JPH1190312A - Sensitive material liquid application and sensitive material liquid applying device as well as production of dissolved oxygen decreasing sensitive material liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the formation of a peroxide and the change in the properties of a sensitive material liquid arising therefrom and to prevent the change in characteristics at the time of forming a photosensitive film for an electrophotographic photoreceptor by decreasing the dissolved oxygen in the sensitive material liquid, then applying the sensitive material liquid on a base material for the electrophotographic photoreceptor. SOLUTION: A dissolved oxygen decreasing vessel 2b functions as a dissolved oxygen decreasing means for decreasing the dissolved oxygen in the sensitive material liquid by bringing gas having a decreased oxygen component from a satd. gas forming vessel 9 into contact with the sensitive material liquid. A sensitive material liquid discharge port 22 is formed at the bottom of a dissolved oxygen decreasing sensitive material liquid holding vessel 2c. This sensitive material liquid discharge port 22 is connected via a pump 4, piping 5 and a valve 6 to the sensitive material liquid introducing port 11 of a sensitive material liquid applying mechanism 1. This mechanism is so constituted that the sensitive material liquid from the dissolved oxygen decreasing sensitive material liquid holding vessel 2c is supplied to the immersion vessel 10 of the sensitive material liquid applying mechanism 1. The sensitive material liquid applying mechanism 1 functions as the sensitive material liquid applying means for applying the sensitive material liquid decreased in the dissolved oxygen supplied from the dissolved oxygen decreasing vessel 2b as the dissolved oxygen decreasing means on a substrate 8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for applying a sensitizer solution to a substrate for an electrophotographic photoreceptor, and a method for producing a sensitizer solution with reduced dissolved oxygen. .

[0002]

2. Description of the Related Art Conventionally, as a method of applying a sensitizer solution (for example, a sensitizer solution for a charge generation layer or a sensitizer solution for a charge transport layer) to a substrate (substrate) for an electrophotographic photosensitive member, dip coating, Blade coating, ring coating, nozzle coating, curtain coating and the like are known. In each of these coating methods, not only the case where the remaining sensitizing solution after performing the coating operation is circulated and used, but also the case where almost the entire amount is coated on the substrate without circulating the remaining sensitizing solution. However, unless the temperature is intentionally changed, the sensitizer solution is in a state close to air saturation, so that oxygen is usually dissolved in the sensitizer solution.

[0003]

However, when the solvent constituting the sensitizer solution is unstable, the solvent is oxidized by oxygen dissolved in the sensitizer solution to form a peroxide. There is. Therefore, an antioxidant is usually added to the sensitizer solution in order to prevent the generation of peroxide, but the sensitizer solution repeatedly comes into contact with air, and the dissolved oxygen amount in the sensitizer solution is saturated or the When the state is close to the above, and the state is prolonged, all the antioxidant is consumed. Therefore, there is a problem that the peroxide is generated by dissolved oxygen in the sensitizer solution thereafter.

[0004] When the temperature is intentionally lowered in order to reduce the peroxide generation rate, oxygen in the air is also easily dissolved. There is a problem that peroxide is generated by oxygen dissolved in the sensitizer solution. Here, the action of the peroxide is not known in detail, but, for example, in the case of the charge-generating layer sensitizing solution in which the peroxide is generated during long-term storage, compared to the sensitizing solution which has just been prepared. As a result, an increase in the viscosity of the sensitizer solution, agglomeration of the pigment component, and a decrease in the characteristics when the electrophotographic photosensitive film is formed are observed.

Generally, a peroxide having a stronger oxidizing action is more unstable, and reacts with a substance accepting oxygen in a sensitizer solution, and the peroxide itself is decomposed into an acid and other substances. Accordingly, although the peroxide concentration in the sensitizer solution is reduced, the damage to the sensitizer solution is large at this time. On the other hand, a peroxide having a weak oxidizing action is stable, hardly reacts with a substance that accepts oxygen in a sensitizer solution, and has little decomposition of the peroxide itself. Then, if the generation of peroxide continues due to the reaction between the solvent constituting the sensitizer solution and the dissolved oxygen, the peroxide concentration in the sensitizer solution may increase. However, at this time, the damage to the sensitizer solution is small.

As described above, the damage received by the sensitizer solution is as follows.
It is determined by the quality of the peroxide produced, and the higher the peroxide concentration, the greater the damage of the sensitizer solution. The same can be said for the amount of dissolved oxygen. That is, when the solvent constituting the sensitizer solution is unstable, the oxidation rate is high, and the amount of dissolved oxygen in the sensitizer solution decreases. When the rate of dissolution of oxygen in the air into the solvent is not so high, the dissolved oxygen amount does not increase so much, so that the dissolved oxygen amount in the sensitizer solution decreases. However, as a result of the oxidation reaction due to the dissolved oxygen, peroxide is generated as described above, and thus the damage to the sensitizer solution may be increased.

On the other hand, when the solvent constituting the sensitizer solution is stable, the amount of dissolved oxygen in the sensitizer solution hardly decreases due to a low oxidation rate, and as a result, the oxygen exhibits a solubility close to saturation. Will be. Therefore, peroxide is hardly generated, and the damage to the sensitizer solution is small. That is, it cannot be generally said that the greater the amount of dissolved oxygen or the concentration of generated peroxide in the sensitizer solution, the greater the damage to the sensitizer solution.

[0008] However, the total amount of peroxide produced and the total amount of substances oxidized by decomposition of the peroxide are closely related to the amount of oxygen dissolved in the sensitizer solution. That is, it is considered that the smaller the amount of oxygen dissolved in the sensitizer solution, the smaller the total amount of peroxide produced and the smaller the total amount of the substance oxidized by decomposition of the peroxide. The present invention has been made in view of the above-described problems, and reduces the amount of oxygen dissolved in a sensitizer solution to prevent generation of a peroxide and deterioration of the sensitizer solution due to the peroxide. The present invention aims to provide a method and an apparatus for applying a sensitizer liquid in which a change in characteristics when a photosensitive film for an electrophotographic photoreceptor is formed is provided. The aim is to provide a method.

[0009]

Therefore, in the method of applying a sensitizer solution of the present invention, when a sensitizer solution is applied to a substrate for an electrophotographic photosensitive member, first, a gas having a low oxygen partial pressure is applied to the sensitizer solution. The dissolved oxygen in the sensitizer solution is reduced by contact with the sensitizer solution, and then the sensitizer solution in which the dissolved oxygen is reduced in this manner is applied to the electrophotographic photoreceptor substrate. It is a feature (claim 1).

At this time, the gas used for reducing the dissolved oxygen in the sensitizer solution may include a vapor of a solvent used for preparing the sensitizer solution (claim 2). Further, the sensitizer solution coating apparatus of the present invention includes a solvent containing a vapor used in preparing a sensitizer solution for an electrophotographic photoreceptor, and bringing a gas having a low oxygen partial pressure into contact with the sensitizer solution. Dissolved oxygen reducing means for reducing the dissolved oxygen in the sensitizer solution,
And a sensitizer solution application unit for applying the sensitizer solution supplied from the dissolved oxygen reduction unit with the dissolved oxygen reduced to the electrophotographic photoreceptor substrate. Item 3).

Further, the method for producing a dissolved oxygen-reducing sensitizer solution of the present invention comprises contacting a gas having a low oxygen partial pressure with a sensitizer solution for an electrophotographic photoreceptor to thereby reduce the dissolved oxygen-reduced sensitizer solution. It is characterized by being manufactured (claim 4). Also at this time, the gas used for reducing the dissolved oxygen in the sensitizer solution may include the vapor of the solvent used for preparing the sensitizer solution (claim 5).

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to the drawings, but are not limited to the following description without departing from the gist of the invention. (A) Description of First Embodiment FIG. 1 is a schematic diagram showing the configuration of a sensitizer application device according to a first embodiment of the present invention. The sensitizer application device 15 shown in FIG. It is used for applying a sensitizer solution (for example, a sensitizer solution for a charge generation layer or a sensitizer solution for a charge transport layer) to a photoconductor substrate (electrophotographic photoconductor substrate) 8.

The sensitizer application device 15 according to the first embodiment of the present invention employs a dip coating method, and as shown in FIG. 1, a sensitizer application mechanism 1, a sensitizer reservoir, 2 and a saturated gas generation tank 9. Here, the sensitizer liquid application mechanism 1 is a part for actually applying the sensitizer liquid to the base 8, and is a dipping tank 10 for holding the sensitizer liquid and a sensitizer liquid for receiving the sensitizer liquid overflowing from the immersion tank 10. It is constituted by a receiving gutter 12.

A sensitizing solution inlet 11 is formed at the bottom of the immersion tank 10, and a sensitizing solution outlet 13 is formed at the bottom of the sensitizing solution receiving trough 12. And the sensitizer liquid outlet 13
Is connected to the sensitizer liquid storage tank 2 by a pipe 3. The sensitizing solution storage tank 2 is a part for holding the sensitizing solution overflowing from the sensitizing solution applying mechanism 1 and reducing dissolved oxygen in the sensitizing solution.
Dissolved oxygen reduction tank 2b and dissolved oxygen reduction sensitizer liquid holding tank 2c
It is composed of

Reference numerals 21a and 21b denote partition walls for separating the respective tanks.
As shown in FIG. 1, a filter 21c is attached, and each partition is configured to be separated by the partition 21b and the filter 21c. Note that the filter 21c allows the sensitizer liquid from the dissolved oxygen reducing tank 2b to pass therethrough, while preventing the transmission of bubbles in the sensitizer liquid.

Here, the concentration equalizing tank 2a holds the sensitizer liquid flowing through the sensitizer liquid outlet 13 of the sensitizer liquid application mechanism 1 via the pipe 3, and stirs the inside of the tank with a stirrer 7. By doing so, it is a site where the concentration of the sensitizer solution is made uniform. Further, the dissolved oxygen reducing tank 2b is a part that holds the sensitizer solution overflowing from the concentration equalizing tank 2a and blows gas from the saturated gas generation tank 9 to reduce dissolved oxygen in the sensitizer solution. .

That is, the dissolved oxygen reducing tank 2b functions as a dissolved oxygen reducing means for reducing dissolved oxygen in the sensitizer solution by bringing the gas having a low oxygen component from the saturated gas generating tank 9 into contact with the sensitizer solution. Is what you do. The principle of reducing dissolved oxygen will be described later in detail. Further, the dissolved oxygen reducing sensitizer liquid holding tank 2c is provided with a filter 2 for filtering the sensitizer liquid after the treatment in the dissolved oxygen reducing tank 2b.
When it flows in through 1c, it is the part that holds it.

At the bottom of the dissolved oxygen reducing sensitizer liquid holding tank 2c, a sensitizer liquid outlet 22 is formed.
Is connected to a sensitizer liquid inlet 11 of the sensitizer liquid application mechanism 1 via a pump 4, a pipe 5, and a valve 6. Then, the sensitizer liquid from the dissolved oxygen-reducing sensitizer liquid holding tank 2 c is supplied to the immersion tank 10 of the sensitizer liquid application mechanism 1.

Therefore, the above-described sensitizer solution application mechanism 1 applies the sensitizer solution to the substrate 8 by applying the sensitizer solution with reduced dissolved oxygen supplied from the dissolved oxygen reducing tank 2b as the dissolved oxygen reducing means. It functions as a means. By the way, the saturated gas generation tank 9 saturates the gas having a low oxygen partial pressure with the vapor of the solvent A used when preparing the sensitizer liquid, thereby dissolving dissolved oxygen in the sensitizer liquid storage tank 2 as described above. This is to generate a gas used for reduction.

Here, the saturated gas generation tank 9 holds a solvent A, which is a solvent used for preparing the sensitizer solution and is a component of the sensitizer solution, and a pipe 27 is provided in the solvent A. Is inserted. Further, a perforated nozzle 26 is fixed to the tip of the pipe 27, and the gas from the pipe 27 is dispersed by the perforated nozzle 26 and blown into the solvent A.

Here, a gas having a low oxygen partial pressure, that is, a gas containing almost no oxygen as a component, is blown from the pipe 27. As the gas having a low oxygen partial pressure, for example, an inert gas such as nitrogen gas, carbon dioxide gas, or argon can be used. In the first embodiment, the case where nitrogen gas is used as the gas having a low oxygen partial pressure is used. explain.
The nitrogen gas is adjusted in pressure and sent out from a tank (not shown) to the pipe 27.

After the gas blown from the pipe 27 is saturated with the vapor of the solvent A, the saturated gas generation tank 9
It is configured to be discharged through a pipe 24 connected to the upper part of the container. Further, this pipe 24 is inserted into the dissolved oxygen reducing tank 2b of the sensitizer liquid storage tank 2, and
A multi-hole nozzle 23 is fixed to the tip of the nozzle. Then, the gas from the pipe 24 is dispersed by the multi-hole nozzle 23 and is blown into the sensitizer liquid.

When the sensitizer application device 15 is actually used, the sensitizer is injected into the immersion tank 10 of the sensitizer application mechanism 1 until immediately before the overflow. After the sensitizer liquid is injected into the concentration equalizing tank 2a of the sensitizer liquid storage tank 2 to fill the tank, the sensitizer liquid is further injected to overflow, and the sensitizer liquid is injected into the dissolved oxygen reducing tank 2b. I do. Then, the sensitizer liquid injected into the dissolved oxygen reduction tank 2b flows out from the bottom of the dissolved oxygen reduction tank 2b through the filter 21c so that about half of the sensitizer liquid is stored in the dissolved oxygen reduction sensitizer liquid holding tank 2c. .

Further, a solvent A, which is a constituent of the sensitizer solution, is charged into the saturated gas generating tank 9 by a volume of 5% of the saturated gas generating tank 9.
Add about 0 to 70%. With the above-described configuration, in the sensitizer liquid application device 15 according to the first embodiment of the present invention, when the sensitizer liquid is applied to the substrate 8, first, in the dissolved oxygen reducing tank 2 b of the sensitizer liquid storage tank 2. By bringing the gas from the saturated gas generation tank 9 into contact with the sensitizer solution, the dissolved oxygen in the sensitizer solution is reduced.

Thereafter, the sensitizer solution in which dissolved oxygen has been reduced in this way (dissolved oxygen-reduced sensitizer solution) is applied to the sensitizer solution application mechanism
The immersion tank 10 is used to apply the substrate 8 using the dissolved oxygen reducing sensitizer solution. The operation of the sensitizer liquid application device 15 at this time will be described in more detail. First, when the pump 4 is operated, the sensitizer solution in which the dissolved oxygen is reduced in the dissolved oxygen-reduced sensitizer solution holding tank 2c is injected into the immersion tank 10 of the sensitizer solution application mechanism 1 through the pipe 5 and the valve 6. Is done.

In the immersion tank 10, the sensitizer liquid discharged from the pump 4 overflows the sensitizer liquid in the immersion tank 10, and the overflowed sensitizer liquid passes through the pipe 3 to the sensitizer liquid storage tank 2. It flows into the concentration equalizing tank 2a. Further, in the concentration uniformizing tank 2a, the flowing sensitizer liquid causes
The sensitizer solution in the concentration uniformization tank 2a overflows, and the overflowed sensitizer solution flows into the dissolved oxygen reduction tank 2b, and the dissolved oxygen is reduced as follows.

First, in the saturated gas generating tank 9, when nitrogen gas whose pressure is adjusted is blown from the pipe 27, the nitrogen gas is dispersed into small bubbles by the multi-hole nozzle 26 and then blown into the solvent A. Then, the nitrogen gas dispersed in the multi-hole nozzle 26 is saturated with the vapor of the solvent A, and the nitrogen gas saturated with the solvent (that is, the nitrogen gas containing the vapor of the solvent A) is supplied through the pipe 24 to the photosensitive liquid storage tank. 2 to the dissolved oxygen reduction tank 2b.

Further, in the dissolved oxygen reducing tank 2b, the piping 2
The nitrogen gas saturated with the solvent from No. 4 is dispersed into small bubbles by the multi-aperture nozzle 23 and then blown into the sensitizer liquid in the dissolved oxygen reducing tank 2b. When the nitrogen gas is blown into the sensitizer liquid, the blown nitrogen gas exchanges gas with gas components dissolved in the sensitizer solution, and substantially dissolves with the nitrogen gas containing less oxygen component. After reaching equilibrium, it is discharged from the dissolved oxygen reduction tank 2b.

That is, when nitrogen gas having a low oxygen partial pressure comes into contact with the sensitizer solution, dissolved oxygen in the sensitizer solution is released into the nitrogen gas due to dissolution equilibrium, so that the amount of dissolved oxygen in the sensitizer solution is reduced. Reduced. At this time, since the nitrogen gas is solvent-saturated, the solvent component in the sensitizer solution is not released into the nitrogen gas, and the concentration of the sensitizer solution does not change. The gas discharged from the dissolved oxygen reduction tank 2b (nitrogen gas containing dissolved oxygen released from the sensitizer liquid) is collected by an exhaust gas collector outside the sensitizer liquid storage tank 2 and subjected to exhaust gas treatment. The exhaust gas is exhausted through the tower (both the exhaust gas collector and the exhaust gas treatment tower are not shown).

The sensitizer solution deoxygenated in the dissolved oxygen reducing tank 2b flows into the dissolved oxygen reducing sensitizer liquid holding tank 2c through the filter 21c. Then, by repeating the above-described operation, the deoxygenated sensitizer liquid in the dissolved oxygen-reducing sensitizer liquid holding tank 2c circulates in the sensitizer liquid coating device 15.
Under such circumstances, in the sensitizer liquid application mechanism 1, the base 8 is pulled up after being immersed in the immersion tank 10,
Dip coating is performed.

Here, when dip coating the substrate 8 or when the sensitizer solution overflows from the immersion tank 10 or the like, oxygen in the air dissolves because the sensitizer solution comes into contact with air.
Since the deoxygenation rate in the dissolved oxygen reduction tank 2b is higher than the dissolution rate of oxygen in the air, it is necessary to lower the dissolved oxygen concentration in the sensitizer solution used when performing application by the sensitizer solution application mechanism 1. it can.

As described above, according to the sensitizer solution applying apparatus 15 according to the first embodiment of the present invention, the gas having a low oxygen partial pressure is brought into contact with the sensitizer solution to reduce the dissolved oxygen in the sensitizer solution. Thereby, generation of peroxide and deterioration of the sensitizer solution due to the peroxide can be prevented, and further, change in characteristics when a photosensitive film for an electrophotographic photosensitive member is formed can be prevented.

Further, since the gas used for reducing the dissolved oxygen in the sensitizer solution contains the vapor of the solvent used for preparing the sensitizer solution, the change in the concentration of the sensitizer solution can be reduced. Can be prevented. (B) Description of the Second Embodiment FIG. 2 is a schematic diagram showing the configuration of a sensitizer solution application device according to a second embodiment of the present invention. The sensitizer solution application device 30 shown in FIG. It is used for applying a sensitizer liquid (for example, a sensitizer liquid for a charge generation layer or a sensitizer liquid for a charge transport layer) to a photoconductor substrate (electrophotographic photoconductor substrate) 31.

The sensitizing solution application device 30 according to the second embodiment of the present invention employs a blade applying method. As shown in FIG. 2, a sensitizing solution application mechanism 46, a sensitizing solution storage tank, and the like. 50 and a saturated gas generation tank 58. The sensitizer liquid application mechanism 46 is a part that actually applies the sensitizer liquid to the base 31, and includes a drive mechanism 46 a that horizontally supports and rotates the base 31 and a drive mechanism 46 a that moves in the axial direction of the base 31 to rotate the base 31. Sensitive liquid supply mechanism 46 for supplying a sensitizing liquid to the surface
b.

Here, the drive mechanism 46a is horizontally arranged via a pair of support plates 32 with bearings vertically arranged on the left and right at predetermined intervals, and bearings provided on the upper portions of the respective support plates 32. A rotation shaft 33, a timing pulley 34 fixed to one of the rotation shafts 33, a pulley drive motor 35, and a timing belt 36 for transmitting the rotation of the pulley drive motor 35 to the pulley 34.

The base 31 is provided with flanges 37 at both ends. In addition, a fitting hole for fitting and fixing the rotating shaft 33 is provided at the center of the flange 37, and the flange 37 is mounted so that the fitting hole matches the axis of the base 31. The base 31 is arranged between the two rotating shafts 33, the rotating shafts 33 are fitted and fixed in the central holes of the flanges 37, and are configured to rotate by driving the pulley driving motor 35. I have.

The sensitizing solution supply mechanism 46b is provided with a pair of support plates 3 vertically arranged at right and left sides at a predetermined interval.
8, two guide rods 39 disposed between the pair of support plates 38, a ball screw 40 disposed between the pair of support plates 38 and between the guide rods 39, one end of which protrudes from the support plate 38, a support plate 38 of the ball screw 40 A pulley 41 fixed to the end protruding from the pulley, a pulley driving motor 42, a timing belt 43 for transmitting the rotation of the pulley driving motor 42 to the pulley 41, and a moving body 44 disposed between the pair of support plates 38. It is configured.

The moving body 44 is disposed between the pair of support plates 38 through a fitting hole for the guide rod 39 and a ball screw bearing provided in the center of the fitting hole for fitting the ball screw 40. And a nozzle 48 for discharging the sensitizing liquid supplied from the sensitizing liquid storage tank 50. The nozzle 48 is fixed to a header 49.

Further, a blade (not shown) functioning as a smoothing member is provided at the end of the nozzle 48 on the contact side with the base 31, and the photosensitive liquid discharged from the nozzle 48 is uniformly distributed by the blade. Thus, it is configured to have a uniform film thickness. By the way, the sensitizer liquid storage tank 50 is a part that holds the sensitizer liquid and reduces the dissolved oxygen in the sensitizer liquid, and includes a dissolved oxygen reduction tank 50b and a dissolved oxygen reduction sensitizer liquid holding tank 50c. Have been. In addition,
Reference numeral 52 indicates a lid member.

Here, reference numeral 51a denotes a partition separating the tanks, and a filter 51b is attached below the partition 51a as shown in FIG.
1b is configured to separate each tank. In addition,
The filter 51b allows the sensitizer solution from the dissolved oxygen reducing tank 50b to pass therethrough, while preventing the transmission of bubbles in the sensitizer solution.

The dissolved oxygen reducing tank 50b is a part for holding the sensitizing solution and blowing the gas from the saturated gas generating tank 58 to reduce the dissolved oxygen in the sensitizing solution. That is, the dissolved oxygen reduction tank 50b is configured to bring the gas from the saturated gas generation tank 58 into contact with the sensitizer liquid,
It functions as a dissolved oxygen reducing means for reducing dissolved oxygen in the sensitizer solution.

Further, the dissolved oxygen reducing sensitizer liquid holding tank 50c
Is a portion that holds the sensitizer liquid after the treatment in the dissolved oxygen reduction tank 50b flows through the filter 51b. The dissolved oxygen reducing sensitizer liquid holding tank 50c
Is formed at the bottom portion of the pump, and the liquid outlet 50d is connected to the pump 47 via a pipe 53.

Then, the dissolved oxygen reducing sensitizer liquid holding tank 50c
Is supplied to a sensitizing liquid supply mechanism 46b of a sensitizing liquid application mechanism 46 through a pump 47 and a pipe 45. Therefore, the sensitizer liquid application mechanism 46
The sensitizer liquid with reduced dissolved oxygen supplied from the dissolved oxygen reduction tank 50b as the dissolved oxygen reduction means is used for the substrate 31.
It functions as means for applying a sensitizer liquid to the surface.

The pump 47 is stopped as soon as the nozzle 48 reaches the end.
A valve that turns on and off in synchronization with the header 49 may be provided near the header 49. In addition, the saturated gas generation tank 58 saturates a gas having a low oxygen partial pressure with the vapor of the solvent A used when preparing the sensitizer liquid, thereby dissolving dissolved oxygen in the sensitizer liquid storage tank 50 as described above. It generates gas to be used for reduction, and has the same configuration as the saturated gas generation tank 9 in the first embodiment.

That is, the saturated gas generation tank 58 holds a solvent A which is a component of the sensitizer solution, and a pipe 57 is inserted into the solvent A. A perforated nozzle 56 is fixed to the end of the pipe 57, and a gas having a low oxygen partial pressure blown from the pipe 57 (the case where nitrogen gas is used also in the second embodiment will be described). It is configured to be dispersed at 56 and blown into the solvent A.

After the gas blown from the pipe 57 is saturated with the vapor of the solvent A, the saturated gas generation tank 5
It is configured to be discharged through a pipe 55 connected to the upper part of the pipe 8. Further, the pipe 55 is inserted into the dissolved oxygen reducing tank 50b of the sensitizer liquid storage tank 50, and a perforated nozzle 54 is fixed to the tip of the pipe 55.
Then, the gas from the pipe 55 is dispersed by the multi-hole nozzle 54 and is blown into the sensitizer liquid.

With the above-described configuration, in the sensitizer liquid application apparatus 30 according to the second embodiment of the present invention, when applying the sensitizer liquid to the substrate 31, first, the dissolved oxygen reducing tank of the sensitizer liquid storage tank 50 is used. At 50b, the gas from the saturated gas generation tank 58 is brought into contact with the sensitizer solution, whereby the dissolved oxygen in the sensitizer solution is reduced. Thereafter, the sensitizer solution in which the dissolved oxygen has been reduced in this manner (dissolved oxygen-reducing sensitizer solution) is supplied to the sensitizer solution supply mechanism 46b of the sensitizer solution application mechanism 46, and the sensitizer solution application mechanism 46 performs this process. Substrate 31 using dissolved oxygen reducing sensitizer solution
Is applied.

The operation of the sensitizer liquid application device 30 at this time will be described in more detail. First, the saturated gas generation tank 58
Then, when the pressure adjusted nitrogen gas is blown from the pipe 57, the nitrogen gas is blown into the solvent A after being dispersed into small bubbles by the multi-hole nozzle 56. And
The nitrogen gas dispersed in the multi-hole nozzle 56 is saturated with the vapor of the solvent A, and the nitrogen gas saturated with the solvent (that is, the nitrogen gas containing the vapor of the solvent A) flows through the pipe 55 into the storage tank 50 for the sensitizer liquid. It is sent to the dissolved oxygen reduction tank 50b.

Further, in the dissolved oxygen reducing tank 50b, the solvent-saturated nitrogen gas from the pipe 55 is dispersed into small bubbles by the multi-aperture nozzle 54, and then dispersed in the dissolved oxygen reducing tank 50b.
It is blown into the sensitizer solution inside. When the solvent-saturated nitrogen gas is blown into the sensitizer solution, as described in detail in the first embodiment, the dissolved oxygen in the sensitizer solution is released into the nitrogen gas due to the dissolution equilibrium. The amount of dissolved oxygen in the liquid is reduced.

Further, the sensitizer liquid deoxygenated in the dissolved oxygen reducing tank 50b flows into the dissolved oxygen reducing sensitizer liquid holding tank 50c through the filter 51b, and then is applied to the sensitizer liquid applying mechanism 46.
Is supplied to the photosensitive solution supply mechanism 46b. In the sensitizing liquid application mechanism 46, the supplied sensitizing liquid is discharged from the opening of the nozzle 48 of the sensitizing liquid supply mechanism 46b onto the surface of the base 31, and is made uniform by a blade (not shown) to form a uniform film. The blade is applied by being separated from the blade after it becomes thick.

The base 31 is rotated for a while after being applied, and is naturally dried (air-dried).
Removed from Here, also in the sensitizer liquid application apparatus 30 according to the second embodiment, since the dissolved oxygen in the sensitizer liquid is reduced in the dissolved oxygen reduction tank 50b of the sensitizer liquid storage tank 50, the sensitizer liquid application is performed. The concentration of dissolved oxygen in the sensitizer solution used when applying by the mechanism 46 can be reduced.

As described above, according to the sensitizer liquid application apparatus 30 according to the second embodiment of the present invention, the gas having a low oxygen partial pressure is brought into contact with the sensitizer liquid to reduce the dissolved oxygen in the sensitizer liquid. Further, generation of peroxide and deterioration of the sensitizer solution due to the peroxide can be prevented, so that a change in characteristics when a photosensitive film for an electrophotographic photosensitive member is formed can be prevented. Further, the gas used for reducing the dissolved oxygen in the sensitizer solution contains the vapor of the solvent used for preparing the sensitizer solution, thereby preventing a change in the concentration of the sensitizer solution. it can.

(C) Description of the Third Embodiment FIG. 3 is a schematic view showing the configuration of a device for producing a dissolved oxygen-reducing sensitizer solution according to a third embodiment of the present invention. Is a sensitizer liquid in which dissolved oxygen is reduced by bringing a gas having a low oxygen partial pressure into contact with a sensitizer liquid for an electrophotographic photoreceptor (for example, a sensitizer liquid for a charge generation layer or a sensitizer liquid for a charge transport layer). It is provided with a sensitizer liquid storage tank 60 and a saturated gas generation tank 64.

Here, the sensitizing solution storage tank 60 holds the sensitizing solution, and for example, a petroleum can for storing the sensitizing solution is used. Further, the sensate liquid storage tank 60 is configured such that gas from the saturated gas generation tank 64 is blown therein, and the dissolved oxygen in the sensitizer liquid is reduced in the sensitizer liquid storage tank 60.

Further, the saturated gas generation tank 64 saturates a gas having a low oxygen partial pressure with the vapor of the solvent A used for preparing the sensitizer liquid, so that the dissolved oxygen is reduced in the sensitizer liquid storage tank 60. To generate a gas to be used for reduction.
It has the same configuration as the saturated gas generation tank 9 in the first embodiment. That is, the saturated gas generation tank 64 holds the solvent A, which is a component of the sensitizer solution, and the pipe 66 is inserted into the solvent A.

At the tip of the pipe 66, a multi-hole nozzle 6 is provided.
5 is fixed, and the gas with a low oxygen partial pressure blown from the pipe 66 (the case where nitrogen gas is used in the third embodiment will also be described) is dispersed by the multi-hole nozzle 65 and blown into the solvent A. It is configured to be. The gas blown from the pipe 66 is configured to be saturated with the vapor of the solvent A and then discharged through the pipe 62 connected to the upper part of the saturated gas generation tank 64.

Further, the piping 62 is connected to the photosensitive solution storage tank 6.
0, and a multi-hole nozzle 61 is fixed to the tip of the pipe 62. The gas from the pipe 62 is dispersed by the multi-hole nozzle 61 and is blown into the sensitizer liquid. The multi-hole nozzle 61 has such a shape that it can be taken out from the opening of the sensitizer liquid storage tank 60.

Here, the pipe 62 and the multi-hole nozzle 61 are
As shown in FIG. 3, it is formed integrally with the fixing lid member 63 so as to be easily inserted / removed into / from the photosensitive solution storage tank 60. After the dissolved oxygen amount of the sensitizer solution in the sensitizer solution storage tank 60 has been reduced (that is, after the production of the dissolved oxygen-reduced sensitizer solution has been completed), the fixing lid member is removed from the sensitizer solution storage tank 60. 63 is removed, the inner lid having a gas barrier property and the outer lid for fixing the inner lid having air permeability are fitted, and the sensitizer solution is stored in a state where the dissolved oxygen content is low. I have.

Here, the inner lid having gas barrier properties is as follows:
It has the same shape as a normal inner lid, but has polyethylene (PE), polypropylene (PP),
A sheet having a thickness of about 50 μm formed by laminating a film of polytetrafluoroethylene (PTFE) or the like and a film of polyethylene terephthalate (PET) having a gas barrier property, nylon, polyvinylidene fluoride, etc., is formed of a resin, metal or the like. It is manufactured by laminating on the surface of a plate member of the above, and subjecting the plate member to a heating and punching process.

With the above configuration, in the apparatus for producing a dissolved oxygen-reducing sensitizer solution 70 according to the third embodiment of the present invention, the gas having a low oxygen partial pressure from the saturated gas generation tank 64 is
By contacting with the sensitizer solution in the sensitizer solution storage tank 60,
A sensitizer solution with reduced dissolved oxygen is produced. That is, when the nitrogen gas whose pressure has been adjusted is blown from the pipe 66, the nitrogen gas in the saturated gas generation tank 64 is
After being dispersed into small bubbles at 5, it is blown into the solvent A.

Then, the nitrogen gas dispersed in the multi-hole nozzle 65 is saturated with the vapor of the solvent A, and the nitrogen gas saturated with the solvent (that is, the nitrogen gas containing the vapor of the solvent A) is supplied through the pipe 62 to the photosensitive agent. The liquid is sent to the liquid storage tank 60. Furthermore, in the sensitizer liquid storage tank 60, the nitrogen gas from the pipe 62 is dispersed into small bubbles by the multi-hole nozzle 61,
It is blown into the sensitizer liquid in the sensitizer liquid storage tank 60.

Then, when the solvent-saturated nitrogen gas is blown into the sensitizer solution, the dissolved oxygen in the sensitizer solution is released into the nitrogen gas due to the dissolution equilibrium as described in detail in the first embodiment. In addition, the amount of dissolved oxygen in the sensitizer solution is reduced, and as a result, a sensitizer solution with reduced dissolved oxygen is produced. Thus, according to the apparatus for producing a dissolved oxygen-reducing sensitizer liquid 70 according to the third embodiment of the present invention, a gas having a low oxygen partial pressure is brought into contact with the sensitizer liquid to reduce the dissolved oxygen in the sensitizer liquid. This can prevent generation of peroxides and deterioration of the sensitizer solution due to the peroxides, and prevent changes in characteristics when a photosensitive film for an electrophotographic photosensitive member is formed.

Further, since the gas used for reducing the dissolved oxygen in the sensitizer solution contains the vapor of the solvent used for preparing the sensitizer solution, the change in the concentration of the sensitizer solution can be reduced. Can be prevented.

[0064]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. (D) Example 1 In Example 1, a case will be described in which the apparatus for producing a dissolved oxygen-reducing sensitizer solution shown in FIG. 3 is used. (1) Preparation of Sensitizer Solution for Electrophotographic Photoreceptor First, dimethoxyethane (D) was added to 10 parts by weight of oxytitanium phthalocyanine represented by the following general formula (A).
ME) (200 parts by weight) and pulverized and dispersed in a sand grind mill for 10 hours.

[0065]

Embedded image

(Wherein, X represents a halogen atom, and n represents a number from 0 to 1) and 5 parts by weight of polyvinyl butyral [Denka Butyral # -6000C manufactured by Denki Kagaku Kogyo KK] It was mixed with a 10% dimethoxyethane solution to prepare a sensitizer solution for an electrophotographic photosensitive member (dispersion liquid for an electrophotographic photosensitive member charge generation layer). The viscosity of the solution immediately after the preparation was 2.0 cp, and no aggregation of the pigment components was observed. (2) Treatment for Reducing Dissolved Oxygen in Sensitizer Solution for Electrophotographic Photoreceptor As the saturated gas generation tank 64 shown in FIG.
Using a 300 mm high stainless steel cylinder with a lid, 1.5 liters of dimethoxyethane (a solvent that is a component of the sensitizer solution) is charged into the cylinder, and a pipe 66 with a porous nozzle 65 is inserted into the solution. Inserted.

Here, the multi-hole nozzle 65 has an inner diameter of 5 mmφ.
(Φ means diameter, the same shall apply hereinafter), a stainless pipe with an outer diameter of 10 mmφ is bent to form a ring with an outer diameter of 90 mmφ, and a small hole of 1 mmφ on the upper curved surface of the ring is about 15 mm.
It is constituted by providing about 20 at intervals. Also,
As the pipe 66, a stainless steel pipe having the same size as the multi-hole nozzle 65 was used, and the multi-hole nozzle 65 and the pipe 66 were fixed by welding.

On the other hand, the perforated nozzle 61 inserted into the photosensitive solution storage tank 60 closes one end of a stainless steel pipe having an inner diameter of 5 mmφ and an outer diameter of 10 mmφ, and has a horizontal portion having a length of about 20 mm.
It is formed by making a round so as to have a radius of 0 mm and providing about 20 small holes of 1 mmφ at an interval of about 10 mm in the upper curved surface portion of the horizontal portion. As the pipe 62, the gas discharge pipe of the cylinder with a stainless steel lid is used to connect the porous nozzle 61 and the pipe 62, and the coupled pipe 62 and the porous nozzle 61 are connected to the fixing lid member 6
3 (see FIG. 3).

Further, an 18 liter petroleum can was used as the sensitizer liquid storage tank 60, and 15 liters of the sensitizer liquid prepared in the above (1) was charged into this petroleum can, and the above-mentioned oil was put into the opening of the petroleum can. The integrated fixing lid member 63 was attached. In such a state, nitrogen gas having an oxygen concentration of about 2 ppm is blown into the saturated gas generation tank 64 from the pipe 66 with the multi-hole nozzle 65 at a rate of 30 liter (normal) / minute, so that dimethoxyethane vapor (the composition of the sensitizer liquid) is blown. Nitrogen gas saturated with the vapor of the solvent as a component) was generated, and the nitrogen gas was blown into the sensitizing solution storage tank 60 to perform a process of reducing dissolved oxygen in the sensitizing solution in the sensitizing solution storage tank 60.

The dissolved oxygen reduction process of the sensitizer solution is performed for about 1 hour, and thereafter, the fixing cover member 63 is opened through the opening of the petroleum can.
Was removed, an inner lid having a gas barrier property and an outer lid for fixing the inner lid were fitted, and stored at room temperature for 3 months.
The inner lid having gas barrier properties is a 50 μm-thick sheet obtained by laminating a solvent-resistant film and a gas barrier polyethylene terephthalate (PET) film on a 1 mm-thick polyethylene plate (plate). It was produced by laminating on the surface of a member) and performing a heating and punching treatment.

The sensitizer solution after storage for 3 months was taken out of a petroleum can and the viscosity was measured. The viscosity was almost the same as that of the sensitizer solution immediately after preparation. Further, the dispersion state of the sensitizer solution was observed, but no aggregation of the pigment component was observed as in the case of the sensitizer solution immediately after preparation. (3) Comparative Example 1 The sensitizer liquid prepared in the above (1) was charged into a petroleum can,
Without performing the dissolved oxygen reduction treatment in (2), a normal inner lid having no gas barrier properties and an outer lid for fixing the inner lid were fitted and stored at room temperature for 3 months.

The sensitizer solution after storage for 3 months was taken out of the petroleum can and the viscosity was measured. The viscosity was 3 cp, and the viscosity was higher than that after the treatment for reducing dissolved oxygen. When the dispersion state of the sensitizer solution was observed, it seemed that there was some coagulation as compared with the case where the dissolved oxygen reduction treatment was performed. (E) Example 2 In Example 2, a case will be described in which the sensitizer liquid application device shown in FIG. 1 is used.

The immersion tank 10 shown in FIG.
Using a dip coating bath having a height of 400 mm and a height of 400 mm, a sensitizer solution subjected to a dissolved oxygen reduction treatment (dissolved oxygen reducing sensitizer solution) was injected until the tank became full. In addition, as the said sensitizer liquid,
After performing the dissolved oxygen reduction treatment described in (2) of Example 1 for about 1 hour, the one stored for 15 days was used.

Further, the concentration uniforming tank 2 of the photosensitive solution storage tank 2
a, dissolved oxygen reducing tank 2b, dissolved oxygen reducing sensitizer liquid holding tank 2
c is 4 liters, 2 liters, and 2 liters, respectively, and the sensitizer liquid is stored in the concentration equalizing tank 2a in 4 liters, and in the dissolved oxygen reduction tank 2b and the dissolved oxygen reduction sensitizer liquid holding tank 2c, respectively. 1.2 liters were injected. Further, a pipe 24 with a multi-hole nozzle 23 was inserted into the dissolved oxygen reducing tank 2b. In addition, as the pipe 24 with the multi-hole nozzle 23,
The same pipe as the pipe 66 with the multi-hole nozzle 65 (see FIG. 3) in (2) of Example 1 described above was used.

Further, as the saturated gas generation tank 9, the saturated gas generation tank 64 in FIG.
(See Reference). Then, the sensitizing solution introduced into each tank of the sensitizing solution applying device 15 was circulated at a flow rate of 1.8 liter / min. In such a state, the diameter of the photosensitive solution applying mechanism 1 of the photosensitive solution applying device 15 is 80 m.
The substrate 8 having a height of 360 mm and a height of 360 mm is immersed in the immersion tank 10,
Dip coating was performed by pulling up at a speed of 300 mm / min.

At the same time, nitrogen gas was blown into the saturated gas generation tank 9 from the pipe 27 with the multi-hole nozzle 26,
Nitrogen gas saturated with the solvent vapor was generated, and the nitrogen gas was blown into the dissolved oxygen reduction tank 2b of the sensitizer liquid storage tank 2 to perform a dissolved oxygen reduction treatment of the sensitizer liquid in the dissolved oxygen reduction tank 2b. See (2) of the first embodiment described above).

After performing dip coating of the substrate 8 for 50 pieces,
The sensitizer liquid circulated and used in the sensitizer liquid application device 15 is
It was withdrawn from an unillustrated withdrawal valve into a petroleum can, fitted with an inner lid having a gas barrier property and an outer lid for fixing the inner lid, and stored at room temperature for 1.5 months. The oil can, the inner lid having gas barrier properties, and the outer lid for fixing the inner lid used were the same as those in (2) of Example 1 described above.

The sensitizer solution after storage for 1.5 months was taken out of a petroleum can and the viscosity was measured to be 2.1 cp.
The viscosity was almost the same as that of the sensitizer solution immediately after the preparation. Further, the dispersion state of the sensitizer solution was observed, but no aggregation of the pigment component was observed as in the case of the sensitizer solution immediately after preparation. further,
No defects occurred on the substrate after coating. (1) Comparative Example 2 A difference from Example 2 described above is that when dip coating is performed, nitrogen gas saturated with solvent vapor is dissolved in the dissolved oxygen reduction tank 2b.
The only difference is that the dissolved oxygen reduction treatment of the sensitizer solution in the dissolved oxygen reduction tank 2b was not performed.

After the same coating operation was completed, the film was similarly pulled out from a petroleum can, fitted with an inner lid having a gas barrier property and an outer lid for fixing the inner lid, and stored at room temperature for 1.5 months.
The sensitizer solution after storage for 1.5 months was taken out of the petroleum can and the viscosity was measured. As a result, the viscosity was 2.8 cp, which was higher than that of the solution subjected to the dissolved oxygen reduction treatment. Also,
When the dispersion state of the sensitizer solution was observed, some aggregation of the pigment component was also observed.

[0080]

As described in detail above, according to the first to fifth aspects of the present invention, a gas having a low oxygen partial pressure is brought into contact with a sensitizer solution to reduce dissolved oxygen in the sensitizer solution. By doing
There is an advantage that generation of peroxide and deterioration of the sensitizer solution due to the peroxide can be prevented, and further, a change in characteristics when a photosensitive film for an electrophotographic photosensitive member is formed can be prevented.

According to the second, third, and fifth aspects of the present invention, the gas used for reducing the dissolved oxygen in the sensitizer solution is a vapor of a solvent used for preparing the sensitizer solution. , There is an advantage that a change in the concentration of the sensitizer solution can be prevented.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a configuration of a sensitizer liquid application device according to a first embodiment of the present invention.

FIG. 2 is a schematic diagram illustrating a configuration of a sensitizer liquid application device according to a second embodiment of the present invention.

FIG. 3 is a schematic view illustrating a configuration of a device for producing a dissolved oxygen-reducing sensitizer solution according to a third embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Sensitive liquid application mechanism 2 Sensitive liquid reservoir 2a Concentration equalizing tank 2b Dissolved oxygen reduction tank 2c Dissolved oxygen reduced sensitizer liquid holding tank 3, 5, 24, 27 Piping 4 Pump 6 Valve 7 Stirrer 8 Electrophotography Base for body (substrate for electrophotographic photoreceptor) 9 Saturated gas generation tank 10 Immersion tank 12 Sensitive liquid receiving trough 15 Sensitive liquid applicator 23, 26 Perforated nozzle 30 Sensitive liquid applicator 31 Electrophotographic photoreceptor base (Electrophotographic photoreceptor base material) 45, 53, 55, 57 Piping 46 Sensitive liquid application mechanism 46a Drive mechanism 46b Sensitive liquid supply mechanism 47 Pump 50 Sensitive liquid storage tank 50b Dissolved oxygen reduction tank 50c Dissolved oxygen reduction sensitivity Chemical liquid holding tank 52 Lid members 54, 56 Multi-hole nozzle 58 Saturated gas generation tank 60 Sensitive liquid liquid storage tank 61, 65 Multi-hole nozzle 62, 66 Piping 63 Fixing lid member 64 Saturated gas generation tank 70 Manufacturing equipment

Claims (5)

[Claims] When applying a sensitizer solution to a substrate for an electrophotographic photoreceptor, first, a gas having a low oxygen partial pressure is brought into contact with the sensitizer solution to reduce dissolved oxygen in the sensitizer solution. And thereafter, applying the sensitizer solution in which the dissolved oxygen is reduced in this manner to the electrophotographic photoreceptor substrate,
Sensitizer liquid application method. 2. The method according to claim 1, wherein the gas used for reducing the dissolved oxygen in the sensitizer solution contains a vapor of a solvent used for preparing the sensitizer solution. 2. The method for applying a sensitizer liquid according to 1. 3. A method for preparing a sensitizer solution for an electrophotographic photoreceptor, comprising bringing a gas containing a solvent used in preparing a sensitizer solution and having a low oxygen partial pressure into contact with the sensitizer solution. A dissolved oxygen reducing means for reducing dissolved oxygen; and a sensitizer liquid applying means for applying the sensitized liquid reduced in dissolved oxygen supplied from the dissolved oxygen reducing means to the electrophotographic photosensitive member substrate. A sensitizer liquid application device, characterized in that: 4. A dissolved oxygen-reduced sensitizer solution characterized by producing a sensitizer solution with reduced dissolved oxygen by bringing a gas having a low oxygen partial pressure into contact with a sensitizer solution for an electrophotographic photoreceptor. Manufacturing method. 5. The method according to claim 1, wherein the gas used for reducing the dissolved oxygen in the sensitizer solution contains a vapor of a solvent used for preparing the sensitizer solution. 5. The method for producing a dissolved oxygen-reducing sensitizer liquid according to item 4.