JPH0713467A - Method for recovery from fatigue of electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To improve the electrostatic chargeability of the electrophotographic photoreceptor constituted by providing the surface of a conductive base with a photosensitive layer contg. specific compds., to lower the relative humidify at and under a high temp. and high humidity and to prevent the dew condensation of the photoreceptor at the time of a low temp. by subjecting the electrophotographic photoreceptor to a heat treatment in or out of an image forming device. CONSTITUTION:The electrophotographic photoreceptor constituted by providing the surface of the conductive base with the photosensitive layer contg. the compds. expressed by formulas I to III, etc., is subjected to the heat treatment in or out of the image forming device. In the formula I, Ar denotes a phenylene group or biphenylene group; R<1>, R<2> denote alkyl groups or aryl groups; n denotes an integer from 1 to 4. In the formula II, R1 to R5 denote hydrogen atoms, alkyl groups, alkoxy groups or halogen atoms which may be the same or different. In the formula III, R1, R2 denote alkyl groups or aryl groups; at least either of R1 and R2 denote aryl groups. As a result, the degradation in electrostatic characteristics, etc., after repetitive use of the org. photosensitive body are prevented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming apparatus using an electrophotographic photosensitive member, and more particularly to improvement of a fatigue recovery method for the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Photoreceptors used in electrophotographic copying machines are
In recent years, a material using an organic photosensitive material, which has advantages of low cost, productivity, and no pollution, has begun to be used. For organic electrophotographic photoreceptors, photoconductive resin typified by polyvinylcarbazole (PVK), charge transfer complex type typified by PVK-TNF (2,4,7 trinitrofluorenone), phthalocyanine-binder Representatively known are pigment dispersion type and function-separated type photoreceptors in which a charge generation substance and a charge transport substance are used in combination, and in particular, function-separated type photoreceptors are receiving attention.

When such an organic photoconductor is applied to the Carlson process, the chargeability is low, the charge retention property is poor (dark decay is large), and these properties are largely deteriorated due to repeated use. In addition, there are drawbacks such as density unevenness, fog, and background stain in the case of reversal development.

That is, the chargeability of the organic photoconductor is lowered by pre-exposure fatigue. Since this pre-exposure fatigue is mainly caused by the light absorbed by the charge generation material, the longer the time the charge generated by the light absorption remains in the photoconductor in a movable state, the more the number of the charges increases. It is considered that the deterioration of the charging property due to the pre-exposure fatigue becomes remarkable. That is, even if the charging operation is performed with the electric charge generated by light absorption remaining, the surface charge is neutralized by the movement of the remaining carriers, so that the surface potential increases until the residual charge is consumed. do not do. Therefore, the rise of the surface potential is delayed by the amount of pre-exposure fatigue, and the apparent charging potential becomes low.

As a method for improving these drawbacks, there is known a method in which an inorganic material such as SiO or Al ₂ O ₃ is provided between the support and the charge generation layer by a method such as vapor deposition, sputtering or anodic oxidation. It is also known to contain Al ₂ O ₃ in the charge generation layer (JP-A-55-142354) and also to contain a metal powder in the charge generation layer (JP-A-60-214364). ).

Further, as an undercoat layer, a polyamide resin (JP-A-58-30757, JP-A-58-98739), an alcohol-soluble nylon resin (JP-A-60-196766), a water-soluble polyvinyl butyral Resin layers such as a resin (JP-A-60-232553) and a polyvinyl butyral resin (JP-A-58-106549) have been proposed.

However, chargeability due to repeated use,
Regarding the decrease in charge retention, the means for improving the photoconductor side is:
Sufficient photoreceptor was not obtained. JP-A-51-111338
In the publication, an As ₂ Se ₃ photoreceptor is used, which is 10 to 30% higher than room temperature,
It is disclosed that the rate of fatigue (dark decay) is slowed down when maintained at a temperature not exceeding 0 ° C.

On the other hand, even in the environment of use of the copying machine, image blurring, image distortion, etc. occur under high temperature and high humidity, and there is a problem such as dew condensation on the photoconductor and scumming at low temperatures. .

Regarding this environmental dependence, Japanese Patent Laid-Open No. 61-8433
Japanese Patent Laid-Open No. 62-121482 discloses that the relative humidity of the photoconductor under high temperature and high humidity can be reduced by heating the support of the photosensitive layer as a planar heating element at a relatively low temperature. A method of wiping hot air or cold air onto the photoconductor is disclosed, and a method of preventing dew condensation on the photoconductor at low temperature and a method of preventing deterioration of the photoconductor at high temperature are disclosed, but a method which is not always satisfactory. Was not.

[0010]

SUMMARY OF THE INVENTION The present invention can improve the charging property of a photoconductor, reduce the relative humidity under high temperature and high humidity, and prevent dew condensation on the photoconductor at low temperature. An object is to provide a method for recovering from fatigue of an electrophotographic photosensitive member.

[0011]

According to the present invention, an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer containing a compound represented by the following general formula (I) is provided in an image forming apparatus. Alternatively, there is provided a method for recovering fatigue from an electrophotographic photosensitive member, which is characterized by performing heat treatment outside the image forming apparatus.

[Chemical 1] Further, according to the present invention, on the conductive support, the following general formula
Provided is a method for recovering fatigue from an electrophotographic photosensitive member, which comprises heat-treating an electrophotographic photosensitive member provided with a photosensitive layer containing a compound represented by (II) in an image forming apparatus or outside the image forming apparatus. To be done.

[Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and these may be the same or different.) Further, according to the present invention. For example, on the conductive support, the following general formula
Provided is a method for recovering fatigue from an electrophotographic photosensitive member, which comprises heat-treating an electrophotographic photosensitive member provided with a photosensitive layer containing a compound represented by (III) in an image forming apparatus or outside the image forming apparatus. To be done.

[Chemical 3] Further, according to the present invention, on the conductive support, the following general formula
Provided is a method for recovering fatigue from an electrophotographic photosensitive member, which comprises heat-treating an electrophotographic photosensitive member provided with a photosensitive layer containing a compound represented by (IV) in an image forming apparatus or outside the image forming apparatus. To be done.

[Chemical 4] Further, according to the present invention, on the conductive support, the following general formula
Provided is a method for recovering fatigue from an electrophotographic photosensitive member, which comprises heat-treating an electrophotographic photosensitive member provided with a photosensitive layer containing a compound represented by (V) inside an image forming apparatus or outside the image forming apparatus. To be done.

[Chemical 5]

The inventors of the present invention have conducted studies to eliminate the drawback of deterioration of chargeability with respect to an electrophotographic photosensitive member comprising an electroconductive support and at least an organic photosensitive layer provided thereon. When the layer is made to contain the compound represented by any one of the general formulas (I) to (V) and is heated in the image forming apparatus or outside the image apparatus, the rising of the electrostatic potential is the same as before the repeated use. It has been found that there is no delay and a clear copy image can be obtained even after repeated use.

Generally, although the photosensitive member varies to some extent, image blurring and image distortion occur at high temperature and humidity, dew condensation of the photosensitive member occurs at low temperature, and image background stain occurs at low temperature and low humidity. In addition, when the photosensitive layer has an organic photosensitive layer, when it is repeatedly used, a delay in rising of the charging property is observed.

However, the inventors of the present invention have found that by heating in a dark place, even after repeated use, the same characteristics as in the initial stage are exhibited. Means for achieving such heat treatment in the dark of the photoconductor (hereinafter abbreviated as heat treatment or treatment) will be described below.

A method of heating the photoconductor in the image forming apparatus will be described. Since this method is extremely closely related to the process, it is necessary to describe each shape of the photoconductor. The shape of the photoconductor currently used can be roughly divided into two. One is a belt-shaped photoreceptor,
The other is divided into cylindrical metal, paper, or plastic whose surface is subjected to a conductive treatment and whose surface is coated with a photosensitive layer.

First, a method for heating the belt-shaped photosensitive member will be described. Usually, the drive system and process of the belt photosensitive member are usually shaped as shown in FIG. 5 or FIG.

Although FIG. 5 shows the case where the number of driven rollers is two, there may be one or a plurality of driven rollers in some cases. Also, if the belt is rotated at a high speed to some extent, it may have vibrations in a direction perpendicular to the traveling direction (the thickness direction of the belt). To prevent this, when using a driven roller like 36 in FIG. There is also.

There are three methods for heating the thus set photosensitive member. One is to bring some kind of heat source to the inside of the belt by utilizing the space open in the figure. It is a method of heating from the outside, the second is a method of heating the photoconductor by using a roller (mainly a roller not in contact with the developing roller) as a heating element, and the third is a planar heating element of the belt itself. . Although various methods are conceivable as the first specific method, for example, (a) a method of irradiating the photoreceptor with an infrared lamp. (FIG. 7) (At that time, it is more preferable to include an infrared absorbing agent in the substrate or the photosensitive layer.) (B) Method of applying hot air. (C) Method of high frequency heating. (D) Method using PTC heating element. Etc.

Of these methods, the method using an infrared lamp is shown in FIG. In this method, an infrared lamp is applied to a belt-shaped photoreceptor. According to this method
For example, in a photoconductor for a laser printer or the like, the absorption of the photoconductor extends to the near infrared. Therefore, a cut filter such as 36 in the figure is used to cut light having a wavelength shorter than the infrared.
In addition, a cover such as 37 prevents light from leaking into the entire machine, and in order to improve efficiency, a mirror such as 38 irradiates infrared rays only on the front surface.

Next, a method of heating the photosensitive member by using the roller as a heating element will be described. Although various methods can be considered as a specific method of using this roller as a heating element, for example, the following means can be mentioned. -An infrared lamp (lamp that can emit infrared rays) is built in the roller. -A heat pipe built in the roller.
(Fig. 8) ・ Mechanical seal is attached and hot water is poured inside the roller. -A heating element with PTC characteristics is built in the roller. -The roller is a sheet heating element. -The resistance heater is built in the roller. (Fig. 9) ・ Heating by high frequency induction heating. Of these methods, a method using a heat pipe and a method using a resistance heater are shown in FIGS. 8 and 9, respectively.

Finally, a method of using the sheet heating element for the belt itself will be described. Such methods include the case where the belt support itself is a sheet heating element, the case where the sheet heating element is attached to the inside of the support (or the photosensitive layer side is also possible), or such a coating is applied. The street method is possible. In the former case, the belt support is a metallic sheet heating element, or the sheet heating element can be formed by filling a plastic film with carbon powder or metal fibers when forming the belt. . Regarding the latter, the same effect can be obtained by coating the inner surface or the outer surface of the belt support with, for example, a coating material in which a carbon powder, a metal fiber, a metal filler and the like are dispersed in a resin liquid.

It is also possible to heat the photoconductor without using the external heater as described above, by making a photoconductor using the support thus made and passing an electric current.

Next, a photosensitive member having a photosensitive layer provided on a support (hereinafter collectively referred to as a drum) obtained by subjecting a cylindrical metal, paper, or plastic to a conductive layer treatment (hereinafter referred to as a drum-shaped member). A method of heating the photoconductor will be described. There are various possible methods for heating the drum-shaped photoconductor, but there are two
It can be classified into two. One uses an external heat type heater, and the other uses a heater without a heater, and the drum itself is a heating element. There are various possible concrete methods of the former, for example, a method of incorporating an infrared lamp (a lamp capable of emitting infrared rays) inside the drum or irradiating from the outer surface.・ A method in which a heat pipe is built in the drum and is heated from the inside.・ A mechanical seal is attached to the drum openings (both ends), and a liquid is circulated inside the drum with a circulation device (such as Coolnix) that can control humidity. (Fig. 10) ・ Using a resistance heater built in the drum. -A method of heating with a heating element having PTC characteristics. (Fig. 1
1) ・ Method using high frequency induction heating. Etc.

According to the above method, the injection part and the discharge part at both ends do not rotate, but only the photoconductor, the mechanical seal part and the gear part rotate. Further, if a liquid having a large specific heat such as water is used as the liquid circulating inside, it is possible to uniformly heat the photoconductor even if the heat capacity of the photoconductor is large. Also, if a heating element having the above PTC characteristics is used, the resistance is low at low temperatures, a large amount of current flows, and at high temperatures, the resistance rapidly increases, making it difficult for current to flow, and for a certain set temperature. Therefore, there is an advantage that heating can be performed effectively and safely. The idea that the latter drum is a heating element is the same as the idea that the belt support is a heating element, and is omitted.

The above-described method is a method of heating the photoconductor in the image forming apparatus, and since it is necessary to consider the influence on the photoconductor other than the photoconductor at the time of heating. Also, it is very effective to use the photoconductor cooling device together as a means for preventing overheat, and of course, it can be used.

Next, the photoreceptor is heated outside the image forming apparatus,
Describe how to recover from fatigue. When heat-treating the photoconductor outside the image forming apparatus, the minimum required requirements are:
There are the following two points. It has a heating device. It is possible to heat the photoconductor while shielding it from light. That is, if the entire room can be kept in a light-shielded state by using, for example, a commercially available dryer or oven, it is possible to recover the fatigue of the photoconductor. However, in general, the following problems remain when such a setting is made. Unless you consider a good drum set, the surface of the photoconductor will be scratched. Uniform heating is difficult. There are no such heaters in general offices.

Therefore, a device for exclusive use in fatigue recovery of the photoconductor, which is compact and lightweight and does not have the above-mentioned drawbacks, is required. One example is shown in FIGS. 12 (a), 12 (b) and 12 (c). 12 (a) is a sketch, FIG. 12 (b) is a view with the door removed, and FIG. 12 (C) is a cross-sectional view from the side (these are collectively referred to as FIG.
Call). In FIG. 12, a planar heating element is used as the heat source, but if the method can uniformly apply heat to the photoconductor,
Anything can be used. Further, as the drum receiving jig, a double-cutting drum jig (up to two kinds of thickness is possible in the figure) is shown in FIG. 12, but the jig needs to be changed each time depending on the shape of the drum.

Next, the temperature, conditions, etc. of the method for heating the photosensitive member described above will be described. Up to now, the method for recovering from heat fatigue of the photoconductor has been described, but there are two methods for heating in the image forming apparatus. One is to constantly give a constant temperature during the time when the image forming apparatus is used, and the other is to use it by raising it to a certain temperature and then lowering it to a certain temperature (usually in a room). Is the way.

In the former case, the temperature (4
This is a method of suppressing the fatigue while keeping the temperature of the photoconductor at 0 to 80 ° C. and recovering the fatigue while using it. Therefore, in order to control the temperature of the photoconductor to a certain temperature, heating is started, and after reaching a certain temperature, a small amount of heat energy is continuously applied. There is also an intermittent method in which the heat energy supply is stopped when the temperature reaches, and the heat energy is supplied again when the temperature drops to a certain temperature (or after a certain time elapses).

Next, the latter will be described. this is,
This is not a method of constantly heating the photoreceptor, but a method of raising fatigue for a short time if necessary to recover from fatigue. For example, when the power of the image forming apparatus is turned on, it takes time to heat the fixing unit (so-called first copy time), and at the same time, a method of heating the photosensitive member or a surface potential immediately after charging is set. This is a method of heating when a detection device is installed and the voltage drops below a certain threshold potential. Furthermore, there is a method in which the material is heated during so-called preheating, that is, during the time when image formation is not performed, and the temperature is lowered before use.

Regarding the heat treatment temperature, in the former case (that is, the method of constantly providing temperature), if the temperature is too high, the stress on the surface of the photoconductor becomes large, so the lower limit is preferably 40 ° C. or higher, and more preferably 50. The temperature is not lower than 0 ° C and the upper limit is preferably not higher than 100 ° C, more preferably not higher than 80 ° C.

In the latter case (method of applying heat in a non-steady manner), heat treatment is carried out outside the photosensitive member during use,
The temperature can be higher than the former. Preferably 40 ℃ or more, more preferably 50 ℃ or more, the upper limit is preferably 150
C. or lower, more preferably 120.degree. C. or lower. However, in the latter method, when processing is carried out in the image forming apparatus at a considerably high temperature, the heating time should be shortened or the image formation should be stopped. Alternatively, it is preferable to install a mechanism.

Next, the electrophotographic photosensitive member used in the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing a constitutional example of a photosensitive member used in the present invention, in which a photosensitive layer 14 is provided on a conductive support 11. 2 (a) and 2 (b)
FIG. 4 is a cross-sectional view showing another configuration example, in which the photosensitive layer is a charge generation layer.
21 and a charge transport layer 22 are laminated. 3 and 4 are cross-sectional views showing still another configuration example.
Shows an intermediate layer 13 provided between the conductive support 11 and the photosensitive layer 14, and FIG. 4 shows a protective layer 15 provided on the photosensitive layer 14.

The conductive support 11 has a volume resistance of 10 ¹⁰ Ω.
Those exhibiting electroconductivity under cm, for example, metals such as aluminum, nickel, chromium, nichrome, copper, silver, gold and platinum, and metal oxides such as tin oxide and indium oxide are formed into a film or by vapor deposition or sputtering. Cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel plates, etc., and DI, II, extrusion, drawing, etc., after forming a raw tube, cutting, superfinishing, polishing, etc. It is possible to use a tube whose surface has been treated with.

Next, the photosensitive layer 14 will be described. First, the laminated photosensitive layer will be described. The laminated photosensitive layer comprises a charge generation layer 21 and a charge transport layer 22. The charge generation layer 21 is a layer containing a charge generation substance as a main material, and a binder resin may be used if necessary.

As the binder resin, polyamide, polyurethane, polyester, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, polyacrylamide, etc. are used. To be

As the charge generating substance, for example, CI Pigment Blue 25 [Color Index (CI) 2118
0], CI Pigment Red 41 (CI 21200), CI Acid Red 52 (CI 45100), CI Basic Red 3 (CI 45210), further, a phthalocyanine pigment having a porphyrin skeleton, an azo pigment having a carbazole skeleton (JP 53-95033), azo pigments having a distyrylbenzene skeleton (described in JP-A-53-133455), azo pigments having a triphenylamine skeleton (JP-A
53-132547), an azo pigment having a dibenzothiophene skeleton (described in JP-A-54-21728), an azo pigment having an oxadiazole skeleton (described in JP-A-54-12742), Azo pigments having a fluorenone skeleton
-22834), azo pigments having a bisstilbene skeleton (described in JP-A-54-17733), azo pigments having a distyryl oxadiazole skeleton (described in JP-A-54-2129) , An azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-17734), and further, a phthalocyanine-based pigment such as CI Pigment Blue 16 (CI 74100), CIVAT Brown 5 (CI 73410), CIVAT dye Examples thereof include indigo pigments such as (CI 73030), perylene pigments such as Argos scarlet B (manufactured by Violet), and indense scarlet R (manufactured by Bayer). Among these charge generating substances, disazo or trisazo pigments shown in Table 1 below are preferably used.

[0038]

[Table 1- (1)]

[Table 1- (2)]

[Table 1- (3)]

[Table 1- (4)]

[Table 1- (5)]

[Table 1- (6)]

Examples of these coupler residues Cp include compounds having a phenolic hydroxyl group such as phenols and naphthols, aromatic amino compounds having an amino group, or aminonaphthols having an amino group and a phenolic hydroxyl group, and aliphatic compounds. Alternatively, a compound having an aromatic enolic ketone group (a compound having an active methylene group) or the like is used, and preferably the following (general formula (1) to
It is represented by (11).

[0040]

[Chemical 6] [In the above formulas (1), (2), (3) and (4), X, Y ₁ , Z, m and n represent the following, respectively. X: —OH, —N (R ₁ ) (R ₂ ) or —NHSO ₂ —R ₃ (R ₁ and R ₂ represent hydrogen or a substituted or unsubstituted alkyl group, and R ₃ is a substituted or unsubstituted alkyl group. Represents a group or a substituted or unsubstituted aryl group.) Y ₁ : hydrogen, halogen, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, carboxy group, sulfone group, substituted or unsubstituted sulfamoyl group or —CON (R ₄ ) Y ₂ (R ₄ represents hydrogen, an alkyl group or a substituted product thereof, a phenyl group or a substituted product thereof, and Y ₂
Is a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or —N═C (R ₅ ) (R ₆ ) (wherein R ₅ is a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or A substituent thereof or a styryl group or a substituent thereof, R ₆ represents hydrogen, an alkyl group, a phenyl group or a substituent thereof, or R ₅ and R ₆ may form a ring together with the carbon atom bonded to them. .) Is shown. ) Z: Hydrocarbon ring or its substitution product or heterocycle or its substitution product n: integer of 1 or 2] m: integer of 1 or 2

[0041]

[Chemical 7] [In the formula (5), R ₇ represents a substituted or unsubstituted hydrocarbon group, and X is the same as above. ]

[0042]

[Chemical 8] [In the formula (6), A represents a divalent group of an aromatic hydrocarbon or a heterocyclic divalent group containing a nitrogen atom in the ring. (These rings may be substituted or unsubstituted). X is the same as above. ]

[0043]

[Chemical 9] [In the formula, R ₈ represents an alkyl group, a carbamoyl group, a carboxy group or an ester thereof, Ar ₁ represents a hydrocarbon ring group or a substituted product thereof, and X is the same as defined above. ]

[0044]

[Chemical 10] [In the above formulas (8) and (9), R ₉ represents hydrogen or a substituted or unsubstituted hydrocarbon group, and Ar ₂ represents a hydrocarbon ring group or a substituted product thereof. ]

Examples of the Z hydrocarbon ring in the above general formula (1), (2), (3) or (4) include a benzene ring and a naphthalene ring, and a heterocycle (which may have a substituent). Examples of) include an indole ring, a carbazole ring, a benzolane ring, and a dibenzofuran ring. Examples of the substituent on the ring of Z include halogen atoms such as chlorine atom and bromine atom.

The hydrocarbon ring group for Y ₂ or R ₅ is a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, etc., and the heterocyclic group is a pyridyl group, a cenyl group, a furyl group, an indolyl group, benzofuranyl group. Group, a carbazolyl group, a dibenzofuranyl group, and the like. Further, examples of the ring formed by combining R ₅ and R ₆ include a fluorene ring and the like.

The hydrocarbon ring group or heterocyclic group of Y ₂ or R ₅ or the substituent in the ring formed by R ₅ and R ₆ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, Methoxy group, ethoxy group, propoxy group, alkoxy group such as butoxy group, chlorine atom, halogen atom such as bromine atom, dimethylamino group, dialkylamino group such as diethylamino group, halomethyl group such as trifluoromethyl group, nitro group, Examples thereof include a cyano group, a carboxyl group or an ester thereof, a hydroxyl group, and a sulfonate group such as —SO ₃ Na.

Examples of the substituted phenyl group of R ₄ include halogen atoms such as chlorine atom and bromine atom. Representative examples of the hydrocarbon group for R ₇ or R ₉ include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, aryl groups such as phenyl group, and substituted products thereof. As the substituent in the hydrocarbon group of R ₇ or R ₉ , a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a methoxy group, an ethoxy group, a propoxy group, an alkoxy group such as a butoxy group, a chlorine atom, Examples include halogen atoms such as bromine atom, hydroxyl group, and nitro group.

Typical examples of the hydrocarbon ring group in Ar ₁ or Ar ₂ include a phenyl group and a naphthyl group.
Further, as a substituent in these groups, a methyl group,
Alkyl group such as ethyl group, propyl group, butyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, halogen atom such as nitro group, chlorine atom, bromine atom, cyano group, dimethylamino group, diethylamino Examples thereof include dialkylamino groups such as groups.

In X, a hydroxyl group is particularly suitable. Among the above coupler residues, preferred are those represented by the above general formulas (2), (5), (6), (7), (8) and (9), in which X in the general formula is a hydroxyl group. Are preferred. Among these, the coupler residue represented by Chemical formula 11 (general formula (10)) is preferable, and more preferable is Chemical formula 1
It is a coupler residue represented by 2 (general formula (11)).

Furthermore, among the above-mentioned preferred coupler residues, those represented by Chemical formula 10 (general formula (12) or (13)) are suitable.

[Chemical 11]

[Chemical 12]

[Chemical 13]

Examples of coupler residues (Cp) are shown below in Table 2.
Shown in.

[Table 2- (1)]

[Table 2- (2)]

[Table 2- (3)]

[Table 2- (4)]

[Table 2- (5)]

[Table 2- (6)]

[Table 2- (7)]

[Table 2- (8)]

[Table 2- (9)]

[Table 2- (10)]

[Table 2- (11)]

[Table 2- (12)]

[Table 2- (13)]

[Table 2- (14)]

[Table 2- (15)]

[Table 2- (16)]

[Table 2- (17)]

[Table 2- (18)]

[Table 2- (19)]

[Table 2- (20)]

[Table 2- (21)]

[Table 2- (22)]

[Table 2- (23)]

[Table 2- (24)]

[Table 2- (25)]

[Table 2- (26)]

[Table 2- (27)]

[Table 2- (28)]

[Table 2- (29)]

[Table 2- (30)]

[Table 2- (31)]

[Table 2- (32)]

[Table 2- (33)]

[Table 2- (34)]

[Table 2- (35)]

[Table 2- (36)]

[Table 2- (37)]

[Table 2- (38)]

[Table 2- (39)]

[Table 2- (40)]

[Table 2- (41)]

[Table 2- (42)]

[Table 2- (43)]

[Table 2- (44)]

These charge generating substances may be used alone or
Used in combination of two or more. The binder resin is appropriately used in an amount of 0 to 100 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of the charge generating substance.

In the charge generation layer, the charge generation substance is dispersed together with a binder resin if necessary using a solvent such as tetrahydrofuran, cyclohexane, dioxane, dichloroethane, etc. by a ball mill, attritor, sand mill or the like, and the dispersion is appropriately diluted. Can be formed by coating. The coating can be performed by using a dip coating method, a spray coating method, a bead coating method, or the like. The film thickness of the charge generation layer is appropriately 0.01 to 5 μm, preferably 0.1 to 2 μm.

The charge transport layer 22 can be formed by dissolving or dispersing a charge transport substance and a binder resin in an appropriate solvent, applying the solution on the charge generating layer, and drying. If necessary, a plasticizer, a leveling agent, etc. may be added.

In the present invention, as described above, the compound represented by any one of the general formulas (I) to (V) is contained in the photosensitive layer as the charge transporting substance. In this case, these compounds may be used alone or in combination of two or more kinds. To use. As the compound represented by the general formula (I), those having a chemical structural formula shown in the following Table 3 are preferably used.

[0057]

[Table 3- (1)]

[0058]

[Table 3- (2)]

As the compound represented by the general formula (II), those having the chemical structural formulas shown in Table 4 below are preferably used.

[0060]

[Table 4- (1)]

[0061]

[Table 4- (2)]

As the compound represented by the general formula (III), those having the chemical structural formula shown in the following Table 3 are preferably used.

[0063]

[Table 5- (1)]

As the compound represented by the general formula (IV), those having the chemical structural formula shown in Table 6 below are preferably used.

[0065]

[Table 6- (1)]

[0066]

[Table 6- (2)]

[0067]

[Table 6- (3)]

[0068]

[Table 6- (4)]

As the compound represented by the general formula (V), those having the chemical structural formulas shown in Table 7 below are preferably used.

[0070]

[Table 7- (1)]

[0071]

[Table 7- (2)]

[0072]

[Table 7- (3)]

[0073]

[Table 7- (4)]

As described above, these charge transport substances may be used alone or in combination of two or more.

As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate , Polyvinylidene chloride, polyacrylate resin, phenoxy resin, polycarbonate,
Thermoplastic or thermosetting of cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin, etc. Resins may be mentioned.

As the solvent, tetrahydrofuran, dioxane, toluene, monochlorobenzene, dichloroethane, methylene chloride or the like can be used.

A suitable thickness of the charge transport layer 22 is about 5 to 50 μm.

Next, the case where the photosensitive layer 14 has a single layer structure will be described. In this case as well, in most cases, a function-separated type of charge-generating substance and charge-transporting substance is used. That is, the compounds shown above can be used as the charge generating substance and the charge transporting substance.

The single-layer photosensitive layer can be formed by dissolving or dispersing the charge-generating substance, the charge-transporting substance and the binder resin in a suitable solvent, and coating and drying the solution. If necessary, a plasticizer, a leveling agent, etc. may be added.

As the binder resin, in addition to the binder resin mentioned above for the charge transport layer 23 as it is,
The binder resins mentioned for the charge generation layer 21 may be mixed and used.

The single-layer photosensitive layer comprises a charge generating substance, a charge transporting substance and a binder resin dispersed in a dispersing machine or the like using a solvent such as tetrahydrofuran, dioxane, dichloroethane, cyclohexanone or the like by dip coating or spray coating. It can be formed by coating with a bead coat or the like.

The film thickness of the single-layer photosensitive layer is preferably about 5 to 50 μm. In the present invention, an insulating layer may be further provided on the photosensitive layer 14. Further, as shown in FIG. 3 in the present invention, by providing the intermediate layer 13 between the conductive support and the photosensitive layer, it is possible to further improve the first effect of the present invention, It can also improve adhesion.

The intermediate layer 13 is provided with an inorganic material such as SiO or Al ₂ O _{3 by} a method such as vapor deposition, sputtering or anodic oxidation, or a polyamide resin (Japanese Patent Laid-Open No. 58-30757, Japanese Patent Laid-Open No. 30757/1983). 58-98739), alcohol-soluble nylon resin
(JP-A-60-196766), water-soluble polyvinyl butyral resin (JP-A-60-232553), polyvinyl butyral resin (JP-A-58-106549), using a resin layer such as polyvinyl alcohol You can

Further, the resin intermediate layer in which pigment particles such as ZnO, TiO ₂ , and ZnS are dispersed can also be used as the intermediate layer.

Further, as the intermediate layer 13 of the present invention, a silane coupling agent, a titanium coupling agent, a chromium coupling agent or the like can be used. The thickness of the intermediate layer 13 is 0 to 5
μm is suitable.

The resin used for the protective layer 15 is ABS.
Resin, ACS resin, olefin vinyl copolymer resin, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyarylate, polyallyl sulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyether sulfone, polyethylene ,polyethylene terephthalate,
Examples thereof include polyimide, methacrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene resin, polyurethane, polyvinyl chloride, polyvinylidene chloride and epoxy resin.

From the viewpoint of wear resistance, polytetrafluoroethylene resin, fluororesin and silicone resin can be added as additives to lower the wear coefficient and improve wear resistance and scratch resistance. Even if an inorganic compound such as titanium oxide, tin oxide or potassium titanate is dispersed in the resin, the abrasion resistance is improved. The thickness of this surface protective layer is 0.
It is 5 to 10 μm, preferably 1 to 5 μm.

[0088]

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.

Example 1 An aluminum drum having a diameter of 8 mm and a length of 340 mm was provided with an intermediate layer of 0.3 μm, a charge generation layer of 0.1 μm, and a charge transport layer of the following composition.
20 μm was sequentially applied by a dipping method and dried. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 2 parts by weight Water 150 parts by weight Methanol 150 parts by weight (2) Charge generating layer coating liquid Pigment No. A-9-56 azo pigment 2 parts by weight Cyclohexanone 80 parts by weight Methyl ethyl ketone 18 parts by weight The mixture having the above composition was dispersed by a ball mill for 48 hours and then used as a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport substance Nos. 19 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 81 parts by weight Created 1.

Examples 2 to 22 Pigment Nos. Used in Example 1 Instead of a-9-56, the azo pigments shown in Table 8 below were used, and the charge-transporting substance Nos. A photoreceptor N was prepared in the same manner as in Example 1 except that the charge transporting substances shown in Table 8 below were used in place of 1.
o. Created 2-22. The photoconductor created as described above,
It was mounted on a copying machine (Recopy FT4080) modified so as to be negatively charged, and a heat pipe as shown in Fig. 5-8 was used and set so that the drum temperature was always 50 ± 2 ° C. Further, a probe of a surface electrometer was set in the copying machine so that the surface potential of the drum immediately after charging could be measured. After adjusting the conditions as described above, continuous 8000 copies were made in an environment of 20 ° C-60% RH.

Comparative Examples 1 to 22 The same evaluations as in Examples 1 to 22 were made except that the drum temperature control by the heat pipe was not performed.
The photoconductor surface potential was measured at the start of copying (3 to 5 sheets) and 8000 sheets. Examples 1-22 and Comparative Examples 1-22
The results are shown in Table 8.

[Table 8]

Example 23 An aluminum drum having a length of 340 mm and a diameter of 120 mm was sequentially coated with an intermediate layer (3.5 μ), a charge generation layer (0.2 μ) and a charge transport layer (22 μ) having the following composition and dried. (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butane 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. A-13-51 azo pigment 3 parts by weight Cyclohexanone 160 parts by weight Cyclohexane 40 parts by weight The liquid mixed as described above was dispersed for 36 hours and used as a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport substance Nos. 13 9 parts by weight Polyarylate (Unitika: U-100) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight Photoreceptor No. 23 created.

Examples 24 to 44 Pigment No. used in Example 23. Instead of a-13-51, the azo pigments shown in Table 9 below were used, and the charge-transporting substance Nos. A photoreceptor N was prepared in the same manner as in Example 23 except that the charge transporting substances shown in Table 9 below were used instead of 13.
o. Created 24 to 44. The photoconductor prepared as described above is mounted on a copying machine (Recopy FT7050) modified to be negatively charged, and a resistance heater as shown in FIG.
1001 under the condition that each sheet is stopped, the drum temperature is heated to 100 ° C, and it is cooled to room temperature by a separately provided fan.
I copied up to 0. The environmental conditions were 25 ° C and 45% RH. As an evaluation method, the black solid areas of the 10th and 10010th images were image density (hereinafter ID
Abbreviated. ) Was measured.

Comparative Examples 23-44 Evaluations were made under exactly the same conditions except that the heat treatment in Examples 23-44 was omitted. However, copying was stopped for a time corresponding to the heat treatment, and the photoconductor was allowed to rest. Examples 23-44, Comparative Example 23
The results of ~ 44 are shown in Table 9.

[Table 9]

Example 45 A polyester film having an aluminum conductive layer was applied to a support, a coating solution having the following composition was sequentially applied, and the coating solution was dried.
A charge generation layer (0.2μ) and a charge transport layer (18μ) were formed. (1) Coating liquid for charge generation layer Pigment No. 1 in the present invention. a-2-64 azo pigment 10 parts by weight Polyvinyl butyral (Denka Butyral # 4000-1) 4 parts by weight Cyclohexanone 500 parts by weight Methyl isobutyl ketone 200 parts by weight Disperse the liquid mixed as above for 72 hours. After that, a coating liquid was prepared. (2) Charge Transport Layer Coating Liquid In the present invention, the charge transport substance Nos. 2 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 180 parts by weight 45 was created.

Examples 46 to 66 Pigment Nos. Used in Example 45 Instead of a-2-64, the azo pigments shown in Table 10 below were used, and the charge transporting substance Nos. In the same manner as in Example 45 except that the charge transporting substances shown in Table 10 below were used instead of 2, the photoconductor No. Created 46-66. Also, N created as above
o. Conductive layer coating and belt bonding were performed on the photoconductors 45 to 66 to prepare a photoconductor for mounting. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT2050). The probe of the surface electrometer was set so that the surface potential of the photoreceptor immediately before development could be measured. In the process as shown in FIG. 6, the conventional roller was used as a sheet heating element, and the temperature of the photosensitive member was set to 40 ± 3 ° C. The cyclic condition is 18 ° C.-35% RH. In this state, 7500 sheets were continuously copied, and the surface potentials of the 1st sheet and the 7500th sheet were measured.

Comparative Examples 45 to 66 Evaluations were made under the same conditions except that the temperature control in Examples 45 to 66 was not performed. Examples 45-66, comparative examples
The results of 45 to 66 are shown in Table 10.

[Table 10]

Example 67 An aluminum drum having a diameter of 80 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form a charge transport layer.
15μ, charge generation layer 3μ, intermediate layer 0.5μ, protective layer 5μ
Was formed. (1) Charge Transport Layer Coating Solution In the present invention, the charge transport material No. 1 10 parts by weight Polycarbonate (Teijin: Panlite L-1250) 10 parts by weight Tetrahydrofuran 100 parts by weight Cyclohexanone 80 parts by weight (2) Charge generation layer coating liquid Pigment No. 1 in the present invention. A-7-40 azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight The above-mixed liquid was dispersed for 40 hours to obtain a coating liquid. (3) Intermediate layer coating liquid Polyamide (Toray: CM-4000) 4 parts by weight Methanol 100 parts by weight (4) Protective layer coating liquid Styrene-methyl methacrylate-2-hydroxyethyl methacrylate copolymer 8 parts by weight Conductivity Titanium 10 parts by weight Toluene 240 parts by weight Butanol 60 parts by weight The liquid mixed as described above was dispersed for 80 hours to obtain a coating liquid.
As described above, the photoconductor No. 67 created.

Examples 68 to 88 Pigment No. used in Example 67 Table 1 below instead of a-7-40
The azo pigment shown in FIG. Photosensitive member No. 1 was obtained in the same manner as in Example 67 except that the charge transporting substances shown in Table 11 below were used instead of 1.
Created 68-88. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT5510). The probe of the surface electrometer was set so that the surface potential immediately after charging could be measured. Attach an infrared lamp house as shown in Fig. 7, stop copying every 3000 sheets, heat the photoconductor temperature to 80 ℃,
After cooling to 40 ° C., copying was started again, and 12001 copies were made. Surface potential of the 10th sheet and 120
The surface potential of the first sheet was measured. Running environment is 30 ℃
It was performed under the condition of -80% RH. A sharp cut filter (Fuji Photo SC-72) was used as the filter. Comparative Examples 67 to 88 The same evaluations as in Examples 67 to 88 were made except that the temperature control was not performed. However, copying was stopped after every 3000 sheets, and the photoconductor was rested for the time required for heating and cooling in the examples. The results of Examples 67 to 88 and Comparative Examples 67 to 88 are shown in Table 11.

[Table 11]

Example 89 A polyester film support having an aluminum conductive layer was successively coated with a coating solution having the following composition and dried,
An intermediate layer (0.2μ), a charge generation layer (0.1μ), and a charge transport layer (20μ) were formed. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 2 parts by weight Water 200 parts by weight Methanol 100 parts by weight (2) Charge generating layer coating liquid Pigment No. A-18-3 azo pigment 3 parts by weight Cyclohexanone 97 parts by weight The liquid mixed as described above was dispersed for 60 hours to obtain a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport substance Nos. 1 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 90 parts by weight Dioxane 90 parts by weight Photoreceptor No. 89 created.

Examples 90 to 110 Pigment Nos. Used in Example 89 Instead of a-18-3, the azo pigments shown in Table 12 below were used, and the charge-transporting substance Nos. Photosensitive member No. 1 was obtained in the same manner as in Example 89, except that the charge transporting substances shown in Table 12 below were used instead of 1. 90-110 created. The No. created as described above. 8
Conducting conductive layer coating and belt joining on 9 to 110 photoconductors,
It was a photoconductor for mounting. The photoconductor thus created was mounted on a copying machine (Recopy FT2070). PTC in driven roller
A heating element having characteristics was provided, and the temperature of the photoconductor was set to 35 ± 3 ° C by turning on and off. Environmental conditions are 10 ℃ -60% R
H. In this state, continuous copying of 7,000 sheets was performed, and the image states of the fifth and 7,000th sheets were evaluated.

Comparative Examples 89 to 110 The same evaluations as in Examples 89 to 110 were made except that the temperature control was not performed. Examples 89-110, Comparative Example 89
The results of ~ 110 are shown in Table 12.

[Table 12]

Example 111 An aluminum drum having a diameter of 120 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer (5
μ), a charge generation layer (0.3 μ), and a charge transport layer (25 μ). (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butanone 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. a-17-49 Azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight (3) Charge transport layer coating liquid 2 9 parts by weight Polyarylate (Unitika: U-100) (Teijin: Panlite C-1400) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight As described above, the photoconductor No. Created 111.

Examples 112 to 132 Pigment Nos. Used in Example 111 Instead of a-17-49, the azo pigments shown in Table 13 below may also be used.
o. In the same manner as in Example 111, except that the charge-transporting substance shown in Table 13 below was used instead of 2, the photoconductor No. 112 ~
132 created. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT6080) modified so as to be negatively charged, and a probe of a surface electrometer was set so that the surface potential of the photoconductor immediately before development could be measured. In addition, after continuous copying of 9,990 sheets, the photoconductor was taken out of the copying machine, and subjected to heat treatment at 130 ° C. for 20 minutes with a fatigue recovery device as shown in FIG. Return, total 10,000
Copying was performed up to the number of sheets, and the surface potentials of the tenth sheet and the 10,000th sheet were measured. The environmental conditions were 25 ° C-50% RH.

Comparative Examples 111 to 132 Except that the heat treatment in Examples 111 to 132 was performed at 25 ° C. (that is, the same as room temperature), the same evaluation was performed. Example 111
˜132 and Comparative Examples 111 to 132 are shown in Table 13.

[Table 13]

Example 133 An aluminum drum having a length of 80 mm and a diameter of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer.
(0.3μ), charge generation layer (0.2μ), charge transport layer (20μ). (1) Intermediate layer coating liquid Water-soluble polyvinyl butyral 25% aqueous solution (Sekisui Chemical Co., Ltd .: S-REC W-201) 50 parts by weight Water 150 parts by weight Methanol 200 parts by weight (2) Charge generating layer coating liquid Pigment No. in the present invention ． a-7-69 azo pigment 2 parts by weight Water-soluble polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 0.7 parts by weight Tetrahydrofuran 80 parts by weight Ethylcellosolve 120 parts by weight (3) Charge transport layer coating solution In the invention, the charge transporting substance Nos. 16 10 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 80 parts by weight Photoreceptor No. Created 133.

Examples 134 to 154 Pigment No. used in Example 133. Instead of a-7-69, the azo pigments shown in Table 14 below were also used, and the charge-transporting substance N shown in Table 3 was used.
o. Photosensitive member No. 16 was obtained in the same manner as in Example 133 except that the surface charge transporting substances shown in Table 14 below were used instead of 16. 134
Created ~ 154. The photoconductor created as above is mounted on a copier (Recopy FT5050) modified to be negatively charged,
Using a 2.45 GHz magnetron as a high-frequency power source, a separately provided ferromagnetic material (the photoconductor temperature is controlled by a heating element equipped with electrodes on a plate in which Felock sprayer particles are dispersed in resin)
The temperature was set to 50 ± 2 ° C. After setting each condition, the copier was repeatedly used to make 9,000 continuous copies. The environment was 23 ° C-50% RH. Evaluation is an example
The ID value was evaluated by the same method as used in -23.

Comparative Examples 133 to 154 The same evaluations as in Examples 133 to 154 were made except that the high frequency heating was not performed. Examples 133-154, Comparative Examples 133-154
The results are shown in Table 14.

[Table 14]

Example 155 On an aluminum drum having a diameter of 80 mm and a length of 340 mm,
0.3 μ of an intermediate layer having the following composition and 0.1 of a charge generation layer
μ and a charge transport layer of 20 μ were applied by a dip coating method and dried. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 20 parts by weight Water 150 parts by weight Methanol 150 parts by weight (2) Charge generation layer coating liquid Pigment No. a-9-173 azo pigment 2 parts by weight Cyclohexane 80 parts by weight Methyl ethyl ketone 18 parts by weight A mixture having the above composition was dispersed for 48 hours in a ball mill and then used as a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport material Nos. 209 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 81 parts by weight 155 was created.

Examples 156 to 176 Pigment Nos. Used in Example 155 In place of aa-9-173, the azo pigments shown in Table 15 below were also used. In the same manner as in Example 155 except that the charge transporting substances shown in Table 15 below were used instead of 20, the photoconductor No. 156-176 were created. The photoconductor prepared as above is mounted on a copier (Recopy FT4080) modified so as to be negatively charged, a heat pipe is used as shown in FIG. 8, and the drum temperature is always 50 ± 2 ° C. The heat pipe is used for the drum temperature is always 50 ± 2 ℃
I set it to become. Further, a probe of a surface electrometer was set in the copying machine so that the surface potential of the drum immediately after charging could be measured. After adjusting the conditions as above, 20 ℃ -6
8,000 copies were continuously made under the environment of 0% RH.

Comparative Examples 155 to 176 The same evaluations as in Examples 155 to 176 were made except that the drum temperature control by the heat pipe was not performed. The photoconductor surface potential is measured at the start of copying (3 to
(5th sheet) and 8000 sheets. Examples 155-1
The results of 76 Comparative Examples 155 to 176 are shown in Table 15.

[Table 15]

Example 177 An aluminum drum having a length of 340 mm and a diameter of 120 mm was sequentially coated with an intermediate layer (3.5 μ), a charge generation layer (0.2 μ) and a charge transport layer (22 μ) having the following composition and dried. (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butane 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. A-13-31 azo pigment 3 parts by weight Cyclohexanone 160 parts by weight Cyclohexane 40 parts by weight The liquid mixed as described above was dispersed for 36 hours and used as a coating liquid. (3) Charge transport layer coating liquid 28 9 parts by weight Polyarylate (Unitika: U-100) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight Photoreceptor No. 177 was created.

Examples 178 to 198 Pigment No. 1 used in Example 177. Instead of a-13-31, the azo pigments shown in Table 16 below were also used. Example 177 except that the charge transport materials shown in Table 16 below were used instead of 28.
Similarly to the photoconductor No. 177-198 were created. The photoconductor prepared as above is mounted on a copying machine (Recopy FT7050) modified to be negatively charged, and a resistance heater as shown in Fig. 9 is used. Was heated up to 100 ° C. and cooled down to room temperature by a separately provided fan, so that 10010 sheets were copied.
The environmental conditions were 25 ° C and 45% RH. As an evaluation method, the black solid portions of the 10th and 10010th images were measured for image density (hereinafter abbreviated as ID) with a commercially available Macbeth densitometer.

Comparative Examples 177 to 198 Except that the heat treatment in Examples 177 to 198 was omitted,
It was evaluated under exactly the same conditions. However, copying was stopped for a time corresponding to the heat treatment, and the photoconductor was allowed to rest. Example 177-
The results of 198 and Comparative Examples 177 to 198 are shown in Table 16.

[Table 16]

Example 199 A polyester film having an aluminum conductive layer was applied to a support, a coating solution having the following composition was successively applied, and the coating solution was dried.
A charge generation layer (0.2μ) and a charge transport layer (18μ) were formed. (1) Coating liquid for charge generation layer Pigment No. 1 in the present invention. a-18-59 azo pigment 10 parts by weight Polyvinyl butyral (Denka Butyral # 4000-1) 4 parts by weight Cyclohexanone 500 parts by weight Methyl isobutyl ketone 200 parts by weight Disperse the liquid mixed as above for 72 hours. After that, a coating liquid was prepared. (2) Charge Transport Layer Coating Solution In the present invention, the charge transport material No. 4 in Table 4 is used. 17 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 180 parts by weight Photoreceptor No. 199 was created.

Examples 200 to 220 Pigment No. 1 used in Example 199. Instead of a-18-59, the azo pigments shown in Table 17 below were used, and the charge transporting substance Nos. Example 199 except that the charge transport material shown in Table 17 below was used in place of 17.
Similarly to the photoconductor No. 200-220 were created. In addition, the No. Conductive layer coating and belt bonding were performed on the photoconductors 199 to 220 to prepare a photoconductor for mounting. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT2050). The probe of the surface electrometer was set so that the surface potential of the photoreceptor immediately before development could be measured.
In the process as shown in FIG. 6, the conventional roller was used as a sheet heating element, and the temperature of the photosensitive member was set to 40 ± 3 ° C. The cyclic condition is 18 ° C.-35% RH. In this state, 7500 sheets were continuously copied, and the surface potentials of the 1st sheet and the 7500th sheet were measured.

Comparative Examples 199 to 220 Evaluations were made under the same conditions except that the temperature control in Examples 199 to 220 was not performed. Example 199
Table 220 shows the results for ~ 220 and Comparative Examples 199-220.

[Table 17]

Example 221 An aluminum drum having a diameter of 80 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form a charge transport layer.
15μ, charge generation layer 3μ, intermediate layer 0.5μ, protective layer 5μ
Was formed. (1) Charge Transport Layer Coating Solution In the present invention, the charge transport material No. 20 10 parts by weight Polycarbonate (Teijin: Panlite L-1250) 10 parts by weight Tetrahydrofuran 100 parts by weight Cyclohexanone 80 parts by weight (2) Charge generation layer coating liquid Pigment No. in the present invention. a-10-22 Azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight The above mixed liquid was dispersed for 40 hours to obtain a coating liquid. (3) Intermediate layer coating liquid Polyamide (Toray: CM-4000) 4 parts by weight Methanol 100 parts by weight (4) Protective layer coating liquid Styrene-methyl methacrylate-2-hydroxyethyl methacrylate copolymer 8 parts by weight Conductivity Titanium 10 parts by weight Toluene 240 parts by weight Butanol 60 parts by weight The liquid mixed as described above was dispersed for 80 hours to obtain a coating liquid.
As described above, the photoconductor No. 221 was created.

Examples 222 to 242 Pigment Nos. Used in Example 221 The azo pigments shown in Table 18 below were used in place of a-10-22, and the charge-transporting substance Nos. Table 1 below instead of 20
In the same manner as in Example 221, except that the charge transport material shown in FIG. 222-242 were created. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT5510). The probe of the surface electrometer was set so that the surface potential immediately after charging could be measured. Install an infrared lamp house as shown in Fig. 7, stop copying every 3000 sheets,
The photoconductor temperature was heated to 80 ° C., cooled to 40 ° C., and then copying was restarted to make 12001 copies. The surface potential of the 10th sheet and the surface potential of the 12001th sheet were measured. The running environment was 30 ° C-80% RH. A sharp cut filter (Fuji Photo SC-72) was used as the filter.

Comparative Examples 221 to 242 The same evaluations as in Examples 221 to 242 were made except that the temperature control was not performed. However, copying was stopped after every 3000 sheets, and the photoconductor was rested for the time required for heating and cooling in the examples. Examples 221-242, Comparative Example 221
The results of ~ 242 are shown in Table 18.

[Table 18]

Example 243 A polyester film support having an aluminum conductive layer was sequentially coated with a coating solution having the following composition and dried,
An intermediate layer (0.2μ), a charge generation layer (0.1μ), and a charge transport layer (20μ) were formed. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 2 parts by weight Water 200 parts by weight Methanol 100 parts by weight (2) Charge generating layer coating liquid Pigment No. A-9-57 azo pigment 3 parts by weight Cyclohexanone 97 parts by weight The liquid mixed as described above was dispersed for 60 hours to obtain a coating liquid. (3) Charge transport layer coating liquid 37 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 90 parts by weight Dioxane 90 parts by weight Photoreceptor No. 243 was created.

Examples 244 to 264 Pigment Nos. Used in Example 243 Instead of a-9-57, the azo pigments shown in Table 19 below were used, and the charge-transporting substance Nos. Example 243, except that the charge transport materials shown in Table 19 below were used in place of 37
Similarly to the photoconductor No. 244-264 were created. The No. created as described above. Conductive layer coating and belt bonding were performed on the photoconductors 243 to 264 to obtain a mounting photoconductor. The photoconductor prepared in this way is used in a copying machine (Recopy FT
2070). A heating element having PTC characteristics was provided in the driven roller, and the temperature of the photoconductor was set to 35 ± 3 ° C by turning on and off. Environmental conditions are 10 ℃ -60% RH. In this state, continuous copying of 7,000 sheets was performed, and the image states of the fifth and 7,000th sheets were evaluated.

Comparative Examples 243 to 264 The same evaluations as in Examples 243 to 264 were made except that the temperature control was not performed. Examples 243-26
4, the results of Comparative Examples 243 to 264 are shown in Table 19.

[Table 19]

Example 265 An aluminum drum having a diameter of 120 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer (5
μ), a charge generation layer (0.3 μ), and a charge transport layer (25 μ). (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butanone 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. a-16-20 azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight (3) Charge transport layer coating liquid 34 9 parts by weight Polyarylate (Unitika: U-100) (Teijin: Panlite C-1400) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight Photoreceptor No. Created 265.

Examples 266 to 286 Pigment Nos. Used in Example 265 Instead of a-16-20, the azo pigments shown in Table 20 below were used, and the charge-transporting substance Nos. In the same manner as in Example 265 except that the charge transporting substances shown in Table 20 below were used instead of 34, the photoconductor No. 266-286 were created. A copying machine (Recopy FT60) modified to negatively charge the photoconductor prepared above.
80), and the probe of the surface electrometer was set so that the surface potential of the photoreceptor immediately before development could be measured. In addition, after continuous copying of 9,990 sheets, the photoconductor was taken out of the copying machine, and subjected to heat treatment at 130 ° C. for 20 minutes with a fatigue recovery device as shown in FIG. After returning, copying was performed up to a total of 10,000 sheets, and the surface potentials of the tenth sheet and the 10,000th sheet were measured. The environmental conditions were 25 ° C-50% RH.

Comparative Examples 265 to 286 The same evaluations were made except that the heat treatment in Examples 265 to 286 was performed at 25 ° C. (that is, the same as room temperature). The results of Examples 265 to 286 and Comparative Examples 265 to 286 are shown in Table 2.
Write 0.

[Table 20]

Example 287 An aluminum drum having a length of 80 mm and a diameter of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer.
(0.3μ), charge generation layer (0.2μ), charge transport layer (20μ). (1) Intermediate layer coating liquid Water-soluble polyvinyl butyral 25% aqueous solution (Sekisui Chemical Co., Ltd .: S-REC W-201) 50 parts by weight Water 150 parts by weight Methanol 200 parts by weight (2) Charge generating layer coating liquid Pigment No. in the present invention ． a-18-59 azo pigment 2 parts by weight Water-soluble polyvinyl butyral (Sekisui Chemical Co., Ltd .: Eslec BL-1) 0.7 parts by weight Tetrahydrofuran 80 parts by weight Ethylcellosolve 120 parts by weight (3) Charge transport layer coating liquid In the invention, the charge-transporting substance Nos. 9 10 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 80 parts by weight Photoreceptor No. 287 was created.

Examples 288-308 Pigment Nos. Used in Example 287 Instead of a-18-59, the azo pigments shown in Table 21 below were also used, and the charge transport substance Nos. Photosensitive member No. 9 was carried out in the same manner as in Example 287 except that the surface charge transporting substances shown in Table 21 below were used instead of 9. 288-308 were created. A copying machine (Recopy FT50) modified to negatively charge the photoconductor prepared above.
50), using a 2.45 GHz magnetron as a high-frequency power source, a separately provided ferromagnetic material (a plate in which Ferroc sprayer particles are dispersed in resin is provided with an electrode and a photoconductor temperature of 50 ± 2 After setting each condition, the copying machine was repeatedly used to make 9,000 continuous copies.The environment was 23 ° C-50% RH. The ID value was evaluated by the same method as used in 177.

Comparative Examples 287 to 308 The same evaluations as in Examples 287 to 308 were made except that high frequency heating was not performed. The results of Examples 287 to 308 and Comparative Examples 287 to 308 are shown in Table 21.

[Table 21]

Example 309 An aluminum drum having a diameter of 8 mm and a length of 340 mm was provided with an intermediate layer having the following composition: 0.3 μ, a charge generation layer: 0.1 μ, and a charge transport layer.
20 μm was sequentially applied by a dipping method and dried. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 2 parts by weight Water 150 parts by weight Methanol 150 parts by weight (2) Charge generating layer coating liquid Pigment No. a-11-24 Azo pigment 2 parts by weight Cyclohexanone 80 parts by weight Methyl ethyl ketone 18 parts by weight A mixture having the above composition was dispersed by a ball mill for 48 hours and then used as a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport substance No. 5 in Table 5 is used. 6 9 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 81 parts by weight 309 was created.

Examples 310 to 330 Pigment Nos. Used in Example 310 Instead of a-11-24, the azo pigments shown in Table 22 below were also used in Example 309.
Of the charge transport material No. In the same manner as in Example 309 except that the charge transporting substances shown in Table 22 below were used instead of 6,
Photoconductor No. Made 310-330. The photoconductor created as described above was modified into a copier (Recopy FT4
080) and using a heat pipe as shown in Fig. 5-8, set so that the drum temperature was always 50 ± 2 ° C.
Further, a probe of a surface electrometer was set in the copying machine so that the surface potential of the drum immediately after charging could be measured. After adjusting the conditions as described above, continuous 8000 copies were made in an environment of 20 ° C-60% RH.

Comparative Examples 309 to 330 The same evaluations as in Examples 1 to 22 were made except that the drum temperature control by the heat pipe was not performed.
The photoconductor surface potential was measured at the start of copying (3 to 5 sheets) and 8000 sheets. Examples 309-330 and Comparative Example 309
The results for ~ 330 are shown in Table 22.

[Table 22]

Example 331 An aluminum drum having a length of 340 mm and a diameter of 120 mm was sequentially coated with an intermediate layer (3.5 μ), a charge generation layer (0.2 μ) and a charge transport layer (22 μ) having the following composition and dried. (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butane 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. A-10-24 azo pigment 3 parts by weight Cyclohexanone 160 parts by weight Cyclohexane 40 parts by weight The liquid mixed as described above was dispersed for 36 hours and used as a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport substance No. 5 in Table 5 is used. 8 9 parts by weight Polyarylate (Unitika: U-100) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight Photoreceptor No. Created 331.

Examples 332 to 352 Pigment No. used in Example 331 Instead of a-10-24, the azo pigments shown in Table 23 below were also used in Example 331.
Of the charge transport material No. In the same manner as in Example 331 except that the charge transporting substances shown in Table 23 below were used instead of 8,
Photoconductor No. 332-352 created. The photocopier created as described above was modified so that it would be negatively charged (Recopy FT705
0), using a resistance heater as shown in Fig. 9, stopping after every 5,000 copies, heating the drum temperature to 100 ° C, and cooling to room temperature with a separately provided fan. I copied up to 10010 copies. The environmental conditions are 25 ℃ -45
It was% RH. As an evaluation method, the black solid areas of the 10th and 10010th images were measured with a commercially available Macbeth densitometer.
(Hereinafter abbreviated as ID) was measured.

Comparative Examples 331 to 352 Evaluations were made under exactly the same conditions except that the heat treatment in Examples 331 to 352 was omitted. However, copying was stopped for a time corresponding to the heat treatment, and the photoconductor was allowed to rest. The results of Examples 331 to 352 and Comparative Examples 331 to 352 are shown in Table 23.

[Table 23]

Example 353 A polyester film having an aluminum conductive layer was applied to a support, a coating solution having the following composition was sequentially applied, and the coating solution was dried.
A charge generation layer (0.2μ) and a charge transport layer (18μ) were formed. (1) Coating liquid for charge generation layer Pigment No. 1 in the present invention. a-16-37 azo pigment 10 parts by weight Polyvinyl butyral (Denka Butyral # 4000-1) 4 parts by weight Cyclohexanone 500 parts by weight Methyl isobutyl ketone 200 parts by weight Disperse the above mixture for 72 hours. After that, a coating liquid was prepared. (2) Charge transport layer coating liquid 2 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 180 parts by weight 353 was created.

Examples 354 to 374 Pigment No. 1 used in Example 353. Instead of a-16-37, the azo pigments shown in Table 24 below were also used in Example 353.
Of the charge transport material No. In the same manner as in Example 353 except that the charge transporting substances shown in Table 24 below were used instead of 2,
Photoconductor No. 354-374 were created. In addition, the No. Conductive layer coating and belt bonding were performed on the photoconductors 353 to 374 to obtain a mounting photoconductor. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT2050). The probe of the surface electrometer was set so that the surface potential of the photoreceptor immediately before development could be measured. In the process as shown in Figure 6,
A conventional roller was used as a sheet heating element, and the temperature of the photoconductor was set to 40 ± 3 ° C. The cyclic condition is 18 ° C.-35% RH. Continuously copy 7500 sheets in this state, and
The surface potential of the 500th sheet was measured.

Comparative Examples 353 to 374 Evaluations were made under the same conditions except that the temperature control in Examples 353 to 374 was not performed. The results of Examples 353 to 374 and Comparative Examples 353 to 374 are shown in Table 24.

[Table 24]

Example 375 An aluminum drum having a diameter of 80 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form a charge transport layer.
15μ, charge generation layer 3μ, intermediate layer 0.5μ, protective layer 5μ
Was formed. (1) Charge Transport Layer Coating Liquid In the present invention, the charge transport material No. 6 in Table 5 was used. 8 10 parts by weight Polycarbonate (Teijin: Panlite L-1250) 10 parts by weight Tetrahydrofuran 100 parts by weight Cyclohexanone 80 parts by weight (2) Charge generation layer coating liquid Pigment No. in the present invention. a-4-236 azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight The above-mixed liquid was dispersed for 40 hours to obtain a coating liquid. (3) Intermediate layer coating liquid Polyamide (Toray: CM-4000) 4 parts by weight Methanol 100 parts by weight (4) Protective layer coating liquid Styrene-methyl methacrylate-2-hydroxyethyl methacrylate copolymer 8 parts by weight Conductivity Titanium 10 parts by weight Toluene 240 parts by weight Butanol 60 parts by weight The liquid mixed as described above was dispersed for 80 hours to obtain a coating liquid.
As described above, the photoconductor No. Created 375.

Examples 376 to 796 Pigment No. used in Example 375. The azo pigments shown in Table 25 below were used in place of a-4-236, and the charge-transporting substance Nos. Photosensitive member No. 8 was obtained in the same manner as in Example 375 except that the charge transporting substances shown in Table 25 below were used instead of No. 8. Created 376-396. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT5510). The probe of the surface electrometer was set so that the surface potential immediately after charging could be measured. Install an infrared lamp house as shown in Fig. 7, stop copying every 3000 sheets, heat the photoconductor temperature to 80 ° C, cool to 40 ° C, and then start copying again. I did. The surface potential of the 10th sheet and the surface potential of the 12001th sheet were measured. The running environment was 30 ° C-80% RH. A sharp cut filter (Fuji Photo SC-72) was used as the filter.

Comparative Examples 375 to 396 The same evaluation as in Examples 375 to 396 was carried out except that the temperature control was not performed. However, copying was stopped after every 3000 sheets, and the photoconductor was rested for the time required for heating and cooling in the examples. The results of Examples 375 to 396 and Comparative Examples 375 to 396 are shown in Table 25.

[Table 25]

Example 397 A polyester film support having an aluminum conductive layer was sequentially coated with a coating solution having the following composition and dried,
An intermediate layer (0.2μ), a charge generation layer (0.1μ), and a charge transport layer (20μ) were formed. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 2 parts by weight Water 200 parts by weight Methanol 100 parts by weight (2) Charge generating layer coating liquid Pigment No. A-15-12 azo pigment 3 parts by weight Cyclohexanone 97 parts by weight The liquid mixed as described above was dispersed for 60 hours to obtain a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport substance No. 5 in Table 5 is used. 7 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 90 parts by weight Dioxane 90 parts by weight Photoreceptor No. Created 397.

Examples 398 to 418 Pigment No. used in Example 397 Instead of a-15-12, the azo pigments shown in Table 26 below were also used in Example 397.
Of the charge transport material No. In the same manner as in Example 397 except that the charge transporting substances shown in Table 26 below were used instead of 7,
Photoconductor No. 398-418 were created. The No. created as described above. Conductive layer coating and belt bonding were performed on the photoconductors 397 to 418 to prepare a photoconductor for mounting. The photoconductor thus created was mounted on a copying machine (Recopy FT2070). A heating element having PTC characteristics was provided in the driven roller, and the temperature of the photoconductor was set to 35 ± 3 ° C by turning on and off. Environmental condition is 1
0 ℃ -60% RH. In this state, continuous copying of 7,000 sheets was performed, and the image states of the fifth and 7,000th sheets were evaluated.

Comparative Examples 397 to 418 The same evaluations as in Examples 397 to 418 were made except that the temperature control was not performed. Examples 397 to 418, Comparative Example 39
The results of 7 to 418 are shown in Table 26.

[Table 26]

Example 419 An aluminum drum having a diameter of 120 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer (5
μ), a charge generation layer (0.3 μ), and a charge transport layer (25 μ). (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butanone 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. a-16-117 azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight (3) Charge transport layer coating liquid 9 parts by weight Polyarylate (Unitika: U-100) (Teijin: Panlite C-1400) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight Photoreceptor No. Created 419.

Examples 420 to 440 Pigment Nos. Used in Example 419 Instead of a-16-117, the azo pigments shown in Table 27 below may also be used, and the charge transport material N shown in Table 5 may be used.
o. In the same manner as in Example 419 except that the charge transporting substances shown in Table 27 below were used instead of 9, the photoconductor No. 420 ~
440 created. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT6080) modified so as to be negatively charged, and a probe of a surface electrometer was set so that the surface potential of the photoconductor immediately before development could be measured. In addition, after continuous copying of 9,990 sheets, the photoconductor was taken out of the copying machine, and subjected to heat treatment at 130 ° C. for 20 minutes with a fatigue recovery device as shown in FIG. Return, total 10,000
Copying was performed up to the number of sheets, and the surface potentials of the tenth sheet and the 10,000th sheet were measured. The environmental conditions were 25 ° C-50% RH.

Comparative Examples 419 to 440 Exactly the same evaluations were made except that the heat treatment in Examples 419 to 440 was carried out at 25 ° C. (that is, the same as room temperature). Example 419
.About.440 and Comparative Examples 419 to 440 are shown in Table 27.

[Table 27]

Example 441 An aluminum drum having a length of 80 mm and a diameter of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer.
(0.3μ), charge generation layer (0.2μ), charge transport layer (20μ). (1) Intermediate layer coating liquid Water-soluble polyvinyl butyral 25% aqueous solution (Sekisui Chemical Co., Ltd .: S-REC W-201) 50 parts by weight Water 150 parts by weight Methanol 200 parts by weight (2) Charge generating layer coating liquid Pigment No. in the present invention ． a-13-11 Azo pigment 2 parts by weight Water-soluble polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 0.7 parts by weight Tetrahydrofuran 80 parts by weight Ethylcellosolve 120 parts by weight (3) Charge transport layer coating liquid In the invention, the charge transport material Nos. 13 10 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 80 parts by weight Photoreceptor No. Created 441.

Examples 442 to 462 Pigment No. used in Example 441. Instead of a-13-11, the azo pigments shown in Table 28 below are also used, and the charge-transporting substance N shown in Table 5 is used.
o. In the same manner as in Example 441 except that the surface charge transport substance shown in Table 28 below was used instead of 13, the photoconductor No. 442
Created ~ 462. The photoconductor created as above is mounted on a copier (Recopy FT5050) modified to be negatively charged,
Using a 2.45 GHz magnetron as a high-frequency power source, a separately provided ferromagnetic material (the photoconductor temperature is controlled by a heating element equipped with electrodes on a plate in which Felock sprayer particles are dispersed in resin)
The temperature was set to 50 ± 2 ° C. After setting each condition, the copier was repeatedly used to make 9,000 continuous copies. The environment was 23 ° C-50% RH. Evaluation is an example
Evaluation was made with the ID value by the same method as used for -331.

Comparative Examples 441 to 462 The same evaluations as in Examples 441 to 462 were made except that high frequency heating was not performed. Examples 441 to 462, Comparative Examples 441 to 462
The results are shown in Table 28.

[Table 28]

Example 463 On an aluminum drum having a diameter of 80 mm and a length of 340 mm,
0.3 μ of an intermediate layer having the following composition and 0.1 of a charge generation layer
μ and a charge transport layer of 20 μ were applied by a dip coating method and dried. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 20 parts by weight Water 150 parts by weight Methanol 150 parts by weight (2) Charge generation layer coating liquid Pigment No. a-9-228 azo pigment 2 parts by weight Cyclohexane 80 parts by weight Methyl ethyl ketone 18 parts by weight A mixture having the above composition was dispersed for 48 hours by a ball mill, and then used as a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport material Nos. 27 9 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 81 parts by weight 463 was created.

Examples 464 to 484 Pigment Nos. Used in Example 463 In place of aa-9-228, the azo pigments shown in Table 29 below were also used. Photosensitive member No. 27 was carried out in the same manner as in Example 463 except that the charge transporting substances shown in Table 29 below were used instead of 27. 464 to 484 were created. The photoconductor prepared as above is mounted on a copier (Recopy FT4080) modified so as to be negatively charged, a heat pipe is used as shown in FIG. 8, and the drum temperature is always 50 ± 2 ° C. The heat pipe is used for the drum temperature is always 50 ± 2 ℃
I set it to become. Further, a probe of a surface electrometer was set in the copying machine so that the surface potential of the drum immediately after charging could be measured. After adjusting the conditions as above, 20 ℃ -6
8,000 copies were continuously made under the environment of 0% RH.

Comparative Examples 463 to 484 The same evaluations as in Examples 463 to 484 were made except that the drum temperature control by the heat pipe was not performed. The photoconductor surface potential is measured at the start of copying (3 to
(5th sheet) and 8000 sheets. Examples 463-4
Table 29 shows the results of No. 84 and Comparative Examples 463 to 484.

[Table 29]

Example 485 An aluminum drum having a length of 340 mm and a diameter of 120 mm was sequentially coated with an intermediate layer (3.5 μ), a charge generation layer (0.2 μ) and a charge transport layer (22 μ) having the following composition and dried. (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butane 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. A-1-25 azo pigment 3 parts by weight Cyclohexanone 160 parts by weight Cyclohexane 40 parts by weight The liquid mixed as described above was dispersed for 36 hours and used as a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport material No. 6 in Table 6 was used. 18 9 parts by weight Polyarylate (Unitika: U-100) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight Photoreceptor No. 485 was created.

Examples 486 to 506 Pigment No. used in Example 485. Instead of a-1-25, the azo pigments shown in Table 30 below were used, and the charge-transporting substance Nos. Example 485 except that the charge-transporting materials shown in Table 30 below were used instead of 18.
Similarly to the photoconductor No. 486-506 was created. The photoconductor prepared as above is mounted on a copying machine (Recopy FT7050) modified to be negatively charged, and a resistance heater as shown in Fig. 9 is used. Was heated up to 100 ° C. and cooled down to room temperature by a separately provided fan, so that 10010 sheets were copied.
The environmental conditions were 25 ° C and 45% RH. As an evaluation method, the black solid portions of the 10th and 10010th images were measured for image density (hereinafter abbreviated as ID) with a commercially available Macbeth densitometer.

Comparative Examples 485 to 506 Except that the heat treatment in Examples 485 to 506 is not carried out,
It was evaluated under exactly the same conditions. However, copying was stopped for a time corresponding to the heat treatment, and the photoconductor was allowed to rest. Example 485
The results of 506 and Comparative Examples 485 to 506 are shown in Table 30.

[Table 30]

Example 507 A polyester film having an aluminum conductive layer was applied to a support, a coating solution having the following composition was successively applied, and the coating solution was dried.
A charge generation layer (0.2μ) and a charge transport layer (18μ) were formed. (1) Coating liquid for charge generation layer Pigment No. 1 in the present invention. a-15-232 azo pigment 10 parts by weight Polyvinyl butyral (Denka Butyral # 4000-1) 4 parts by weight Cyclohexanone 500 parts by weight Methyl isobutyl ketone 200 parts by weight Disperse the liquid mixed as above for 72 hours. After that, a coating liquid was prepared. (2) Charge Transport Layer Coating Liquid In the present invention, the charge transport material Nos. 1 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 180 parts by weight Photoreceptor No. 507 was created.

Examples 508 to 528 Pigment Nos. Used in Example 507 Instead of a-15-232, the azo pigments shown in Table 31 below were also used, and Example 507
The charge transport substance No. Example 507 except that the charge transport materials shown in Table 31 below were used instead of 1.
Similarly to the photoconductor No. 508-528 were created. In addition, the No. Conductive layer coating and belt bonding were performed on the photoconductors 508 to 528 to obtain a mounting photoconductor. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT2050). The probe of the surface electrometer was set so that the surface potential of the photoreceptor immediately before development could be measured.
In the process as shown in FIG. 6, the conventional roller was used as a sheet heating element, and the temperature of the photosensitive member was set to 40 ± 3 ° C. The cyclic condition is 18 ° C.-35% RH. In this state, 7500 sheets were continuously copied, and the surface potentials of the 1st sheet and the 7500th sheet were measured.

Comparative Examples 507 to 528 Evaluations were made under the same conditions except that the temperature control in Examples 507 to 528 was not performed. Example 507
˜528 and Comparative Examples 507 to 528 are shown in Table 31.

[Table 31]

Example 529 An aluminum drum having a diameter of 80 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form a charge transport layer.
15μ, charge generation layer 3μ, intermediate layer 0.5μ, protective layer 5μ
Was formed. (1) Charge Transport Layer Coating Liquid In the present invention, the charge transport material No. 6 in Table 6 was used. 23 10 parts by weight Polycarbonate (Teijin: Panlite L-1250) 10 parts by weight Tetrahydrofuran 100 parts by weight Cyclohexanone 80 parts by weight (2) Charge generation layer coating liquid Pigment No. in the present invention. a-13-48 azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight The above-mixed liquid was dispersed for 40 hours to obtain a coating liquid. (3) Intermediate layer coating liquid Polyamide (Toray: CM-4000) 4 parts by weight Methanol 100 parts by weight (4) Protective layer coating liquid Styrene-methyl methacrylate-2-hydroxyethyl methacrylate copolymer 8 parts by weight Conductivity Titanium 10 parts by weight Toluene 240 parts by weight Butanol 60 parts by weight The liquid mixed as described above was dispersed for 80 hours to obtain a coating liquid.
As described above, the photoconductor No. 529 was created.

Examples 530 to 550 Pigment No. used in Example 529. The azo pigments shown in Table 32 below were used in place of a-13-48, and the charge-transporting substance Nos. Table 3 below instead of 23
In the same manner as in Example 529 except that the charge transport material shown in FIG. 530-550 were created. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT5510). The probe of the surface electrometer was set so that the surface potential immediately after charging could be measured. Install an infrared lamp house as shown in Fig. 7, stop copying every 3000 sheets,
The photoconductor temperature was heated to 80 ° C., cooled to 40 ° C., and then copying was restarted to make 12001 copies. The surface potential of the 10th sheet and the surface potential of the 12001th sheet were measured. The running environment was 30 ° C-80% RH. A sharp cut filter (Fuji Photo SC-72) was used as the filter.

Comparative Examples 529 to 550 The same evaluations as in Examples 529 to 550 were made except that the temperature control was not performed. However, copying was stopped after every 3000 sheets, and the photoconductor was rested for the time required for heating and cooling in the examples. Examples 529 to 550, Comparative Example 529
The results of ~ 550 are shown in Table 32.

[Table 32]

Example 551 A polyester film support having an aluminum conductive layer was sequentially coated with a coating solution having the following composition and dried,
An intermediate layer (0.2μ), a charge generation layer (0.1μ), and a charge transport layer (20μ) were formed. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 2 parts by weight Water 200 parts by weight Methanol 100 parts by weight (2) Charge generating layer coating liquid Pigment No. A-6-42 azo pigment 3 parts by weight Cyclohexanone 97 parts by weight The liquid mixed as described above was dispersed for 60 hours to obtain a coating liquid. (3) Charge Transport Layer Coating Liquid In the present invention, the charge transport material No. 6 in Table 6 was used. 37 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 90 parts by weight Dioxane 90 parts by weight Photoreceptor No. 551 was created.

Examples 552-572 Pigment Nos. Used in Example 551 Instead of a-6-42, the azo pigments shown in Table 33 below were used, and the charge transporting substance Nos. Example 551 except that the charge transport materials shown in Table 33 below were used instead of 37.
Similarly to the photoconductor No. 552-572 was created. The No. created as described above. Conductive layer coating and belt bonding were performed on the photoconductors 552 to 572 to prepare a photoconductor for mounting. The photoconductor prepared in this way is used in a copying machine (Recopy FT
2070). A heating element having PTC characteristics was provided in the driven roller, and the temperature of the photoconductor was set to 35 ± 3 ° C by turning on and off. Environmental conditions are 10 ℃ -60% RH. In this state, continuous copying of 7,000 sheets was performed, and the image states of the fifth and 7,000th sheets were evaluated.

Comparative Examples 551-572 The same evaluations as in Examples 551-572 were made except that the temperature control was not performed. Examples 551-57
2, the results of Comparative Examples 551-572 are shown in Table 33.

[Table 33]

Example 573 An aluminum drum having a diameter of 120 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer (5
μ), a charge generation layer (0.3 μ), and a charge transport layer (25 μ). (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butanone 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. a-8-103 azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight (3) Charge transport layer coating liquid 13 9 parts by weight Polyarylate (Unitika: U-100) (Teijin: Panlite C-1400) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight Created 573.

Examples 574 to 594 Pigment Nos. Used in Example 573 Instead of a-8-103, the azo pigments shown in Table 34 below were used, and the charge-transporting substance Nos. In the same manner as in Example 573 except that the charge transporting substances shown in Table 34 below were used instead of 13, the photoconductor No. 574-594 were created. A copying machine (Recopy FT60) modified to negatively charge the photoconductor prepared above.
80), and the probe of the surface electrometer was set so that the surface potential of the photoreceptor immediately before development could be measured. In addition, after continuous copying of 9,990 sheets, the photoconductor was taken out of the copying machine, and subjected to heat treatment at 130 ° C. for 20 minutes with a fatigue recovery device as shown in FIG. After returning, copying was performed up to a total of 10,000 sheets, and the surface potentials of the tenth sheet and the 10,000th sheet were measured. The environmental conditions were 25 ° C-50% RH.

Comparative Examples 573 to 594 The same evaluations as those of Examples 573 to 594 were made except that the heat treatment was carried out at 25 ° C. (that is, the same as room temperature). Table 3 shows the results of Examples 573 to 594 and Comparative Examples 573 to 594.
It writes in 4.

[Table 34]

Example 595 An aluminum drum having a length of 80 mm and a diameter of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer.
(0.3μ), charge generation layer (0.2μ), charge transport layer (20μ). (1) Intermediate layer coating liquid Water-soluble polyvinyl butyral 25% aqueous solution (Sekisui Chemical Co., Ltd .: S-REC W-201) 50 parts by weight Water 150 parts by weight Methanol 200 parts by weight (2) Charge generating layer coating liquid Pigment No. in the present invention ． a-12-65 Azo pigment 2 parts by weight Water-soluble polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 0.7 parts by weight Tetrahydrofuran 80 parts by weight Ethylcellosolve 120 parts by weight (3) Coating liquid for charge transport layer In the invention, the charge-transporting substance Nos. 33 10 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 80 parts by weight Photoreceptor No. 595 was created.

Examples 596 to 616 Pigment No. used in Example 596. Instead of a-12-65, the azo pigments shown in Table 35 below were also used, and the charge transport substance Nos. In the same manner as in Example 595 except that the surface charge transport material shown in Table 35 below was used instead of 33, the photoconductor No. 596-616 were created. The photocopier created as described above was modified so that it would be negatively charged.
5050), using a 2.45 GHz magnetron as a high-frequency power source, a separately provided ferromagnetic material (a plate in which ferroscopic sprayer particles are dispersed in resin is provided with electrodes and a photoconductor temperature of 50 ± 2 After setting each condition, the copying machine was repeatedly used to make 9,000 continuous copies.The environment was 23 ° C-50% RH. The ID value was evaluated by the same method as that used for 485.

Comparative Examples 595 to 616 The same evaluations as in Examples 595 to 616 were made except that high frequency heating was not performed. The results of Examples 595-616 and Comparative Examples 595-616 are shown in Table 35.

[Table 35]

Example 617 On an aluminum drum having a diameter of 80 mm and a length of 340 mm,
0.3 μ of an intermediate layer having the following composition and 0.1 of a charge generation layer
μ and a charge transport layer of 20 μ were applied by a dip coating method and dried. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 2 parts by weight Water 150 parts by weight Methanol 150 parts by weight (2) Charge generation layer coating liquid Pigment No. A-1-72 azo pigment 2 parts by weight Cyclohexane 80 parts by weight Methyl ethyl ketone 18 parts by weight A mixture having the above composition was dispersed for 48 hours by a ball mill, and then used as a coating liquid. (3) Charge transport layer coating liquid 6 9 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 81 parts by weight 617 was created.

Examples 618 to 638 Pigment Nos. Used in Example 617 The charge-transporting substance Nos. used in Example 617 were replaced by the azo pigments shown in Table 36 below instead of a-1-72. In the same manner as in Example 617 except that the charge-transporting substances shown in Table 36 below were used in place of 6, the photoconductor No. 618-638 were created. The photoconductor prepared as described above is mounted on a copier (Recopy FT4080) modified so as to be negatively charged, a heat pipe is used as shown in FIG. 8, and the drum temperature is always 50 ± 2 ° C. A heat pipe was used to set the drum temperature so that it was always 50 ± 2 ° C. Further, a probe of a surface electrometer was set in the copying machine so that the surface potential of the drum immediately after charging could be measured. After adjusting the conditions as above, 20 ℃ -60%
8000 copies were continuously made under the RH environment.

Comparative Examples 617 to 638 The same evaluations as in Examples 617 to 638 were made except that the drum temperature control by the heat pipe was not performed. The photoconductor surface potential is measured at the start of copying (3 to
(5th sheet) and 8000 sheets. Examples 617-6
38, the results of Comparative Examples 617 to 638 are shown in Table 36.

[Table 36]

Example 639 To an aluminum drum having a length of 340 mm and a diameter of 120 mm, an intermediate layer (3.5 μ), a charge generation layer (0.2 μ) and a charge transport layer (22 μ) having the following composition were sequentially applied and dried. (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butane 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. A-9-39 azo pigment 3 parts by weight Cyclohexanone 160 parts by weight Cyclohexane 40 parts by weight The liquid mixed as described above was dispersed for 36 hours and used as a coating liquid. (3) Charge Transport Layer Coating Solution In the present invention, the charge transport material No. 6 in Table 7 was used. 29 parts by weight Polyarylate (Unitika: U-100) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight Photoreceptor No. 639 was created.

Examples 640 to 660 Pigment No. used in Example 639. Instead of a-9-39, the azo pigments shown in Table 37 below were used, and the charge-transporting material Nos. Table 3 below instead of 2
In the same manner as in Example 639 except that the charge transport material shown in FIG. 640-660 were created.
The photoconductor prepared as above is mounted on a copying machine (Recopy FT7050) modified to be negatively charged, and a resistance heater as shown in Fig. 9 is used. Was heated up to 100 ° C. and cooled down to room temperature by a separately provided fan, so that 10010 sheets were copied. still,
The environmental conditions were 25 ° C-45% RH. As an evaluation method,
Image densities (hereinafter abbreviated as ID) of the black solid portions of the 10th and 10010th images were measured with a commercially available Macbeth densitometer.

Comparative Examples 639 to 660 Other than the heat treatment in Examples 639 to 660,
It was evaluated under exactly the same conditions. However, copying was stopped for a time corresponding to the heat treatment, and the photoconductor was allowed to rest. Example 639-
The results of 660 and Comparative Examples 639 to 660 are shown in Table 37.

[Table 37]

Example 661 A polyester film having an aluminum conductive layer was applied to a support, a coating solution having the following composition was successively applied, and the coating solution was dried.
A charge generation layer (0.2μ) and a charge transport layer (18μ) were formed. (1) Coating liquid for charge generation layer Pigment No. 1 in the present invention. a-14-3 Azo pigment 10 parts by weight Polyvinyl butyral (Denka Butyral # 4000-1) 4 parts by weight Cyclohexanone 500 parts by weight Methyl isobutyl ketone 200 parts by weight A liquid mixed as above is dispersed for 72 hours. After that, a coating liquid was prepared. (2) Charge transport layer coating liquid 17 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 180 parts by weight Photoreceptor No. 661 was created.

Examples 662 to 682 Pigment Nos. Used in Example 661 Instead of a-14-3, the azo pigments shown in Table 38 below were also used, and the charge transport material Nos. Example 661 except that the charge transport materials shown in Table 38 below were used instead of 17.
Similarly to the photoconductor No. 662-682 were created. In addition, the No. Conductive layer coating and belt bonding were performed on the photoconductors 662 to 682 to obtain a photoconductor for mounting. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT2050). The probe of the surface electrometer was set so that the surface potential of the photoreceptor immediately before development could be measured.
In the process as shown in FIG. 6, the conventional roller was used as a sheet heating element, and the temperature of the photosensitive member was set to 40 ± 3 ° C. The cyclic condition is 18 ° C.-35% RH. In this state, 7500 sheets were continuously copied, and the surface potentials of the 1st sheet and the 7500th sheet were measured.

Comparative Examples 661 to 682 Evaluations were made under the same conditions except that the temperature control in Examples 661 to 682 was not carried out. Example 661
-682 and the results of Comparative Examples 661-682 are shown in Table 38.

[Table 38]

Example 683 An aluminum drum having a diameter of 80 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form a charge transport layer.
15μ, charge generation layer 3μ, intermediate layer 0.5μ, protective layer 5μ
Was formed. (1) Charge Transport Layer Coating Solution In the present invention, the charge transport material No. 6 in Table 7 was used. 27 10 parts by weight Polycarbonate (Teijin: Panlite L-1250) 10 parts by weight Tetrahydrofuran 100 parts by weight Cyclohexanone 80 parts by weight (2) Charge generation layer coating liquid Pigment No. a-7-119 azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight The liquid mixed as above was dispersed for 40 hours to obtain a coating liquid. (3) Intermediate layer coating liquid Polyamide (Toray: CM-4000) 4 parts by weight Methanol 100 parts by weight (4) Protective layer coating liquid Styrene-methyl methacrylate-2-hydroxyethyl methacrylate copolymer 8 parts by weight Conductivity Titanium 10 parts by weight Toluene 240 parts by weight Butanol 60 parts by weight The liquid mixed as described above was dispersed for 80 hours to obtain a coating liquid.
As described above, the photoconductor No. 683 was created.

Examples 684 to 704 Pigment Nos. Used in Example 683 The azo pigments shown in Table 39 below were used in place of a-7-119, and the charge-transporting substance Nos. Table 3 below instead of 27
In the same manner as in Example 683 except that the charge transport material shown in FIG. 684 to 704 were created. The photoconductor prepared as described above was mounted on a copying machine (Recopy FT5510). The probe of the surface electrometer was set so that the surface potential immediately after charging could be measured. Install an infrared lamp house as shown in Fig. 7, stop copying every 3000 sheets,
The photoconductor temperature was heated to 80 ° C., cooled to 40 ° C., and then copying was restarted to make 12001 copies. The surface potential of the 10th sheet and the surface potential of the 12001th sheet were measured. The running environment was 30 ° C-80% RH. A sharp cut filter (Fuji Photo SC-72) was used as the filter.

Comparative Examples 683 to 704 The same evaluations as in Examples 683 to 704 were made except that the temperature control was not performed. However, copying was stopped after every 3000 sheets, and the photoconductor was rested for the time required for heating and cooling in the examples. Examples 683 to 704, Comparative Example 683
The results of ~ 704 are shown in Table 39.

[Table 39]

Example 705 A polyester film support having an aluminum conductive layer was sequentially coated with a coating solution having the following composition and dried,
An intermediate layer (0.2μ), a charge generation layer (0.1μ), and a charge transport layer (20μ) were formed. (1) Intermediate layer coating liquid Polyvinyl alcohol (Denka Poval H-20) 2 parts by weight Water 200 parts by weight Methanol 100 parts by weight (2) Charge generating layer coating liquid Pigment No. A-5-174 azo pigment 3 parts by weight Cyclohexanone 97 parts by weight The liquid mixed as described above was dispersed for 60 hours to obtain a coating liquid. (3) Charge Transport Layer Coating Solution In the present invention, the charge transport material No. 6 in Table 7 was used. 15 10 parts by weight Polycarbonate (Teijin: Panlite K-1300) 10 parts by weight Tetrahydrofuran 90 parts by weight Dioxane 90 parts by weight Photoreceptor No. 705 was created.

Examples 706 to 726 Pigment Nos. Used in Example 705 Instead of a-5-174, the azo pigments shown in Table 40 below were used, and the charge-transporting material Nos. Example 705, except that the charge transport materials shown in Table 40 below were used in place of 15.
Similarly to the photoconductor No. 706-726 were created. The No. created as described above. Conductive layer coating and belt bonding were performed on the photoconductors 705 to 726 to obtain a photoconductor for mounting. The photoconductor prepared in this way is used in a copying machine (Recopy FT
2070). A heating element having PTC characteristics was provided in the driven roller, and the temperature of the photoconductor was set to 35 ± 3 ° C by turning on and off. Environmental conditions are 10 ℃ -60% RH. In this state, continuous copying of 7,000 sheets was performed, and the image states of the fifth and 7,000th sheets were evaluated.

Comparative Examples 705 to 726 The same evaluations as in Examples 705 to 726 were made except that the temperature control was not performed. Examples 705-72
6, the results of Comparative Examples 705 to 726 are shown in Table 40.

[Table 40]

Example 727 An aluminum drum having a diameter of 120 mm and a length of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer (5
μ), a charge generation layer (0.3 μ), and a charge transport layer (25 μ). (1) Intermediate layer coating liquid Titanium dioxide 10 parts by weight Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 1 part by weight Toluylene-2,4-diisocyanate 0.2 parts by weight 2-butanone 100 parts by weight 4-methyl- 2-Pentanone 60 parts by weight The liquid mixed as described above was dispersed with a ball mill for 12 hours and then used as a coating liquid. (2) Charge Generation Layer Coating Liquid Pigment No. 1 in the present invention. a-14-36 Azo pigment 2 parts by weight Polyester (Toyobo: Byron 200) 1 part by weight Cyclohexanone 97 parts by weight (3) Charge transport layer coating liquid 18 9 parts by weight Polyarylate (Unitika: U-100) (Teijin: Panlite C-1400) 11 parts by weight Methylene chloride 70 parts by weight Chlorobenzene 10 parts by weight Photoreceptor No. 727 was created.

Examples 728 to 748 Pigment Nos. Used in Example 727 Instead of a-14-36, the azo pigments shown in Table 41 below were used, and the charge-transporting substance Nos. In the same manner as in Example 727 except that the charge transporting substance shown in Table 41 below was used in place of 18, the photoconductor No. 728-748 were created. A copying machine (Recopy FT60) modified to negatively charge the photoconductor prepared above.
80), and the probe of the surface electrometer was set so that the surface potential of the photoreceptor immediately before development could be measured. In addition, after continuous copying of 9,990 sheets, the photoconductor was taken out of the copying machine, and subjected to heat treatment at 130 ° C. for 20 minutes with a fatigue recovery device as shown in FIG. After returning, copying was performed up to a total of 10,000 sheets, and the surface potentials of the tenth sheet and the 10,000th sheet were measured. The environmental conditions were 25 ° C-50% RH.

Comparative Examples 727 to 748 The same evaluations as in Examples 727 to 748 were carried out except that the heat treatment was carried out at 25 ° C. (that is, the same as room temperature). The results of Examples 727 to 748 and Comparative Examples 727 to 748 are shown in Table 4.
Note 1.

[Table 41]

Example 749 An aluminum drum having a length of 80 mm and a diameter of 340 mm was sequentially coated with a coating solution having the following composition and dried to form an intermediate layer.
(0.3μ), charge generation layer (0.2μ), charge transport layer (20μ). (1) Intermediate layer coating liquid Water-soluble polyvinyl butyral 25% aqueous solution (Sekisui Chemical Co., Ltd .: S-REC W-201) 50 parts by weight Water 150 parts by weight Methanol 200 parts by weight (2) Charge generating layer coating liquid Pigment No. in the present invention ． a-8-24 azo pigment 2 parts by weight Water-soluble polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 0.7 parts by weight Tetrahydrofuran 80 parts by weight Ethyl cellosolve 120 parts by weight (3) Coating liquid for charge transport layer In the invention, the charge-transporting substance Nos. 29 10 parts by weight Polycarbonate (Teijin: Panlite C-1400) 10 parts by weight Methylene chloride 80 parts by weight Photoreceptor No. 749 was created.

Examples 750 to 770 Pigment No. used in Example 749 Instead of a-8-24, the azo pigments shown in Table 42 below were used, and the charge-transporting substance Nos. Photosensitive member No. 29 was obtained in the same manner as in Example 749 except that the surface charge transporting substances shown in Table 42 below were used instead of 29. 750-770 were created. The photocopier created as described above was modified so that it would be negatively charged.
5050), using a 2.45 GHz magnetron as a high-frequency power source, a separately provided ferromagnetic material (a plate in which Felock sprayer particles are dispersed in resin is provided with an electrode on a plate, the temperature of the photosensitive member is 50 ± 2 After setting each condition, the copying machine was repeatedly used to make 9,000 continuous copies.The environment was 23 ° C.-50% RH. The ID value was evaluated by the same method as used in.

Comparative Examples 749 to 770 The same evaluations as in Examples 749 to 770 were made except that high frequency heating was not performed. The results of Examples 749 to 770 and Comparative Examples 749 to 770 are shown in Table 42.

[Table 42]

[0193]

[Effect] Since the method of the present invention has the above-mentioned constitution, it has the following remarkable operational effects. (1) It is possible to prevent deterioration of charging characteristics after repeated use of the organic photoreceptor. That is, when the image density of a copying machine, a printer or the like is reduced, the image density is uneven, or the reverse development is performed, a good image without background stain can be obtained. (2) Image humidity can be prevented by reducing the relative humidity of the photoconductor atmosphere under high temperature and high humidity. (3) It is possible to prevent the photoconductor from being connected at a low temperature and the image background stain at a low temperature and low humidity.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a configuration example of a photoconductor used in the present invention.

2 (a) and 2 (b) are cross-sectional views showing another constitutional example of a photoconductor used in the present invention.

FIG. 3 is a cross-sectional view showing still another configuration example of the photoconductor used in the present invention.

FIG. 4 is a cross-sectional view showing another configuration example of the photoconductor used in the present invention.

FIG. 5 is an explanatory diagram of a method for heating a belt-shaped photoconductor.

FIG. 6 is an explanatory diagram of another heating method of the belt-shaped photoreceptor.

FIG. 7 is an explanatory diagram of still another heating method of the belt-shaped photoreceptor.

FIG. 8 is an explanatory diagram of a method of heating a photoconductor using a roller as a heating element.

FIG. 9 is an explanatory diagram of still another photosensitive method of a photosensitive member using a roller as a heating element.

FIG. 10 is an illustration of a method for heating a drum-shaped photoconductor.

FIG. 11 is an explanatory diagram of another heating method for the drum-shaped photosensitive member.

12A to 12C are explanatory views of a typical apparatus for recovering fatigue from a photoreceptor used in the present invention.

[Explanation of symbols]

 11 Conductive Support 13 Intermediate Layer 14 Photosensitive Layer 15 Protective Layer 21 Charge Generation Layer 22 Charge Transport Layer 31 Belt-Shaped Photosensitive Body 32 Driven Roller 34 Drive Roller 35 Developing Roller 36 Filter 37 Cover 38 Mirror 39 Infrared Lamp 41 Heat Generation Roller 42 Heat Pipe 43 Resistance heater 51 Drum-shaped photoconductor 52 Mechanical seal part 53 Rotating gear 54 Flow of liquid for temperature adjustment 55 Heating element having PTC characteristics 61 Heating device body 62 Light-shielding packing 63 Door 64 Handle 65 Hinge 71 Surface heating Body 72 Drum receiving jig

Claims (6)

[Claims] 1. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer containing a compound represented by the following general formula (I) is heat-treated in the image forming apparatus or outside the image forming apparatus. A method for recovering fatigue from an electrophotographic photoreceptor, which is characterized by the above. [Chemical 1] 2. An electrophotographic photoreceptor having a photosensitive layer containing a compound represented by the following general formula (II) on a conductive support is heat-treated in an image forming apparatus or outside the image forming apparatus. A method for recovering fatigue from an electrophotographic photoreceptor, which is characterized by the above. [Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and these may be the same or different.) 3. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer containing a compound represented by the following general formula (III) is heat-treated in the image forming apparatus or outside the image forming apparatus. A method for recovering fatigue from an electrophotographic photoreceptor, which is characterized by the above. [Chemical 3] 4. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer containing a compound represented by the following general formula (IV) is heat-treated in the image forming apparatus or outside the image forming apparatus. A method for recovering fatigue from an electrophotographic photoreceptor, which is characterized by the above. [Chemical 4] 5. An electrophotographic photoreceptor having a photosensitive layer containing a compound represented by the following general formula (V) on a conductive support is heat-treated in an image forming apparatus or outside the image forming apparatus. A method for recovering fatigue from an electrophotographic photoreceptor, which is characterized by the above. [Chemical 5] 6. The electrophotographic photosensitive member, in the photosensitive layer,
The method for recovering fatigue from an electrophotographic photosensitive member according to claim 1, further comprising an azo pigment as a charge generating substance.