and nitrogen gas is radially inward in a state surrounding the work transport path space S. The gas discharge port 25 is provided at a level position lower than the level position where the light exit window 15 is provided, and the nitrogen gas discharged from the gas discharge port 25 is upward. It is what flows in.

  The level position of the light exit window 15 refers to the level position of the lowermost end of the light exit window 15, and the level position of the gas discharge port 25 refers to the level position of the uppermost end of the gas discharge port 25.

More specifically, the light irradiation device includes a substantially cylindrical machine frame 30 that surrounds the work conveyance path space S, and the machine frame 30 is a lower machine made of a cylindrical body having a double-pipe structure. An area including an area defined by the frame 31 and an outer peripheral wall (hereinafter referred to as “outer peripheral wall”) and an intermediate peripheral wall (hereinafter referred to as “partition wall”) on the upper surface of the lower machine casing 31. The ring-shaped triangular prism 16 arranged in contact with the ring-shaped fixing member 19 for fixing the triangular prism 16 includes an upper machine casing 32 having a substantially cylindrical shape as a whole.
Specifically, the triangular prism 16 has an inner peripheral surface extending in the vertical direction, a bottom surface orthogonal to the inner peripheral surface, extending outward in the radial direction continuously from the lower end side of the inner peripheral surface, and a tapered shape. And a shape having an outer peripheral surface. A light exit window 15 is configured by a region where light is actually emitted on the inner peripheral surface of the triangular prism 16 facing the workpiece conveyance path space S.
A gas discharge port 25 is opened at an upper portion of the inner peripheral wall (hereinafter referred to as “inner peripheral wall”) of the lower machine casing 31 of the machine casing 30.

In this light irradiation apparatus, the distance (L ₁ ) between the gas outlet 25 in the machine casing 30 and the lowermost end of the machine casing 30 is the distance (L ₂ ) between the gas outlet 25 and the uppermost end of the machine casing 30. Longer than that is preferred.
By having such a configuration, the nitrogen gas can surely flow upward, and the nitrogen gas can be reliably supplied to the portion of the workpiece W irradiated with light. The reason why the nitrogen gas flows upward is considered to be that as the distance from the gas discharge port 25 to the outlet of the machine frame 30 increases, the pressure increases, and as a result, the nitrogen gas flows in a direction in which the distance to the outlet is shorter. It is done.
The distance (L ₁ ) between the gas discharge port 25 and the lowermost end of the machine casing 30 refers to the distance between the lowermost end of the gas discharge outlet 25 and the lowermost end of the machine casing 30, and the gas discharge outlet 25 and the machine casing 30. The distance (L ₂ ) between the uppermost end of the gas discharge port 25 refers to the distance between the uppermost end of the gas discharge port 25 and the uppermost end of the machine casing 30.

In the light irradiation apparatus of the present invention, the distance (L ₁ ) between the gas discharge port 25 in the machine frame 30 and the lowermost end of the machine frame 30 is the distance (L ₁ ) between the gas discharge port 25 and the uppermost end of the machine frame 30. _{For the} purpose of surely obtaining a longer form than ₂ ), it is preferable to provide a cylindrical leg portion surrounding the work transport path space S in a state of being continuous with the machine frame 30 at the lower part of the machine frame 30.
Moreover, when the light irradiation apparatus of this invention is comprised so that the frame 30 or the leg part provided continuously from this may extend below the lowest end of the workpiece conveyance path space S, nitrogen gas is reliably made upwards. For the purpose of flowing, it is preferable to provide a lid member that closes the opening at the bottom.

[Nitrogen gas discharge means]
The gas discharge port 25 is an annular slit formed on the inner peripheral wall of the lower machine casing 31 of the machine casing 30 over the entire circumference.
Since the gas discharge port 25 is an annular slit, nitrogen gas can be supplied uniformly to the portion of the uncured film that is irradiated with light, and as a result, a protective layer in which curing unevenness is suppressed is formed. Can do.

A gas ascending flow path 21 that extends in the vertical direction and that communicates with the gas discharge port 25 is formed by an internal space defined by the inner peripheral wall and the partition wall of the lower machine casing 31 of the machine casing 30.
The cross-sectional area of the gas rising channel 21 is, for example, ² to 20 cm ² .

  In this light irradiation apparatus, a columnar gas introduction flow path member 23 in which a gas introduction flow path is formed is connected to the lower part of the partition wall of the lower machine casing 31 of the machine frame 30 to be described later. The gas introduction port 28 is provided in a state extending through the 12 accommodating spaces 13 and extending outward in the radial direction, and on the lower wall of the outer end portion (right end portion in FIG. 1) of the gas introduction flow path member 23. Is formed. In this gas introduction channel member 23, the inner end (left end in FIG. 1) of the internal gas introduction channel communicates with the gas ascending channel 21, and the gas introduction port 28 at the outer end is connected to a nitrogen gas supply source (not shown). Has been.

  The gas discharge port 25, the gas rising flow path 21, the gas introduction flow path, and the nitrogen gas supply source constitute nitrogen gas discharge means. In the nitrogen gas discharge means, nitrogen gas from the nitrogen gas supply source is The gas is introduced into the gas introduction channel in the gas introduction channel member 23 through the gas introduction port 28, moves in the lateral direction in the gas introduction channel, and is introduced into the gas ascending channel 21 in the lower machine casing 31. The gas rising passage 21 is moved in the vertical direction and finally discharged from the gas discharge port 25.

[Light irradiation means]
In this light irradiation device, the light source 11 is provided outside the machine casing 30, and the light guide member 12 that guides the light from the light source 11 to the bottom surface of the triangular prism 16 is the lower machine casing 31 of the machine casing 30. Are accommodated in an accommodation space 13 defined by the partition wall and the outer peripheral wall.

The light guide member 12 is composed of a plurality of optical fibers. Specifically, the light guide member 12 extends in the vertical direction on one end side close to the triangular prism 16 and has a cylindrical shape as a whole. The optical fibers are fixed in a state in which the side surfaces are in contact with each other, and the optical fibers are curved independently from each other in the middle portion, and are formed in a state in which the other end side extends and binds in the left-right direction. Has been.
An annular light inlet 13 </ b> A is opened in a region defined by the partition wall and the outer peripheral wall of the upper wall of the lower machine casing 31 of the machine casing 30, and in the lower part of the outer peripheral wall of the lower machine casing 31. The optical guide member 12 has an insertion hole 13B through which one end surface of each optical fiber is brought into contact with the bottom surface of the triangular prism 16 through the optical inlet 13A. It extends outside the lower machine casing 31 through the insertion hole 13 </ b> B and is arranged so that the other end surface is connected to the light source 11.

  One end surface of the light guide member 12 that is in contact with the bottom surface of the triangular prism 16, that is, the light exit surface is formed into an annular shape as a whole, whereby the light exit window 15 through which light is actually emitted on the inner peripheral surface of the triangular prism 16 is formed. Therefore, it is formed over the entire circumference. Therefore, it is possible to irradiate light uniformly in the circumferential direction of the cured film, and as a result, it is possible to form a protective layer in which unevenness of curing is suppressed.

  As the optical fiber constituting the light guide member 12, it is preferable to use one made of quartz glass, multicomponent glass or the like.

As the light source 11, light having sufficient energy for initiating the polymerization reaction, for example, a light emitting a visible ray or an ultraviolet ray having a wavelength of preferably 200 to 500 nm, more preferably 250 to 450 nm can be used.
Specifically, the light source 11 may be a low pressure mercury lamp such as a xenon lamp or a fluorescent chemical lamp, a high pressure discharge lamp such as a high pressure mercury lamp or a metal halide lamp, a short arc discharge xenon lamp, or an LED lamp.
The power of the lamp used as the light source 11 is preferably 0.1 to 5 kW, more preferably 0.5 to 3 kW.

  The triangular prism 16, the light guide member 12, and the light source 11 constitute light irradiating means. In the light irradiating means, the light emitted from the light source 11 is transmitted through the optical fiber of the light guide member 12 by the optical fiber of the triangular prism 16. The light guided to the bottom surface and incident on the bottom surface of the triangular prism 16 is reflected by the outer peripheral surface of the triangular prism 16 and is emitted from the inner peripheral surface (light output window 15) of the triangular prism 16.

An example of the dimensions of the light irradiation device of the present invention is specifically shown. The inner diameter of the lower machine casing 31 of the machine casing 30 is 40 mm, the outer diameter of the lower machine casing 31 is 100 mm, the inner diameter of the partition wall is 46 mm, and the lower machine casing. The vertical length of 31 is 870 mm, the vertical length of the upper machine casing 32 is 8 mm, the vertical size t _{1 of} the gas outlet 25 is 3 mm, and the vertical size t _{2 of the} light exit window 15. 7 mm, the distance (L ₁ ) between the gas discharge port 25 and the lowermost end of the machine frame 30 is 855 mm, the distance (L ₂ ) between the gas discharge port 25 and the uppermost end of the machine frame 30 is 12 mm, and the gas ascending channel 21 The cross-sectional area is 7.82 cm ² , the inner diameter of the triangular prism 16 is 40 mm, the number of optical fibers constituting the light guide member 12 is 4000, and the diameter φ of the optical fiber is 0.2 mm.

According to the light irradiation apparatus of the present invention, the gas discharge port 25 for discharging nitrogen gas is provided at a level position below the light exit window 15 from which light related to curing of the uncured film is emitted, Since the nitrogen gas discharged from the discharge port flows upward, the nitrogen gas can be supplied to a portion of the uncured film that is irradiated with light. Therefore, it is possible to replace the periphery of the portion of the uncured film that is irradiated with light with a nitrogen gas atmosphere, and as a result, the uncured film is sufficiently cured, thus forming a highly durable protective layer. can do.
Further, according to the light irradiation apparatus of the present invention, since nitrogen gas is selectively supplied to the portion of the uncured film that is irradiated with light, the amount of nitrogen gas required for curing the uncured film is Compared with an apparatus configured to replace the inside of the closed system with nitrogen gas, a high degree of design freedom can be obtained, and the light irradiation apparatus can be designed to be small.
Furthermore, according to the light irradiation apparatus of the present invention, since the nitrogen gas can be supplied to the portion irradiated with light in the uncured film even when the work transport path space S is an atmospheric atmosphere, the non-sealed system With this configuration, a plurality of workpieces W can be continuously processed.

  As mentioned above, although embodiment of the light irradiation apparatus of this invention was described concretely, the light irradiation apparatus of this invention is not limited to said example, A various change can be added.

  For example, the light exit window 15 and the gas discharge port 25 are not limited to the configuration provided in the common machine casing 30, and can be configured such that they are provided separately.

Further, for example, it is not limited to a configuration in which one gas discharge port by an annular slit is opened on the inner peripheral wall, and if it is provided so as to surround the periphery of the work transport path space S, it has a plurality of gas discharge ports, The gas discharge ports may be configured to be opened at equal intervals in the circumferential direction.
The number of gas discharge ports is, for example, 4 to 40, and 20 is particularly preferable.
The size of each gas outlet is preferably 0.15 to 7 mm ² , for example.
Even with such a configuration in which a plurality of gas discharge ports are opened, the same effect as in the configuration in which one gas discharge port by an annular slit is opened can be obtained.

Further, for example, the light guide member 12 is not limited to being formed in a state in which the side surfaces are in contact with each other so that the plurality of optical fibers have a cylindrical shape as a whole at one end side close to the triangular prism 16. It is also possible to adopt a multi-point spot configuration in which the annular bottom surface of the triangular prism 16 is arranged at equal intervals in the circumferential direction.
Even with such a multi-point spot configuration, it is possible to obtain the same effect as the configuration in which the side surfaces are in contact with each other so as to form a cylindrical shape as a whole on one end side of the light guide member 12.

Further, for example, the light irradiating means is not limited to the configuration including the triangular prism 16, and a configuration in which a plurality of optical fibers are arranged so that each light exit surface faces the work transport path space S, that is, one end side of the optical fiber is horizontally disposed. It is good also as a structure which has the light guide member arrange | positioned in the state extended in the direction.
In such a light guide member, the plurality of optical fibers may be arranged so that the respective light exit surfaces are continuous, or may be arranged equally spaced apart.

  Further, for example, the light irradiation means is not limited to the configuration in which the light source 11 is disposed outside the machine casing 30, and may be configured to use a plurality of light source chips.

[Method for producing organic photoreceptor]
The organic photoreceptor production method of the present invention is a method for producing an organic photoreceptor in which an organic photoreceptor layer and a protective layer made of a cured resin are laminated in this order on a conductive support, and is cylindrical. The workpiece W having an uncured film formed on the organic photosensitive layer on the conductive support is discharged with nitrogen gas from the gas discharge port 25 and with light from the light exit window 15 using the above-described light irradiation device. While irradiating, the workpiece is conveyed upward in the workpiece conveyance path space S.

[Organic photoconductor]
The organic photoreceptor obtained by the production method of the present invention is not particularly limited as long as an organic photosensitive layer and a protective layer are laminated in this order on a conductive support, but specifically, the following (1 ) And (2).
(1) A layer structure in which a charge generation layer, a charge transport layer, and a protective layer are laminated in this order as an intermediate layer and an organic photosensitive layer on a conductive support.
(2) A layer structure in which an intermediate layer, a single layer containing a charge generation material and a charge transport material as an organic photosensitive layer, and a protective layer are laminated in this order on a conductive support.

  In the present invention, the organic photoreceptor means a structure constituted by an organic compound that exhibits at least one of a charge generation function and a charge transport function essential for the construction of an electrophotographic organic photoreceptor. All known organic photoreceptors such as organic photoreceptors having a photosensitive layer composed of a charge generation material or an organic charge transport material, and organic photoreceptors having a photosensitive layer in which a charge generation function and a charge transport function are composed of a polymer complex Including

The process for producing the organic photoreceptor having the layer structure (1) will be specifically described below.
Step (1): An intermediate layer forming step of forming an intermediate layer by applying and drying an intermediate layer forming coating solution on the outer peripheral surface of the conductive support.
Step (2): a charge generation layer forming step of forming a charge generation layer by applying and drying a charge generation layer forming coating solution on the outer peripheral surface of the intermediate layer formed on the conductive support.
Step (3): a charge transport layer forming step of forming a charge transport layer by applying and drying a charge transport layer forming coating solution on the outer peripheral surface of the charge generation layer formed on the intermediate layer.
Step (4-1): An uncured film forming step of obtaining a workpiece W by applying a coating liquid for forming a protective layer to the outer peripheral surface of the charge transport layer formed on the charge generation layer to form an uncured film.
Step (4-2): a light irradiation step of irradiating the uncured film of the workpiece W with light to form a protective layer.

[Step (1): Intermediate layer forming step]
In this intermediate layer forming step (1), for example, a binder resin is dissolved in a known solvent to prepare an intermediate layer forming coating solution, and this intermediate layer forming coating solution is applied to the outer peripheral surface of the conductive support. Forming a coating film and drying the coating film to form an intermediate layer.

  The intermediate layer formed in the intermediate layer forming step (1) provides a barrier function and an adhesive function between the conductive support and the organic photosensitive layer. From the viewpoint of preventing various failures, it is preferable to provide such an intermediate layer.

(Conductive support)
The conductive support on which the intermediate layer is formed is not particularly limited as long as it has conductivity. For example, a metal such as aluminum, copper, chromium, nickel, zinc, and stainless steel is drum-shaped or Sheet shaped, laminated metal foil such as aluminum or copper on plastic film, deposited aluminum, indium oxide and tin oxide etc. on plastic film, or coated with conductive material alone or with binder resin Examples thereof include metals provided with a conductive layer, plastic films, and paper.

(Binder resin)
Examples of the binder resin used in the intermediate layer forming step (1) include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide resin, polyurethane resin, gelatin, and the like. Preferably there is.

(solvent)
As the solvent used in the intermediate layer forming step (1), those that disperse the inorganic fine particles described later well and dissolve the polyamide resin are preferable. Specifically, ethanol, n-propyl alcohol, isopropyl alcohol, Alcohols having 2 to 4 carbon atoms such as n-butanol, t-butanol, sec-butanol and the like are particularly preferable from the viewpoints of solubility and coatability of the polyamide resin.
In the intermediate layer forming step (1), it is preferable to use a co-solvent together with a solvent in order to improve storage stability and dispersibility of inorganic fine particles. Examples of co-solvents that can be used in combination include methanol and benzyl alcohol. , Toluene, methylene chloride, cyclohexanone, tetrahydrofuran and the like.

(Inorganic fine particles)
The coating liquid for forming an intermediate layer may contain inorganic fine particles such as various conductive fine particles and metal oxide fine particles for the purpose of adjusting the resistance of the formed intermediate layer.

  Examples of the inorganic fine particles contained in the coating liquid for forming the intermediate layer include metal oxide fine particles such as alumina, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, and bismuth oxide, and doped with tin. Ultrafine particles such as indium oxide, antimony-doped tin oxide and zirconium oxide can also be used. These metal oxide fine particles can be used singly or in combination of two or more. When two or more metal oxide fine particles are used in combination, the metal oxide fine particles are in a solid solution state. It may be in a fused state.

The number average primary particle size of such metal oxide fine particles is preferably 0.3 μm or less, more preferably 0.1 μm or less.
In the present invention, the number average primary particle size of the metal oxide fine particles is measured as follows.
That is, a 10000 times magnified photograph was taken with a scanning electron microscope “JSM-7500F” (manufactured by JEOL Ltd.), and a photographic image (excluding aggregated particles) obtained by randomly capturing 300 metal oxide fine particles with a scanner. Calculation is performed using an automatic image processing analysis apparatus “LUZEX AP” (software version Ver. 1.32, manufactured by Nireco).

  The means for dispersing the inorganic fine particles in the intermediate layer forming coating solution is not particularly limited, and examples thereof include a dispersing machine such as an ultrasonic dispersing machine, a ball mill, a sand grinder, and a homomixer.

  The addition amount of the inorganic fine particles is preferably 20 to 400 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the binder resin.

  Although it does not specifically limit as a coating method of the coating liquid for intermediate | middle layer formation, For example, the dip coating method, the spray coating method, etc. are mentioned.

  The method for drying the coating film of the coating solution for forming the intermediate layer can be appropriately selected according to the type of the solvent and the layer thickness of the intermediate layer to be formed, but a method by thermal drying is preferred.

  The layer thickness of the intermediate layer formed in the intermediate layer forming step (1) is preferably 0.1 to 15 μm, more preferably 0.3 to 10 μm.

[Step (2): Charge Generation Layer Formation Step]
In this charge generation layer forming step (2), for example, a charge generation material is added and dispersed in a binder resin dissolved in a known solvent to prepare a charge generation layer forming coating solution. In this step, a coating liquid is applied to the outer peripheral surface of the intermediate layer formed in the intermediate layer forming step (1) to form a coating film, and the coating film is dried to form a charge generation layer.

(Binder resin)
As the binder resin used in the charge generation layer forming step (2), a known resin can be used. For example, polystyrene resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, Polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, and copolymer resin containing two or more of these resins (for example, vinyl chloride-acetic acid) Vinyl copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin), poly-vinylcarbazole resin, and the like, but are not limited thereto.

(solvent)
Examples of the solvent used in the charge generation layer forming step (2) include toluene, xylene, methylene chloride, 1,2-dichloroethane, methyl ethyl ketone, cyclohexane, ethyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, and methyl cellosolve. , Ethyl cellosolve, tetrahydrofuran, 1-dioxane, 1,3-dioxolane, pyridine, diethylamine and the like, but are not limited thereto.

(Charge generating material)
Although it does not specifically limit as a charge generation material used in a charge generation layer formation process (2), For example, azo raw materials, such as Sudan red and Diane blue; Quinone pigments, such as pyrenequinone and anthanthrone; Quinocyanine pigment; Perylene pigments; indigo pigments such as indigo and thioindigo; and phthalocyanine pigments. These charge generation materials can be used alone or in combination of two or more.

  The amount of the charge generating material added is preferably 1 to 600 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the binder resin.

  The means for dispersing the charge generating material is not particularly limited, and examples thereof include a dispersing machine such as an ultrasonic dispersing machine, a ball mill, a sand grinder, and a homomixer.

  The method for applying the charge generation layer forming coating solution is not particularly limited, and examples thereof include a dip coating method and a spray coating method.

  The method for drying the coating film of the coating solution for forming the charge generation layer can be appropriately selected according to the type of the solvent and the layer thickness of the charge generation layer to be formed, but a method by thermal drying is preferred.

  The layer thickness of the charge generation layer formed in the charge generation layer formation step (2) varies depending on the characteristics of the charge generation material, the characteristics of the binder resin, the mixing ratio, etc., but is preferably 0.01 to 5 μm. Preferably it is 0.05-3 micrometers. It should be noted that the coating solution for forming the charge generation layer can prevent the occurrence of image defects by filtering foreign matter and aggregates before coating. The pigment can also be formed by vacuum deposition.

[Step (3): Charge Transport Layer Formation Step]
In this step (3), for example, a charge transport material (CTM) is added to a binder resin dissolved in a known solvent to prepare a coating solution for forming a charge generation layer. In this step, the charge transport layer is formed by coating the outer peripheral surface of the charge generation layer formed in the step (2) to form a coating film and drying the coating film.

(Binder resin)
As the binder resin used in the step (3), a known resin can be used, and polycarbonate resin, polyacrylate resin, polyester resin, polystyrene resin, styrene-acrylonitrile copolymer resin, polymethacrylate resin, styrene. -A methacrylic acid ester copolymer resin etc. are mentioned, However, A polycarbonate resin is preferable. Furthermore, bisphenol A (BPA), bisphenol Z (BPZ), dimethyl BPA, BPA-dimethyl BPA copolymer and the like are preferable in terms of crack resistance, wear resistance, and charging characteristics.

(solvent)
Examples of the solvent used in the step (3) include toluene, xylene, methylene chloride, 1,2-dichloroethane, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, tetrahydrofuran, 1,4- Examples include, but are not limited to, dioxane, 1,3-dioxolane, pyridine, diethylamine and the like.

(Charge transport material)
Examples of the charge transport material used in the step (3) include carbazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, Styryl compound, hydrazone compound, pyrazoline compound, oxazolone derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative, acridine derivative, phenazine derivative, aminostilbene derivative, triarylamine derivative, phenylenediamine derivative, stilbene derivative, benzidine derivative, poly-N -Vinylcarbazole, poly-1-vinylpyrene and poly-9-vinylanthracene, triphenylamine derivatives Etc., and the like. These charge transport materials can be used alone or in combination of two or more.

  The addition amount of the charge transport material is preferably 10 to 500 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the binder resin.

  The charge transport layer forming coating solution may contain an antioxidant, an electronic conductive agent, a stabilizer and the like as necessary. Examples of the antioxidant include those described in Japanese Patent Application No. 11-200135, and examples of the electronic conductive agent include those described in JP-A Nos. 50-137543 and 58-76483.

  The coating method of the charge transport layer forming coating solution is not particularly limited, and examples thereof include a dip coating method and a spray coating method.

  The method for drying the coating film of the coating liquid for forming the charge transport layer can be appropriately selected according to the type of the solvent and the layer thickness of the charge transport layer to be formed, but a method by thermal drying is preferred.

  The layer thickness of the charge transport layer formed in the step (3) varies depending on the characteristics of the charge transport material, the characteristics of the binder resin, the mixing ratio, etc., but is preferably 5 to 40 μm, more preferably 10 to 30 μm. is there.

[Step (4-1): Uncured film forming step]
This step (4-1) includes a polymerizable compound forming a cured resin constituting the protective layer, a photopolymerization initiator, and, if necessary, a metal oxide fine particle, a lubricant particle, an antioxidant, or a resin other than the cured resin. Is added to a known solvent to prepare a coating solution for forming a protective layer, and this coating solution for forming a protective layer is applied to the outer peripheral surface of the charge transport layer formed in step (3) to form an uncured film. In this process, the workpiece W is obtained by drying.

(Polymerizable compound)
Although it does not specifically limit as a polymeric compound used in a process (4), For example, a styrene monomer, an acrylic monomer, a methacrylic monomer, a vinyl toluene monomer, a vinyl acetate monomer, an N-vinyl pyrrolidone monomer, etc. Is mentioned. These polymerizable compounds can be used alone or in combination of two or more.

Since the polymerizable compound can be cured with a small amount of light or in a short time, it is composed of a compound having a reactive group of an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (CH ₂ ═CCH ₃ CO—). It is preferable.

  Specific examples of the compound having an acryloyl group or a methacryloyl group as the polymerizable compound include those shown in the following exemplified compounds (1) to (44). Moreover, the number of groups shown below is the number of acryloyl groups or methacryloyl groups.

  In the exemplary compounds (1) to (44), R is an acryloyl group, and R ′ is a methacryloyl group.

The polymerizable compound is more preferably composed of a compound having two or more acryloyl groups or methacryloyl groups, and particularly preferably composed of a compound having three or more acryloyl groups or methacryloyl groups.
Moreover, although a polymeric compound can be used in combination of 2 or more types, also in this case, it is preferable to use 50 mass% or more of compounds which have 3 or more of acryloyl groups or methacryloyl groups.

(Photopolymerization initiator)
Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (“Irgacure 369” manufactured by BASF Japan Ltd.), 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) Acetophenone or ketal photoinitiators such as oximes; benzoin, benzoin methyl ether Benzoin ether photopolymerization initiators such as benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether; benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyl Benzophenone photopolymerization initiators such as phenyl ether, acrylated benzophenone, 1,4-benzoylbenzene; 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Examples thereof include thioxanthone photopolymerization initiators such as dichlorothioxanthone.

  Examples of other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, and bis (2,4,6-trimethylbenzoyl). Phenylphosphine oxide (“Irgacure 819” manufactured by BASF Japan Ltd.), bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10-phenanthrene, acridine Compounds, triazine compounds, imidazole compounds and the like. In addition, a photopolymerization accelerator having a photopolymerization promoting effect can be used alone or in combination with the photopolymerization initiator. Examples of the photopolymerization accelerator include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, and 4,4′-dimethylaminobenzophenone. Etc.

  As the photopolymerization initiator used in the present invention, an alkylphenone compound or a phosphine oxide compound is preferably used, and more preferably an α-hydroxyacetophenone structure or an acylphosphine oxide structure.

  It is preferable that the addition amount of a photoinitiator is 0.1-30 mass parts with respect to 100 mass parts of polymeric compounds, More preferably, it is 0.5-10 mass parts.

(Metal oxide fine particles)
The coating liquid for forming the protective layer preferably contains metal oxide fine particles for the purpose of imparting high durability to the formed protective layer.
Such metal oxide fine particles may be metal oxide particles including transition metals. For example, silica (silicon oxide), magnesium oxide, zinc oxide, lead oxide, alumina (aluminum oxide), tin oxide, oxide Metal oxides such as tantalum, indium oxide, bismuth oxide, yttrium oxide, cobalt oxide, copper oxide, manganese oxide, selenium oxide, iron oxide, zirconium oxide, germanium oxide, tin oxide, titanium dioxide, niobium oxide, molybdenum oxide, vanadium oxide Among these, fine particles of alumina (Al ₂ O ₃ ), tin oxide (SnO ₂ ), and titanium dioxide (TiO ₂ ) are preferable, and alumina and tin oxide are more preferable.

The number average primary particle size of the metal oxide fine particles is preferably in the range of 1 to 300 nm, more preferably 3 to 100 nm.
In the present invention, the number average primary particle size of the metal oxide fine particles is measured as follows.
That is, a 10000 times magnified photograph was taken with a scanning electron microscope “JSM-7500F” (manufactured by JEOL Ltd.), and a photographic image (excluding aggregated particles) obtained by randomly capturing 300 metal oxide fine particles with a scanner. Calculation is performed using an automatic image processing analysis apparatus “LUZEX AP” (software version Ver. 1.32, manufactured by Nireco).

  The means for dispersing the metal oxide fine particles is not particularly limited, and examples thereof include a disperser such as an ultrasonic disperser, a ball mill, a sand grinder, and a homomixer.

The content of the metal oxide fine particles is preferably 20 to 400 parts by mass, more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the polymerizable compound.
When the content of the metal oxide fine particles is too small, the electrical resistance of the protective layer to be formed becomes low, and it may not be possible to prevent an increase in residual potential and occurrence of fog. On the other hand, when the content of the metal oxide fine particles is excessive, there is a possibility that good film formability cannot be obtained in the formed protective layer, and it is impossible to prevent deterioration of charging performance or occurrence of pinholes. is there.

The metal oxide fine particles are preferably those that have been surface-treated with a surface treatment agent having a reactive group (hereinafter also referred to as “reactive group-containing surface treatment agent”). Alumina fine particles or tin oxide fine particles surface-treated with a treating agent are preferred.
Such a reactive group-containing surface treatment agent may be any one having reactivity with a hydroxyl group or the like present on the surface of the metal oxide fine particles, and specifically, one having an acryloyl group or a methacryloyl group is preferable.
When the metal oxide fine particles are surface-treated with the reactive group-containing surface treatment agent, the bond with the polymerizable compound becomes strong, and the formed protective layer has higher durability.

  Specific examples of the reactive group-containing surface treatment agent include those shown in the following exemplary compounds (S-1) to (S-36).

_{S-1: CH 2 = CHSi} (CH 3) (OCH 3) 2
_{S-2: CH 2 = CHSi} (OCH 3) 3
S-3: CH ₂ = CHSiCl _{3
S-4: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) (OCH 3) 2
_{S-5: CH 2 = CHCOO} (CH 2) 2 Si (OCH 3) 3
_{S-6: CH 2 = CHCOO} (CH 2) 2 Si (OC 2 H 5) (OCH 3) 2
_{S-7: CH 2 = CHCOO} (CH 2) 3 Si (OCH 3) 3
_{S-8: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) Cl 2
_{S-9: CH 2 = CHCOO} (CH 2) 2 SiCl 3
_{S-10: CH 2 = CHCOO} (CH 2) 3 Si (CH 3) Cl 2
S-11: CH ₂ = CHCOO (CH ₂ ) ₃ SiCl _{3
S-12: CH 2 = C} (CH 3) COO (CH 2) 2 Si (CH 3) (OCH 3) 2
_{S-13: CH 2 = C} (CH 3) COO (CH 2) 2 Si (OCH 3) 3
_{S-14: CH 2 = C} (CH 3) COO (CH 2) 2 Si (CH 3) (OCH 3) 2
_{S-15: CH 2 = C} (CH 3) COO (CH 2) 2 Si (OCH 3) 3
_{S-16: CH 2 = C} (CH 3) COO (CH 2) 2 Si (CH 3) Cl 2
_{S-17: CH 2 = C} (CH 3) COO (CH 2) 2 SiCl 3
_{S-18: CH 2 = C} (CH 3) COO (CH 2) 3 Si (CH 3) Cl 2
_{S-19: CH 2 = C} (CH 3) COO (CH 2) 3 SiCl 3
_{S-20: CH 2 = CHSi} (C 2 H 5) (OCH 3) 2
_{S-21: CH 2 = C} (CH 3) Si (OCH 3) 3
_{S-22: CH 2 = C} (CH 3) Si (OC 2 H 5) 3
_{S-23: CH 2 = CHSi} (OCH 3) 3
_{S-24: CH 2 = C} (CH 3) Si (CH 3) (OCH 3) 2
_{S-25: CH 2 = CHSi} (CH 3) Cl 2
_{S-26: CH 2 = CHCOOSi} (OCH 3) 3
_{S-27: CH 2 = CHCOOSi} (OC 2 H 5) 3
_{S-28: CH 2 = C} (CH 3) COOSi (OCH 3) 3
_{S-29: CH 2 = C} (CH 3) COOSi (OC 2 H 5) 3
_{S-30: CH 2 = C} (CH 3) COO (CH 2) 3 Si (OC 2 H 5) 3
_{S-31: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) 2 (OCH 3)
_{S-32: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) (OCOCH 3) 2
_{S-33: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) (ONHCH 3) 2
_{S-34: CH 2 = CHCOO} (CH 2) 2 Si (CH 3) (OC 6 H 5) 2
_{S-35: CH 2 = CHCOO} (CH 2) 2 Si (C 10 H 21) (OCH 3) 2
_{S-36: CH 2 = CHCOO} (CH 2) 2 Si (CH 2 C 6 H 5) (OCH 3) 2

Moreover, as a surface treating agent, the silane compound which has a reactive group in which radical polymerization reaction is possible other than what is shown to the said exemplary compound (S-1)-(S-36) can be used.
These silane compounds can be used alone or in combination of two or more.

  The surface treatment method using a reactive group-containing surface treatment agent for metal oxide fine particles is not particularly limited, and wet treatment or dry treatment can be adopted, but treatment using a wet media dispersion type apparatus is preferable. .

Hereinafter, a surface treatment method using a wet media dispersion type apparatus will be specifically described.
That is, by subjecting a slurry (suspension of solid particles) containing metal oxide fine particles and a reactive group-containing surface treatment agent to wet pulverization, the metal oxide fine particles are refined and the surface treatment of the metal oxide fine particles is performed. Progresses. After that, the surface-treated metal oxide fine particles are obtained by removing the solvent and pulverizing.

  In the surface treatment method as described above, the addition amount of the reactive group-containing surface treatment agent is 0.1 to 100 parts by mass with respect to 100 parts by mass of the metal oxide fine particles, and the addition amount of the solvent is the metal oxide fine particles. It is preferable that it is 50-5000 mass parts with respect to 100 mass parts.

Wet media dispersion type device is a device that crushes and disperses the aggregated particles of metal oxide by filling beads in the container as media and rotating the stirring disk mounted perpendicular to the rotation axis at high speed. The structure is not particularly limited as long as the metal oxide fine particles can be sufficiently dispersed and subjected to the surface treatment when the surface treatment is performed on the metal oxide fine particles. For example, vertical and horizontal types, Various modes such as a continuous type and a batch type can be adopted. Specifically, a sand mill, an ultra visco mill, a pearl mill, a glen mill, a dyno mill, an agitator mill, a dynamic mill, or the like can be used.
In these dispersion-type apparatuses, pulverization and dispersion are performed by impact crushing, friction, shearing, shear stress, and the like using a pulverizing medium (media) such as balls and beads.

  Examples of the beads used in the wet media dispersion type apparatus include pulverization media made of glass, alumina, zircon, zirconia, steel, flint stone, etc., and those made of zirconia or zircon are particularly preferable. The size of the beads is usually about 1 to 2 mm in diameter, but in the present invention, about 0.1 to 1.0 mm is preferable.

  For example, stainless steel, nylon, and ceramic materials are used for the stirring disk and the inner wall of the container used in the wet media dispersion type apparatus, but ceramic materials such as zirconia or silicon carbide are particularly preferable.

  By the surface treatment with the reactive group-containing surface treatment agent as described above, metal oxide fine particles having a reactive group capable of reacting with a reactive acryloyl group and a reactive methacryloyl group can be obtained.

The protective layer constituting the organophotoreceptor of the present invention can also be constituted by using a known resin together with a cured resin.
Examples of known resins include polyester resins, polycarbonate resins, polyurethane resins, acrylic resins, epoxy resins, silicone resins, alkyd resins, and the like.

(Lubricant particles)
Examples of the lubricant particles include fluorine atom-containing resin particles. Examples of the fluorine atom-containing resin particles include tetrafluoroethylene resin, trifluorinated ethylene chloride resin, hexafluoroethylene chloride propylene resin, vinyl fluoride resin, vinylidene fluoride resin, ethylene difluoride dichloride resin, and these It is preferable to select one or two or more of these copolymer particles as appropriate, but tetrafluoroethylene resin particles and vinylidene fluoride resin particles are particularly preferable.

The number average primary particle size of the lubricant particles is preferably 0.01 to 1 μm, more preferably 0.05 to 0.5 μm.
In the present invention, the number average primary particle size of the lubricant particles is measured as follows.
In other words, a 10000x magnified photograph was taken with a scanning electron microscope "JSM-7500F" (manufactured by JEOL Ltd.), and a photographic image (excluding aggregated particles) obtained by randomly capturing 300 lubricant particles with a scanner was automatically displayed. Calculation is performed using a processing analysis apparatus “LUZEX AP” (software version Ver. 1.32, manufactured by Nireco).

  The molecular weight of the resin constituting the lubricant particles can be appropriately selected and is not particularly limited.

  The content of the lubricant particles is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass in the protective layer forming coating solution.

(solvent)
Examples of the solvent used in the step (4-1) include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, sec-butanol, benzyl alcohol, toluene, xylene, methylene chloride, and methyl ethyl ketone. , Methyl isopropyl ketone, cyclohexane, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1-dioxane, 1,3-dioxolane, pyridine, diethylamine, and the like, but are not limited thereto.

The liquid viscosity of the protective layer-forming coating solution is preferably 5 to 50 mP · s, more preferably 10 to 25 mP · s.
When the viscosity of the coating liquid for forming the protective layer is too small, coating unevenness occurs, and there is a possibility that a protective layer having a desired layer thickness and a uniform layer thickness cannot be formed. . On the other hand, when the liquid viscosity of the coating liquid for forming the protective layer is excessive, good fluidity cannot be obtained in the coating liquid for forming the protective layer, causing liquid breakage on the coated surface and forming a uniform uncured film. There is a possibility that it cannot be formed.
The liquid viscosity of the coating liquid for forming the protective layer is measured using “E-type viscometer VISCONIC ELD type” (manufactured by Tokyo Keiki Co., Ltd.).

  In the uncured film forming step (4-1), as a coating method of the coating liquid for forming the protective layer, for example, a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a blade coating method, a beam coating method, Well-known methods, such as a slide hopper method, are mentioned. Among these, the application method by the slide hopper method is preferable.

  Hereinafter, a method of applying by a slide hopper method using a circular slide hopper applicator will be specifically described.

FIG. 3 is a cross-sectional view for explaining an example of the configuration of a circular slide hopper coating apparatus used in the uncured film forming step (4-1) in the method for producing an organic photoreceptor of the present invention. FIG. 3 is a perspective sectional view of the circular slide hopper applicator shown in FIG.
This circular slide hopper coating apparatus includes a cylindrical base material 251, an annular coating head 260 provided so as to surround the periphery thereof, and a storage tank 254 that stores the coating liquid L.

  The substrate 251 here is a substrate for forming a protective layer to which a coating solution for forming a protective layer is to be applied. For example, the substrate 251 has a state in which an intermediate layer and an organic photosensitive layer are formed on a conductive support. Thus, the protective layer is not formed.

The coating head 260 has a narrow coating liquid distribution slit 262 having a coating liquid outlet 261 that opens to the base 251 side along the entire direction of the annular coating head 260 along the direction perpendicular to the longitudinal direction of the base 251. Is formed over. The coating liquid distribution slit 262 communicates with the annular coating liquid distribution chamber 263, and the coating liquid distribution chamber 263 is supplied with the coating liquid L in the storage tank 254 through the supply pipe 264 by the pumping pump 255. Is formed.
On the lower side of the coating liquid outlet 261 of the coating liquid distribution slit 262, there is formed a slide surface 265 that is continuously inclined downward and is formed with a dimension slightly larger than the outer dimension of the substrate 251. Furthermore, a lip portion (bead; liquid reservoir portion) 266 extending downward from the end of the slide surface 265 is formed.

  In such a circular slide hopper coating apparatus, when the coating liquid L is pushed out from the coating liquid distribution slit 262 and allowed to flow down along the slide surface 265 in the process of moving the base 251 in the direction of the arrow, the slide surface 265 ends. The arrived coating liquid L forms a bead between the end of the slide surface 265 and the outer peripheral surface of the substrate 251, and is then applied to the surface of the substrate 251 to form an uncured film F. L is discharged from the discharge port 267.

  In such a coating method using a circular slide hopper coating apparatus, the slide surface end and the base material are arranged with a certain gap (about 2 μm to 2 mm), so that the base material is not damaged and the layers have different properties. Even in the case of forming a multilayer, it can be applied without damaging the already applied layer. Furthermore, when multiple layers with different properties and dissolved in the same solvent are formed, the time in the solvent is much shorter than in the dip coating method. Since it can be applied without elution, for example, it can be applied without deteriorating the dispersibility of the metal oxide fine particles.

Thus, the solvent is removed by drying the uncured film formed by applying the coating liquid for forming the protective layer.
The uncured film may be dried before and after the light irradiation step (4-2) and in the middle thereof, and can be appropriately selected by combining these. After the primary drying to the extent that the fluidity is lost, the light irradiation step (4-2) is performed, and then the secondary drying is performed in order to make the amount of the volatile substance in the protective layer a prescribed amount. preferable.
The method for drying the uncured film can be appropriately selected depending on the type of solvent, the thickness of the protective layer to be formed, and the like. The drying temperature is preferably, for example, room temperature to 180 ° C., more preferably 80 to 140 ° C. The drying time is preferably, for example, 1 to 200 minutes, and more preferably 5 to 100 minutes.

[Step (4-2): Light irradiation step]
In this step (4-2), the uncured film of the workpiece W is irradiated with light using the above-described light irradiation device, and the polymerizable compound in the uncured film is polymerized by irradiation with light such as ultraviolet rays. And forming a protective layer by curing.

  Specifically, as shown in FIG. 5, first, a work W in which an uncured film is formed on an organic photosensitive layer on a cylindrical conductive support is placed in a machine frame 30 in a work transport path space S. From above, the upper end surface of the workpiece W is lowered to a state where it is located at the level position at the center of the gas discharge port 25 (see FIG. 5A). Next, while discharging nitrogen gas from the gas discharge port 25 and irradiating light from the light exit window 15, the workpiece is transported upward at a constant lifting speed in the work transport path space S (see FIG. 5B). Furthermore, the lifting of the workpiece W is stopped in the workpiece conveyance path space S after the lower end surface of the workpiece W passes through the uppermost end of the light exit window 15 (see FIG. 5C), and a protective layer is formed. An organic photoreceptor is obtained.

The outer diameter of the workpiece W is, for example, 25 to 35 mm.
The distance between the workpiece W and the light exit window 15 is preferably 1 to 10 mm, for example.
Moreover, it is preferable that the distance of the workpiece | work W and the gas discharge port 25 shall be 1-5 mm, for example.
Moreover, the pulling speed of the workpiece | work W can be 1-30 mm / sec, for example.

The flow rate of the nitrogen gas may be any flow rate at which nitrogen gas is supplied in an amount around the site where the light of the uncured film is irradiated with an oxygen gas concentration of 500 ppm or less. Although it varies depending on the size of the cross-sectional area 21, for example, it is preferably set to 0.5 to 5 L / min.
When the flow rate of the nitrogen gas is in the above range, the oxygen gas concentration around the portion irradiated with the light of the uncured film can be reliably suppressed. On the other hand, when the flow rate of the nitrogen gas is too small, the oxygen gas concentration around the portion of the uncured film irradiated with light cannot be reliably suppressed, and unevenness of curing occurs in the formed protective layer. There is a fear. In addition, if the flow rate of nitrogen gas is too high, the air flow is disturbed and surrounding oxygen is involved, so it becomes difficult to control the periphery of the portion of the uncured film irradiated with light to a desired oxygen concentration. There is a risk of causing uneven curing.

Irradiation conditions of light according to the curing of the uncured film may vary depending on the type of lamp used for the light source 11, a light irradiation amount is normally 100~5000mJ / cm ^2, is preferably a 500~3000mJ / cm ² The
Further, the irradiation time for obtaining the necessary light irradiation amount is preferably 0.1 second to 10 minutes, and more preferably 0.1 second to 5 minutes from the viewpoint of work efficiency.

  The thickness of the protective layer formed by the light irradiation step (4-2) is preferably 0.2 to 10 μm, more preferably 0.5 to 5 μm.

  According to the organic photoreceptor manufacturing method of the present invention, the gas discharge port 25 for discharging nitrogen gas is provided at a level position below the light emission window 15 from which light related to curing of the uncured film is emitted. Since the uncured film is cured by using a light irradiation device in which nitrogen gas discharged from the gas discharge port 25 flows upward, the uncured film is sufficiently cured, and thus a protective layer having high durability. Can be formed.

[Image forming apparatus]
The organic photoreceptor obtained by the production method of the present invention can be used in various known electrophotographic image forming apparatuses such as a monochrome image forming apparatus and a full color image forming apparatus.
An image forming apparatus using an organic photoreceptor obtained by the production method of the present invention includes, for example, a charging means for applying a uniform charging potential on the organic photoreceptor, and an organic photoreceptor having a uniform charging potential. An exposure unit that forms an electrostatic latent image; a developing unit that develops the electrostatic latent image with toner to develop it into a toner image; a transfer unit that transfers the toner image onto a transfer material; and a toner on the transfer material The image forming apparatus includes a fixing unit that fixes an image and a cleaning unit that removes toner remaining on the organic photoreceptor.

  As mentioned above, although embodiment of this invention was described concretely, embodiment of this invention is not limited to said example, A various change can be added.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

[Work preparation example 1]
(1) Production of conductive support The surface of a drum-shaped aluminum support (outer diameter: 30 mm, length: 360 mm) is cut to have a surface roughness Rz = 1.5 (μm) [1] Was made.

(2) Intermediate layer forming step Using a sand mill with the following raw materials as a disperser, dispersion was performed for 10 hours by a batch method to prepare an intermediate layer forming coating solution [1].
-Binder resin: Polyamide resin "X1010" (manufactured by Daicel Degussa) 1 part by mass-Solvent: 20 parts by mass of ethanol-Metal oxide fine particles: Titanium oxide fine particles "SMT500SAS" (manufactured by Teika) with a number average primary particle size of 0.035 µm 1.1 parts by mass On the conductive support [1], the intermediate layer-forming coating solution [1] is applied by a dip coating method to form a coating film, and the coating film is formed at 110 ° C. for 20 minutes. Dried to form an intermediate layer [1] having a layer thickness of 2 μm.

(3) Organic photosensitive layer forming step (charge generating layer forming step)
Dispersion for 10 hours was performed using a sand mill with the following raw materials as a disperser to prepare a coating solution [1] for forming a charge generation layer.
Charge generating material: titanyl phthalocyanine pigment (having a maximum diffraction peak at a position of 5 at least 27.3 ° by Cu-Kα characteristic X-ray diffraction spectrum measurement) 20 parts by mass Binder resin: polyvinyl butyral resin “# 6000-C (Electric Chemical Industry Co., Ltd.)
10 parts by mass / solvent: 700 parts by mass of t-butyl acetate / solvent: 300 parts by mass of 4-methoxy-4-methyl-2-pentanone On the intermediate layer [1], this coating solution for forming a charge generation layer [1] ] Was applied by a dip coating method to form a coating film, and a charge generation layer [1] having a layer thickness of 0.3 μm was formed.

(Charge transport layer forming step)
The following raw materials were mixed and dissolved to prepare a charge transport layer forming coating solution [1].
Charge transport material: 150 parts by mass of the compound represented by the following formula (A) Binder resin: Polycarbonate resin “Z300” (Mitsubishi Gas Chemical Co., Ltd.)
300 parts by mass / solvent: toluene / tetrahydrofuran = 1/9 vol% 2000 parts by mass / antioxidant: “Irganox 1010” (manufactured by Ciba Geigy Japan) 6 parts by mass / leveling agent: silicone oil “KF-54” (Shin-Etsu Chemical) 1 part by mass On the charge generation layer [1], the charge transport layer forming coating solution [1] is applied by dip coating to form a coating film, which is dried at 120 ° C. for 70 minutes. Then, a charge transport layer [1] having a layer thickness of 20 μm was formed.

(4-1) Uncured film forming step The following polymerizable compound, solvent and metal oxide fine particles were dispersed for 10 hours under light shielding using a sand mill as a disperser, and then the following photopolymerization initiator was added, and light shielding was performed. The mixture was stirred and dissolved by stirring to prepare a coating solution [1] for forming a protective layer.
Polymerizable compound: Exemplified compound (42) 100 parts by mass Solvent: sec-butanol 400 parts by mass Solvent: methyl isopropyl ketone 100 parts by mass Metal oxide fine particles: Surface treatment agent shown in Exemplified compound (S-15) Surface-treated number average primary particle diameter of 20 nm tin oxide fine particles 100 parts by mass / photopolymerization initiator: “Irgacure 819” (manufactured by BASF Japan) 10 parts by mass The protective layer-forming coating solution [1] is charged with the above charge. On the transport layer [1], an uncured film was formed by coating using a circular slide hopper coating apparatus and dried at room temperature for 20 minutes. This is designated as an organic photoreceptor work [1].

<Example 1>
A protective layer [1] is formed by irradiating the above-mentioned organophotoreceptor work [1] with light using the light irradiation apparatus shown in FIG. Thus, an organic photoreceptor [1] was obtained. The dimensions of the light irradiation device and the workpiece and the manufacturing conditions are shown below.
・ Inner diameter of lower machine casing: 40 mm
・ Outer diameter of lower machine casing: 100mm
・ Inner diameter of partition wall: 46mm
・ Vertical length of the lower machine casing: 870 mm
-Vertical length of the upper machine casing: 8mm
・ Vertical size of gas outlet: 3mm
・ Vertical size of light exit window: 7mm
・ Distance between gas discharge port and lowest end of machine frame (L ₁ ): 855 mm
・ Distance between gas discharge port and uppermost end of machine frame (L ₂ ): 12 mm
・ Cross sectional area of gas rising channel: 7.82 cm ²
・ Inner diameter of triangular prism: 40mm
-Number of optical fibers constituting the light guide member: 4000-Optical fiber diameter: 0.2 mm
・ Light source: Xenon lamp, 4kW
Intensity (near light exit window, wavelength 365 nm): 4000 mW / cm ²
Light irradiation intensity (work surface): 1800 mW / cm ²
・ Light irradiation time: 18 seconds ・ Nitrogen gas flow rate (constant): 4 L / min
-Work lifting speed: 20mm / sec
-Workpiece outer diameter: 30mm
(・ Distance between workpiece and light exit window: 5mm)
(・ Distance between workpiece and gas outlet: 5mm)

<Comparative Example 1>
An organic photoreceptor work [2] was produced in the same manner as in Workpiece Production Example 1.
An organic photoreceptor [2] was obtained in the same manner as in Example 1 except that this organic photoreceptor work [2] was used to irradiate light while moving from above the work conveyance path space downward.

  The organic photoreceptors [1] and [2] obtained as described above are converted into a full-color image forming apparatus “bizhub PRO C6500” (manufactured by Konica Minolta Business Technologies, Inc .; exposure, reversal development, and intermediate transfer member of 780 nm semiconductor laser). The following evaluations 1 to 4 were performed. The results are shown in Table 1.

[Evaluation 1: Surface contamination of organic photoreceptor]
Visual observation of the surface condition of the organic photoreceptor before and after the printing test in which 500,000 sheets of A4 images with 2.5% YMCBk color printing rate are printed on neutral paper of A4 size under the conditions of temperature 30 ° C and humidity 80% RH And the state of the wound was evaluated according to the following evaluation criteria. It is assumed that the evaluated organic photoreceptor is installed in the cyan position.
-Evaluation criteria-
A: No surface damage after printing 500,000 sheets (good)
B: 1 to 5 surface scratches after printing 500,000 sheets (no practical problem)
C: 6 or more surface scratches after printing 500,000 sheets (practical problem)

[Evaluation 2: Cleaning property (CL property)]
Under a 10 ° C., 15% RH environment, the spring load was changed with a deteriorated blade having an edge worn by 10 μm, and the cleaning limit load of the solid image was evaluated as follows. The rank indicates a cleaning limit load (g / cm (per blade longitudinal direction)).

Less than 5: 9 4: 9 or more, less than 13 3:13 or more, less than 17 2:17 or more, less than 21 1:21 or more Rank 3 or more is practical.

[Evaluation 3: Image blur]
Immediately after the printing endurance test to print 500,000 A4 images of 2.5% YMCBk color printing on neutral paper of A4 size under the condition of temperature 30 ° C and humidity 80% RH, the main power source of the image forming apparatus is immediately turned on. Chopped. Immediately after the main power supply was turned off and the main power supply was turned on and printing was possible, a halftone image (relative reflection density of 0.4 with a Macbeth densitometer) and a 6-dot grid image on the entire surface of neutral paper of A3 size immediately. And printed. The state of the printed image was visually observed and evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: No blurring occurs in both halftone image and grid image (good)
B: A thin strip-like density decrease in the longitudinal direction of the photoreceptor is observed only in the halftone image (no problem in practical use)
C: Lattice image loss or line width narrowing due to image blurring (practical problem)

[Evaluation 4: Image memory]
A monochrome halftone image (average relative reflection density of 0.4 with a Macbeth densitometer) was copied on the entire surface of A3 neutral paper under the conditions of a temperature of 10 ° C. and a humidity of 20% RH. A total of 8 points at a distance of 180 mm from the corner and 33 mm from the end in the vertical direction are a1, a2,... A8, respectively, and a total of 8 points at a position of 195 mm in the horizontal direction from the corner and 33 mm from the vertical end. Are similarly b1, b2,..., B8, and the reflection density at each point was measured with a Macbeth densitometer. The difference between the measured values of a1 and b1, the difference between the measured values of a2 and b2, and the difference in the measured values of eight combinations in total were calculated and evaluated according to the following evaluation criteria. In addition, it is thought that generation | occurrence | production of an image memory is suppressed, so that the maximum value of the difference of a measured value is small.
-Evaluation criteria-
A: Maximum difference in measured values is less than 0.01 (good)
○: The maximum difference between measured values is 0.01 or more and less than 0.02 (no problem in practical use)
Δ: The maximum difference between the measured values is 0.02 or more and less than 0.04 (practical use)
×: The maximum difference in measured values is 0.04 or more (there is a problem in practical use)

DESCRIPTION OF SYMBOLS 11 Light source 12 Light guide member 13 Accommodating space 13A Light inlet 13B Insertion hole 15 Light exit window 16 Triangular prism 19 Fixing member 21 Gas rising flow path 23 Gas introduction flow path member 25 Gas discharge port 28 Gas introduction port 30 Machine frame 31 Lower part Machine frame 32 Upper machine frame S Work conveyance path space W Work 251 Base material 254 Storage tank 255 Pressure feed pump 260 Application head 261 Application liquid outlet 262 Application liquid distribution slit 263 Application liquid distribution chamber 264 Supply pipe 265 Slide surface 266 Sliding surface 266 267 Discharge port L Coating liquid F Uncured film

Claims (9)

In the production process of an electrophotographic organic photoreceptor in which an organic photosensitive layer and a protective layer made of a cured resin are laminated in this order on a cylindrical conductive support, on the organic photosensitive layer on the cylindrical conductive support A light irradiation device used to form a protective layer made of a cured resin by irradiating light to an uncured film formed in
In a state of surrounding the periphery of the work conveyance path space, the work in which an uncured film is formed on the organic photosensitive layer on the cylindrical conductive support in a columnar shape extending in the vertical direction is conveyed upward. A light exit window that emits light radially inward is provided,
A gas discharge port for discharging nitrogen gas radially inward is provided in a state surrounding the work transport path space.
The light irradiation apparatus, wherein the gas discharge port is provided at a level position lower than the level position where the light exit window is provided, and nitrogen gas discharged from the gas discharge port flows upward.   The light irradiation apparatus according to claim 1, further comprising a gas ascending channel extending in a vertical direction, wherein an upper portion of the gas ascending channel communicates with the gas discharge port. The light exit window and the gas outlet are commonly provided in a substantially cylindrical machine frame that surrounds the periphery of the work transport path space,
The light irradiation apparatus according to claim 2, wherein a distance between the gas discharge port in the machine frame and the lowermost end of the machine frame is longer than a distance between the gas discharge port and the uppermost end of the machine frame.   The light irradiation device according to claim 1, wherein the gas discharge port is an annular slit.   The light irradiation apparatus according to claim 1, wherein a plurality of the gas discharge ports are provided, and the gas discharge ports are arranged at equal intervals in the circumferential direction. A light source, a light guide member composed of a plurality of optical fibers, and a ring-shaped triangular prism;
Each of the optical fibers is disposed so as to guide light from the light source to one surface of the triangular prism, and a light exit window is configured by a surface orthogonal to the one surface of the triangular prism. The light irradiation apparatus in any one of Claims 1-5.   The light irradiation apparatus according to claim 6, wherein the light source is a xenon lamp, and the optical fiber is made of quartz glass. A method for producing an electrophotographic organic photoreceptor using the light irradiation device according to claim 1,
While discharging nitrogen gas from the gas outlet and emitting light from the light exit window,
A workpiece in which an uncured film is formed on an organic photosensitive layer on a cylindrical conductive support,
A method for producing an electrophotographic organic photoreceptor, comprising conveying upward in a work conveyance path space. The method for producing an electrophotographic organic photoreceptor according to claim 8, wherein the uncured film contains metal oxide fine particles.