DE60110013T2 - An electrophotographic photoreceptor, image recording method and apparatus unit including the photoreceptor - Google Patents

Description

BACKGROUND THE INVENTION

Territory of invention

The The present invention relates to an electrophotographic photoreceptor. moreover The present invention relates to an electrophotographic image recording method and an electrophotographic image recording apparatus, the use the photoreceptor. Furthermore, the present invention relates a process cartridge for the electrophotographic image recording apparatus which includes the photoreceptor.

discussion of the background

When Electrophotographic image recording methods are various Methods using a photoreceptor, such as the Carlson method and the methods derived therefrom are known for image recording devices, like photocopiers and printers. Among those for such image recording methods currently used photoreceptors are a use organic photosensitive material, put into use because they have advantages such as low cost, good productivity and low pollution.

• (1) organische photoleitende Harzschichten, wie in typischer Weise Poly-N-vinylcarbazol;
• (2) lichtempfindliche Schichten vom Typ der Charge-Transfer-Komplexe, wie in typischer Weise eine Kombination von Poly-N-vinylcarbazol (PVK) mit 2,4,7-Trinitrofluorenon (TNF);
• (3) lichtempfindliche Schichten vom Typ der Pigmentdispersion, wie in typischer Weise eine Kombination von Phthalocyanin und einem Bindemittelharz; und
• (4) funktionsmäßig getrennte lichtempfindliche Schichten, wie in typischer Weise eine Kombination eines ladungserzeugenden Materials und eines Ladungstransportmaterials.

Specific examples of the organic photoreceptors include the photoreceptors including one of the following photosensitive layers:

• (1) organic photoconductive resin layers such as typically poly-N-vinylcarbazole;
• (2) charge-transfer type photosensitive layers, typically a combination of poly-N-vinylcarbazole (PVK) with 2,4,7-trinitrofluorenone (TNF);
• (3) pigment dispersion type photosensitive layers, as typically a combination of phthalocyanine and a binder resin; and
• (4) functionally separate photosensitive layers, such as typically a combination of a charge generating material and a charge transport material.

Under These photoreceptors excite the functionally separate photoreceptors currently considerable Attention.

• (1) Aufladen eines elektrophotographischen Photorezeptors an einem dunklen Ort (Aufladungsvorgang);
• (2) Bestrahlen des aufgeladenen Photorezeptors mit bildmäßigem Licht, um ein elektrostatisches latentes Bild darauf zu bilden (Belichtungsvorgang);
• (3) Entwickeln des latenten Bildes mit einem Entwickler, der einen Toner, zusammengesetzt hauptsächlich aus einem farbgebenden Mittel und einem Bindemittel, beinhaltet, um darauf ein Tonerbild zu erzeugen (Entwicklungsvorgang);
• (4) gegebenenfalls Übertragen des Tonerbildes auf ein intermediäres Übertragungsmedium (erster Übertragungsvorgang);
• (5) Übertragen des Tonerbildes auf ein Empfangsmaterial, wie ein Empfangspapier (zweiter Übertragungsvorgang);
• (6) Erwärmen des Tonerbildes, um das Tonerbild auf dem Empfangsmaterial zu fixieren (Fixiervorgang); und
• (7) Reinigen der Oberfläche des Photorezeptors (Reinigungsvorgang).

The electrophotographic image recording methods typically include the following operations:

• (1) Charging an electrophotographic photoreceptor in a dark place (charging operation);
• (2) irradiating the charged photoreceptor with imagewise light to form an electrostatic latent image thereon (exposure process);
• (3) developing the latent image with a developer containing a toner composed mainly of a coloring agent and a binder to form thereon a toner image (developing process);
• (4) optionally transferring the toner image to an intermediate transfer medium (first transfer operation);
• (5) transferring the toner image to a receiving material such as a receiving paper (second transfer operation);
• (6) heating the toner image to fix the toner image on the receiver (fixing process); and
• (7) Cleaning the surface of the photoreceptor (cleaning process).

• (1) wenn die lichtempfindliche Schicht belichtet wird, nachdem sie aufgeladen wurde, durchläuft Licht die durchsichtige Ladungstransportschicht und erreicht dann die Ladungserzeugungsschicht;
• (2) das in der Ladungserzeugungsschicht beinhaltete Ladungserzeugungsmaterial absorbiert das Licht und erzeugt einen Ladungsträger, wie Elektronen und positive Löcher;
• (3) der Ladungsträger wird in die Ladungstransportschicht injiziert und durch die Ladungstransportschicht transportiert, was von dem durch die Aufladung auf der lichtempfindlichen Schicht erzeugten elektrischen Feld bewirkt wird;
• (4) zum Schluss erreicht der Ladungsträger die Oberfläche der lichtempfindlichen Schicht und neutralisiert die Ladung darauf, was die Bildung eines elektrostatischen latenten Bildes zur Folge hat.

The mechanism of forming an electrostatic latent image in the functionally separated photosensitive layer having a charge generation layer and a charge transport layer formed on the charge generation layer is as follows.

• (1) when the photosensitive layer is exposed after being charged, light passes through the transparent charge transport layer and then reaches the charge generation layer;
• (2) the charge generation material included in the charge generation layer absorbs the light and generates a carrier such as electrons and positive holes;
• (3) the carrier is injected into the charge transport layer and transported by the charge transport layer, which is caused by the electric field generated by the charge on the photosensitive layer;
• (4) Finally, the carrier reaches the surface of the photosensitive layer and neutralizes the charge thereon, resulting in the formation of an electrostatic latent image.

For such functionally separate Photoreceptors is a combination of a predominantly ultraviolet Light-absorbing charge transport material and one mainly visible Light absorbing charge generating material known for useful to be.

Currently There is a need for a long life photoreceptor. In particular, became mainly then researched, the mechanical life (that is, the abrasion resistance) of the photoreceptors. For example, in Japanese Patent publication (on such publications will hereinafter be referred to as "JPP") No. 8-20739, etc. new binder resins have been proposed, and Various photoreceptors having a novel structure are also disclosed Service. That's because the life of a photoreceptor essentially does not depend on the abrasion of the photosensitive layer about the deterioration of the electrostatic properties of the photoreceptor.

However, when the abrasion resistance of photoreceptors is improved by various methods, it is believed that there is a significant demand for improving the degradation of the electrostatic characteristics such as the decrease of the charging potential (that is, the potential of a dark region V _{D of} the photoreceptor) sometimes referred to as dark field potential) and the increase in residual potential (that is, the potential of an exposed area V _{L of} the photoreceptor, which will hereinafter sometimes be referred to as bright area potential). In an attempt to improve the degradation of the electrostatic characteristics, principal materials constituting organic photoreceptors such as charge-generating materials and charge-transporting materials have been improved. Moreover, such methods as adding various additives, such as antioxidants, to the photoreceptors have also been proposed. However, there is an exchange relationship between the deteriorated electrostatic properties, that is, the decrease of the charging potential and the increase of the residual potential. Therefore, there is no method to improve both the decrease of the charging potential and the increase of the residual potential. Therefore, a photoreceptor having a good combination of high dark area potential and low residual potential is eagerly desired.

When one of the measures against abrasion of the photoreceptors, methods have been proposed in those on the surface a photoreceptor is formed a protective layer. investigations for the formation of a protective layer were first used for inorganic Photoreceptors are employed and are disclosed, for example, in JPP 2-3171, 2-7058 and 3-43618. In these cases, in which a protective layer is formed on inorganic photoreceptors is used for the protective layer preferably a filler with a relatively low Resistor used. Therefore, when such photoreceptors charged be, the entire protective layer or the boundary layer between the protective layer and the inorganic photosensitive layer typically charged rather than the surface of the photoreceptor.

If a latent image not on the surface of the photoreceptor, but is formed on the inside of the protective layer, the photoreceptor the advantage that the resulting electrostatic latent Image barely of defects on the surface of the photoreceptor, such as Scratches, is affected. However, it has a large amount of electrically conductive Filler, Like metal oxides, the protective layer can be added to the protective layer to give a protective function. In such a case, the Resistance of the entire protective layer or the surface resistance the protective layer, even if the protective layer made transparent is used by using a suitable metal oxide, which makes the occurrence more washed out Images with repeated use. In the attempt To solve the problem of blurred images have JPP 2-7057 and the Japanese Patent No. 2,675,035 proposed methods in which the concentration of an electrically conductive metal oxide in the depth direction the protective layer changes.

Around moreover, solving the problem of washed-out images on the process side becomes a device including a heater which heats the photoreceptor is proposed. By heating the Photoreceptor can avoid the appearance of blurred images become. However, if a drum heater is used in the photoreceptor the diameter of the photoreceptor must be made larger.

Currently, electrophotographic image recording devices are becoming more and more miniaturized, and therefore, photoreceptors having a small diameter are mainly used. Because this heating method can not be used for such a small diameter photoreceptor, it is difficult to provide a small diameter photoreceptor having a good lifetime. Moreover, when a drum heater is provided in an image forming apparatus, the apparatus has many disadvantages in that the apparatus becomes large; the electrical power consumption increases strongly; and it takes a long time for the device to warm up.

If a protective layer containing a filler with a low electrical resistance as a surface layer on an organic Photoreceptor (a so-called OPC) is formed, which is a charge-generating material and involves a charge transport material, the problem arises that the resulting images have a pulling effect when the photoreceptor is used repeatedly. Moreover, if that is above mentioned Procedure for OPC's used which is the concentration of one in a protective layer included electrically conductive Metal oxide in the depth direction of the protective layer changes, the for inorganic Photoreceptors useful is, almost the same results received (that is, arise Pictures with pulling effect).

Of the the reason for this is not clear yet but it is believed to be that the current Image forming method in which dot images according to digital Signals on the surface of a photoreceptor are highly dependent on the differentiate old imaging methods, in which typically an inorganic photoreceptor is used (that is, in which an analog image is formed on an inorganic photoreceptor becomes). This means, the level of resolution requirements on a current photoreceptor formed latent images, placed from the machine side be, is to a great extent things have become different, and therefore the pulling effect can be felt be.

If such situations are taken into account, it is essential in the surface layer of a optical photoreceptor a filler high resistance in place of a low resistance filler to use. However, if a filler is used with high resistivity, a problem tends to occur in such a way that the residual potential of the resulting Photoreceptor increases. When the residual potential increases (that is, the Potential of the exposed area of a photoreceptor in one Image recording device increases), the image density and the halftone reproduction of the resulting images deteriorates. When one seeks to solve such problems, the darkroom potential should elevated become. However, if the dark field potential is increased, takes the electric field strength also to, what mistakes like background development and short Life of the photoreceptor entails.

In the effort to avoid the increase of the residual potential are in JPP 44-834, 43-16198 and 49-10258 methods in which a photoconductive protective layer produced has been disclosed. However, it becomes imagewise light absorbed by the protective layer, and therefore the amount of light decreases which reaches the photosensitive layer, which decreases the Photosensitivity of the photoreceptor has the consequence. It will therefore scored little effect.

The Japanese Patent Laid-Open Publication (to these publications hereinafter referred to as JOP) No. 57-30846 a method in which a metal or a metal oxide with a middle Particle diameter of not more than 0.3 μm as a filler in a protective layer is included to produce a transparent protective layer, which prevents the increase of the residual potential. However, that is Impact of preventing the increase in residual potential not sufficient, and therefore the problem can not be solved.

The This is because the increase in residual potential is due to charge trapping because of the added filler and uneven distribution of the filler as by deterioration of the efficiency of charge generation is caused. Even if a filler with a medium Particle diameter of not greater than 0.3 μm used the transparency of the resulting protective layer decreases, if the filler aggregated. In contrast, a transparent protective layer be formed when a filler having an average particle diameter of not less than 0.3 μm if the filler is equally distributed is.

Moreover, JOP 4-281461 discloses an effort to produce a photoreceptor capable of preventing the increase of the residual potential while having a good mechanical strength, a method in which a charge transport material together with a filler is protected layer is included. The incorporation of a charge transport material in a protective layer improves the charge mobility, and therefore the increase of the residual potential can be reduced to some extent. However, when a filler is added, the residual potential is significantly increased, which is caused by the increase in the resistance of the protective layer and the number of charge trapping sites in the protective layer. Therefore, the limitation of the increase of the residual potential by means of this method meets with a limit. The thickness of the protective layer must be reduced or the filler content reduced. Accordingly, the demand for a good life photoreceptor can not be satisfied.

When other methods of containment The increase of the residual potential is a method in which a Lewis acid in a Protective layer is included (JOP 53-133444); a method in which a organic proton acid included in a protective layer (JOP 55-157748); a procedure, in which an electron acceptor material is included in a protective layer is (JOP 2-4275); and a method in which a wax with a acid value of 5 mgKOH / g in a protective layer (JOP 2000-66434), been revealed.

These Methods improve charge injection at the interface between the protective layer and the charge transport layer. It is believed, that by means of these methods subregions with a low resistance be generated in the protective layer and the charge the surface of the Protective layer can achieve what a decrease of the residual potential to Episode has. However, those produced by these methods tend to be Pictures to be washed out. When an organic acid in the In addition, the degree of dispersion tends to be protective of the filler in the protective layer to be deteriorated. Consequently have These procedures have detrimental effects, and therefore can be said be that the problem can not be solved.

In Photoreceptors in which a filler is included, in order to improve their lifespan, it is necessary avoiding the production of washed-out images and the rise of the residual potential to curb High quality pictures manufacture. moreover It is also important that charges in the photoreceptor be straightforward to the surface move the photoreceptor, without being in the protective layer included filler disturbed to become. Therefore, the filler included in the protective layer must be be well distributed in it. If that included in a protective layer filler The balling up, the movements of the charges that come out the charge transport layer are injected into the protective layer, through the filler disturbed, when the charges move to the surface of the protective layer. Therefore, a toner image composed of scattered toner particles becomes resulting in deterioration of the resolving power of the toner image Has.

If moreover pictorial light such a protective layer radiates, which is a zusammenge filler includes, the light is scattered by the filler, causing deterioration the translucency entails, and thereby worsens the resolution of the resulting image.

Further influences the degree of dispersion of one included in the protective layer filler to a large extent the Abrasion resistance of the photoreceptor. When a filler clumps together, (this means, the filler is poorly dispersed), the abrasion resistance of the resulting Photoreceptor deteriorates. To provide a photoreceptor in which a filler Included in a protective layer is the life of the photoreceptor It is, therefore, to improve that can produce high quality images important, not just the appearance of blurred images and the increase of the residual potential, but also the degree of dispersion of the filler to improve in the protective layer.

A Solution, by means of which these problems are solved at the same time however, it has not yet been found. Namely, when a filler in a surface layer a photoreceptor is included to improve its life, Slurred images tend to be produced and the residual potential tends to increase, and therefore the problem remains that images high quality can not be obtained. As mentioned above, should be a drum heater in an image recording apparatus to improve such a problem. Meanwhile, a drum heater in a small size photoreceptor that desirably should have a good life, not be installed. There is Therefore, no small photoreceptor with good life, too High quality pictures can produce. The installation of a drum heater is a hindrance to a miniaturized An image recording apparatus and an image recording apparatus with low consumption of electrical energy.

At present, organic photoreceptors have advantages over inorganic photoreceptors, such as high photosensitivity, broad spectral photosensitivity, low environmental pollution and good electrostatic lifetime. In order to make full use of such advantages, the mecha nical life and the electrostatic lifetime of the organic photoreceptors can be improved. Moreover, a photoreceptor capable of producing high quality images while having a good life is particularly desirable for producing a good life imaging device.

SUMMARY THE INVENTION

Accordingly, it is an object of the present invention to provide a photoreceptor the pictures of high quality can produce and has a good life. Specific is It is an object of the present invention to provide a stable photoreceptor to provide a good mechanical life and good has electrostatic lifetime (that is, the increase in residual potential and the occurrence of blurred images can be contained), and the images high quality even with repeated use.

One Another object of the present invention is to provide a photoreceptor to provide the stable photosensitivity properties even if environmental conditions such as temperature and humidity change, and the resistant against reaction gases such as ozone and NOx.

Yet Another object of the present invention is an image recording method which uses the above-mentioned photoreceptor and with the stable quality pictures a long time Can be produced for a long time.

One Another object of the present invention is to provide an image recording apparatus small size and one Process cartridge provide, with which images in a stable manner high quality can be made for a long time, often without the To change the photoreceptor.

Short can said These objects and other objects of the present invention as herein hereinafter will be more readily apparent by means of an electrophotographic Photoreceptor can be achieved, the at least one electrically conductive substrate, a photosensitive layer formed on the substrate; a binder, and a protective layer on the photosensitive Layer is formed and a binder resin and a filler wherein the binder resin for the protective layer and optionally also the binder resin for the photosensitive layer comprises a material such that when a solution, in which the binder resin is in an organic solvent, which is incompatible with water, is dissolved with deionized Water with an electrical conductivity of not more than 1 μS / cm and essentially the same weight as that of the solvent mixed and stirred the deionized water becomes an electrical conductivity of not more than 2 μs / cm having.

It it is preferred that the binder resin beforehand a cleaning treatment, such as washing treatments that use a caustic and / or an acid, is subjected to remove ionic impurities from it.

The Binder resin preferably includes a polycarbonate resin.

The protective layer (that is, the surface layer) includes a filler. The filler is preferably an inorganic pigment having a resistivity of not less than 10 ¹⁰ Ω · cm. The inorganic pigment is preferably a metal oxide selected from the group consisting of silica, alumina and titanium oxide.

Of the pH and the dielectric constant of the inorganic pigment are preferably not less as 5 or not less than 5. The surface of the inorganic pigment was preferably subjected to a treatment being a material selected from the group consisting of titanate coupling agents, aluminum coupling agents, higher fatty acids, Alumina, titania and zirconia and mixtures thereof, and the mixtures thereof with a silane coupling agent having at least one of the aforementioned Materials is preferably used. The ratio (Ws / Wf) of the Weight of surface treatment agent to the weight (Wf) of the filler is from 0.03 to 0.30. The mean primary particle diameter of the filler is preferably from 0.01 to 0.5 μm.

The Protective layer preferably includes a charge transport material. The charge transport material is preferably a charge transport polymer, such as a polycarbonate resin having a triarylamine structure in the main chain and / or side chain.

worin R1 und R2 unabhängig voneinander ein Wasserstoffatom, eine substituierte oder unsubstituierte aliphatische Gruppe, einen substituierten oder unsubstituierten Kohlenstoffring oder eine substituierte oder unsubstituierte aromatische Gruppe darstellen; und R3 bis R10 unabhängig voneinander ein Wasserstoffatom, ein Halogenatom, eine substituierte oder unsubstituierte aliphatische Gruppe oder einen substituierten oder unsubstituierten Kohlenstoffring darstellen, und

worin R3 bis R10 unabhängig voneinander ein Wasserstoffatom, ein Halogenatom, eine substituierte oder unsubstituierte aliphatische Gruppe oder einen substituierten oder unsubstituierten Kohlenstoffring darstellen, und Z eine Atomgruppe, die zur Bildung eines substituierten oder unsubstituierten Kohlenstoffrings oder einer unsubstituierten heterocyclischen Gruppe notwendig ist, darstellt.The polycarbonate resin preferably has a structural unit selected from the following formulas (A) and (B):

wherein R1 and R2 independently represent a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted carbon ring or a substituted or unsubstituted aromatic group; and R3 to R10 independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted carbon ring, and

wherein R3 to R10 independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted carbon ring, and Z represents an atomic group necessary for forming a substituted or unsubstituted carbon ring or an unsubstituted heterocyclic group.

The structural unit is preferably one of the following structural units (1) to (3):

In Another aspect of the present invention is an image recording method providing the steps of charging the photoreceptor of the present invention, exposing the charged photoreceptor, to form an electrostatic latent image of developing of the latent image with a developer to form a toner image on the To form photoreceptor, and transferring the toner image includes on a receiving material. The exposure process will be preferably in a digital manner using a laser diode (LD) or a light emitting diode (LED, Light Emitting Diode) carried out (that is, out Points existing light images are by irradiation of a light beam formed on the photoreceptor).

The Image recording method preferably further includes a Step of applying zinc stearate to the surface of the Photoreceptor. moreover contains the toner is preferably zinc stearate. It is also preferable that if the one mentioned above Image recording process is not performed, a cleaning process, including the steps of adhering the toner to the surface of the toner Photoreceptor in the development area and collecting the toner in the cleaning area.

In Still another aspect of the present invention is an image recording apparatus providing the photoreceptor of the present invention, a charging device configured to charge the photoreceptor is an image irradiation apparatus configured to expose the photoreceptor is to form an electrostatic latent image on it Image development device used to develop the latent image with a developer configured to apply a toner image to it form, and a transmission device, those for transfer the toner image is configured on a receiving material includes.

Preferably the charging device is a contact charging device or a close charging device. Preferably is to the charger a DC voltage, which superimposes an AC voltage was created. It is preferred that the exposure device using a laser diode (LD) or a light emitting diode (LED) as light source writes digital photographs. Furthermore, it is preferable in that the image recording apparatus further comprises a lubricant applicator, which applies a lubricant such as stearic acid to the photoreceptor.

In Another aspect of the present invention is a process cartridge for one Imaging device provided, which is the photoreceptor of the present invention, a housing and at least one device from a charging device, an image irradiation device, a Image development device, an image transfer device, a Cleaning device and a discharge device includes.

These and other objects, features and advantages of the present invention will become apparent when the following description of the preferred embodiments of the present invention, in conjunction with the accompanying drawings, considering is pulled.

SHORT DESCRIPTION THE DRAWINGS

Various other objectives, characteristics and related benefits of the present Invention become more complete appreciated can be if better understood from the description in detail when used in conjunction with the accompanying drawings in consideration is drawn, in which same reference letters are the same throughout denote corresponding parts and wherein:

1 Fig. 12 is a schematic view illustrating the cross section of one embodiment of the photoreceptor of the present invention;

2 Fig. 12 is a schematic view illustrating the cross section of another embodiment of the photoreceptor of the present invention;

3 Fig. 12 is a schematic view illustrating an embodiment of the image recording apparatus of the present invention and serving to explain the image recording method of the present invention;

4 Fig. 12 is a schematic view illustrating another embodiment of the image recording apparatus of the present invention and serving to explain the image recording method of the present invention;

5 Fig. 12 is a schematic view illustrating an embodiment of the process cartridge of the present invention;

6 an X-ray spectrum of the titanyl phthalocyanine used in Examples of the present invention; and

7 is a schematic view showing still another embodiment of the image recording Device of the present invention illustrated.

DETAILED DESCRIPTION OF THE INVENTION

Of the Inventor has investigated why the electrostatic properties of photoreceptors deteriorate if used repeatedly or if they are used in an atmosphere that is reactive Gases like ozone and NOx are included. As a result, the Properties improved to some extent Be the main components of the photoreceptor, such as the materials for charge generation and charge transport materials become. This means, by the skeleton and / or physical properties of the main components are changed, can the electrostatic properties of the photoreceptor in some way Extent improved become. The inventor has found that the purity of such Components to a large extent the electrostatic properties affected. Among the main components is the content of the binder resin in the photoreceptor about 50% or more, based on the total weight the layers such as the photosensitive layer and the protective layer. conventional Way, the binder resins have been improved, with their mechanical Properties attention has been paid to the purity of binder resins but was not investigated.

Of the Inventor has the purity, the purification method and so on investigated the photoreceptor-based binder resins. When a result is found that by removing ionic Impurities from the binder resins contained in a photoreceptor dramatically improves the electrostatic properties can be and specifically the decline the dark potential of the photoreceptor and the increase of its residual potential contained can be.

The Purity and cleaning methods used by photoreceptors Binder resins are disclosed in JOP 7-84377 and 10-133405 Service.

In JOP 7-84377 is disclosed that a polycarbonate resin containing free chlorine in an amount of not more than 2 ppm, in the photosensitive Layer is used. Typical polycarbonate resins include free Chlorine in an amount of about 2 to 10 ppm. If a polycarbonate resin, the free chlorine in a big one Amount includes used in a photosensitive layer The problem that occurs is that unwanted little black dot images (or pinholes in solid tones) are formed. JOP 7-84377 discloses that this problem can be avoided by the mentioned above Polycarbonate resin is used.

Of the The photoreceptor disclosed in JOP 7-84377 has a structure in which a photosensitive layer is formed on a substrate, or a layered structure in which a charge generation layer and a charge transport layer as a photosensitive layer are formed on a substrate. In such photoreceptors For repeated use, the photosensitive layer is widely used subjected to abrasion. Therefore, the unwanted images appear as washed out Pictures for the photoreceptors containing a protective layer are typical are not up. This means, JOP 7-84377 relates Do not focus on the problem that occurs when using a protective coating containing photoreceptors are used. The goal of the present The invention is to provide a photoreceptor which is a protective layer and does not cause such a problem.

In JOP 7-84377 discloses that the photoreceptor is a protective layer may include. However, there is no description regarding the above mentioned specific polycarbonate exists, and therefore it is not clear whether the aforementioned Problem of the photoreceptor, which has a protective layer can be solved can.

In The examples disclosed in JOP 7-84377 will be the electrical conductivity the aqueous Layer measured, which is formed when a polycarbonate resin cleaned becomes. The specific data of electrical conductivity are 4.4, 3.5, 3.9 and 12.7 μS / cm. These data are almost the same as those of the following mentioned Comparative Examples in the present application. As follows mentioned, The resulting photoreceptor can not solve the problem if Such polycarbonate resins for a Photoreceptor can be used, that is, the formation of washed-out Pictures can not be avoided.

In other words, in order to solve the problem of the blurred images, it is necessary to treat the polycarbonate resins with a purification treatment for a higher purity level than that of the cleaning treatment disclosed in JOP 7-84377. It can be said that even if the in JOP 7-84377 disclosed polycarbonate resins are used in a protective layer, the problem of blurred images can not be solved.

moreover The problem of blurred images is due to various ionic Impurities contained in the resin contained in the protective layer are caused. As a result of the investigations The inventor makes different materials with low electrical resistance, which added from the photoreceptors from the outside Ion-formed salts are found in the photoreceptors. It It is therefore assumed that anions and cations are traps or adsorption sites serve. Accordingly, there is no effect if only the amount of free chlorine is reduced.

JOP 10-133405 discloses a charge transport polymer material whose Degree of purification is represented by the pH and a the Charge transport polymer using photoreceptor. Specific JOP 10-133405 discloses that the properties of a photoreceptor on the purity of the charge transport material included in the photoreceptor be influenced and that for materials with low Molecular weight useful Cleaning procedures should not be applied to polymer materials can. It also discloses that by using a charge transport polymer material in a photoreceptor that has been purified so that the pH the extracted solution in the cleaning process falls within a specific range, the resulting photoreceptor has stable electrical properties.

If such a charge transport polymer material as disclosed in JOP 10-133405, is used in a charge transport layer has the charge transport layer a better abrasion resistance than that of a charge transport layer, in which a low molecular weight charge transport material is dispersed in a polymer (on this charge transport layer sometimes referred to as an MDP layer).

Charge transport polymer materials have a group with a charge transport function in their main chain or side chain. In particular, a triphenylamine structure is for charge transport polymer materials useful, as in JOP-133405 is disclosed. The triphenylamine structure is a propeller structure, whose center is a nitrogen atom, and it is very bulky. Therefore, such a charge transport polymer layer has in comparison to MDP layers a relatively high Abrasion resistance. However, the abrasion resistance is the charge transport polymer layer at the most about twice that of MDP layers, as in the JOP 9-311479 and 9-311487.

of course is it is possible To reduce the content of the charge transport group to the abrasion resistance of to improve the resulting charge transport layer. However, it will by using this method, the charge transportability of Charge transport layer decreases, similar to the case in the content of a low molecular weight charge transport material which is included in an MDP layer, and it This causes problems such that the mobility is reduced and increase of the residual potential occurs. Therefore this procedure is not useable.

If the photoreceptor disclosed in JOP 10-1433405 and the Charge transport polymer material in the charge transport layer In practice, abrasion is reduced. However, the photoreceptor is still pretty much eroded, so the problem of blurred images does not occur. Therefore it is not clear if the problem prevents the blurred images can be when the charge transport polymer material used in JOP 10-133405 in a protective layer is used.

In the examples of JOP 10-133405 is the electrical conductivity used for the washing treatment of the charge transport polymer material aqueous solution in the range of 2.30 to 8.69 μS / cm. moreover In the examples, the amount of deionized water is one solution of the charge transport polymer material in methylene chloride, which is four times the amount of the Dissolve of the charge transport polymer material used methylene chloride. In contrast, in the method for determining the electrical conductivity in the present application, the amount of added deionized Water is the same as that of the solvent containing the binder resin solves. Therefore, must the conductivity (2.30 to 8.69 μS / cm) in JOP 10-133405 be multiplied by 4 when using the electrical conductivity is compared in the present application. That is, actually is the conductivity the aqueous solution in the examples of JOP 10-133405 about 8 to 30 μS / cm. These Data are almost the same as those of Comparative Examples of the present application.

Therefore the problem of blurred images can not be solved even if such a charge transport polymer material for the protective layer is used. In other words, it solves the problem of being washed-out Pictures needed, the charge transport polymer materials with a cleaning treatment for a higher Purity level than that of the cleaning treatment disclosed in JOP 10-133405 to treat.

moreover will the extent of Purification of charge transport polymer materials based on the pH of the aqueous solution assessed. This means, This process attracts water-soluble basic impurities in the aqueous solution into consideration. Definitely cause such water-soluble basic impurities increase the residual potential of a Photoreceptor using positive holes as a support become. However, the problem of washed-out images is due to basic and also caused by acid impurities. Therefore, that is impossible To avoid the problem of washed-out images by simply using the Concentration of the basic impurities is controlled.

Of the Reason why the deterioration of the electrostatic properties of a photoreceptor when used repeatedly or when used in an atmosphere which includes reactive gases by purifying the binder resin (this means by removing ionic impurities from the binder resin) can be improved has not been established with certainty Service. However, it is assumed that the reason is as follows.

If a photoreceptor with pictorial light is exposed, the photosensitive layer absorbs the light and generates photo-carriers. The photo-charge carriers thus generated pass through the photosensitive Layer to its surface or to the substrate, and finally neutralize the charges (or the charges induced by the charges), which is the fulfillment of the Functions result. In terms of these features, this has Binder resin nothing to the generation of photo-charge carriers too but it plays an important role in transporting the Photo-carriers.

In OPC's takes place Transport of the charge carriers essentially by jumping line. Cation radicals (if positive holes transported) or anion radicals (when transporting electrons be) move through the photosensitive layer by holes or electrons are exchanged. Therefore, it is for the binder resin, which has nothing to do with the transport of cargo, very important, neutral to be when loads are transported. In other words become charge carriers with one polarity, the polarity of the ionic impurities is opposite to the impurities captured when ionic impurities in the binder resin are included. Therefore, it is believed that avoidance of a Such capture very effective against the increase of the residual potential is. Such ionic impurities move with repeated use along the electric generated on the photosensitive layer Field, and therefore tend to be weak spots in the photosensitive Layer to be damaged by the impurities, causing an acceleration the deterioration of the components of the photosensitive layer entails.

The electrostatic properties of a photoreceptor are degraded, if the photoreceptor is used repeatedly or if the photoreceptor in an atmosphere is used, which contains reactive gases. In the latter case will the deterioration caused by a phenomenon in the charge carriers, the captured in the photosensitive layer before charging are discharged when the photosensitive layer is charged is, or by a phenomenon, in the thermal carrier due of the electric field that is formed when the photosensitive Layer is charged, generated. It is believed that the ionic impurities the trapping of the charge carriers and trigger the generation of thermal charge carriers.

In In the latter case, the constitutive components of the photosensitive Shift reduced in quality, when the photoreceptor is exposed to reactive gases. This deterioration can not only be explained by the gas permeability of the materials, and it is believed that any absorption sites in the photosensitive layer are present which the reactive Absorbing gases. In view of this phenomenon, the moisture can the photosensitive layer are not neglected. The ionic Impurities have a high affinity for water and the reactive Gases. Therefore, it is believed that by sufficient removal such impurities, the deterioration of the electrostatic Properties can be avoided.

In order for the life of a photoreceptor not to depend on its abrasion, the mechanical durability of the photoreceptor (that is, its abrasion resistance) must also be improved. Under the From the viewpoint, a photoreceptor in which the abrasion resistance of its photosensitive layer has been improved merely by improving the binder resin can not meet the requirements (that is, the long life requirement) for photoreceptors for use in the present image recording apparatus. Therefore, for use in the present image recording apparatus, the photoreceptor must have a protective layer on its surface.

In the present invention, the protective layer over the photosensitive layer formed to the photosensitive Layer against mechanical hazards and protect abrasion. Therefore, the protective layer has an abrasion resistance better than that of the MDP-type charge transport layer and a charge transport polymer including protective layer.

in the Generally, the abrasion of the protective layer is different from that used Image recording system depends, not bigger than the half that of the MDP charge transport layer and that of a charge transport polymer material containing charge transport layer. If, for example, a typical cylindrical photoreceptor is used, which has a diameter of 30 mm and having an MDP charge transport layer as one surface layer includes, amounts to the abrasion of the layer about 1.5 to 2 microns, when 10,000 receiving materials the size A4 fed to create toner images. If, in contrast, the photoreceptor is used with a protective layer of the present invention, the abrasion is not greater than about 0.5 μm and preferably not greater than 0.3 μm.

It Different protective layers are known. When the life of a current organic photoreceptor with respect to electrostatic properties with respect to its lifetime the abrasion resistance is compared, has a photoreceptor for Use in such a current image recording apparatus, as mentioned above, preferably an abrasion resistance several times that of the photoreceptors the type of MDP layer, which are still mainly for electrophotographic image recording devices be used. In other words, photoreceptors are one Charge transport polymer material include and about twice Abrasion resistance as the abrasion resistance of photoreceptors of Type of MDP layer, for the current image recording device unsatisfactory.

In The aim of the present invention is the desired level of abrasion resistance the protective layer not less than the multiple (preferably Five-time) Abrasion resistance of the photoreceptors of the MDP-layer type. One specific example of a protective layer with such good abrasion resistance, as mentioned above, is a protective layer consisting of a binder resin and a consists in the binder resin dispersed filler.

In In this case, the binder resin may be an electrically inactive polymer or a charge transport polymer.

The Protective layer is preferred for organic photoreceptors used. However, as mentioned above, the technical procedures used for conventional inorganic photoreceptors not necessarily for organic photoreceptors be used.

If namely a protective layer on an organic photosensitive layer is formed, a filler is typically included to the give the resulting photoreceptor a good abrasion resistance. However, if a material with a low resistivity (this means, an electrically conductive Material), which is typical for inorganic photoreceptors is used for organic photoreceptors is used from the beginning or with repeated use undesirable Images, such as washed-out images and those with a pulling effect, made. Therefore, a filler needs with a relatively high specific resistance can be used.

If but a filler with a relatively high Resistivity is used, the production of such undesirable Images are avoided, but there is another problem as the residual potential increases.

Conventional inorganic photoreceptors are used with or without a protective layer for positive charging processes. With respect to the charge transport materials for use in organic photoreceptors, materials for transport by positive holes and materials for electron transport have been studied. However, only the materials for transportation by means of holes were practically used. Therefore, almost all current functionally separated organic photores become Receivers are used for negative charge processes to ensure their good performance. provide. There are several photoreceptors having a monolayer photosensitive layer or having a contrasting structure in which a charge transport layer is formed on a charge generation layer, but these photoreceptors are not the primary ones.

When the reason why the technical process of protective coatings for inorganic Photoreceptors not applied to organic photoreceptors can be it is assumed that the polarity of the charges formed on the organic photoreceptors of one is different on the inorganic photoreceptors. The dark area potential of organic photoreceptors is almost the same as that of inorganic photoreceptors, though the polarity is different is. In terms of the efficiency of the charging of the charging devices is the Efficiency of the positive charge higher than that of the negative Charging.

moreover is the amount of reactive gases that occur during negative charge be generated much larger than the amount of reactive gases that generates when positively charged become. It is believed that the problem of washed-out images by the decrease of the surface resistance caused by the photoreceptor. It is also known that the Surface resistivity mainly reduced by the materials with low resistivity is generated by the reactive gases and at the surface of the photoreceptor.

Around to solve this problem, For example, methods of contact charging have been disclosed. It is sure that the concentration of ozone near the contact charging devices is present, compared to that when conventional Chargers (that is, Chargers without contact) are used, relatively low is. However, as a result of the inventor's investigations, the amount of low-resistance materials that are on the surface of a adhering to a contact charging device charged photoreceptor, almost the same as when charging with a charger without contact. It is believed that the reason for this The result is that when a contact charging device is used, the materials produced with low resistivity Plastic effect on the surface of the photoreceptor, and the adhering materials low resistivity can not be detached from the surface can, because no air flow is present between the charging device and the photoreceptor.

As from the aforementioned To understand the result of the investigation, it is essential to have a filler with a high resistivity in the surface layer to use if a surface layer on a for negative charge used photoreceptor is generated. Therefore A protective layer should be created on organic photoreceptors be that of the for conventional inorganic photoreceptors used protective layer differently is.

• (1) Vermeidung der Verschlechterung der Aufladungseigenschaften des Photorezeptors (das heißt, Abnahme des Dunkelgebietspotentials) bei Wiederholtverwendung, während die Zunahme des Restpotentials (das heißt, Zunahme des Hellgebietspotentials) verhindert wird; und
• (2) Vermeidung des Auftretens von ungewünschten Bildern, wie verwaschenen Bildern und Bildern mit niedriger Dichte, die durch die Ausbildung einer Schutzschicht, um die Abriebfestigkeit des Photorezeptors zu verbessern, verursacht werden.

That is, the following is needed to provide a photoreceptor with excellent lifetime:

• (1) prevention of deterioration of charge characteristics of the photoreceptor (that is, decrease in dark potential) in repeated use while preventing the increase in residual potential (that is, increase in bright spot potential); and
• (2) Prevention of the occurrence of undesired images such as washed-out images and low-density images caused by the formation of a protective layer to improve the abrasion resistance of the photoreceptor.

In the aforementioned Both points have the following three exchange relationships:

(A) an exchange relationship between the deterioration of the charging characteristics and the Increase in residual potential.

These Problems are caused by phenomena caused in the photosensitive layer and protective layer total or the interface occur in between. A measure like a change of used materials or layering to one of the problems to solve, worsens the other problem.

(B) an exchange relationship between the improvement of the abrasion resistance and the reduction the residual potential.

The Decrease of the residual potential of a photoreceptor is by a filler caused which is added to the protective layer to the abrasion resistance of the photoreceptor, or by those in the binder resin in the protective layer contained impurities which transport of carriers through the protective layer due to the increase in volume resistivity hinder the protective layer and the number of traps in it increase.

(C) an exchange relationship between the improvement of the abrasion resistance and the prevention washed-out pictures

If the abrasion resistance of the surface layer is improved, low resistance materials adhere caused by charging reactive gases generated are, at the surface layer, without being removed, resulting in a decrease in surface resistance the surface layer entails.

When a result of the investigations of the three described above phenomena (Exchange Relationships) by the inventor is found to be with outer or internal ionic contaminants have to do. That is, the three problems can solved at the same time be by for the protective layer and / or the photosensitive layer is a binder resin is used, removed from the ionic impurities to the highest degree have been. This means, a photoreceptor can be provided which has a good lifetime and the good pictures with repeated use can produce. moreover can an image recording method and an image recording apparatus and a process cartridge are provided by means of which stable way about good pictures can be produced over a long period of time. On This is how the present invention was made.

According to the present Invention provides an electrophotographic photoreceptor including at least one electrically conductive substrate, a photosensitive one Layer that is produced on the substrate and one on the photosensitive Layer produced protective layer containing a binder resin and a filler where, if a solution, in which the binder resin is in an organic solvent, which is incompatible with water, is dissolved with deionized Water with an electrical conductivity of not more than 1 μS / cm and substantially the same volume as that of the solvent mixed and shaken the water will then have an electrical conductivity of not more than 2 μS / cm having.

The Binder resin is preferably a cleaning treatment, such as Washing treatments by means of a caustic and / or acid subjected to ionic Remove impurities from it.

The Reaction due to impurities adhering to the photoreceptor, which increases the residual potential, takes place first at the surface of the photoreceptor. For a photoreceptor that does not have a protective layer has, the damaged will Part of the surface the photosensitive layer slightly rubbed off with repeated use, even if such a reaction on the surface of the photosensitive Layer takes place, and therefore the above-mentioned undesirable Images barely made. However, if the abrasion resistance by Formation of a protective layer is improved (that is, the Abrasion speed of the surface of the photoreceptor), the electrostatic Properties of the photoreceptor significantly worsened (that is, the Residual potential increases and the dark potential decreases).

moreover be when the surface of the photoreceptor is charged, which is an essential process The electrophotographic image recording method is reactive Gases are generated and it becomes due to the reactive gases materials generated with low resistance on the surface. Such materials with low resistance are removed when the surface of the Photoreceptor is easily subject to abrasion, which has the consequence that no problem occurs. However, if the surface barely Abrasion is washed away by such a photoreceptor Pictures made.

This phenomenon also concerns impurities contained in the protective layer, and it is believed that the chemical degradation the surface for the same reason as mentioned above.

In contrast, with regard to the problem of blurred images, it was assumed that the reactive gases generated by charging devices generate low resistance materials by contacting moisture contained in the atmosphere surrounding the photoreceptor. The low resistance materials settle on the surface of the photoreceptor, thereby reducing the surface resistivity of the photoreceptor. However, there has not been a discussion of adsorption sites. That is, a solution in that such low-resistance materials are prevented from being adsorbed on the adsorption sites has not been studied.

When a result of the inventor's investigations into the binder resin, that in a protective layer in an amount of not less than 50% is included, it is found that the occurrence of washed-out Images can essentially be prevented by reducing the amount the ionic impurities contained in the binder resin is reduced. Therefore, it is assumed that the materials produced with low resistance by those present on the surface of the photoreceptor ionic impurities are adsorbed, or the materials produced with low resistance because of the ionic impurities become.

Even though the mechanism is not clarified is, can the aforementioned three problems (exchange relationships) can be solved at the same time by using a binder resin in the protective layer ionic impurities are removed to the highest degree.

When next the process of how to clean the binder resin will be explained.

One Example of the cleaning method is as follows, the cleaning method but is not limited to that and it can Known methods are used when the binder resin as mentioned above so that it can be cleaned.

The to be used binder resin is in an organic solvent solved, this is incompatible with deionized water (that is, not can be mixed) or hardly compatible. The solution will be with stirring with an aqueous alkaline solution (this means a solution in the sodium hydroxide or potassium hydroxide in deionized water solved is mixed). The mixture is placed in a separatory funnel to the organic layer of the aqueous Separate layer. The thus prepared organic layer (the is called, the mixture of the binder resin and the organic solvent) is washed with deionized water and then heated to to obtain a dried binder resin.

In in this case, the organic solvent, this is incompatible with deionized water or hardly compatible is as an organic solvent defined that at 20 ° C a solubility in water of not more than 3 grams per 100 grams of water.

at This process can be the aqueous alkaline solution through an aqueous Acid solution (the is called hydrochloric acid, acetic acid and so on) to be replaced. Furthermore the washed organic layer may be added to a solvent, which can not dissolve the binder resin to precipitate the resin.

On this way, the binder resin is cleaned. It is preferable that the suitable cleaning process is determined experimentally, such that the binder resin to be used is purified as mentioned above can be. This means, if a solution in the thus purified binder resin in one with water incompatible organic solvent solved is, stirring mixed with deionized water which has an electrical conductivity of not more than 1 μS / cm has, and the conductivity the aqueous Layer of it almost the same as that of the deionized Water (that is, not more than 2 μS / cm) is, then it can be said that the binder resin completely cleaned is.

When next For example, the photoreceptor of the present invention will be described with reference to FIG Drawings are explained.

1 Fig. 12 is a schematic view illustrating the cross section of one embodiment of the photoreceptor of the present invention.

In 1 is a single-layer photosensitive layer 33 comprising a charge generation material and a charge transport material as main components on an electrically conductive substrate 31 educated. It is also a protective layer 39 on the surface of the photosensitive layer 33 educated. The protective layer 39 includes a binder resin from which ionic impurities are removed to a very high degree.

2 Fig. 12 is a schematic view illustrating the cross section of another embodiment of the photoreceptor of the present invention.

In 2 are a charge generation layer 35 containing a charge generation material as a main component and a charge transport layer 37 containing a charge transport material as a main component on an electrically conductive substrate 31 arranged one above the other. It is also a protective layer 39 on the charge transport layer 37 educated. The protective layer 39 includes a binder resin from which ionic impurities are removed to a very high degree.

Suitable materials for use as the electrically conductive substrate 31 include materials having a volume resistivity not larger than 10 ¹⁰ Ω · cm. Specific examples of such materials include plastic cylinders, plastic films or paper sheets on the surface of which a metal such as aluminum, nickel, chromium, nickel-chromium, copper, gold, silver, platinum and the like or a metal oxide such as tin oxides, indium oxides and the like are deposited or sputtered , Moreover, a metal sheet such as aluminum, aluminum alloys, nickel and stainless steel may be used. It can also be a metal cylinder as the substrate 31 which is prepared by forming a metal such as aluminum, aluminum alloys, nickel and stainless steel into a tube by a method such as impact extraction or direct stretching and then treating the surface of the tube by trimming, vibrating, polishing and the like. Further, endless belts of a metal such as nickel, stainless steel and the like, which have been disclosed in, for example, Japanese Patent Application Laid-Open No. 52-36016, may also be used as the substrate 31 be used.

Further, substrates in which a coating liquid including a binder resin and an electroconductive powder is coated on the above-mentioned supports may be used as the substrate 31 be used. Specific examples of such an electroconductive powder include carbon black, acetylene black, powders of metals such as aluminum, nickel, iron, nickel-chromium, copper, zinc, silver and the like, and metal oxides such as electroconductive tin oxides, ITO (indium tin oxide) and like. Specific examples of the binder resin include known thermoplastic resins, thermosetting resins and photocrosslinkable resins such as polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-maleic anhydride copolymers, polyesters, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, Polyvinylidene chloride, polyarylates, phenoxy resins, polycarbonates, cellulose acetate resins, ethylcellulose resins, polyvinyl butyral resins, polyvinylformal resins, polyvinyltoluene, poly-N-vinylcarbazole, acrylic resins, silicone resins, epoxy resins, melamine resins, urethane resins, phenolic resins, alkyd resins, and the like resins.

A such electrically conductive Layer can be produced by applying a coating liquid, in which is an electrically conductive Powder and a binder resin in a suitable solvent, such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, toluene and the same solvents dispersed or dissolved, coated and then the coated liquid is dried.

In addition, substrates in which a heat-shrinkable resin tube made of a combination of a resin such as polyvinyl chloride, polypropylene, polyesters, polyvinylidene chloride, polyethylene, chlorinated rubber and fluorine-containing resins with an electroconductive material can be an electroconductive resin film the surface of a cylindrical substrate is formed as the substrate 31 be used.

Next, the photosensitive layer 33 of the photoreceptor of the present invention.

In According to the present invention, the photosensitive layer may include a single-layer photosensitive layer or a multilayer be photosensitive layer.

First, the multilayer photosensitive layer including the charge generation layer 35 and the charge transport layer 37 to be explained.

The charge generation layer 35 (hereinafter referred to as the CGL 35 (Charge Generation Layer) includes a charge generation material as a main component. In the CGL 35 For example, known charge generation materials can be used. Specific examples of such charge-generating materials include monoazo pigments, bisazo pigments, trisazo pigments, perylene pigments, perinone pigments, quinacridone pigments, quinone-type condensed polycyclic compounds, squaric acid type dyes, phthalocyanine pigments other than TiO 2 phthalocyanine underlying invention, naphthalocyanine pigments, azulenium salt type dyes and the like pigments and dyes. These charge generation materials may be used alone or in combination.

worin R₂₀₁ und R₂₀₂ unabhängig voneinander ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe, eine Alkoxygruppe oder eine Cyanogruppe darstellen; und Cp₁ und Cp₂ unabhängig voneinander eine Restgruppe eines Kupplers darstellen, der die folgende Formel (5) hat:

worin R₂₀₃ ein Wasserstoffatom, eine Alkylgruppe, wie eine Methylgruppe und eine Ethylgruppe, oder eine Arylgruppe, wie eine Phenylgruppe, darstellt; R₂₀₄, R₂₀₅, R₂₀₆, R₂₀₇ und R₂₀₈ unabhängig voneinander ein Wasserstoffatom, eine Nitrogruppe, eine Cyanogruppe, ein Halogenatom, wie ein Fluoratom, ein Chloratom, ein Bromatom und ein Jodatom, eine Alkylgruppe, wie eine Trifluormethylgruppe, eine Methylgruppe und eine Ethylgruppe, eine Alkoxygruppe wie eine Methoxygruppe und eine Ethoxygruppe, eine Dialkylaminogruppe oder eine Hydroxylgruppe darstellen; und Z eine Atomgruppe darstellt, die zur Bildung eines substituierten oder unsubstituierten aromatischen Kohlenstoffrings oder eines substituierten oder unsubstituierten aromatischen heterocyclischen Ringes notwendig ist, darstellen.Among these charge generation materials, azo pigments and / or phthalocyanine pigments are preferably used. In particular, titanyl phthalocyanine having an X-ray diffraction spectrum in which a peak is observed at a Bragg 2θ angle of 27.2 ° ± 0.2 ° when a specific X-ray of Cu-Kα having a wavelength of 1.541 Å irradiates the titanyl phthalocyanine pigment; and azo pigments represented by the following formula (4) are preferably used.

wherein R ₂₀₁ and R ₂₀₂ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group; and Cp ₁ and Cp ₂ independently represent a residual group of a coupler having the following formula (5):

wherein R _{203 represents} a hydrogen atom, an alkyl group such as a methyl group and an ethyl group, or an aryl group such as a phenyl group; R _204, R _205, R _206, R ₂₀₇ and R ₂₀₈ independently represent a hydrogen atom, a nitro group, a cyano group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkyl group such as trifluoromethyl group, a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a dialkylamino group or a hydroxyl group; and Z represents an atomic group necessary for forming a substituted or unsubstituted aromatic carbon ring or a substituted or unsubstituted aromatic heterocyclic ring.

• (1) ein Ladungserzeugungsmaterial wird mit einem geeigneten Lösungsmittel gemischt, gegebenenfalls zusammen mit einem Bindemittelharz;
• (2) die Mischung wird unter Verwendung einer Kugelmühle, einer Rührwerkskugelmühle, einer Sandmühle oder einer Ultraschall-Dispergiervorrichtung gemischt, um eine Beschichtungsflüssigkeit herzustellen; und
• (3) wird die Beschichtungsflüssigkeit auf ein elektrisch leitfähiges Substrat beschichtet und dann getrocknet, um eine Ladungserzeugungsschicht herzustellen.

The CGL 35 (Charge generation layer 35 ) can be produced, for example, by the following method:

• (1) a charge generation material is mixed with a suitable solvent, optionally together with a binder resin;
• (2) the mixture is mixed by using a ball mill, an agitating ball mill, a sand mill or an ultrasonic disperser to prepare a coating liquid; and
• (3) The coating liquid is coated on an electroconductive substrate and then dried to prepare a charge generation layer.

suitable Binder resins, which optionally the coating liquid for the Charge generation layer are mixed include polyamides, Polyurethanes, epoxy resins, polyketones, polycarbonates, silicone resins, Acrylic resins, polyvinyl butyral, polyvinyl formal, polyvinyl ketones, Polystyrene, polysulfone, poly-N-vinylcarbazole, Polyacrylamide, polyvinylbenzene, polyesters, phenoxy resins, vinyl chloride-vinyl acetate copolymers, Polyvinyl acetate, polyphenylene oxide, polyamides, polyvinylpyridine, Cellulose resins, casein, polyvinyl alcohol, polyvinylpyrrolidone and like resins.

The content of the binder resin in the CGL 35 is preferably from 0 to 500 parts by weight, and preferably from 10 to 300 parts by weight per 100 parts by weight of that in the CGL 35 included charge generation material.

Suitable solvents for use in the coating liquid for CGL include iso propanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, ligroin and the like solvents. In particular, ketone-type solvents, ester-type solvents, and ether-type solvents are preferably used.

The coating liquid for the CGL can be coated by a coating method such as dip coating, spray coating, bead coating, die coating, spin coating and ring coating. The thickness of the CGL 35 is preferably from 0.01 to 5 μm, and more preferably from 0.1 to 2 μm.

• (1) ein Ladungstransportmaterial und ein Bindemittelharz werden in einem geeigneten Lösungsmittel gelöst oder dispergiert, um eine Beschichtungsflüssigkeit für eine CTL herzustellen; und
• (2) wird die Beschichtungsflüssigkeit auf die CGL 35 beschichtet und getrocknet, um eine Ladungstransportschicht herzustellen.

The charge transport layer 37 (hereinafter referred to as a CTL 37 Can be generated, for example, by the following method:

• (1) a charge transport material and a binder resin are dissolved or dispersed in a suitable solvent to prepare a coating liquid for a CTL; and
• (2) the coating liquid is applied to the CGL 35 coated and dried to produce a charge transport layer.

The CTL 37 If desired, it may contain additives such as plasticizers, leveling agents, antioxidants and the like.

Charge transport materials are used in charge transport materials through positive holes and materials classified as charge transport by electrons.

specific Examples of materials for charge transport by electrons include electron-accepting materials such as chloranil, bromanil, Tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetanitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-trinitrodibenzothiphene-5,5-dioxide, benzoquinone derivatives and like.

specific Examples of materials for charge transport through positive holes include known materials, such as poly-N-carbazole and its derivatives, poly-γ-carbazolylethylglutamate and its derivatives, pyrene-formaldehyde condensation products and their derivatives, Polyvinylpyrene, polyvinylphenanthrene, polysilane, oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, monoarylamines, diarylamines, Triarylamines, stilbene derivatives, α-phenylstilbene derivatives, Benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, Pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, Butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives and the same.

These Charge transport materials can used alone or in combination.

Specific examples of the binder resin for use in the CTL 37 include known thermoplastic resins, thermosetting resins and photo-crosslinkable resins such as polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-maleic anhydride copolymers, polyesters, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyvinylidene chloride, polyarylates, phenoxy resins, Polycarbonates, cellulose acetate resins, ethyl cellulose resins, polyvinyl butyral resins, polyvinyl formal resins, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resins, silicone resins, epoxy resins, melamine resins, urethane resins, phenolic resins, alkyd resins, and the like.

It is preferable that the resins for the CTL 37 used after ionic impurities have been removed therefrom.

The content of the charge transport material in the CTL 37 is preferably from 20 to 300 parts by weight, more preferably from 40 to 150 parts by weight, per 100 parts by weight of that in the CTL 37 included binder resin. The thickness of the CTL 37 is preferably not larger than 25 μm in view of the resolving power of the resulting images and the reaction (that is, the photosensitivity). In addition, with regard to the charging potential, the thickness of the CTL 37 not less than 5 μm. The lower limit changes depending on which imaging system the photoreceptor is used for.

suitable solvent for use in the coating liquid for the CTL include tetrahydrofuran, Dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, Methyl ethyl ketone, acetone and the like solvents.

The charge transport layer 37 may contain additives such as plasticizers and leveling agents. Specific examples of the plasticizers include known plasticizers used for plasticizing resins, such as dibutyl phthalate, dioctyl phthalate, and the like. The addition amount of the plasticizer is from 0 to 30% by weight of that in the CTL 37 included binder resin.

Specific examples of the leveling agents include silicone oils such as dimethylsilicone oil and methylphenylsilicone oil; Polymers or oligomers containing a perfluoroalkyl group in their side chain; and the same. The addition amount of the leveling agent is from 0 to 1% by weight of that in the CTL 37 included binder resin.

Next, the monolayer photosensitive layer 33 , as in 1 shown, explained. The photosensitive layer 33 can be prepared by coating a coating liquid in which a charge-generating material, a charge-transporting material and a binder resin are dissolved or dispersed in a suitable solvent, and then drying the coated liquid. In addition, the photosensitive layer 33 include the aforementioned charge transport material to produce a functionally separate photosensitive layer. The photosensitive layer 33 may include additives such as plasticizers, leveling agents and antioxidants.

Suitable binder resins for use in the photosensitive layer 33 include the aforementioned resins for use in the charge transport layer 37 , The above-mentioned resins for use in the charge generation layer 35 can be added as a binder resin. Moreover, the above-mentioned charge transport polymer materials can also be used as a binder resin. In particular, it is preferred that these resins and charge transport polymer materials are cleaned so that ionic impurities are removed therefrom before being used as the binder resin.

The content of the charge-generating material is preferably from 5 to 40 parts by weight per 100 parts by weight of that in the photosensitive layer 33 included binder resin. The content of the charge transport material is preferably from 0 to 190 parts by weight, more preferably from 50 to 150 parts by weight, per 100 parts by weight of that in the photosensitive layer 33 included binder resin.

The monolayer photosensitive layer 33 can be produced by coating a coating liquid in which a charge generation material and a binder resin and optionally a charge transport material in a solvent such as tetrahydrofuran, dioxane, dichloroethane, cyclohexane and so on are coated by a coating method such as dip coating, spray coating, bead coating and the like. The thickness of the photosensitive layer 33 is preferably from 5 to 25 microns.

In the photoreceptor of the present invention, a base coat can be formed between the substrate 31 and the photosensitive layer (that is, the photosensitive layer 33 in 1 and the charge generation layer in 2 ) be formed.

The Undercoating includes a resin as a main component. As a photosensitive layer typically on the basecoat is formed by a liquid coated, which includes an organic solvent has the resin in the basecoat preferably has good resistance to resistance across from general organic solvents.

specific Examples of such resins include water-soluble resins such as polyvinyl alcohol resins, casein and sodium salts of polyacrylic acid; Alcohol-soluble resins such as nylon copolymers and methoxymethylated nylon resins; and thermosetting resins, who are able to form a three-dimensional network such as polyurethane resins, melamine resins, alkyd melamine resins, epoxy resins and the same.

The Base coat can be a fine powder of metal oxides such as titanium oxide, Silica, alumina, zirconia, tin oxide and indium oxide involve the appearance of moire in the recorded images to prevent and to reduce the residual potential of the photoreceptor.

The Base coat can also be made by adding Use of a suitable solvent and one above for use in the photosensitive layer mentioned suitable coating method, a coating liquid is coated.

The base coat can be made using a silane coupling agent, a titanium coupler agent or a chromium coupling agent.

Moreover, it is also preferable to use a layer of alumina produced by an anodic oxidation method and a layer of an organic compound such as polyparaxylene, or an inorganic compound such as SiO ₂ , SnO ₂ , TiO ₂ , ITO or CeO ₂ produced by a vacuum vapor deposition process.

The Thickness of the base coat is preferably from 0 to 5 microns.

In the photoreceptor of the present invention, the protective layer becomes 39 over the photosensitive layer (that is, the photosensitive layer 33 in 1 and the charge transport layer 37 in 2 ) to protect the photosensitive layer.

Suitable materials for use in the protective layer 39 include ABS resins, ACS resins, olefin-vinyl monomer copolymers, chlorinated polyethers, aryl resins, phenolic resins, polyacetal, polyamides, polyamideimides, polyacrylates, polyarylsulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimides, acrylic resins, polymethylpentene , Polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resins, butadiene-styrene copolymers, polyurethane, polyvinyl chloride, polyvinylidene chloride, epoxy resins, and the like.

Under These resins are preferably polycarbonate resins which have one above mentioned Structural unit having the formula (A) and / or (B) used. In particular, polycarbonate resins which are an above-mentioned structural unit of the formula (1), (2) or (3) are preferably used.

These Binder resins can used alone or in combination. As mentioned above It is preferable that these resins are so purified that ionic Impurities in the highest Measure removed when used as a binder resin. Whether ionic Impurities in the highest Measure off a resin can be removed by the above-mentioned evaluation method be judged, where a solution by dissolving of the resin in an organic solvent that is not compatible with Water is miscible, was prepared with stirring with deionized water is mixed and the electrical conductivity of the water layer of the Mixture is measured.

Specific examples of the compounds represented by the formula (A) include the compounds shown in Table 1. Table 1

specific Examples of the compounds of the formula (B) include the compounds which are shown in Table 2.

Table 2

As mentioned above, For example, the protective layer includes a filler such as organic fillers and inorganic fillers.

specific Examples of organic fillers include powders of fluorine-containing resins such as polytetrafluoroethylene, Silicone resin powder and amorphous carbon powder. Specific examples of inorganic fillers include powders of metals such as copper, tin, aluminum and indium; Metal oxides such as silica, tin oxide, zinc oxide, titanium oxide, indium oxide, Antimony oxide, bismuth oxide, antimony doped tin oxide, tin doped indium oxide and potassium titanate. Among these fillers are preferably inorganic from the viewpoint of hardness fillers used. In particular, preferably, silica, titania and alumina used.

The average primary particle diameter of the filler included in the protective layer is preferably from 0.01 to 0.5 μm in order to increase the light transmittance and abrasion resistance of the protective layer improve. When the average primary particle diameter of the filler used is too small, the abrasion resistance of the protective layer and the dispersibility of the filler in a coating liquid are deteriorated. On the contrary, if the average primary particle diameter of the filler used is too large, the amount of precipitation in a coating liquid increases, and a problem such that a film of the toner used is formed on the protective layer tends to occur.

ever higher the Concentration of the filler included in the protective layer is, the better the abrasion resistance of the protective layer. If however, the concentration is too high will be detrimental generated as the residual potential increases and the permeability the protective layer for the light used to write the pictures deteriorates becomes. Therefore, the concentration is not larger than 50% by weight, and more preferable not bigger than 30 weight percent, based on the total weight of the protective layer.

The Lower limit of the filler concentration should depend on the abrasion resistance of the filler used be determined (that is, by the relationship between the concentration of the filler used and abrasion is pulled). The abrasion resistance of a protective layer depends largely on that Filler content in the surface area the protective layer. The filler content is preferably not less than 5% by weight, and more preferably not less than 10 Wt .-%.

In order to prevent the occurrence of washed-out images, fillers having a relatively high resistivity of not less than 10 ¹⁰ Ω · cm are preferably used in the protective layer. Moreover, fillers having a pH of not less than 5 and / or a dielectric constant of not less than 5 are preferably used. These fillers can be used alone or in combination. For example, a combination of a filler having a pH of not less than 5 and a filler having a pH of not more than 5; or a combination of a filler having a dielectric constant of not less than 5 and a filler having a dielectric constant of not more than 5.

Under these fillers is alumina in the α-form, which has a hexagonal close-packed structure, preferably used to reduce the abrasion resistance of the resulting protective layer to improve and prevent the problem of blurred images. This is because the alumina has a high insulating power, a high heat stability and good Has abrasion resistance.

These fillers are preferably treated with at least one surface treatment agent, to improve their dispersibility. Deterioration of dispersibility a filler included in the protective layer not only causes an increase of the residual potential, but also a reduction the transparency of the protective layer, the generation of coating defects and deterioration of the Abrasion resistance, and this results in a big problem so that a photoreceptor with good life and good fortune Can not be provided images.

Suitable surface-treating agents include known surface-treating agents, but preferred are surface-treating agents which can maintain the insulating properties of the filler to be used in the protective layer. Specific examples of such surface treatment agents include titanate coupling agents, aluminum coupling agents, zirconium aluminate coupling agents, higher fatty acids and combinations of these silane coupling agent agents; and Al ₂ O ₃ , TiO ₂ , ZrO ₂ ; Silicones, aluminum stearate and mixtures thereof. These are preferred because they are capable of imparting good dispersibility to fillers and preventing the problem of blurred images.

If Silane coupling agents used, the problem tends to be washed out Pictures to be caused. If combined, however with the aforementioned Surface treatment agents is used, there is a case in which the problem is avoided can be.

Of the Content of a surface treatment agent in a coated filler, that of the primary Particle diameter of the filler depends is from 3 to 30% by weight, and more preferably from 5 to 20% by weight. If the Content is too low, good dispersibility can not be achieved become. On the contrary, if the content is too high, it will increase Residual potential strong.

These fillers can used alone or in combination.

The Thickness of the protective layer is preferably from 0.1 to 10 microns.

These fillers can be dispersed by using a suitable dispersing apparatus. The average particle diameter of the in the coating liquid for the Protective layer of dispersed filler is preferably not larger than 1 μm and more preferably not greater than 0.5 μm.

The Protective layer may be by means of a general coating method be generated. Among the general coating methods, preferably spray and ring coating methods.

The protective layer 39 may include a charge transport material to reduce the residual potential and improve the responsiveness of the resulting photoreceptor. Specific examples of charge transport materials include those above for use in the charge transport layer 37 mentioned charge transport materials. When a low molecular weight charge transport material is used in the protective layer, the concentration of the low molecular weight charge transporting material may have a gradient in its thickness direction. In this case, it is preferable that the concentration of the charge transport material at the surface of the protective layer is lower than that at the bottom of the protective layer to improve the abrasion resistance of the resulting photoreceptor.

The Contains protective layer preferably a charge transport polymer material comprising a binder resin Function and also has a charge transport function, because the itself then resulting protective layer has a good abrasion resistance.

worin R₁, R₂ und R₃ unabhängig voneinander eine substituierte oder unsubstituierte Alkylgruppe oder ein Halogenatom darstellen; R₄ ein Wasserstoffatom oder eine substituierte oder unsubstituierte Alkylgruppe darstellt; R₅ und R₆ unabhängig voneinander eine substituierte oder unsubstituierte Arylgruppe darstellen; r, p und q unabhängig voneinander 0 oder eine ganze Zahl von 1 bis 4 darstellen; k eine Zahl von 0,1 bis 1,0 ist und j eine Zahl von 0 bis 0,9 ist; n eine ganze Zahl von 5 bis 5000 ist; und X eine zweiwertige aliphatische Gruppe, eine zweiwertige alicyclische Gruppe oder eine zweiwertige Gruppe mit der folgenden Formel darstellt:

worin R₁₀₁ und R₁₀₂ unabhängig voneinander eine substituierte oder unsubstituierte Alkylgruppe, eine substituierte oder unsubstituierte Arylgruppe oder ein Halogenatom darstellen; t und m 0 oder eine ganze Zahl von 1 bis 4 darstellen; v 0 oder 1 ist; und Y eine geradkettige Alkylengruppe, eine verzweigte Alkylengruppe, eine cyclische Alkylengruppe, -O-, -S-, -SO-, -CO-, -CO-O-Z-O-CO- (Z stellt eine zweiwertige aliphatische Gruppe dar) oder eine Gruppe mit der folgenden Formel darstellt:

worin a eine ganze Zahl von 1 bis 20 ist; b eine ganze Zahl von 1 bis 2000 ist; und R₁₀₃ und R₁₀₄ unabhängig voneinander eine substituierte oder unsubstituierte Alkylgruppe oder eine substituierte oder unsubstituierte Arylgruppe darstellen, wobei R₁₀₁, R₁₀₂, R₁₀₃ und R₁₀₄ gleich oder voneinander verschieden sein können.

worin R₇ und R₈ unabhängig voneinander eine substituierte oder unsubstituierte Arylgruppe darstellen; Ar₁, Ar₂ und Ar₃ unabhängig voneinander eine Arylengruppe darstellen; und X, k, j und n vorstehend in Formel (6) definiert werden.

worin R₉ und R₁₀ unabhängig voneinander eine substituierte oder unsubstituierte Arylgruppe darstellen; Ar₄, Ar₅ und Ar₆ unabhängig voneinander eine Arylengruppe darstellen; und X, k, j und n vorstehend in Formel (6) definiert werden.

worin R₁₁ und R₁₂ unabhängig voneinander eine substituierte oder unsubstituierte Arylgruppe darstellen; Ar₇, Ar₈ und Ar₉ unabhängig voneinander eine Arylengruppe darstellen; p eine ganze Zahl von 1 bis 5 ist; und X, k, j und n vorstehend in Formel (6) definiert werden.

worin R₁₃ und R₁₄ unabhängig voneinander eine substituierte oder unsubstituierte Arylgruppe darstellen; Ar₁₀, Ar₁₁ und Ar₁₂ unabhängig voneinander eine Arylengruppe darstellen; X₁ und X₂ unabhängig voneinander eine substituierte oder unsubstituierte Ethylengruppe oder eine substituierte oder unsubstituierte Vinylengruppe darstellen; und X, k, j und n vorstehend in Formel (6) definiert werden.

worin R₁₅, R₁₆, R₁₇ und R₁₈ unabhängig voneinander eine substituierte oder unsubstituierte Arylgruppe darstellen; Ar₁₃, Ar₁₄, Ar₁₅ und Ar₁₆ unabhängig voneinander eine Arylengruppe darstellen; Y₁, Y₂ und Y₃ unabhängig voneinander eine substituierte oder unsubstituierte Alkylengruppe, eine substituierte oder unsubstituierte Cycloalkylengruppe, eine substituierte oder unsubstituierte Alkylenethergruppe, ein Sauerstoffatom, ein Schwefelatom oder eine Vinylengruppe darstellen; u, v und w unabhängig voneinander 0 oder 1 darstellen; und X, k, j und n vorstehend in Formel (6) definiert werden.

worin R₁₉ und R₂₀ unabhängig voneinander ein Wasserstoffatom oder eine substituierte oder unsubstituierte Arylgruppe darstellen, und R₁₉ und R₂₀ einen Ring bilden können; Ar₁₇, Ar₁₈ und Ar₁₉ unabhängig voneinander eine Arylengruppe darstellen; und X, k, j und n vorstehend in Formel (6) definiert werden.

worin R₂₀ eine substituierte oder unsubstituierte Arylgruppe darstellt; Ar₂₀, Ar₂₁ Ar₂₂ und Ar₂₃ unabhängig voneinander eine Arylengruppe darstellen; und X, k, j und n vorstehend in Formel (6) definiert werden.

worin R₂₂, R₂₃, R₂₄ und R₂₅ unabhängig voneinander eine substituierte oder unsubstituierte Arylgruppe darstellen; Ar₂₄, Ar₂₅, Ar₂₆, Ar₂₇ und Ar₂₈ unabhängig voneinander eine Arylengruppe darstellen; und X, k, j und n vorstehend in Formel (6) definiert werden.

worin R₂₆ und R₂₇ unabhängig voneinander eine substituierte oder unsubstituierte Arylgruppe darstellt; Ar₂₉, Ar₃₀ und Ar₃₁ unabhängig voneinander eine Arylengruppe darstellen; und X, k, j und n vorstehend in Formel (6) definiert werden.Suitable charge transport polymeric materials include known charge transport polymeric materials. Among these materials, polycarbonate resins having a triarylamine structure in their main chain and / or side chain are preferably used. In particular, charge transport polymer materials having the following formulas (6) to (15) are preferably used:

wherein R ₁ , R ₂ and R ₃ independently represent a substituted or unsubstituted alkyl group or a halogen atom; R _{4 represents} a hydrogen atom or a substituted or unsubstituted alkyl group; R ₅ and R ₆ independently represent a substituted or unsubstituted aryl group; r, p and q independently represent 0 or an integer of 1 to 4; k is a number from 0.1 to 1.0 and j is a number from 0 to 0.9; n is an integer of 5 to 5,000; and X represents a divalent aliphatic group, a divalent alicyclic group or a divalent group having the following formula:

wherein R ₁₀₁ and R ₁₀₂ independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom; t and m represent 0 or an integer from 1 to 4; v is 0 or 1; and Y is a straight-chain alkylene group, a branched alkylene group, a cyclic alkylene group, -O-, -S-, -SO-, -CO-, -CO-OZO-CO- (Z represents a divalent aliphatic group) or a group represents the following formula:

wherein a is an integer of 1 to 20; b is an integer from 1 to 2,000; and R ₁₀₃ and R _{104 are} independent each represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, wherein R ₁₀₁ , R ₁₀₂ , R ₁₀₃ and R _{104 may be the} same or different.

wherein R ₇ and R ₈ independently represent a substituted or unsubstituted aryl group; Ar ₁ , Ar ₂ and Ar ₃ independently represent an arylene group; and X, k, j and n are defined above in formula (6).

wherein R ₉ and R ₁₀ independently represent a substituted or unsubstituted aryl group; Ar ₄ , Ar ₅ and Ar ₆ independently represent an arylene group; and X, k, j and n are defined above in formula (6).

wherein R ₁₁ and R ₁₂ independently represent a substituted or unsubstituted aryl group; Ar ₇ , Ar ₈ and Ar ₉ independently represent an arylene group; p is an integer from 1 to 5; and X, k, j and n are defined above in formula (6).

wherein R ₁₃ and R ₁₄ independently represent a substituted or unsubstituted aryl group; Ar ₁₀ , Ar ₁₁ and Ar ₁₂ independently represent an arylene group; X ₁ and X ₂ independently represent a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group; and X, k, j and n are defined above in formula (6).

wherein R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ independently represent a substituted or unsubstituted aryl group; Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ independently represent an arylene group; Y ₁ , Y ₂ and Y ₃ independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom or a vinylene group; u, v and w independently represent 0 or 1; and X, k, j and n are defined above in formula (6).

wherein R ₁₉ and R ₂₀ independently represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring; Ar ₁₇ , Ar ₁₈ and Ar ₁₉ independently represent an arylene group; and X, k, j and n are defined above in formula (6).

wherein R _{20 represents} a substituted or unsubstituted aryl group; Ar ₂₀ , Ar ₂₁ Ar ₂₂ and Ar ₂₃ independently represent an arylene group; and X, k, j and n are defined above in formula (6).

wherein R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ independently represent a substituted or unsubstituted aryl group; Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ independently represent an arylene group; and X, k, j and n are defined above in formula (6).

wherein R ₂₆ and R ₂₇ independently represent a substituted or unsubstituted aryl group; Ar ₂₉ , Ar ₃₀ and Ar _{31 are} independently an arylene group; and X, k, j and n are defined above in formula (6).

at The photoreceptor of the present invention may be an intermediate layer generated between the photosensitive layer and the protective layer become. The intermediate layer includes a resin as a main component. Specific examples of the resin include polyamides, alcohol-soluble nylons, water-soluble Polyvinyl butyral, polyvinyl butyral, polyvinyl alcohol and the like. The intermediate layer may be known by means of one of the aforementioned Coating process can be generated. The thickness of the intermediate layer is preferably from 0.05 to 2 microns.

In The photoreceptor of the present invention may contain one or more additives such as antioxidants, plasticizers, lubricants, UV absorbers, charge transport materials low molecular weight and leveling agent in one or more of the layers used to be adverse to stability Improve environmental conditions, that is, the decline in photosensitivity and to avoid the increase of the residual potential.

suitable Antioxidants for use in the layers of the photoreceptor include, but are not limited to, the following compounds.

(a) Phenolic compounds

• 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, Bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, Tocophenol compounds and the like.

(b) Paraphenylenediamine compounds

• N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N, N'-di-isopropyl-p-phenylenediamine, N, N'-dimethyl-N, N'-di-t-butyl-p-phenylenediamine and the same.

(c) hydroquinone compounds

• 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-Dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- (2-octadecenyl) -5-methylhydroquinone and the same.

(d) Organic sulphurous links

• Dilauryl 3,3'-thiodipropionate, Distearyl 3,3'-thiodipropionate, Ditetradecyl-3,3'-thiodipropionate,

(e) Organic phosphorus-containing links

• Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, Tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

suitable Plasticizers for use in the layers of the photoreceptor include the following compounds, but are not limited thereto.

(a) phosphoric acid ester

• Triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, Octyldiphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, Tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate and like.

(b) phthalic acid ester

• Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, Diunde cylphthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl olefin phthalate, octyl decyl phthalate, dibutyl fumarate, dioctyl fumarate and the like.

(c) Aromatic carboxylic acid esters

• Trioctyl trimellitate, tri-n-octyl trimellitate, octyloxybenzoate and the same.

(d) esters of dibasic fatty acids

• Dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, Di-n-octyl adipate, n-octyl-n-decyl adipate, Diisodecyl adipate, dialkyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, Dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, Di-2-ethylhexyl, Di-2-ethoxyethyl sebacate, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, Di-n-octyltetrahydrophthalate and the like.

(e) fatty acid ester derivatives

• Butyl oleate, glycerol monooleate, methyl acetylricinolate, pentaerythritol ester, Dipentaerythritol hexaester, triacetin, tributyrin and the like.

(f) esters of oxyacids

• Methylacetylricinolate, butylacetylricinolate, butylphthalylbutylglycolate, Tributyl acetyl citrate and the like.

(g) Epoxy compounds

• epoxidized soybean oil, epoxidized linseed oil, Butylepoxystearate, decylepoxystearate, octylepoxystearate, benzylepoxystearate, Dioctylepoxyhexahydrophthalate, didecylepoxyhexahydrophthalate and like.

(h) esters of divalent alcohols

diethylene glycol, Triethylene glycol di-2-ethyl butyrate and the like.

(i) Chlorine-containing compounds

• chlorinated paraffin, chlorinated diphenyl, methyl ester of chlorinated fatty acids, Methyl esters of methoxylated fatty acids and the like.

(j) polyester compounds

• Polypropylene adipate, polypropylene sebacate, acetylated polyesters and the same.

(k) sulfonic acid derivatives

• p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfonylethylamide, o-toluenesulfonylethylamide, toluenesulfone-N-ethylamide, p-toluenesulfone-N-cyclohexylamide and the same.

(I) citric acid derivatives

• Triethyl citrate, triethyl acetyl citrate, tributyl citrate, tributyl acetyl citrate, Tri-2-ethylhexyl acetyl citrate, n-octyl decyl acetyl citrate and the like.

(m) Other compounds

• Terphenyl, partially hydrogenated terphenyl, camphor, 2-nitro-diphenyl, Dinonylnaphthalene, methylabietate and the like.

suitable Include lubricants for use in the layers of the photoreceptor the following compounds, but are not limited thereto

(a) hydrocarbons

• liquid Paraffins, paraffin waxes, microwaxes, low-density polyethylenes Molecular weight and the like.

(b) fatty acids

• lauric acid, myristic, palmitic acid, stearic acid, arachidonic acid, behenic and the same.

(c) fatty acid amides

• stearic acid amide, Palmitic acid amide, oleic acid amide, methylenebis, ethylenebis and the same.

(d) ester compounds

• Esters of fatty acids with lower alcohols, esters of fatty acids with polyhydric alcohols, Polyglycol esters of fatty acids and the same.

(e) alcohols

• Cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol, Polyglycerol and the like.

(f) metal soaps

• Lead stearate, cadmium stearate, barium stearate, calcium stearate, Zinc stearate, magnesium stearate and the like.

(g) Natural waxes

• Carnauba wax, candelilla wax, beeswax, spermacet wax, Insect wax, montan wax and the like.

(h) Other compounds

• Silicone compounds, fluorine compounds and the like.

suitable Include UV absorbers for use in the layers of the photoreceptor the following compounds, but are not limited thereto

(a) benzophenone compounds

• 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and the same.

(b) salicylate compounds

• Phenyl salicylate, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate and the same.

(c) Benzotriazole compounds

• (2'-hydroxyphenyl) benzotriazole, (2'-hydroxy-5'-methylphenyl) benzotriazole, (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole and the same.

(d) cyanoacrylate compounds

• Ethyl 2-cyano-3,3-diphenylacrylate, methyl-2-carbomethoxy-3- (paramethoxy) acrylate and the same.

(e) quenchers (metal complexes)

• Nickel (2,2'-thiobis (4-t-octyl) phenolate) -n-butylamine, nickel dibutyl dithiocarbamate, cobalt dicyclohexyl dithiophos phat and the like.

(f) HALS connections (hindered amines)

• Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- {3- (3,5 -di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetrametylpyridin, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4.5] undecane-2,4-dione, 4-Benzoyloxy-2,2,6,6-tetramethylpiperidine and the like.

Here in Hereinafter, the image recording method and the image recording apparatus will be described of the present invention with reference to drawings.

3 Fig. 12 is a schematic view for explaining an embodiment of the image recording method and apparatus of the present invention.

In 3 denotes the reference numeral 1 a cylindrical photoreceptor. The photoreceptor 1 is the photoreceptor of the present invention wherein at least one photosensitive layer and a protective layer are over an electrically conductive substrate, with ionic impurities being most removed from the binder resin included in the photosensitive layer. Although the photoreceptor 1 a cylindrical shape, arcuate photoreceptors or endless belt photoreceptors may also be used.

To the photoreceptor 1 around are a lamp to discharge 7 , a loader 8th , a device for imagewise exposure 5 , a development device 11 , a cleaning device that has a cleaning brush 18 and a cleaning scraper 19 arranged, wherein they touch the photoreceptor or close to it. That on the photoreceptor 1 generated toner image is printed on a receiving paper 14 transferred by means of a pair of register rollers 13 on a transmission belt 15 is supplied. The receipt paper 14 with the toner image on it is by means of a separation device 12 from the photoreceptor 1 separated.

In the image recording apparatus of the present invention, if desired, a device 12 for charging before transfer, a device 15a for charging during transmission, a device 15b for charging when disconnecting and a device 17 be arranged for charging before cleaning. Known loading devices such as wire-wound superchargers (corotron), metal grid rechargers (scorotron), semiconductor superchargers and charging rollers can be used. It is preferred that a DC voltage superimposed with an AC voltage to the photoreceptor 1 is applied to reduce uneven charging.

As the transfer device 15 For example, the aforementioned charging devices may be used. Among the charging devices is preferably a combination of the device 15a for charging during transmission and the device 15b used to charge when disconnecting.

Suitable light sources for use in the imagewise exposure apparatus 10 and the discharge lamp 7 include fluorescent tubes, tungsten lamps, halogen lamps, mercury vapor lamps, sodium vapor lamps, light emitting diodes (LED's), laser diodes (LD's), electroluminescent light sources (EL), and the like. In addition, filters such as edge filters, bandpass filters, near-infrared (IR) filters, dichroic filters, interference filters, light-temperature conversion filters and the like can be used to obtain light having a desired wavelength range.

In the image recording apparatus of the present invention, it is preferable that the lamp for discharging 7 not used. This is because the substances constituting the photosensitive layer tend to be deteriorated by the light, resulting in an increase of the residual potential and a decrease of the dark-field potential. This depends on the species of materials used in the photosensitive layer. Will the lamp discharge? 7 not used, the effect of the photoreceptor of the present invention can be fully realized.

The above-mentioned lamps can be used not only for the above-mentioned and in 3 but also for other processes that use light irradiation, such as a transfer process using light irradiation, a discharge process, a light irradiation-containing cleaning process, and a pre-exposure process.

If that's on the photoreceptor 1 by means of the development unit 11 generated toner image on the receiving paper 14 will not transfer anything from the toner image to the receiving paper 14 transferred, and remaining toner particles remain on the surface of the photoreceptor 1 , The remaining toner is removed by means of a fur brush 18 and a cleaning blade 19 from the photoreceptor 1 away. The residual toner on the photoreceptor 1 can also be removed only by means of a cleaning brush. Suitable cleaning brushes include known cleaning brushes such as fur brushes and magnetic brushes. A lubricant application device 20 may be provided to a lubricant such as zinc stearate by means of the fur brush 18 apply to the photoreceptor.

When the photoreceptor 1 which was previously charged positively (or negatively), exposed to imagewise light, becomes on the photoreceptor 1 generates an electrostatic latent image with a positive or negative charge. When the latent image having a positive (or negative) charge is developed with a toner having a negative (or positive) charge, a positive image can be obtained. On the contrary, when the latent image having a positive (negative) charge is developed with a toner having a positive (negative) charge, a negative image (that is, a reverse image) can be obtained. As the development method, known development methods can be used. In addition, known discharge methods can be used as the discharge methods.

The image-recording device may have a mechanism comprising a lubricant such as zinc stearate on the surface of the photoreceptor 1 applying. By applying zinc stearate on the protective layer, it is possible to form film on the surface of the photoreceptor 1 used toner, while at the same time the good abrasion resistance of the photoreceptor 1 is maintained. In addition, in the image recording method of the present invention, the problem of the drawing effect images can be prevented by repeatedly adhering the toner on the surface of the photoreceptor and collecting the toner on the cleaning portion, if the above-mentioned image forming operations are not performed.

If the amount of on the photoreceptor 1 If the applied zinc stearate is too high, the problem arises that insufficiently fixed toner images are generated because too much amount of zinc stearate is applied to the toner image. In addition, if the friction coefficient of the surface of the photoreceptor 1 becomes about 0.1 by applying an excess of zinc stearate thereto, the image density of the resulting image decreases. On the contrary, if the amount of zinc stearate is too small, the problem of film formation of the toner components on the surface of the photoreceptor occurs 1 on, which results in the problem of the appearance of the images with a pulling effect and uneven halftone images.

A lubricant such as zinc stearate may be included in the toner used on the surface of the photoreceptor 1 is applied. In this case, the content of the lubricant in the toner is from 0.1 to 0.2% by weight.

In the image recording method, the problem of film formation on the surface of the photoreceptor 1 used toner and the problem that caused by the charging materials on the surface of the photoreceptor 1 to adhere and deposit, by repeatedly adhering the toner to the photoreceptor in the developing section and collecting the toner in the cleaning section when the above-mentioned image recording operations are not performed. This is because in the cleaning section, the on the surface of the photoreceptor 1 adhering materials can be removed together with the toner.

• 1) Der Toner auf dem Entwicklungsabschnitt (der Walze) wird am Photorezeptor haften gelassen, während der Photorezeptor und die Entwicklungswalze gedreht werden, ohne dass eine Vorspannung angelegt wird (in diesem Fall haftet eine beträchtliche Menge von Tonerteilchen an dem Photorezeptor, wenn der Photorezeptor nur leicht erschöpft ist);
• 2) der Toner auf der Entwicklungswalze wird am Photorezeptor haften gelassen, während gesteuerte Vorspannungen an den Photorezeptor und die Entwicklungswalze gelegt werden und Photorezeptor und Entwicklungswalze sich drehen, so dass eine gewünschte Menge von Tonerteilchen an dem Photorezeptor haftet; und
• 3) nachdem die gesamte Oberfläche des Photorezeptors geladen und dann dem Licht ausgesetzt wurde, wird der Toner auf der Entwicklungswalze auf der Oberfläche des Photorezeptor haften gelassen, während der Photorezeptor und die Entwicklungswalze gedreht werden. In diesem Fall wird auf der gesamten Oberfläche des Photorezeptors ein Vollton-Tonerbild erzeugt (das heißt, eine große Menge des Toners haftet daran).

For a toner to adhere to the surface of a photoreceptor, for example, the following methods can be used:

• 1) The toner on the developing section (the roller) is allowed to adhere to the photoreceptor while the photoreceptor and the developing roller are rotated without applying a bias (in this case, a considerable amount of toner particles adhere to the photoreceptor when the photoreceptor only is slightly exhausted);
• 2) the toner on the development roller is allowed to adhere to the photoreceptor while applying controlled biases to the photoreceptor and the development roller and rotating the photoreceptor and development roller so that a desired amount of toner particles adhere to the photoreceptor; and
• 3) After the entire surface of the photoreceptor has been charged and then exposed to light, the toner on the developing roller is allowed to adhere to the surface of the photoreceptor while the photoreceptor and the developing roller are rotated. In this case will be on the entire upper surface of the photoreceptor produces a solid toner image (that is, a large amount of the toner adheres to it).

4 Fig. 12 is a schematic view for explaining another embodiment of the image recording method and apparatus of the present invention. In this embodiment, a photoreceptor 21 the photoreceptor of the present invention and having at least a photosensitive layer and a protective layer overlying an electrically conductive substrate, with ionic impurities being most removed from the binder layer forming the protective layer.

The belt-shaped photoreceptor 21 gets through the rollers 22a and 22b turned. The photoreceptor 21 is through a charging device 23 loaded and then through a device for imagewise exposure 24 imagewise exposed to light in the photoreceptor 21 to create an electrostatic latent image. The latent image is recorded with a development unit (in 4 not shown) designed to work on the photoreceptor 21 to create a toner image. The toner image is formed using a transfer charger 25 transferred to a (not shown) receiving paper. After the process of transferring the toner image, the surface of the photoreceptor becomes 21 with a cleaning brush 27 cleaned after using a pre-cleaning light irradiation device 26 a pre-cleaning light irradiation process was performed. Then the photoreceptor 21 discharged by it from a light source for discharge 28 is exposed to emitted light. These operations are performed repeatedly.

In the image recording apparatus, as in 4 is shown, the pre-cleaning light irradiation from the side of the substrate of the photoreceptor 21 carried out from. In this case, the substrate must be translucent.

The image recording apparatus of the present invention is not limited to those disclosed in U.S. Pat 3 and 4 limited imaging elements shown. For example, in 4 the pre-cleaning light irradiation from the photosensitive layer side of the photoreceptor 21 be carried out from. In addition, the light irradiations in the process of image exposure and the discharge process from the substrate side of the photoreceptor 21 be carried out from.

When Light irradiation processes become the imagewise exposure process, the pre-cleaning light irradiation and the discharging process such as mentioned above carried out. Furthermore can also a light irradiation process before the transmission, before the transmission of the toner image , and a previous light irradiation process, before the pictorial exposure carried out and other light irradiation processes will be performed.

The mentioned above Image recording unit can be fixed in a copier, a fax machine or a Printer be installed. However, the image recording unit can also be used as a process cartridge in it. The process cartridge means an image recording unit (or device) which a photoreceptor, a housing and at least one of a charging device, a device for imagewise exposure, an image developing device, an image transfer device, a Cleaning device and a discharge device includes.

Various process cartridges may be used in the present invention. 5 Fig. 10 is a schematic view illustrating an embodiment of the process cartridge of the present invention. In 5 The process cartridge contains a photoreceptor 43 and a loader 40 , a device for imagewise exposure 41 , a development roller 45 , a transfer roller 44 and a cleaning brush 42 which are around the photoreceptor 43 are arranged around. The numbers 46 and 47 denotes a housing and an unloading device. The photoreceptor 43 is the photoreceptor of the present invention having at least one photosensitive layer and a protective layer over an electrically conductive substrate, with ionic impurities being most removed from the binder layer forming the protective layer.

7 Fig. 12 is a diagram for explaining still another embodiment of the image recording method and apparatus of the present invention.

In 7 For example, the image recording apparatus has a transmission endless belt 100 and four color image forming sections, that is, a black image forming section 106K , a yellow image generation section 106Y , a section on magenta imaging 106M and a cyan image generation section 106C , A receipt paper 107 is through a feed roller 108 supplied and by means of a Pair of register rollers 109 Timely the belt photoreceptor 100 fed.

On the other hand, a cyan color image is formed by a method similar to the above-mentioned image recording method using a charging roller 102C , a device for imagewise exposure 103C , an image development device 104C and a cleaning device 105C on a photoreceptor 101C generated. That on the photoreceptor 101C generated cyan image is made using a transfer brush 111C at the gap between the transmission belt 100 and the photoreceptor 101C on the receiving material 107 transfer.

Likewise, a magenta color image, a yellow color image and a black color image are displayed on the respective photoreceptors 101M . 101Y and 101K are generated, also one after the other using the transfer brushes 111M . 111Y respectively 111K on the receiving material 107 transfer. This will produce a complete color image on the receiver 107 generated. The complete color image is then taken with a fixator 112 fixed.

The numbers 102K . 102Y and 102M denote charging rollers. The numbers 103K . 103Y and 103M refer to imagewise exposure devices. The numbers 104K . 104Y and 104M , image developing devices configured to produce black, yellow and magenta toner images, respectively. The numbers 105K . 105Y and 105M denote cleaning devices.

After this the invention has been described in general terms, another Understanding through Reference to certain specific examples can be obtained which are provided herein for purposes of illustration only and not as limiting are meant. In the descriptions in the following examples the numbers represent weight ratios in parts, unless otherwise expressly stated.

EXAMPLES

Cleaning Example 1

Five parts of a polycarbonate resin of the bisphenol A form were in 95 parts Dissolved methylene chloride. The solution was charged with 100 parts of deionized water with an electric conductivity of 0.83 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was 3.44 μS / cm.

Then the organic layer was mixed with a 5% aqueous sodium hydroxide solution, and the mixture was stirred vigorously for 30 minutes. After separating the organic layer of the mixture by means of a separating funnel the organic layer was mixed with a 2% hydrochloric acid, and the mixture was stirred vigorously for one hour. The Organic layer was made using a separatory funnel separated from the mixture.

The organic layer was then washed with 100 parts of deionized water with an electrical conductivity from 0.90 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was measured. These procedures were repeated until the electrical conductivity the aqueous Shift to a desired one Value (that is, not higher than 2 μS / cm) has been. In this case, the electrical conductivity of the aqueous Layer 1.31 μS / cm.

Then The methylene chloride solution prepared in this manner (the is called, the organic layer) in 2000 ml of methanol was added dropwise to the polycarbonate resin precipitate. The mixture was filtered using a suction device, to get the resin. The resin thus obtained became 2 For days at 100 ° C Vacuum dried.

On in this way, a purified polycarbonate resin 1 was prepared.

Cleaning example 2

Five parts of a polycarbonate resin of the bisphenol Z-form were dissolved in 95 parts of methylene chloride. The solution was mixed with 100 parts of deionized water having an electrical conductivity of 0.83 μS / cm and the mixture was stirred vigorously for 30 minutes. The mixture was separated into an organic layer and an aqueous layer using a separatory funnel. The electrical conductivity of the aqueous layer was 2.28 μS / cm.

Then the organic layer was mixed with a 5% aqueous sodium hydroxide solution, and the mixture was stirred vigorously for 30 minutes. After separating the organic layer of the mixture by means of a separating funnel the organic layer was mixed with a 2% hydrochloric acid, and the mixture was stirred vigorously for one hour. The Organic layer was made using a separatory funnel separated from the mixture. The organic layer was then washed with 100 parts of deionized water with an electrical conductivity of 0.61 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was measured. These procedures were repeated until the electrical conductivity the aqueous Shift to a desired one Value (that is, not higher than 2 μS / cm) has been. In this case, the electrical conductivity of the aqueous layer was 1.64 μS / cm.

Then The methylene chloride solution prepared in this manner (the is called, the organic layer) in 2000 ml of methanol was added dropwise to the polycarbonate resin precipitate. The mixture was filtered using a suction device, to get the resin. The resin thus obtained became 2 For days at 100 ° C Vacuum dried.

On thus, a purified polycarbonate resin 2 was prepared.

Cleaning example 3

Five parts of a polycarbonate resin of bisphenol C-form were in 95 parts Dissolved methylene chloride. The solution was charged with 100 parts of deionized water with an electric conductivity of 0.73 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was 3.88 μS / cm.

Then the organic layer was mixed with a 5% aqueous sodium hydroxide solution, and the mixture was stirred vigorously for 30 minutes. After separating the organic layer of the mixture by means of a separating funnel the organic layer was mixed with a 2% hydrochloric acid, and the mixture was stirred vigorously for one hour. The Organic layer was made using a separatory funnel separated from the mixture. The organic layer was then washed with 100 parts of deionized water with an electrical conductivity from 0.90 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was measured. These procedures were repeated until the electrical conductivity the aqueous Shift to a desired one Value (that is, not higher than 2 μS / cm) has been. In this case, the electrical conductivity of the aqueous layer was 1.87 μS / cm.

Then The methylene chloride solution prepared in this manner (the is called, the organic layer) in 2000 ml of methanol was added dropwise to the polycarbonate resin precipitate. The mixture was filtered using a suction device, to get the resin. The resin thus obtained became 2 For days at 100 ° C Vacuum dried.

On in this way, a purified polycarbonate resin 3 was prepared.

Cleaning example 4

Five parts of a polycarbonate resin of the bisphenol C-form, the sample of a batch was taken from the batch of in the cleaning example 3 used polycarbonate resin was different, were in 95 parts Dissolved methylene chloride. The solution was charged with 100 parts of deionized water with an electric conductivity of 0.59 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was 3.95 μS / cm.

Then, the organic layer was mixed with a 5% sodium hydroxide aqueous solution, and the mixture was stirred vigorously for 30 minutes. After separating the organic layer from the mixture by means of a separatory funnel, the organic layer was mixed with a 2% hydrochloric acid, and the mixture was vigorously stirred for one hour. The organic layer was separated from the mixture using a separatory funnel. The organic layer was then mixed with 100 parts of deionized water having an electrical conductivity of 0.70 μS / cm, and the mixture was stirred vigorously for 30 minutes. The mixture was separated into an organic layer and an aqueous layer using a separatory funnel. The electrical conductivity of the aqueous layer was measured. These operations were repeated until the electrical conductivity of the aqueous layer became a desired value (that is, not higher than 2 μS / cm). In this case, the electrical conductivity of the aqueous layer was 1.53 μS / cm.

Then The methylene chloride solution prepared in this manner (the is called, the organic layer) in 2000 ml of methanol was added dropwise to the polycarbonate resin precipitate. The mixture was filtered using a suction device, to get the resin. The resin thus obtained became 2 For days at 100 ° C Vacuum dried.

On thus, a purified polycarbonate resin 4 was prepared.

Cleaning example 5

Five parts of a polycarbonate resin of the bisphenol C-form, the sample of a batch was taken from the batches of the cleaning examples 3 and 4 used polycarbonate resins were different in Dissolved 95 parts of methylene chloride. The solution was charged with 100 parts of deionized water with an electric conductivity of 0.93 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was 5.26 μS / cm.

Then the organic layer was mixed with a 5% aqueous sodium hydroxide solution, and the mixture was stirred vigorously for 30 minutes. After separating the organic layer of the mixture by means of a separating funnel the organic layer was mixed with a 2% hydrochloric acid, and the mixture was stirred vigorously for one hour. The Organic layer was made using a separatory funnel separated from the mixture. The organic layer was then washed with 100 parts of deionized water with an electrical conductivity of 0.60 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was measured. These procedures were repeated until the electrical conductivity the aqueous Shift to a desired one Value (that is, not higher than 2 μS / cm) has been. In this case, the electrical conductivity of the aqueous layer was 1.49 μS / cm.

Then The methylene chloride solution prepared in this manner (the is called, the organic layer) in 2000 ml of methanol was added dropwise to the polycarbonate resin precipitate. The mixture was filtered using a suction device, to get the resin. The resin thus obtained became 2 For days at 100 ° C Vacuum dried.

On thus, a purified polycarbonate resin 5 was prepared.

Cleaning example 6

wobei das auf Polystyrol umgerechnete Gewichtsmittel des Molekulargewichtes (Mw) 145.000 beträgt und das Verhältnis Mw/Mn des Gewichtsmittels des Molekulargewichtes (Mw) zu dem Zahlenmittel des Molekulargewichtes (Mn) 3,0 beträgt.Five parts of a charge transport polymer containing a structural unit represented by the following formula were dissolved in 95 parts of methylene chloride.

wherein the polystyrene-reduced weight-average molecular weight (Mw) is 145,000 and the ratio Mw / Mn of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) is 3.0.

The solution was charged with 100 parts of deionized water with an electric conductivity of 0.68 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was 4.67 μS / cm.

Then the organic layer was mixed with a 5% aqueous sodium hydroxide solution, and the mixture was stirred vigorously for 30 minutes. After separating the organic layer of the mixture by means of a separating funnel the organic layer was mixed with a 2% hydrochloric acid, and the mixture was stirred vigorously for one hour. The organic. Layer was made using a separatory funnel separated from the mixture. The organic layer was then washed with 100 parts of deionized water with an electrical conductivity of 0.59 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was measured. These procedures were repeated until the electrical conductivity the aqueous Shift to a desired one Value (that is, not higher than 2 μS / cm) has been. In this case, the electrical conductivity of the aqueous layer was 1.32 μS / cm.

Then The methylene chloride solution prepared in this manner (the is called, the organic layer) in 2000 ml of methanol was added dropwise to the polymer precipitate. The mixture was filtered using a suction device, to get the polymer. The polymer thus obtained was kept at 100 ° C for 2 days Vacuum dried.

On thus, a purified charge transport polymer 6 was prepared.

Cleaning example 7

wobei das auf Polystyrol umgerechnete Gewichtsmittel des Molekulargewichtes 153.000 beträgt und das Verhältnis Mw/Mn des Gewichtsmittels des Molekulargewichtes (Mw) zu dem Zahlenmittel des Molekulargewichtes (Mn) 2,9 beträgt.Five parts of a charge transport polymer containing a structural unit represented by the following formula were dissolved in 95 parts of methylene chloride.

wherein the polystyrene-reduced weight-average molecular weight is 153,000 and the ratio Mw / Mn of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) is 2.9.

The solution was charged with 100 parts of deionized water with an electric conductivity of 0.68 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was 5.23 μS / cm.

Then the organic layer was mixed with a 5% aqueous sodium hydroxide solution, and the mixture was stirred vigorously for 30 minutes. After separating the organic layer of the mixture by means of a separating funnel the organic layer was mixed with a 2% hydrochloric acid, and the mixture was stirred vigorously for one hour. The Organic layer was made using a separatory funnel separated from the mixture. The organic layer was then washed with 100 parts of deionized water with an electrical conductivity of 0.62 μS / cm mixed and the mixture was stirred vigorously for 30 minutes. The Mixture became organic using a separating funnel Layer and an aqueous one Layer separated. The electrical conductivity of the aqueous Layer was measured. These procedures were repeated until the electrical conductivity the aqueous Shift to a desired one Value (that is, not higher than 2 μS / cm) has been. In this case, the electrical conductivity of the aqueous layer was 1.48 μS / cm.

Then The methylene chloride solution prepared in this manner (the is called, the organic layer) in 2000 ml of methanol was added dropwise to the polymer precipitate. The mixture was filtered using a suction device, to get the polymer. The polymer thus obtained was kept at 100 ° C for 2 days Vacuum dried.

On in this way, a purified charge transport polymer 7 was prepared.

example 1

generation the base layer

The following components were mixed to prepare a coating liquid for a base coat. Titanium dioxide (CR-EL from Ishihara Sangyo Kaisha, Ltd.) 400 melamine resin 65 alkyd resin 120 2-butanone 400

The coating liquid for one Base layer was applied by a dip coating method coated an aluminum cylinder and then dried. To this As a result, a base layer having a thickness of 3.5 μm was produced.

generation the charge generation layer

Polyvinylbutyral 2 2-Butanon 200 Cyclohexanon 400 The following components were mixed to prepare a coating liquid for a charge generation layer. Bisazo pigment with the following formula 10

polyvinyl butyral 2 2-butanone 200 cyclohexanone 400

The coating liquid for one Charge generation layer was prepared by a dip coating method coated on the base coat and then dried. To this As a result, a charge generation layer having a thickness of 0.2 μm was produced.

generation the charge transport layer

Tetrahydrofuran 200 The following components were mixed to prepare a charge transport layer coating liquid. Polycarbonate of bisphenol A form 10 Low molecular weight charge transport material having the following formula (a) 8th

tetrahydrofuran 200

The coating liquid for one Charge transport layer was by a dip coating method coated on the charge generation layer and then dried. In this way, a charge transport layer having a thickness of 20 μm generated.

generation the protective layer

The following components were mixed to prepare a coating liquid for a protective layer. Purified polycarbonate resin 1 10 Low molecular weight charge transport material having the above formula (a) 7 Particulate alumina (resistivity of 2.5 × 10 ¹² Ω · cm and average particle diameter of primary particles of 0.3 μm) 4 tetrahydrofuran 400 cyclohexanone 200

The coating liquid for one Protective layer was applied by a spray coating method coated the charge transport layer and then dried. On in this way, a protective layer with a thickness of 5 μm was produced.

On thus, the photoreceptor of Example 1 was prepared.

Example 2

The procedure for preparing the photoreceptor in Example 1 was repeated except that the formulation of the coating liquid for a charge transport layer was changed to the following. Coating liquid for a charge transport layer Purified polycarbonate resin 1 10 Low molecular weight charge transport material having the above formula (a) 8th tetrahydrofuran 200

On thus, the photoreceptor of Example 2 was prepared.

Example 3

Of the Procedure for preparing the photoreceptor in Example 1 was repeated except that is, the purified polycarbonate resin 1 in the coating liquid for one Protective layer was replaced by the purified polycarbonate resin 2.

On thus, the photoreceptor of Example 3 was prepared.

Example 4

Of the Procedure for preparing the photoreceptor in Example 2 was repeated except that is, the purified polycarbonate resin 1 in the coating liquid for one Protective layer was replaced by the purified polycarbonate resin 2.

On thus, the photoreceptor of Example 4 was prepared.

Example 5

Of the Procedure for preparing the photoreceptor in Example 1 was repeated except that is, the purified polycarbonate resin 1 in the coating liquid for one Protective layer was replaced by the purified polycarbonate resin 3.

On thus, the photoreceptor of Example 5 was prepared.

Example 6

The procedure for preparing the photoreceptor in Example 1 was repeated except that the formulation of the protective layer was changed to the following. Coating liquid for a protective layer Purified charge transport polymer material 6 17 Particulate alumina (resistivity of 2.5 × 10 ¹² Ω · cm and average particle diameter of primary particles of 0.3 μm) 4 tetrahydrofuran 400 cyclohexanone 200

On thus, the photoreceptor of Example 6 was prepared.

Example 7

The procedure for preparing the photoreceptor in Example 2 was repeated except that the formulation of the protective layer was changed to the following one, and the thickness of the charge transport layer and the protective layer, respectively, were changed to 23 μm and 2 μm, respectively. Coating liquid for a protective layer Purified polycarbonate resin 1 17 Particulate alumina (resistivity of 2.5 × 10 ¹² Ω · cm and average particle diameter of primary particles of 0.3 μm) 4 tetrahydrofuran 400 cyclohexanone 200

On thus, the photoreceptor of Example 7 was prepared.

Example 8 (reference example)

The procedure for producing the photoreceptor in Example 4 was repeated except that the formulation of the protective layer was changed to the following. Coating liquid for a protective layer Purified polycarbonate resin 2 10 Purified charge transport polymer material 6 10 tetrahydrofuran 400 cyclohexanone 200

On thus, the photoreceptor of Example 8 was prepared.

Comparative Example 1

Of the Procedure for preparing the photoreceptor in Example 1 was repeated except that the purified polycarbonate resin 1 by the in the cleaning example 1 uncleaned polycarbonate resin used was replaced.

On thus, the photoreceptor of Comparative Example 1 was prepared.

Comparative Example 2

Of the Procedure for preparing the photoreceptor in Example 1 was repeated except that the purified polycarbonate resin 1 by the in the cleaning example 2 uncleaned polycarbonate resin used was replaced.

On thus, the photoreceptor of Comparative Example 2 was produced.

Comparative Example 3

Of the Procedure for preparing the photoreceptor in Example 1 was repeated except that the purified polycarbonate resin 1 by the in the cleaning example 3 uncleaned polycarbonate resin used was replaced.

On thus, the photoreceptor of Comparative Example 3 was produced.

Comparative Example 4

Of the Procedure for preparing the photoreceptor in Example 1 was repeated except that the purified polycarbonate resin 1 by the in the cleaning example 6 used uncleaned charge transport polymer material replaced has been.

On thus, the photoreceptor of Comparative Example 4 was prepared.

Comparative Example 5

Of the Procedure for preparing the photoreceptor in Example 1 was repeated except that the protective layer was not generated and the thickness of the charge transport layer to 25 μm changed has been.

On thus, the photoreceptor of Comparative Example 5 was prepared.

Comparative Example 6

The procedure for preparing the photoreceptor in Example 1 was repeated except that the protective layer was not formed, the formulation of the coating liquid for a charge transport layer was changed to the following, and the thickness of the charge transport layer was changed to 25 μm. Coating liquid for a protective layer Purified charge transport polymer material 6 10 tetrahydrofuran 200

On thus, the photoreceptor of Comparative Example 6 was prepared.

Rating 1

Each of the photoreceptors of Examples 1 to 8 and Comparative Examples 1 to 6 was evaluated by placing it in a copying machine having a construction like that in FIG 3 was shown used. An operation test in which 30,000 images were continuously produced at room temperature and normal humidity was carried out with the pre-cleaning light irradiation not performed and a scorotron-type charging device was used as the charging device. Using a laser diode having a wavelength of the emitted light of 655 nm as a light source and a polygon mirror, light images were written on the photoreceptor.

At the Beginning and the end of the audit were the qualities of visually assessed images produced by each photoreceptor. moreover the bright spot potential (VL) of each photoreceptor on the Development section measured. In addition, the amount of abrasion was also measured by each photoreceptor.

The results are shown in Table 3. Table 3

As from Table 3, the photoreceptors of the present Invention with a protective layer containing the purified binder resin includes, a relatively small Amount of abrasion (that is, a relatively good one Life) compared to that of the photoreceptors without Protective layer (that is, Comparative Examples 5 and 6). In addition, the photoreceptors have the present invention good charging properties, so that the increase of the residual potential is lower than that of the comparative photoreceptors is, and thereby can good pictures are produced.

By doing a purified binder resin in the photosensitive layer (this means, the charge transport layer), the increase of the Residual potential further contained become.

If an unpurified binder resin with ionic contaminants used in an amount of not less than 2 μS / cm in the protective layer becomes, the residual potential increases sharply, and thereby become images made that not desirable although the photoreceptors have good abrasion resistance.

If a filler Included in the protective layer, the abrasion resistance can be dramatic be improved, and the effect can be further enhanced, if the filler used in combination with a charge transport polymer.

Example 9

Of the Process for evaluating the photoreceptor of Example 1 was repeated, except that the metal grid loading device in the copying machine to a Charging roller changed which was a DC bias of -920V put the photoreceptor while she touched the photoreceptor.

When one result was the first pictures and the thirty thousandth Picture good. However, that had thirty thousand Image slight background development, which by the formation of a Toner film was caused on the charge roller. The ozone smell at continuous copying was much lower than in the case where the metal grid loader has been used.

Example 10

Of the Process for evaluating the photoreceptor of Example 9 was repeated except that an insulating tape with a thickness of 50 microns and a width of 5 mm was glued to both ends of the charging roller to a gap of 50 μm between the photoreceptor and the charger.

When a result has not been the formation of toner film on the charge roller watched, and the first and thirty thousandth pictures were good. However, the halftones produced after the audit were slightly uneven what of uneven charging is caused.

Example 11

Of the Process for evaluating the photoreceptor of Example 10 was repeated except that the charging conditions have been changed as follows.

Applied DC voltage bias: -900V
Applied AC bias: 2.0 kV (peak-to-peak voltage), 2kHz (frequency).

When one result, the first and the thirty-thousandth picture had good picture qualities. The Contamination of the charge roller observed in Example 9 and the uneven halftone images observed in Example 10 not observed.

Example 12

generation the base layer

The following components were mixed to prepare a coating liquid for a base coat. titanium dioxide powder 100 Alcohol-soluble nylon 100 methanol 500 butanol 300

The coating liquid for one Base layer was applied by a dip coating method a nickel belt coated and then dried to a base coat with a Thickness of 3 microns too produce.

Generation of the charge generation layer

Trisazopigment mit der folgenden Formel 8

Polyvinylbutyral 2 2-Butanon 200 Cyclohexanon 400 The following components were mixed to prepare a coating liquid for a charge generation layer. Bisazo pigment with the following formula 2

Trisazo pigment with the following formula 8th

polyvinyl butyral 2 2-butanone 200 cyclohexanone 400

The coating liquid for one Charge generation layer was prepared by a dip coating method coated on the base layer and then dried to a charge generation layer with a thickness of 0.3 microns to create.

Generation of the charge transport layer

Tetrahydrofuran 200 The following components were mixed to prepare a charge transport layer coating liquid. Polycarbonate of bisphenol Z-form 10 Charge transport material having the following formula (b) 7

tetrahydrofuran 200

The coating liquid for one Charge transport layer was by a dip coating method coated on the charge generation layer and then dried, to produce a charge transport layer having a thickness of 22 μm.

generation the protective layer

The following components were mixed to prepare a coating liquid for a protective layer. Purified polycarbonate resin 2 10 Charge transport material of the formula (b) 6 Particulate alumina (resistivity of 1.5 × 10 ¹² Ω · cm) 4 toluene 600

The coating liquid for one Protective layer was applied by means of a ring coating method coated the charge transport layer and then dried, a To produce protective layer with a thickness of 3 microns.

On thus, the photoreceptor of Example 12 was prepared.

Example 13

Of the Procedure for preparing the photoreceptor in Example 12 was repeated except that the polycarbonate resin in the coating liquid for a protective layer the purified polycarbonate resin 4 was replaced.

On thus, the photoreceptor of Example 13 was prepared.

Example 14

Of the Procedure for preparing the photoreceptor in Example 12 was repeated except that the polycarbonate resin in the coating liquid for a protective layer the purified polycarbonate resin 5 was replaced.

On thus, the photoreceptor of Example 14 was prepared.

Example 15

Teilchenförmiges Aluminiumoxid (spezifischer Widerstand von 1,5 × 10¹² Ω·cm) 4 Toluol 600 The procedure for producing the photoreceptor in Example 12 was repeated except that the coating liquid for a protective layer was changed to the following. Coating liquid for a protective layer Purified Charge Transport Polymer Material 7 16 Compound of the following formula (c) 1

Particulate alumina (resistivity of 1.5 × 10 ¹² Ω · cm) 4 toluene 600

On thus, the photoreceptor of Example 15 was prepared.

Example 16

The procedure for producing the photoreceptor in Example 12 was repeated except that the coating liquid for a protective layer was changed to the following. Coating liquid for a protective layer Purified polycarbonate resin 2 10 Charge transport material of the formula (b) 6 Particulate silica (resistivity of 5 × 10 ¹³ Ω · cm) 5 toluene 600

On thus, the photoreceptor of Example 16 was prepared.

Example 17

The procedure for producing the photoreceptor in Example 12 was repeated except that the coating liquid for a protective layer was changed to the following. Coating liquid for a protective layer Purified polycarbonate resin 2 10 Charge transport material of the formula (b) 6 Electrically conductive titanium oxide (resistivity of 7.1 × 10 ⁷ Ω · cm) 5 toluene 600

On thus, the photoreceptor of Example 17 was prepared.

Comparative Example 7

Of the Procedure for preparing the photoreceptor in Example 12 was repeated except that the polycarbonate resin in the coating liquid for a protective layer the unpurified polycarbonate resin used in the cleaning example 2 was replaced.

On thus, the photoreceptor of Comparative Example 7 was prepared.

Comparative Example 8

Of the Procedure for producing the photoreceptor in Example 13 was repeated except that the polycarbonate resin in the coating liquid for a protective layer the unpurified polycarbonate resin used in the purification example 4 was replaced.

On thus, the photoreceptor of Comparative Example 8 was produced.

Comparative Example 9

Of the Procedure for preparing the photoreceptor in Example 14 was repeated except that the polycarbonate resin in the coating liquid for a protective layer the unpurified polycarbonate resin used in the cleaning example 5 was replaced.

On thus, the photoreceptor of Comparative Example 9 was prepared.

Comparative Example 10

Of the Procedure for preparing the photoreceptor in Example 15 was repeated except that the charge transport polymer material in the coating liquid for one Protective layer by the unpurified used in the cleaning example 7 Charge transport polymer material has been replaced.

On thus, the photoreceptor of Comparative Example 10 was prepared.

Comparative Example 11

The procedure for preparing the photoreceptor in Example 12 was repeated except that the protection layer was not generated and the thickness of the charge transport layer was changed to 25 microns.

On thus, the photoreceptor of Comparative Example 11 was prepared.

Each of the photoreceptors of Examples 12 to 17 and Comparative Examples 7 to 11 thus prepared was set in a copying machine having a construction such as that shown in Figs 4 and an operation test was conducted in which 30,000 images were continuously produced at room temperature and normal humidity using a laser diode having a wavelength of emitted light of 780 nm as the light source of the image exposure apparatus and the pre-cleaning light irradiation operation was not performed.

At the Beginning and the end of the audit were the qualities of visually assessed images produced by each photoreceptor. moreover became the dark area potential (VD) of each photoreceptor measured in the development section. In addition, the amount of abrasion was measured by each photoreceptor.

The Results are shown in Table 4.

Table 4

As from Table 4, the photoreceptors of the present Invention with a protective layer containing the purified binder resin includes, a relatively small Amount of abrasion (that is, a relatively good one Life) compared to that of the photoreceptors without Protective layer. Furthermore the photoreceptors of the present invention have good charging characteristics, so that the decrease in dark field potential is less than that is the comparative photoreceptor, and this can be good Pictures are produced.

If an unpurified binder resin with ionic contaminants used in an amount of not less than 2 μS / cm in the protective layer dark space potential decreases sharply, and thereby becomes Images produced that are not desirable are.

One filler included in the protective layer improves the abrasion resistance dramatically, and the effect can be further enhanced if the filler used in combination with a charge transport polymer.

In addition, were the photoreceptors subjected to the audit with 30,000 images then subjected to another audit, in the 500th Images continuously at 30 ° C, 90% r.F. were manufactured. The photoreceptor of the comparative example 11 was the tax audit not subject with 500 pictures, because its picture qualities much were too bad.

When a result were the photoreceptors of Examples 12 to 16 not pictures that are not desirable but the photoreceptors of Example 17 and Comparative Examples 7 to 10 produced blurred images, causing deterioration the resolution which results in pictures. That of the photoreceptor of the example The faded image produced was better than that of the photoreceptors Comparative Examples 7 to 10 produced images.

Examples 18 and 19 and Comparative Examples 12 and 13

The photoreceptors of Examples 12 and 13 and Comparative Examples 7 and 8 were subjected to a gas exposure test in which each photoreceptor was settled in an atmosphere containing NOx for 4 days (that is, thereafter, the photoreceptors of Figs Examples 18 and 19 and Comparative Examples 12 and 13). Before and after the gas exposure test, using each of the photoreceptors and the in 4 shown image recording device images produced.

When One result took the resolution that produced by the photoreceptors of Examples 18 and 19 Images barely, however, took the resolution of the photoreceptors of Comparative Examples 12 and 13, because the pictures were washed out.

Examples 20 to 22

Of the in the coating liquid for the Protective layer used filler was treated with a titanate coupling agent or alumina, so that the weight of the treatment agent was 20%.

The coating liquids for the Protective layer were prepared in the same manner as in Example 12, the one with the titanate coupling agent coated filler (Example 21) or the alumina-coated filler (Example 22) was used.

Of the mean particle diameter of the filler used with the CAPA500 device from Horiba, ltd. was measured, and the dispersibility of the filler with respect to the coating liquids for the protective layer from Example 12 (that is, Example 20) and Examples 21 and 22 were evaluated. In relation to the dispersibility became that contained in a test tube filler in every coating liquid visually observed to see if the filler settled down.

The Results are shown in Table 5.

Table 5

Examples 23 to 25

The procedure for preparing the photoreceptor of Example 12 was repeated using the coating liquids for the protective layer of Examples 20 to 22 repeated.

It was also each of the coating liquids for the Protective layer coated on each one polyester film to on top to create a protective layer. The transmittance of the on the Polyester film-produced protective layers were used of light with one wavelength measured at 780 nm.

Further also the average roughness was over 10 points of the protective layers measured. The results are shown in Table 6.

Table 6

Examples 26 and 27

Of the Procedure for evaluating the photoreceptor of Example 12 was below Using the photoreceptors of Examples 24 and 25 repeated.

When one result was the resolution the images produced by the photoreceptors of Examples 24 and 25 better than the photoreceptor of Example 12.

Example 28

Generation of the base layer

The following components were mixed to prepare a coating liquid for a reason layer. Titanium dioxide 400 melamine resin 65 alkyd resin 120 2-butanone 400

The coating liquid for one Base coat was coated on an aluminum cylinder and then dried to produce a base layer having a thickness of 3.5 microns.

generation the charge generation layer

The following components were mixed to prepare a coating liquid for a charge generation layer. Titanylphthalocyanine with the X-ray diffraction spectrum as shown in Fig. 6 8th polyvinyl butyral 5 2-butanone 400

The coating liquid for one Charge generation layer was coated on the base layer and then dried to form a charge generation layer having a Thickness of 0.2 μm to create.

generation the charge transport layer

Methylenchlorid 80 The following components were mixed to prepare a charge transport layer coating liquid. polyarylate 10 Charge transport material having the following formula (d) 7

methylene chloride 80

The coating liquid for one Charge transport layer was coated on the charge generation layer and then dried to form a charge transport layer having a thickness of 21 μm to create.

generation the protective layer

The following components were mixed to prepare a coating liquid for a protective layer. Purified polycarbonate resin 2 9 Charge transport material of the formula (d) 7 Particulate alumina (resistivity of 2.5 × 10 ¹² Ω · cm and average particle diameter of primary particles of 0.3 μm) 3 tetrahydrofuran 400 cyclohexanone 200

The coating liquid for one Protective layer was coated on the charge transport layer and then dried to produce a protective layer having a thickness of 4 μm.

On thus, the photoreceptor of Example 28 was prepared.

Example 29

The procedure for preparing the photoreceptor of Example 28 was repeated except that the protective layer coating liquid was changed to the following. Coating liquid for a protective layer Purified Charge Transport Polymer Material 7 16 Compound of the above formula (c) 1 Particulate alumina (resistivity of 2.5 × 10 ¹² Ω · cm and average particle diameter of primary particles of 0.3 μm) 3 Tetrahyrdofuran 400 cyclohexanone 200

On thus, the photoreceptor of Example 29 was prepared.

Comparative Example 14

Of the Procedure for preparing the photoreceptor of Example 28 was repeated, except that in the coating liquid for the Protective layer used polycarbonate resin by that in the cleaning example 2 uncleaned polycarbonate resin used was replaced.

On thus, the photoreceptor of Comparative Example 14 was prepared.

Comparative Example 15

Of the Procedure for preparing the photoreceptor of Example 28 was repeated, except that in the coating liquid for the Protective layer used by charge transport polymer material the unpurified charge transport polymer material used in the purification example 7 was replaced.

On thus, the photoreceptor of Comparative Example 15 was prepared.

Each of the thus-prepared photoreceptors of Examples 28 and 29 and Comparative Examples 14 and 15 was placed in a process cartridge having a construction like that in Figs 5 and an operation test was carried out in which 20,000 images were continuously produced by using a laser diode having a wavelength of 780 nm as a light source for imagewise exposure and a polygon mirror. The image qualities of the first and the twenty thousandth image were evaluated. In addition, the amount of abrasion of each photoreceptor was measured.

The Results are shown in Table 7.

Table 7

Example 30

Of the Procedure for preparing the photoreceptor of Example 1 was repeated, except that the toner used for development was changed to a toner, in which a zinc stearate powder is added to the toner in an amount of 0.15% was added. This was an audit with 50,000 pictures performed. For comparison purposes was also an audit with 50,000 images using the toner containing the zinc stearate powder was not added (that is, under the conditions of Example 1) also carried out.

When One result was the image qualities of the first and fifty thousand Image excellent under the conditions of Example 30. Specific had fifty thousandth Image no uneven halftones. moreover There were no disturbances on the surface of the photoreceptor.

in the In contrast, this was produced under the conditions of Example 1 fifty thousandth picture slightly uneven halftone images. moreover Some toner film formation was observed on the surface of the photoreceptor.

Example 31

Of the Procedure for implementation the 50,000 pictures audit using the photoreceptor of Example 1 was repeated, except that processes, which do not produce an image including a light irradiation process for irradiating the entire surface of the photoreceptor with pictorial light (that is, irradiation the surface of the photoreceptor, leaving one everywhere black image is generated); a development process with the Toner; and a toner collection process collecting the toner on the surface of the photoreceptor at the Cleaning section, after every 1,000 pictures were performed.

When one result had the fifty thousandth Picture excellent picture qualities and it had no uneven halftone pictures.

In addition, were after the audit ten pictures at 30 ° C and 90% r.F. produced. The pictures had just as good picture qualities as the fifty-thousandth produced at room temperature and normal humidity Image.

in the Contrary to that was the resolution the ten at 30 ° C and 90% r.F. after the 50,000 pictures-auditing without performing the operations that does not produce an image (that is, under the conditions of example 1) produced images slightly deteriorated.

Example 32

Of the Procedure for implementation the 50,000 pictures audit using the photoreceptor of Example 1 was repeated, except the lamp is removed from the imaging device for discharge has been.

The image quality and the bright spot potential (VL) of the photoreceptor are shown in Table 8.

Table 8

Examples 33 and 34 and Comparative Examples 16 and 17

The photoreceptors of Examples 28 and 29 and Comparative Examples 14 and 15 were set in a tandem-type image forming apparatus having a structure as shown in FIG 7 shown used to carry out a 20,000 image inspection.

When the result was the photoreceptors of Examples 28 and 29 after the audit good pictures, however, the photoreceptors of Comparative Examples 14 and 15 pictures with the problem that the hue of halftones different from that of the original picture.

effects of the present invention

As mentioned above, can the problems caused by creating a protective layer on the surface of a Photoreceptor to improve the life of the photoreceptor, caused, solved by removing ionic impurities from the in the protective layer be removed to the maximum use of binder resin. Thereby can be a good life photoreceptor capable of to stably produce high quality images become.

Specific becomes a photoreceptor with good mechanical life and good electrostatic lifetime (that is, increase in residual potential, Decrease in dark field potential and by the appearance of washed-out Images are causing deterioration in image quality prevented). In other words, it's a photoreceptor, which can stably produce high quality images even when he over used over a long period of time. Moreover, the photoreceptor is stable, even when environmental conditions such as temperature and humidity change, and even when used in an atmosphere containing reactive gases becomes.

Further can be miniaturized by the use of such a photoreceptor An image forming apparatus including a photoreceptor with a small diameter, or a high speed image forming apparatus, in which both the photoreceptor is used over a long period of time can be provided. Moreover, an electrophotographic image recording method, an electrophotographic image recording apparatus and a Process cartridge for one electrophotographic image recording apparatus by means of which High quality pictures even when using over be produced in a stable manner over a long period of time can, provided.

Claims (33)

An electrophotographic photoreceptor comprising: an electroconductive substrate, a photosensitive layer overlying the substrate and comprising a binder, and a protective layer overlying the photosensitive layer and comprising a binder resin and a filler, characterized in that the binder resin is for the Protective layer and optionally also the binder resin for the photosensitive layer include a material, so that when a solution in which the binder resin is dissolved in an organic solvent which is incompatible with water, with deionized water having an electrical conductivity of not more than 1 μS / cm and mixed and stirred substantially the same weight as that of the solvent, the deionized water has an electrical conductivity of not more than 2 μS / cm. A photoreceptor according to claim 1, wherein the binder resin a cleaning treatment has been subjected to ionic impurities to remove it. A photoreceptor according to claim 2, wherein the binder resin has been subjected to a cleaning treatment in which a Acid and / or an alkali is used. A photoreceptor according to any one of claims 1 to 3, wherein the binder resin comprises a polycarbonate resin. A photoreceptor according to claim 4, wherein the polycarbonate resin comprises a structural unit selected from the following formulas (A) and (B):

wherein R1 and R2 independently represent a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted carbon ring or a substituted or unsubstituted aromatic group; and R3 to R10 independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted carbon ring,

wherein R3 to R10 independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted carbon ring; and Z represents an atomic group necessary to form a substituted or unsubstituted carbon ring or an unsubstituted heterocyclic group. A photoreceptor according to claim 5, wherein the structural unit of the polycarbonate resin has any of the following formulas (1), (2) and (3):

A photoreceptor according to any one of claims 1 to 6, wherein the photosensitive layer is a charge generation layer and a charge transport layer comprising a binder resin, wherein the binder resin comprises a material such that when a Solution, in which the binder resin in the charge transport layer in a organic solvents, which is incompatible with water, is dissolved with deionized Water with an electrical conductivity of not more than 1 μS / cm and substantially the same weight as that of the solvent mixed and stirred the deionized water becomes an electrical conductivity of not more than 2 μS / cm having. A photoreceptor according to any one of claims 1 to 7, wherein the filler comprises an inorganic pigment having a resistivity of not less than 10 ¹⁰ Ω · cm. A photoreceptor according to claim 8, wherein the inorganic Pigment is a metal oxide. A photoreceptor according to claim 9, wherein the metal oxide is selected from silica, alumina and titania. A photoreceptor according to any one of claims 8 to 10, wherein the inorganic pigment has a pH of not less than 5 has. A photoreceptor according to any one of claims 8 to 11, wherein the inorganic pigment has a dielectric constant of not less than 5. A photoreceptor according to any one of claims 8 to 12, wherein the inorganic pigment has a surface with a Surface treatment agent is treated. A photoreceptor according to claim 13, wherein the surface is a surface treated with a surface treatment agent selected from titanate coupling agents, aluminum coupling agents, higher fatty acids, Al ₂ O ₃ , TiO ₂ and ZrO ₂ and mixtures thereof and combinations of a silane coupling agent at least one of titanate coupling agents, aluminum coupling agents, higher fatty acids, Al ₂ O ₃ , TiO ₂ and ZrO _{2 is} treated. A photoreceptor according to claim 13 or 14, wherein said relationship (Ws / Wf) of the weight (Ws) of the surface treatment agent to Weight (Wf) of the filler 0.03 to 0.30. A photoreceptor according to any one of claims 1 to 15, wherein the filler a mean primary particle diameter from 0.01 to 0.5 μm having. A photoreceptor according to any one of claims 1 to 16, wherein the protective layer further comprises a charge transport material. The photoreceptor of claim 17, wherein the charge transport material is a charge transport polymer. The photoreceptor of claim 18, wherein the charge transport polymer a triarylamine structure in a main chain and / or a side chain of the charge transport polymer. A photoreceptor according to any one of claims 1 to 19, further comprising a base coat between the electrical conductive Substrate and the photosensitive layer. A photoreceptor according to any one of claims 1 to 20, further comprising an intermediate layer between the photosensitive Layer and the protective layer. An image recording method, comprising: charging a photoreceptor, exposing the photoreceptor to form an electrostatic latent image on a surface of the photoreceptor, developing the electrostatic latent image with a toner to form a toner image on the photoreceptor, transferring the toner image to a receiver, wherein the photoreceptor is a photoreceptor according to any one of claims 1 to 21. An image recording method according to claim 22, wherein the irradiation step uses a digitally irradiating light using a laser diode and / or a light emitting diode includes. An image recording method according to claim 22 or 23, further comprising applying zinc stearate to a surface of the Photoreceptor. An image recording method according to any one of claims 22 to 24, wherein the development step is the development of the electrostatic comprising a latent image comprising a toner comprising zinc stearate. An image recording method according to any one of claims 22 to 25, further comprising cleaning the surface of the Photoreceptor, wherein the cleaning step comprises: the clinging the toner on the surface of the photoreceptor and then collecting the toner, in which the cleaning step is performed at a time when the charging, irradiation, development and transfer steps not done become. An image recording apparatus comprising: a photoreceptor ( 1 . 21 . 101K . 101Y . 101M and 101C ), a loading device ( 8th . 23 . 102K . 102Y . 102M and 102C ) configured to charge the photoreceptor, an image irradiation apparatus ( 10 . 103K . 103Y . 103M and 103C ) configured to expose the photoreceptor to form an electrostatic latent image on the photoreceptor, an image development apparatus ( 11 . 104K . 104Y . 104M and 104C ) configured to develop the electrostatic latent image with a toner to form a toner image on the photoreceptor, and an image transfer device ( 15 . 15a . 15b . 111K . 111Y . 111M and 111C ) configured to transfer the toner image to a receiver, the photoreceptor being a photoreceptor according to any one of claims 1 to 21. An image recording apparatus according to claim 27, further comprising a laser diode or a light emitting diode for emitting of light configured by the image irradiation device is used to irradiate the photoreceptor in a digital manner. An image recording apparatus according to claim 27, wherein the charging device is a contact charging device or a close-loading device configured to charge the photoreceptor while it is near on the surface of the photoreceptor, but it does not touch. An image recording apparatus according to claim 27, wherein the charging device is configured to pass through the photoreceptor Applying a DC voltage superimposed with an AC voltage is, on the surface of the photoreceptor. An image recording apparatus according to claim 27, further comprising a lubricant applicator ( 20 ) configured to apply zinc stearate to the surface of the photoreceptor. An image recording apparatus according to claim 27, wherein said recording apparatus is not a discharge apparatus ( 7 . 28 ) configured to discharge a residual potential of the photoreceptor using light. A process cartridge comprising: a photoreceptor ( 43 ), a housing ( 46 ) configured to contain the photoreceptor and at least one of the following devices: a charging device ( 40 ) configured to charge the photoreceptor, an image irradiation device ( 41 ) configured to expose the photoreceptor to form an electrostatic latent image thereon, an image development apparatus ( 45 ) configured to develop the electrostatic latent image with a toner to form a toner image on the photoreceptor, an image transfer device ( 44 ) configured to transfer the toner image to a receiver, a cleaning device ( 42 ) configured to clean the surface of the photoreceptor, and an unloading device ( 47 ) configured to reduce the residual potential on the photoreceptor, the photoreceptor being a photoreceptor according to any one of claims 1 to 21.