JP2006301436A - Electrophotographic photoreceptor, image forming method, image forming apparatus, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having a photosensitive layer comprising a single layer structure or a multilayer structure on a conductive supporting body, the photoreceptor having high durability against wear and abrasion or scratches and excellent electric characteristics against image degradation, and stably giving a high quality image even when repeatedly used for a long period, and to provide an image forming method, an image forming apparatus and a process cartridge using the photoreceptor. <P>SOLUTION: The photoreceptor has a multilayer photosensitive layer 53 on a conductive supporting body 50, the layer 53 including a charge generating layer 51 containing a charge generating substance, a lower charge transporting layer 52a containing a charge transporting substance, and an upper charge transporting layer 53b containing an organic-inorganic hybrid material integrated by polycondensation of a hybrid polymer having a predetermined structural unit and a metal alkoxide group with a metal alkoxide. The photoreceptor is used to constitute the image forming apparatus and the process cartridge. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrophotographic photosensitive member having a surface layer formed of an organic-inorganic hybrid material. Specifically, the electrophotographic photosensitive member is highly durable with a surface layer having excellent surface hardness, water repellency, scratch resistance, and abrasion resistance. The present invention also relates to an electrophotographic photosensitive member capable of forming a high-quality image even when used for a long period of time, an image forming method using the same, an image forming apparatus, and a process cartridge.

In recent years, organic photoreceptors (OPCs) have good performance and various advantages, and are therefore frequently used in copying machines, facsimiles, laser printers, and their combined machines in place of inorganic photoreceptors. Good performance and advantages of such OPC include, for example, (1) optical characteristics [width of light absorption wavelength range and magnitude of absorption, etc.], (2) electrical characteristics [high sensitivity, stable Charging characteristics, etc.], (3) wide selection range of materials, (4) ease of production, (5) low cost, (6) non-toxicity, and the like.
On the other hand, along with the recent downsizing of the image forming apparatus, the diameter of the photoreceptor has been reduced, and the speed of the machine and the maintenance-free movement have also been added, so that the durability of the photoreceptor has been eagerly desired.

In the case of organic photoreceptors, from the viewpoint of high durability, the outermost surface layer is generally soft because it is mainly composed of a low molecular charge transport material and an inert polymer, and has been repeatedly used in electrophotographic processes. At the same time, there is a drawback that wear is likely to occur due to a mechanical load by the developing system and the cleaning system.
In addition, in order to meet the demands for higher image quality and energy saving, toner particles have been reduced in size and spheroidized (polymerized spherical particles), and with this purpose, the rubber of the cleaning blade has been improved for the purpose of improving cleaning properties. Increasing the hardness and the contact pressure are unavoidable, and this also promotes the wear of the photoreceptor.

When the photoconductor is worn, the electrical characteristics such as sensitivity deterioration or chargeability deterioration are deteriorated, and this causes a decrease in image density and occurrence of abnormal images such as background stains. In addition, scratches in which wear locally occurs result in streak-like stain images due to poor cleaning. Under the present circumstances, the wear and scratches are rate-determined and the life of the photoconductor has been replaced.
Therefore, it is indispensable to reduce the above-mentioned wear amount in order to increase the durability of the organic photoreceptor, and this is the most pressing issue in this field.

  As a technique for improving the abrasion resistance of the photosensitive layer, (a) a method using a curable binder for the surface layer (for example, refer to Patent Document 1), (b) a method using a polymer type charge transport material (for example, Patent Literature 2), (c) a method of dispersing an inorganic filler in the surface layer (for example, see Patent Literatures 3, 4, 5, 6, 7, 8, and 9) has been proposed.

  However, in the above proposal (a) using the curable binder, the residual potential increases due to poor compatibility between the curable binder and the charge transport material, and impurities such as a polymerization initiator or an unreacted residue. There is a tendency that a decrease in image density tends to occur. Further, although the method (b) using the polymer charge transport material and the method (c) dispersing the inorganic filler can improve the abrasion resistance to some extent, the durability required for the organic photoreceptor is improved. It has not been fully satisfied. Furthermore, since the inorganic filler (c) dispersed does not have a bond that directly binds the inorganic filler and the binder, the residual potential increases due to traps present on the surface of the inorganic filler, and the image density decreases. It tends to occur. Furthermore, since light scattering of the inorganic filler is unavoidable, it is difficult to realize high image quality. Therefore, in the above methods (a), (b), and (c), the total durability including the electrical durability and mechanical durability required for the organic photoreceptor is sufficiently satisfied. Has not reached.

In order to improve the abrasion resistance and scratch resistance in the above (c), a method of hydrolyzing and polycondensing alkoxysilane or the like in the presence of a polycarbonate resin has been proposed. (For example, refer to Patent Document 10).
In this method, the silica component in the product and the binder resin can be combined, but the content of the silica component is extremely small due to restrictions on the material preparation method, and thus the merit of the inorganic material is fully exploited. Not in.

In addition, a technique for obtaining an organic-inorganic hybrid polymer material using a terminal silyl-modified polycarbonate has been proposed (see, for example, Patent Document 11).
However, when this organic-inorganic hybrid polymer material is used for an organic photoreceptor, it is necessary to add a low-molecular charge transport material, and this addition demonstrates the synergistic characteristics of the organic-inorganic hybrid material. This makes it difficult to use the original performance of the hybrid material.

JP 56-48637 A Japanese Patent Laid-Open No. 64-1728 JP-A-4-281461 Japanese Patent Application Laid-Open No. 61-132594 JP-A-2-240655 JP 7-261440 A JP-A-5-306335 JP-A-6-32884 Japanese Patent Laid-Open No. 6-282094 JP 2000-105474 A JP 2002-241383 A

As described above, it is indispensable to reduce the amount of wear in order to increase the durability of the organic photoreceptor, and as a result of studies by the present inventors to cope with this problem, an organic material composed of a structural unit having a charge transport function is proposed. Using an organic-inorganic hybrid material obtained by polycondensation after hydrolysis using a polymer having a metal alkoxide group as a component, it is very effective in improving abrasion resistance when used as the outermost layer of an organic photoreceptor. I found out. However, the organic-inorganic hybrid material obtained by this method is still strong as an organic polymer, and is not necessarily sufficient to exhibit the properties as an inorganic material.
The present invention has been made in view of the above, and a photosensitive layer comprising a charge generation material and a charge transport material and comprising a single layer or multiple layers is provided on a conductive support, and the outermost layer of the photosensitive layer is provided. In the electrophotographic photoreceptor configured as a surface layer,
While maintaining high durability against the occurrence of wear and scratches, it has excellent electrical characteristics against image degradation, and stable high-quality images that do not generate abnormal images even when used repeatedly for a long time. An object of the present invention is to provide an electrophotographic photoreceptor obtained in the above manner.
In addition, by using a long-life, high-performance electrophotographic photoreceptor having high durability according to the present invention, it is unnecessary to replace the photoreceptor as much as possible, and high-speed printing, reducing the diameter of the photoreceptor, and making the toner particles spherical. An object of the present invention is to provide an image forming method, an image forming apparatus, and a process cartridge that can cope with the problem and that can stably obtain a high-quality image even in repeated use.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the inventions described in the following 1) to 12), and have reached the present invention. Hereinafter, the present invention will be specifically described.

1) In an electrophotographic photoreceptor in which a photosensitive layer including a charge generation material and a charge transport material and having a single layer or a multilayer is provided on a conductive support, and the outermost layer of the photosensitive layer is configured as a surface layer.
The surface layer is
(1) a hybrid polymer having a structural unit mainly represented by the following general formula (I) and having a metal alkoxide group as a functional group;
(2) a metal alkoxide compound;
An electrophotographic photoreceptor comprising an organic-inorganic hybrid material in which the two are combined and integrated as a constituent material.

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an aryl group. Ar ¹ represents an aryl group, and Ar ² and Ar ³ represent an arylene group.)

  2) The electrophotographic photoreceptor according to 1), wherein the structural unit represented by the general formula (I) is represented by the following general formula (II).

(In the formula, Ar ² , Ar ³ and Ar ⁴ represent an arylene group. R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group and aryl group.)

  3) The electrophotographic photoreceptor according to 2), wherein the structural unit represented by the general formula (II) is represented by the following general formula (III).

(In the formula, R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group, and aryl group.)

  4) The hybrid polymer includes a structural unit represented by the following general formula (IV) together with a structural unit represented by the general formula (I), and the structural unit represented by the general formula (I) The ratio of the composition ratio k to the total composition ratio (k + j) is 0 <k / (k + j) ≦ 1, where k is the composition ratio and j is the composition ratio of the structural unit represented by the following general formula (IV). 1) The electrophotographic photosensitive member according to 1).

[Wherein, X is an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or the following formula (1) or (2),

(Wherein R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group, an aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, and c and d are each independently integers of from 0 to 3, Y is a single bond, a straight-chain alkylene group having 2 to 12 carbon atoms, -O -, - S -, - SO-, SO 2 -, - CO- Or the following formulas (3) to (11),

Z ¹ and Z ^{2 each} represent an aliphatic divalent group or an arylene group, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, Represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group, and R ⁶ and R ⁷ are bonded to form a carbocyclic or heterocyclic ring having 6 to 12 carbon atoms. R ⁶ and R ⁷ may form a carbocyclic or heterocyclic ring together with R ² and R ^3, and R ¹³ and R ¹⁴ are a single bond or an alkylene group having 1 to 4 carbon atoms. R ¹⁵ and R ¹⁶ each independently represents an alkyl group having 1 to 5 carbon atoms or an aryl group, e is an integer of 0 to 4, f is an integer of 0 to 20, and g is an integer of 0 to 2000. Represents. ). ]

  5) The electrophotographic photoreceptor according to claim 4, wherein the structural unit represented by the general formula (I) is represented by the following general formula (II).

(In the formula, Ar ² , Ar ³ and Ar ⁴ represent an arylene group. R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group and aryl group.)

  6) The electrophotographic photoreceptor according to 5), wherein the structural unit represented by the general formula (II) is represented by the following general formula (III).

(In the formula, R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group, and aryl group.)

  7) The organic-inorganic hybrid material is crosslinked and integrated by hydrolysis and polycondensation between the metal alkoxide group of the hybrid polymer and the metal alkoxide compound, and the organic-inorganic hybrid material is any one of 1) to 6) The electrophotographic photoreceptor as described.

  8) Each metal element in the metal alkoxide group and metal alkoxide compound of the hybrid polymer is at least one element selected from Si, Ti, and Zr. An electrophotographic photoreceptor.

  9) The electrophotographic photoreceptor according to 8), wherein each metal element in the metal alkoxide group and the metal alkoxide compound of the hybrid polymer is Si.

  10) An image forming method, wherein at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to any one of 1) to 9).

  11) An image forming apparatus comprising at least the electrophotographic photosensitive member according to any one of 1) to 9), a charging unit, an image exposing unit, a developing unit, and a transferring unit.

  12) The electrophotographic photosensitive member according to any one of 1) to 9) and at least one unit selected from a charging unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit, A process cartridge characterized by being detachable.

An electrophotographic photosensitive member (hereinafter referred to as “photosensitive member”) having a surface layer composed of a strong crosslinked film containing an organic-inorganic hybrid material having the characteristics of an organic material and an inorganic material in the present invention as a constituent material. The surface hardness, water repellency, scratch resistance, and abrasion resistance of the surface layer are greatly improved, while maintaining high durability against the occurrence of wear and scratches, as well as deterioration of sensitivity and charging. High-quality images that have excellent electrical characteristics that prevent deterioration of image quality and do not cause image deterioration, and that do not cause image density reduction, background stains, or streak-like stains even after repeated use over a long period of time. Can be provided.
In addition, the photoreceptor of the present invention can be mounted on image forming apparatuses having various configurations, and processes using this photoreceptor can cope with high-speed printing, reduction in the diameter of the photoreceptor, and spheroidization of toner particles. Even in repeated use, a high-density and high-quality image can be stably obtained throughout.
Furthermore, if the photoconductor of the present invention is incorporated in a process cartridge, it is possible to make it compact and facilitate maintenance work, and the above characteristics are exhibited, and a stable and high-quality image can be obtained even after repeated use.

  As described above, the electrophotographic photoreceptor according to the present invention includes a single-layered or multilayered photosensitive layer containing a charge generating substance and a charge transporting substance on a conductive support, and the outermost layer of the photosensitive layer is a surface. A hybrid polymer having a structural unit represented by the following general formula (I) and having a metal alkoxide group as a functional group; and (2) a metal alkoxide compound. And an organic-inorganic hybrid material integrated with each other as a constituent material. Hereinafter, the electrophotographic photoreceptor of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an electrophotographic photosensitive member in which a photosensitive layer comprising a single layer including a charge generating material and a charge transporting material is provided on a conductive support in the present invention.
In the photoreceptor of FIG. 1, a photosensitive layer 21 comprising a single layer containing both a charge generating substance and a charge transport substance and containing the organic-inorganic hybrid material in the present invention as a constituent material is provided on a conductive support 20. The photosensitive layer 21 has a charge generation function and a charge transport function at the same time. In this configuration example, the photosensitive layer 21 is the outermost layer and forms the surface layer 22.

FIG. 2 is a schematic cross-sectional view showing an example of the configuration of an electrophotographic photosensitive member in which a photosensitive layer including a charge generating material and a charge transporting material and having a multilayer structure is provided on a conductive support in the present invention.
In the photoreceptor of FIG. 2, a lower photosensitive layer 31a containing both a charge generating substance and a charge transporting substance on the conductive support 30, and an upper photosensitive layer 31b containing the organic-inorganic hybrid material in the present invention as constituent materials. The photosensitive layer 31 has a charge generation function and a charge transport function at the same time. In this configuration example, the upper photosensitive layer 31b is the outermost layer and forms the surface layer 32.

FIG. 3 is a schematic cross-sectional view showing another configuration example of an electrophotographic photosensitive member in which a multi-layered photosensitive layer including a charge generating material and a charge transporting material is provided on a conductive support in the present invention. .
In the photoreceptor of FIG. 3, a multilayer structure in which a charge generation layer 41 containing a charge generation material and a charge transport layer 42 containing the organic-inorganic hybrid material of the present invention as a constituent material are sequentially formed on a conductive support 40. A photosensitive layer 43 is provided. In this configuration example, the charge transport layer 42 is the outermost layer and forms the surface layer 44.

FIG. 4 is a schematic cross-sectional view showing still another configuration example of an electrophotographic photosensitive member in which a photosensitive layer including a charge generating material and a charge transporting material is provided on a conductive support in the present invention. is there.
In the photoreceptor shown in FIG. 4, the charge generating layer 51 containing a charge generating substance, the lower charge transporting layer 52a containing a charge transporting substance, and the organic-inorganic hybrid material of the present invention are included as constituent materials on the conductive support 50. A photosensitive layer 53 having a multilayer structure in which upper charge transport layers 52b are sequentially formed is provided. In this configuration example, the upper charge transport layer 52b is the outermost layer and constitutes the surface layer 54.
Hereinafter, each constituent layer in the electrophotographic photosensitive member of the present invention will be described in detail.

[Surface layer]
As described above, the surface layer has (1) a hybrid polymer mainly having a structural unit represented by the general formula (I) and having a metal alkoxide group as a functional group, and (2) a metal alkoxide compound. The organic-inorganic hybrid material obtained from is contained as a constituent material.
The structural unit represented by the general formula (I) is preferably a structural unit represented by the general formula (II) or the general formula (III).

  In general, organic-inorganic hybrid materials are roughly classified into types in which the constituent components are bonded by a gentle interaction such as hydrogen bonding, and types bonded by a covalent bond. Covalent bonding increases the interfacial strength between the two components, and enables microscopic dispersion. In the present invention, an organic-inorganic hybrid material in which an organic component and an inorganic component are combined is used for the surface layer of the organic photoreceptor in order to maximize the characteristics of the material.

As described in the prior art, when an organic-inorganic hybrid material having no charge transporting structural unit in the molecule is applied to the organic photoreceptor, it is necessary to add a low molecular charge transport material. However, since ordinary low-molecular charge transport materials do not have a reactive functional group, when forming an organic-inorganic hybrid material, the cross-linking reaction is inhibited and it is difficult to become a strong material. The transport material is precipitated, and the transparency of the obtained photoreceptor is also impaired.
In the organic-inorganic hybrid material according to the present invention, the structural unit represented by the general formula (I) and the hybrid polymer having a metal alkoxide group are combined and integrated with the metal alkoxide compound. The photoreceptor contained as a constituent material has good durability and excellent electrical characteristics. Furthermore, since the metal alkoxide compound is used as one reaction component, the amount of the inorganic component in the organic-inorganic hybrid material is greatly increased, and various properties possessed by the inorganic component are sufficiently exhibited.

  This improves the level of mechanical durability that has been a factor that hinders the high durability of conventional electrophotographic photoreceptors. For example, surface hardness, water repellency, scratch resistance, and abrasion resistance of the surface layer are improved. Greatly improved, high durability against wear and scratches can be maintained. According to the photoreceptor having such a surface layer, it is possible to suppress deterioration in sensitivity and chargeability, and exhibit excellent electrical characteristics with little image deterioration. In addition, even when used for a long period of time, there is no decrease in image density, generation of background stains, streak-like stain images, etc., and high density and high quality images can be obtained stably throughout.

[Organic-inorganic hybrid material]
The organic-inorganic hybrid material for forming the surface layer in the present invention can be produced generally as follows.
First, a charge-transporting structural unit represented by the general formula (I), that is, a polymer organic component having at least a polycarbonate structure having a charge-transporting function and having at least one functional group in a molecule is a metal. It reacts with an alkoxide compound (hereinafter, sometimes abbreviated as “metal alkoxide (a)”), has a structural unit represented by the general formula (I), and has a metal alkoxide group as a functional group. A hybrid polymer is obtained. Here, as the structural unit represented by the general formula (I), those represented by the general formula (II) or the general formula (III) are preferable.
Next, the obtained hybrid polymer having a metal alkoxide group and a metal alkoxide compound having a functional group having reactivity with the polymer (hereinafter sometimes abbreviated as “metal alkoxide (b)”). The target organic-inorganic hybrid material is obtained by hydrolysis and polycondensation by a sol-gel method, crosslinking into a three-dimensional structure, and integration.

<Polymer organic component>
A polymer organic component having a charge transporting structural unit (polycarbonate structure having a charge transport function) represented by the general formulas (I), (II), and (III) and having a functional group in the molecule, It is necessary to have at least one, preferably two or more functional groups in the molecule, and there is no particular limitation as long as it can react with the functional group of the metal alkoxide (a) as the functional group.
Specific examples include hydroxyl groups, amino groups, carboxyl groups, thiol groups, alkenyl groups, alkynyl groups, acid halogen groups, acid ester groups, formyl groups, halogen groups, epoxy groups, and isocyanate groups. Preferable are functional groups having active hydrogen such as a hydroxyl group, an amino group, and a carboxyl group. Most preferred is a hydroxyl group.

The polymer organic component having a polycarbonate structure having the charge transport function can be obtained by a reaction of a conventionally known bisphenol and a carbonic acid derivative.
For example, produced by a transesterification method between a diol and a bisaryl carbonate, a solution or interfacial polymerization method with a halogenated carbonyl compound such as phosgene, or a method using a chloroformate such as a bischloroformate derived from a diol Is done. This will be specifically described below.

  In the case of the method using the halogenated carbonyl compound, trichloromethyl chloroformate which is a dimer of phosgene or bis (trichloromethyl) carbonate which is a trimer of phosgene is also useful as the carbonyl halide compound instead of phosgene. Also useful are carbonyl halide compounds derived from halogens other than chlorine, such as carbonyl bromide and carbonyl iodide. These known production methods are described in, for example, a polycarbonate resin handbook (editor: Shinichi Honma, published by Nikkan Kogyo Shimbun).

  When a polymer organic component containing a polycarbonate structure having a charge transporting function (abbreviated as “polycarbonate resin”) is produced by the known method, it is represented by the following general formulas (V), (VI), and (VII). A diol represented by the following general formula (VIII) can be used in combination with one or more diols having charge transporting ability to obtain a copolymer having improved mechanical properties and the like.

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an aryl group. Ar ¹ represents an aryl group, and Ar ² and Ar ³ represent an arylene group.)

(In the formula, Ar ² , Ar ³ and Ar ⁴ represent an arylene group. R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group and aryl group.)

(In the formula, R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group, and aryl group.)

[Wherein X is an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or the following formula (1) or (2) ,

(Wherein R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group, an aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, and c and d are are each independently represents an integer of 0 to 3, Y is a single bond, a straight-chain alkylene group having 2 to 12 carbon atoms, -O -, - S -, - SO -, - SO 2 -, - CO -Or the following formulas (3) to (11),

Z ¹ and Z ² represent an aliphatic divalent group or an arylene group, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , each independently a hydrogen atom, Represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group, and R ⁶ and R ⁷ are bonded to form a carbocyclic or heterocyclic ring having 6 to 12 carbon atoms. R ⁶ and R ⁷ may form a carbocyclic or heterocyclic ring together with R ² and R ^3, and R ¹³ and R ¹⁴ are a single bond or an alkylene group having 1 to 4 carbon atoms. R ¹⁵ and R ¹⁶ each independently represents an alkyl group having 1 to 5 carbon atoms or an aryl group, e is an integer of 0 to 4, f is an integer of 0 to 20, and g is an integer of 0 to 2000. Represents. ). ]

The ratio of the diol having the charge transport function represented by any one of the above general formulas (V), (VI) and (VII) and the diol represented by (VIII) should be selected from a wide range depending on the desired properties. Can do.
When the organic-inorganic hybrid material described below is used, the composition ratio of the structural unit represented by the general formula (I) is k, and the composition ratio of the structural unit represented by the general formula (IV) is When j is set, the ratio of the composition ratio k to the total composition ratio (k + j) is preferably 0 <k / (k + j) ≦ 1. The structural unit represented by the general formula (I) is naturally the same in the general formula (II) or the general formula (III).

  Usually, the polycarbonate structure composed of the structural unit represented by the general formula (IV) contributes to the toughness of the resin, and therefore can be obtained by adjusting the composition ratio to 0 <k / (k + j) ≦ 1. The organic-inorganic hybrid material has charge transportability and toughness. By using a surface layer containing such an organic-inorganic hybrid material as a constituent material, it is possible to produce a photoreceptor having further durability.

  The number average molecular weight of the polymer organic component is 400 to 40000, preferably 1000 to 10000. When the number average molecular weight is less than 400, the obtained organic-inorganic hybrid material does not exhibit the characteristics as the polymer organic component, whereas when it exceeds 40000, the metal alkoxide group bonded to the polymer organic component is relatively Therefore, the resulting organic-inorganic hybrid material cannot fully exhibit the characteristics of the inorganic material.

Various copolymers such as a random copolymer, an alternating copolymer, a block copolymer, a random alternating copolymer, and a random block copolymer can be obtained by selecting an appropriate polymerization operation.
For example, the diol represented by the general formula (V), the general formula (VI), or the general formula (VII) and the diol represented by the general formula (VIII) is uniformly mixed from the beginning. When the condensation reaction with phosgene is performed, the structural unit represented by the general formula (I), the general formula (II), or the general formula (III) and the general formula (IV) A random copolymer consisting of units is obtained.

  Alternatively, a random block copolymer can be obtained by adding several kinds of diols during the reaction. Further, bischloroformate derived from the diol represented by the general formula (VIII), and the charge transport ability represented by the general formula (V), the general formula (VI), or the general formula (VII). When a condensation reaction with a diol having the following formula is performed, an alternating copolymer composed of repeating units represented by the following general formula (IX), general formula (X), or general formula (XI) can be obtained.

(In the formula, R ¹ , Ar ¹ , Ar ² , Ar ³ , and X are the same as defined above, and n represents the degree of polymerization and represents an integer of 2 to 5000.)

(In the formula, Ar ² , Ar ³ , Ar ⁴ , R ¹⁷ , R ¹⁸ and X are the same as defined above, and n represents the degree of polymerization and represents an integer of 2 to 5000.)

(In the formula, R ¹⁷ , R ¹⁸ and X are the same as defined above, and n represents the degree of polymerization and represents an integer of 2 to 5000.)

In this case, conversely, a bischloroformate derived from a diol having a charge transporting ability represented by the general formulas (V), (VI) and (VII) and a diol represented by the general formula (VIII) In the same manner, an alternating copolymer composed of repeating units represented by the above general formulas (IX), (X), and (XI) can also be obtained by the condensation reaction.
In the condensation reaction between these bischloroformates and diols, a random alternating copolymer can be obtained by using a plurality of bischloroformates and diols.

  In addition, when an interfacial polymerization method is applied using a carbonyl halide compound or chloroformate, an alkaline aqueous solution of diol and a solution that is substantially insoluble in water and dissolves the polycarbonate resin are used. The reaction is carried out in the presence of a carbonic acid derivative and a catalyst between the phases. At this time, a polycarbonate resin having a narrow molecular weight distribution can be obtained in a short time by emulsifying the reaction catalyst by high-speed stirring or addition of an emulsifying substance.

  As the base used in the alkaline aqueous solution, hydroxides or carbonates of alkali metals or alkaline earth metals are used. For example, hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate Carbonates such as calcium carbonate and sodium hydrogen carbonate can be used. These bases may be used alone or in combination. A preferred base is sodium hydroxide or potassium hydroxide. The water used is preferably distilled water or ion exchange water.

  The organic solvent used as the solution for dissolving the polycarbonate resin is, for example, an aliphatic halogenated hydrocarbon such as dichloromethane, 1,2-dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane, dichloropropane, or the like. Of the mixture. Furthermore, an organic solvent in which an aromatic hydrocarbon such as toluene, xylene or ethylbenzene, or an aliphatic hydrocarbon such as hexane or cyclohexane is mixed with these solvents may be used. The organic solvent is preferably an aliphatic halogenated hydrocarbon or an aromatic halogenated hydrocarbon, more preferably dichloromethane or chlorobenzene.

Examples of the polycarbonate-forming catalyst used in the production of the polycarbonate resin include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, nitrogen-containing heterocyclic compounds and salts thereof, imino ethers and salts thereof, and amides. There are compounds having groups.
Specific examples of such a polycarbonate production catalyst include trimethylamine, triethylamine, tri-n-propylamine, tri-n-hexylamine, N, N, N ′, N′-tetramethyl-1,4-tetramethylenediamine. 4-pyrrolidinopyridine, N, N′-dimethylpiperazine, N-ethylpiperidine, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium bromide, phenyltriethylammonium chloride, triethylphosphine, triphenylphosphine , Diphenylbutylphosphine, tetra (hydroxymethyl) phosphonium chloride, benzyltriethylphosphonium chloride, benzyltriphenylphosphine Nium chloride, 4-methylpyridine, 1-methylimidazole, 1,2-dimethylimidazole, 3-methylpyridazine, 4,6-dimethylpyrimidine, 1-cyclohexyl-3,5-dimethylpyrazole, 2,3,5,6 -Tetramethylpyrazine etc. are mentioned.

  The polycarbonate-forming catalyst is preferably a tertiary amine, more preferably a tertiary amine having 3 to 30 carbon atoms, and particularly preferably triethylamine. These polycarbonate formation catalysts may be used alone or in combination. These catalysts can be added before and / or after adding a carbonic acid derivative such as phosgene or bischloroformate to the reaction system.

  Further, an antioxidant such as hydrosulfite may be added to prevent oxidation of the diol in the alkaline aqueous solution. The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is preferably kept at 10 or more.

On the other hand, when the solution polymerization method is applied, a polycarbonate resin is obtained by dissolving a diol in a solvent, adding a deoxidizing agent, and adding a bischloroformate or phosgene multimer thereto.
In this case, tertiary amines such as trimethylamine, triethylamine and tripropylamine and pyridine are used as the deoxidizer.
As the solvent used in the reaction, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene and chloroform, and cyclic ether solvents such as tetrahydrofuran and dioxane, and pyridine are preferable. The reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

A polycarbonate resin can also be produced by a transesterification method. In this case, a diol and bisallyl carbonate are mixed in the presence of an inert gas, and are usually reacted at 120 to 350 ° C. under reduced pressure. The degree of vacuum is changed step by step, and finally the phenols produced to 1 mmHg or less are distilled out of the system. The reaction time is usually about 1 to 4 hours.
Moreover, you may add antioxidant as needed. Examples of bisallyl carbonate include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate.

  A polymer organic component comprising a polycarbonate resin having at least one, preferably two or more functional groups in the molecule obtained by the above-mentioned various methods, and a functional group having reactivity with the functional group in the polymer organic component. A hybrid polymer having a metal alkoxide group bonded to the organic component of the polymer is obtained by reacting and bonding the metal alkoxide (a) that is held. The metal alkoxide (a) is specifically shown below.

<Metal alkoxide (a)>
Preferred as the metal alkoxide (a) having reactivity with the polymer organic component is a compound represented by the following general formula (a).
R _l A _m M (R′X) _n (a)
Wherein R is an alkyl group having 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, A is an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, M is Si, Ti, Zr, Fe, Cu, A metal element selected from the group consisting of Sn, B, Al, Ge, Ce and Ta, preferably a group consisting of Si, Ti and Zr, R ′ is an alkylene having 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms A group or an alkylidene group, X is a functional group selected from the group consisting of an isocyanate group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group, and l is an integer of 0 to 3, and m and n are It is an integer of 1 to 3 independently.)

As described above, the metal element in the structural unit having a metal oxide bond is preferably at least one selected from the group consisting of Si, Ti and Zr. In particular, the metal element is preferably Si. That is, when such a metal is selected, the synthesis of the hybrid polymer in the present invention is easy, and the resulting polymer has chemical stability. Moreover, an organic-inorganic hybrid material is obtained by subjecting the hybrid polymer to hydrolysis and polycondensation (sol-gel reaction) with a metal alkoxide compound (metal alkoxide (b)) described later.
The metal alkoxide (a) having reactivity with the polymer organic component can be widely selected as in the following examples.

  Examples of the metal alkoxide represented by the general formula (a) include monoisocyanate trialkoxymetals, monoisocyanate dialkoxymetals, monoisocyanate monoalkoxymetals, diisocyanate alkoxymetals, triisocyanate alkoxymetals, and epoxy groups. Examples thereof include metal alkoxides having a functional group, alkylalkoxysilanes having an epoxy group as a functional group, metal alkoxides having an acid halide as a functional group, and alkoxysilanes having an amino group or a mercapto group as a functional group. Hereinafter, such metal alkoxides are specifically exemplified.

  Examples of monoisocyanate trialkoxymetals include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-isocyanateethyltriethoxysilane, 2-isocyanateethyltripropoxyzirconium, 2-isocyanateethyltributoxytin, and the like. Can be mentioned.

  Monoisocyanate dialkoxymetals include 3-isocyanatepropylethyldiethoxysilane, 3-isocyanatepropylethyldiisopropoxytitanium, 2-isocyanateethylethyldipropoxyzirconium, 2-isocyanateethylmethyldibutoxytin, and isocyanatemethyldimethoxyaluminum. Etc.

  Examples of monoisocyanate monoalkoxymetals include 3-isocyanatepropyldiethylethoxysilane, 3-isocyanatopropyldimethylisopropoxytitanium, 2-isocyanatoethyldiethylpropoxyzirconium, 2-isocyanatoethyldimethylbutoxytin, and isocyanatomethylmethylmethoxyaluminum. It is done.

Examples of the diisocyanate alkoxymetals include di (3-isocyanatopropyl) diethoxysilane, di (3-isocyanatopropyl) methylisopropoxytitanium, and the like.
Moreover, ethoxysilane triisocyanate etc. are mentioned as triisocyanate alkoxymetals.

  Examples of the metal alkoxide having an epoxy group as a functional group include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropyldimethylethoxy. Silane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, γ-glycidoxypropyltriisopropoxytitanium, γ -Glycidoxypropylmethyl diisopropoxy titanium, γ-glycidoxypropyl dimethyl isopropoxy titanium, 3,4-epoxybutyl tripropoxyzirconium, 3,4-epoxybutylmethyl dipropoxyzirconium, 3,4-epoxybutyl Methyl propoxy zirconium, beta-(3,4-epoxycyclohexyl) ethyl triethoxy tin, and the like.

  Alkyl alkoxysilanes having an alkoxy group as a functional group include methyltrimethoxysilane, ethyltriethoxysilane, isopropyltriisopropoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diisopropyldiisopropoxysilane, trimethylmethoxysilane, and triethyl. Examples thereof include ethoxysilane and triisopropylisopropoxysilane.

  Examples of the metal alkoxide having an acid anhydride as a functional group include 3- (triethoxysilyl) -2-methylpropyl succinic anhydride.

  Examples of the metal alkoxide having an acid halide as a functional group include 2- (4-chlorosulfonylphenyl) ethyltriethoxysilane.

  Other examples of alkoxysilanes having amino groups or mercapto groups as functional groups include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane. Can be mentioned.

Furthermore, the thing preferable as a metal alkoxide (a) reactive with the polymer organic component in this invention can mention the compound shown by the following general formula (b).
A _O M (b)
(In the formula, A is an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, M is a group consisting of Si, Ti, Zr, Fe, Cu, Sn, B, Al, Ge, Ce, Ta and W; Preferably, a metal element selected from the group consisting of Si, Ti, and Zr, o represents an integer of 2-6.)

  As described above, the metal element in the structural unit having a metal oxide bond is preferably at least one selected from the group consisting of Si, Ti and Zr. In particular, the metal element is preferably Si. The reason for this is the same as described above.

  Specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane; tetrapropoxy titanium, tetraisopropoxy titanium, tetraisopropoxy zirconium, tetrapropoxy zirconium, tetrabutoxy tin, tetraisopropoxy tin, Examples thereof include metal alkoxides such as triisopropoxyaluminum.

  The metal alkoxide (a) may be used alone or in combination of two or more. Alternatively, a metal alkoxide in which two or more kinds of metal elements are contained in one molecule or an oligomer type metal alkoxide having two or more repeating units in one molecule may be used.

  As described above, the hybrid polymer in the present invention is obtained by reacting a metal organic alkoxide (a) with a polymer organic component having one, preferably two or more functional groups in the molecule. A catalyst can also be used. Specific examples of the reaction between the polymer organic component and the metal alkoxide (a) will be described below.

  Polymer organic component (substantially, polymer) composed of a polycarbonate resin having a functional group having active hydrogen such as hydroxyl group, amino group, carboxyl group, thiol group, isocyanate group, epoxy group, carboxyl group, acid halide group, The metal alkoxide (a) having a functional group such as an acid anhydride group is reacted in a solvent, preferably in an inert gas atmosphere. Any solvent can be used as long as it dissolves both the polymer and the metal alkoxide (a) well.

In general, a metal alkoxide (a) solution or a metal alkoxide (a) is gradually added to a polymer solution as it is, and then reacted at room temperature or while gently warming. The amount of the functional group in the metal alkoxide with respect to the functional group in the polymer is desirably 1/10 to 10/1 equivalent ratio.
After completion of the reaction, the reaction solution is used as it is, or the reaction solution is concentrated, or poured into a large amount of poor solvent to precipitate the reaction product, followed by treatments such as washing, purification, and drying. It can mix with a metal alkoxide compound (metal alkoxide (b)), and can move to the sol-gel reaction of the next step shown below.

<Metal alkoxide compound>
Next, what is preferable as the metal alkoxide compound (metal alkoxide (b)) to be reacted with the hybrid polymer in the present invention is the following general formula (c):
A _p M (c)
(In the formula, A is an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, M is a group consisting of Si, Ti, Zr, Fe, Cu, Sn, B, Al, Ge, Ce, Ta, W, and the like. , Preferably a metal element selected from the group consisting of Si, Ti, and Zr, and p represents an integer of 2 to 6.).

  Specific examples of such metal alkoxide compounds include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, tetra n-propoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, and the like. Tetraalkoxytitanium, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium and other tetraalkoxyzirconium, and dimethoxycopper, diethoxybarium, trimethoxyboron, triethoxygallium, tributoxyaluminum, tetraethoxygermanium , Metal alkoxides such as tetrabutoxy lead, penta-n-propoxy tantalum, and hexaethoxy tungsten.

  What is preferable as the metal alkoxide (b) to be reacted with the hybrid polymer is at least one metal alkoxide selected from the group consisting of Si, Ti and Zr in the general formula (c), and particularly preferable is Si. Metal alkoxide. Si alkoxide has the most versatility and is characterized by easy application development.

Further, particularly preferred as the metal alkoxide (b) is the following general formula (d):
_{R k A l M (R '} m X) n ... (d)
(In the formula, R is hydrogen or an alkyl or phenyl group having 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, A is an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, M is Si, Ti, Zr. , Fe, Cu, Sn, B, Al, Ge, Ce, Ta, W, etc., preferably a metal element selected from the group consisting of Si, Ti, Zr, R ′ has 1 to 4 carbon atoms, preferably Is an alkylene group or alkylidene group of 2 to 4, X is an isocyanate group, an epoxy group, a carboxyl group, an acid halide group, an acid anhydride group, an amino group, a thiol group, a vinyl group, a methacryl group, or a halogen atom A functional group selected, k is an integer of 0 to 5, l is an integer of 1 to 5, m is 0 or 1, and n is an integer of 0 to 5). it can.

  For example, when M is Si, and specific examples of the metal alkoxide compound include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, dimethoxysilane, diethoxysilane, diisopropoxysilane, and monomethoxysilane. , Monoethoxysilane, monobutoxysilane, methyldimethoxysilane, ethyldiethoxysilane, dimethylmethoxysilane, diisopropylisopropoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, n-propyltrin-propoxysilane, butyltributoxysilane , Dimethyldimethoxysilane, diethyldiethoxysilane, diisopropyldiisopropoxysilane, dibutyldibutoxysilane, trimethylmethoxysilane, triethylethoxysilane, tri-n-propyl - propoxysilane, tributyl-butoxy silane, phenyl trimethoxy silane, diphenyl diethoxy silane, (alkyl) alkoxysilanes such as triphenyl silane;

  3-isocyanatopropyltriethoxysilane, 2-isocyanatoethyltri-n-propoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 2-isocyanatoethylethyldibutoxysilane, 3-isocyanatopropyldimethylisopropoxysilane, 2-isocyanatoethyldiethylbutoxy (Alkyl) alkoxysilanes having an isocyanate group such as silane, di (3-isocyanatopropyl) diethoxysilane, di (3-isocyanatopropyl) methylethoxysilane, ethoxysilane triisocyanate;

  3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3,4-epoxy (Alkyl) alkoxysilanes having an epoxy group such as butyltrimethoxysilane;

  (Alkyl) alkoxysilanes having a carboxyl group such as carboxymethyltriethoxysilane, carboxymethylethyldiethoxysilane, carboxyethyldimethylmethoxysilane and the like;

  (Alkyl) alkoxysilanes having acid anhydride groups such as 3- (triethoxysilyl) -2-methylpropyl succinic anhydride;

  (Alkyl) alkoxysilanes having acid halide groups such as 2- (4-chlorosulfonylphenyl) ethyltriethoxysilane;

  3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, (Alkyl) alkoxysilane having an amino group such as N-phenyl-3-aminopropyltrimethoxysilane;

  (Alkyl) alkoxysilanes having a thiol group such as 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and the like;

  (Alkyl) alkoxysilanes having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane;

  (Alkyl) alkoxysilanes having a methacrylic group such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethylsilane;

  And (alkyl) alkoxysilane having a halogen atom such as triethoxyfluorosilane, 3-chloropropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 2-chloroethylmethyldimethoxysilane, and the like.

Of course, similar compounds can be exemplified not only for Si but also for other metals such as Ti, Zr, Fe, Cu, Sn, B, Al, Ge, Ce, Ta and W.
Preferred as the metal alkoxide (b) is at least one metal alkoxide in which M in the general formula (d) is selected from the group consisting of Si, Ti and Zr, and particularly preferred is a metal alkoxide of Si. As described above, Si alkoxide has the most versatility and is characterized by easy application development.

The said metal alkoxide compound may be only one type, and may use 2 or more types together. Mg [Al (iso-OC ₃ H ₇ ) ₄ ] ₂ , Ba [Zr ₂ (OC ₂ H ₅ ) ₄ ] ₂ , (C ₃ H ₇ O) ₂ Zr [Al (OC ₃ H ₇ ) ₄ ] An oligomer type having two or more repeating units in one molecule, such as a metal alkoxide compound in which two or more metal elements are contained in one molecule such as ₂ , tetramethoxysilane oligomer or tetraethoxysilane oligomer The metal alkoxide compound may be used. Further, the alkoxy group may be an acetoxy group.

A charge transporting organic-inorganic hybrid material is obtained by crosslinking a hybrid polymer and a metal alkoxide (b) by a sol-gel reaction, that is, by hydrolysis and polycondensation of a metal alkoxide group of the hybrid polymer and a metal alkoxide compound. It is obtained by integrating.
In this reaction, the composition ratio between the hybrid polymer having a metal alkoxide group and the metal alkoxide (b) can be freely changed. The weight ratio of the hybrid polymer having a metal alkoxide group to the metal alkoxide (b) is 1:99 to 99: 1, preferably 10:90 to 90:10.

Hydrolysis and polycondensation by the above sol-gel reaction means that a hybrid polymer having a metal alkoxide group in the molecule and a metal alkoxide (b) are reacted with water to convert the alkoxide group into a hydroxyl group, Simultaneous polycondensation causes a polymer having a hydroxy metal group (for example, —Si (OH) ₃ ) and a hydroxy metal compound to undergo a dehydration reaction or a dealcoholization reaction with an adjacent molecule to form an inorganic covalent bond. This is a reaction that crosslinks three-dimensionally.
The water used for the hydrolysis reaction may be added in an amount necessary to convert all alkoxy groups to hydroxyl groups, or may be used by using moisture in the reaction system or absorbing moisture in the atmosphere. Also good. The reaction conditions are preferably from room temperature to 100 ° C. for about 0.5 to 24 hours. At that time, an acidic catalyst such as hydrochloric acid, sulfuric acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, or a basic catalyst such as sodium hydroxide, potassium hydroxide, ammonia, triethylamine, or piperidine may be used. The obtained reaction solution can be used as it is as a coating solution for forming the surface layer of the photoreceptor.

  The surface layer of the electrophotographic photoreceptor of the present invention and the organic-inorganic hybrid material having a charge transport function contained as a constituent material thereof have been described above, but the organic-inorganic hybrid material is further contained in the photosensitive layer. The form will be described below.

  The surface layer of the photoreceptor in the present invention has the structure shown in FIGS. 1 to 4 as described above with reference to the coating liquid containing the hybrid polymer having a metal alkoxide group and the metal alkoxide compound (metal alkoxide (b)) as described above. It is formed by coating in accordance with, and three-dimensionally crosslinking (curing) by hydrolysis and polycondensation. Such a coating solution is applied by diluting with a solvent as necessary.

  Solvents used here include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran, dioxane and propyl. Examples include ethers such as ethers, halogens such as dichloromethane, dichloroethane, trichloroethane, and chlorobenzene, aromatics such as benzene, toluene, and xylene, and cellosolves such as methyl cellosolve, ethyl cellosolve, and cellosolve acetate. These solvents may be used alone or in combination of two or more. The dilution ratio with the solvent varies depending on the solubility of the composition, the coating method, and the target film thickness, and is arbitrary. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.

Before applying the coating liquid containing the hybrid polymer having a metal alkoxide group and the metal alkoxide (b), a small amount of an acidic catalyst is added, and the hydrolysis reaction is performed at room temperature to 100 ° C. for about 0.5 to 24 hours. If the reaction is allowed to proceed, the crosslinking reaction is more likely to proceed.
As a condition for forming the surface layer by sol-gel reaction after the application of the coating liquid, it is preferable to perform heat treatment at 50 to 250 ° C. for about 5 minutes to 24 hours. Below 50 ° C., the reaction rate is slow and the reaction is not completely completed. When the temperature is higher than 250 ° C., the reaction proceeds non-uniformly and a large strain is generated in the surface layer. In order to advance the curing reaction uniformly, it is also effective to complete the reaction by heating at a relatively low temperature of less than 100 ° C. and then heating to 100 ° C. or more.

  The film thickness of the surface layer varies depending on whether the photosensitive layer is a single layer or a multilayer, as described above, or the layer structure of the photoreceptor. The specific film thickness will be described later together with the layer structure.

  The surface layer containing, as a constituent material, an organic-inorganic hybrid material integrated by crosslinking (curing) by hydrolysis and polycondensation is preferably insoluble in an organic solvent. When the film forming the surface layer is not sufficiently cured, it is soluble in an organic solvent and has a low crosslink density, so that the mechanical durability is also lowered.

Hereinafter, the photosensitive layer will be described.
The photosensitive layer may be a multilayer (laminated structure) or a single layer (single layer structure). For example, as shown in FIGS. 1 to 4, as an example of a laminated structure, a photosensitive layer (a charge generating layer containing a charge generating substance and a charge transport layer containing an organic-inorganic hybrid material) FIG. 3: Case 1), or a photosensitive layer in which a charge generation layer containing a charge generation material, a lower charge transport layer containing a charge transport material, and an upper charge transport layer containing an organic-inorganic hybrid material are laminated (FIG. 4: Case 2), or a photosensitive layer (FIG. 2: Case 3) in which a lower photosensitive layer containing both a charge generation material and a charge transport material and an upper photosensitive layer containing an organic-inorganic hybrid material are laminated. is there. Note that a charge generation layer containing a charge generation material is a charge generation layer having a charge generation function, and a charge transport layer containing a charge transport material is a charge transport layer having a charge transport function.
On the other hand, as an example of the single layer structure, there is a photosensitive layer (FIG. 1: Case 4) having a single layer structure including both a charge generation material and a charge transport material. Having a single layer structure including both a charge generation material and a charge transport material means having both a charge generation function and a charge transport function.
Hereinafter, each of the photosensitive layer having a laminated structure and the photosensitive layer having a single layer structure will be described.

[Photosensitive layer]
[Photosensitive layer having a laminated structure: Case 1 and Case 2]
(Charge generation layer)
The charge generation layer is a layer mainly composed of a charge generation material having a charge generation function, and a binder resin (hereinafter also referred to as “binder resin”) may be used in combination as necessary. As the charge generation material, inorganic materials and organic materials can be used.

  Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms, phosphorus atoms, or the like are preferably used.

  On the other hand, a known material can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having carbazole skeleton, azo pigments having triphenylamine skeleton, azo pigments having diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having fluorenone skeleton, azo pigments having oxadiazole skeleton, azo pigments having bis-stilbene skeleton, azo pigments having distyryl oxadiazole skeleton, azo pigments having distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, Goido based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  As a binder resin used as necessary for the charge generation layer, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, Examples include polyacrylamide. These binder resins can be used alone or as a mixture of two or more.

  In addition to the binder resin described above as a binder resin for the charge generation layer, a polymer charge transport material having a charge transport function, such as an arylamine skeleton, benzidine skeleton, hydrazone skeleton, carbazole skeleton, stilbene skeleton, pyrazoline skeleton, etc. Polymer materials such as polycarbonate, polyester, polyurethane, polyether, polysiloxane, and acrylic resin, polymer materials having a polysilane skeleton, and the like can be used.

Specific examples of the former include JP-A-01-001728, JP-A-01-009964, JP-A-01-013061, JP-A-01-019049, JP-A-01-241559, No. 04-011627, No. 04-175337, No. 04-183719, No. 04-2225014, No. 04-230767, No. 04-320420, No. 05 -232727, JP-A 05-310904, JP-A 06-234836, JP-A 06-234837, JP-A 06-234838, JP-A 06-234839, JP-A 06-234840. No. 1, JP-A 06-234841, JP-A 06-239049, Japanese Unexamined Patent Publication Nos. 06-236050, 06-236051, 06-295077, 07-0756374, 08-176293, 08-208820, 08 No. -21640, JP 08-253568, JP 08-269183, JP 09-062019, JP 09-043883, JP 09-71642, JP 09-87376. JP-A 09-104746, JP-A 09-110974, JP-A 09-110976, JP-A 09-157378, JP-A 09-221544, JP-A 09-227669. JP 09-235367 A, JP 09-241369 A Charge transporting polymer materials described in JP 09-268226 A, JP 09-272735 A, JP 09-302084 A, JP 09-302085 A, JP 09-328539 A, etc. Can be mentioned.
Specific examples of the latter include polysilylene polymers described in, for example, JP-A No. 63-285552, JP-A No. 05-19497, JP-A No. 05-70595, JP-A No. 10-73944, and the like. Illustrated.

The charge generation layer may contain a low molecular charge transport material.
Low molecular charge transport materials that can be used in the charge generation layer include hole transport materials and electron transport materials.

  Examples of the electron transporting material include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and diphenoquinone derivatives. These electron transport materials can be used alone or as a mixture of two or more.

  Examples of the hole transporting material include the electron donating materials exemplified below and are used favorably. As hole transport materials, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triaryls Other known materials such as methane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and the like can be given. These hole transport materials can be used alone or as a mixture of two or more.

The method for forming the charge generation layer can be broadly classified into a vacuum thin film preparation method and a casting method from a solution dispersion system.
As the vacuum thin film preparation method, a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-described inorganic materials and organic materials can be formed satisfactorily. .
In addition, in order to provide a charge generation layer by the casting method described later, if necessary, the inorganic or organic charge generation material together with a binder resin, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclohexane. Can be formed by dispersing with a ball mill, attritor, sand mill, bead mill, etc. using a solvent such as pentanone, anisole, xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, etc. . Moreover, leveling agents, such as a dimethyl silicone oil and a methylphenyl silicone oil, can be added as needed. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.
The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, preferably 0.05 to 2 μm.

(Charge transport layer)
The charge transport layer is a layer having a charge transport function, and the organic-inorganic hybrid material having the structural unit having the charge transport structure of the present invention is shown in FIG. 3 (charge transport layer) or FIG. 4 (upper charge transport layer). As shown, it is useful as a constituent material of the surface layer that is configured as the outermost layer of the photosensitive layer.
When the surface layer containing the organic-inorganic hybrid material as a constituent material is the charge transport layer itself as shown in FIG. 3, the metal in the present invention is formed on the charge generation layer as described in the above-mentioned surface layer preparation method. A coating solution containing a hybrid polymer having an alkoxide group and a metal alkoxide (b) is applied, dried if necessary, and then heated to promote a sol-gel reaction to be crosslinked and integrated to form an organic- A surface layer containing an inorganic hybrid material as a constituent material can be formed.
The thickness of the surface layer to be formed is 10 to 30 μm, preferably 10 to 25 μm. If it is thinner than 10 μm, a sufficient charging potential cannot be maintained, and if it is thicker than 30 μm, peeling from the lower layer tends to occur due to volume shrinkage during curing.

When the surface layer containing the organic-inorganic hybrid material as a constituent material is the upper charge transport layer as shown in FIG. 4, first, the lower charge transport layer constituting the charge transport layer has a charge transport function. The charge transport material and the binder resin are formed by coating and drying on the charge generation layer using a coating solution obtained by dissolving or dispersing in a suitable solvent, and the metal alkoxide group in the present invention is formed on the lower charge transport layer. An upper charge containing an organic-inorganic hybrid material as a constituent material by applying a coating liquid containing a hybrid polymer having a alkoxide and a metal alkoxide (b), promoting a sol-gel reaction by heating, and cross-linking and integrating them A transport layer, ie a surface layer, can be formed.
Specifically, for example, after a charge generation layer and a lower charge transport layer are laminated, a coating solution containing a hybrid polymer and a metal alkoxide (b) is applied by spraying or the like. Then, it is dried at a relatively low temperature for a short time (25 to 80 ° C., 1 to 10 minutes), and further heated and cured at 100 to 160 ° C. for 10 to 60 minutes to form a surface layer.

  When the surface layer is an upper charge transport layer, the thickness of the surface layer is 1 to 20 μm, preferably 2 to 10 μm. If the thickness is less than 1 μm, the durability varies due to unevenness of the film thickness. If the thickness is more than 20 μm, the film thickness of the entire charge transport layer is increased, resulting in charge diffusion and lowering of image reproducibility.

In the above, as the charge transport material used for forming the lower charge transport layer, the electron transport material, hole transport material and polymer charge transport material described in the charge generation layer can be used. As described above, the use of the polymer charge transport material can reduce the solubility of the lower charge transport layer when the upper charge transport layer (surface layer) is applied, and is particularly useful.
The binder resin used to form the lower charge transport layer includes polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, and vinyl chloride. -Vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, Examples thereof include thermoplastic or thermosetting resins such as silicone resins, epoxy resins, melamine resins, urethane resins, phenol resins, alkyd resins, and the like.
The amount of the charge transport material is appropriately 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. However, when a polymer charge transport material is used, it can be used alone or in combination with a binder resin.

  As the solvent used for coating the lower charge transport layer, the same solvent as the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin well is suitable. These solvents may be used alone or in combination of two or more. The lower charge transport layer can be formed by the same coating method as that for the charge generation layer.

Moreover, a plasticizer and a leveling agent can also be added to the coating liquid used for forming the lower charge transport layer, if necessary.
As a plasticizer that can be used in combination with the lower charge transport layer, those used as general resin plasticizers such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is 0 with respect to 100 parts by weight of the binder resin. About 30 parts by weight is appropriate.
Leveling agents that can be used in combination with the lower charge transport layer include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. About 0 to 1 part by weight is appropriate for 100 parts by weight of the resin.
The thickness of the lower charge transport layer is suitably about 5 to 40 μm, preferably about 10 to 30 μm.

[Photosensitive layer having a laminated structure (case 3)]
In the case of a multi-layered photosensitive layer as shown in FIG. 2, first, the lower photosensitive layer of the photosensitive layer is made of a charge generating material having a charge generating function, a charge transporting material having a charge transport function, and a binder resin. A hybrid polymer having a metal alkoxide group according to the present invention formed on the lower photosensitive layer by coating and drying on a conductive support using a coating solution dissolved or dispersed in a suitable solvent. And an upper photosensitive layer, ie, a surface layer, containing an organic-inorganic hybrid material which is formed by applying a coating solution containing alkoxide and metal alkoxide (b) and promoting sol-gel reaction by heating to crosslink and integrate them. Can be formed.
The film thickness of the surface layer is 1 to 20 μm, preferably 2 to 10 μm. When the thickness is less than 1 μm, the durability varies due to the film thickness unevenness.

If necessary, a plasticizer, a leveling agent, or the like can be added to the coating solution for the lower photosensitive layer. As the charge generation material dispersion method, the charge generation material, the charge transport material, the plasticizer, the leveling agent and the like, those similar to those already described in the charge generation layer and the charge transport layer can be used. As the binder resin, the binder resin (binder resin) mentioned in the charge generation layer may be mixed and used in addition to the binder resin mentioned above in the charge transport layer. In addition, the above-described polymer charge transport materials can also be used, which is useful in that the use of this can reduce the mixing of the composition of the lower photosensitive layer into the upper photosensitive layer.
The thickness of the lower photosensitive layer is suitably about 5 to 30 μm, preferably about 10 to 25 μm.

  The charge generation material contained in the photosensitive layer of the case 3 is preferably 1 to 30% by weight with respect to the total amount of the photosensitive layer, and the binder resin contained in the lower photosensitive layer of the photosensitive layer is 20 to 80% by weight of the total amount. %, And 10 to 70 parts by weight of the charge transport material is preferably used.

[Photosensitive layer having a single layer structure (case 4)]
A photosensitive layer comprising a single layer as shown in FIG. 1 is prepared by preparing a coating solution containing a charge generating material, a hybrid polymer having a metal alkoxide group in the present invention, and a metal alkoxide (b). A photosensitive layer containing an organic-inorganic hybrid material as a constituent material, that is, a surface layer, is formed by applying a coating solution on a conductive support, drying it if necessary, and heating it. In addition, you may add the liquid in which the charge generation material was previously disperse | distributed with the solvent to the coating liquid for surface layers.

The film thickness of the surface layer is 10 to 30 μm, preferably 10 to 25 μm. If the thickness is less than 10 μm, a sufficient charging potential cannot be maintained. If the thickness is more than 30 μm, peeling from the conductive support or the undercoat layer tends to occur due to volume shrinkage during curing.
The charge generating material contained in the photosensitive layer having a single layer structure is preferably 1 to 30% by weight based on the total amount of the photosensitive layer.

[Conductive support]
Examples of the conductive support include those having a volume resistance of 10 ¹⁰ Ω · cm or less, such as metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, and platinum, tin oxide, and indium oxide. After metal oxide is deposited or sputtered, film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. Pipes that have been subjected to surface treatment such as cutting, super-finishing, and polishing can be used. Further, endless nickel belts and endless stainless steel belts disclosed in JP-A-52-36016 can also be used as the conductive support.

  In addition, those obtained by dispersing and coating conductive powder in an appropriate binder resin on the support can also be used as the conductive support of the present invention.

  Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. Can be mentioned. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, Thermoplastic, thermosetting resin or photo-curing resin such as melamine resin, urethane resin, phenol resin, alkyd resin and the like can be mentioned. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Furthermore, it is electrically conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support of the present invention.

[Middle layer]
In the photoreceptor of the present invention, when the surface layer containing the organic-inorganic hybrid material as a constituent material is the surface portion of the photosensitive layer, it is possible to suppress the mixing of lower layer components into the surface layer, For the purpose of improving adhesiveness, an intermediate layer can be provided. By providing the intermediate layer, it is possible to prevent the lower photosensitive layer composition from being mixed into the surface layer, thereby preventing the curing reaction from being inhibited by the mixed material and the occurrence of irregularities in the surface layer. It is also possible to improve the adhesion between the lower photosensitive layer and the surface layer.

  In the intermediate layer, a binder resin is generally used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a generally used coating method is employed as described above. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.

[Underlayer]
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable.

  Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.

These undercoat layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, in the undercoat layer of the present invention, Al ₂ O ₃ is provided by anodic oxidation, organic substances such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.

<Addition of antioxidant to each layer>
Further, in the present invention, in order to improve environmental resistance, each layer such as a surface layer, a charge generation layer, a charge transport layer, an undercoat layer, an intermediate layer, etc., in particular for the purpose of preventing a decrease in sensitivity and an increase in residual potential. An antioxidant can be added to the. The following are mentioned as antioxidant which can be used for this invention.

(Phenolic compounds)
2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4, 4'-thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-tert-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 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid ] Cryol ester, tocopherols and the like.

(Paraphenylenediamines)
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 like.

(Hydroquinones)
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 like.

(Organic sulfur compounds)
Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.

(Organic phosphorus compounds)
Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.

The above compounds are known as antioxidants such as rubbers, plastics, oils and fats, and are easily available as commercial products.
The addition amount of the antioxidant in the present invention is suitably about 0.01 to 10% by weight based on the total weight of the layer to be added.

[Image forming method and apparatus]
Next, the image forming apparatus and the image forming method of the present invention will be described.
An image forming apparatus of the present invention comprises an electrophotographic photosensitive member having a surface layer containing at least the organic-inorganic hybrid material as a constituent material, a charging unit, an image exposing unit, a developing unit, and a transfer unit. The image forming apparatus repeats, for example, charging of the photoconductor, image exposure, development of a toner image by development, transfer of the toner image to an image carrier (transfer paper), fixing, and cleaning of the surface of the photoconductor. The image forming process is performed. Note that an image forming method or the like in which an electrostatic latent image is directly transferred to a transfer member and developed does not necessarily have the above-described process arranged on a photosensitive member. Hereinafter, an image forming apparatus and an image forming method of the present invention will be described in detail with reference to the drawings.

FIG. 5 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention.
As a means for charging the photoconductor (1) on average, a charging charger (3) is used. As the charging means, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, or the like is used, and a known system can be used.
Next, the image exposure unit (5) is used to form an electrostatic latent image on the uniformly charged photoreceptor (1). As the light source, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

  Next, the developing unit (6) is used to visualize the electrostatic latent image formed on the photoreceptor (1). Development methods include a one-component development method using a dry toner, a two-component development method, and a wet development method using a wet toner. When the photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.

  Next, a transfer charger (10) is used to transfer the toner image visualized on the photoreceptor (1) onto the transfer body (9). In addition, a pre-transfer charger (7) may be used for better transfer. As these transfer means, a transfer charger, an electrostatic transfer method using a bias roller, a mechanical transfer method such as an adhesive transfer method and a pressure transfer method, and a magnetic transfer method can be used. As the electrostatic transfer method, the charging means can be used.

  A separation charger (11) and a separation claw (12) are used as means for separating the transfer body (9) from the photoreceptor (1). As other separation means, electrostatic adsorption induction separation, side end belt separation, tip grip conveyance, curvature separation, and the like are used. As the separation charger (11), the charging means can be used.

  Next, a fur brush (14) and a cleaning blade (15) are used to clean the toner remaining on the photoreceptor after transfer. Further, a pre-cleaning charger (13) may be used in order to perform cleaning more efficiently. Other cleaning means include a web method, a magnet brush method, and the like, but each may be used alone or in combination.

Next, a neutralizing unit is used for the purpose of removing the latent image on the photoconductor as necessary. As the charge removal means, a charge removal lamp (2) and a charge removal charger are used, and the exposure light source and the charging means can be used respectively. In addition, known processes can be used for reading, feeding, fixing, and discharging the document that is not close to the photosensitive member (1).
In FIG. 5, reference numeral 4 denotes an eraser, and reference numeral 8 denotes a registration roller.

  According to the image forming apparatus and the image forming method in which the electrophotographic photosensitive member of the present invention is mounted, it is possible to cope with high speed printing, a reduction in the diameter of the photosensitive member, and a spheroidization of toner particles. A high-density, high-quality image can be obtained stably throughout.

The image forming means shown in FIG. 5 may be fixedly incorporated in a copying machine, a facsimile machine, or a printer, but is incorporated in the apparatus in the form of a process cartridge and is detachable. There may be. An example of the process cartridge is shown in the schematic configuration diagram of FIG.
The process cartridge includes a photosensitive member (101), and at least a charging unit (102), a developing unit (104), a transfer unit (106), a cleaning unit (107), and a discharging unit (not shown). This is an apparatus (part) that includes one and is detachable from the main body of the image forming apparatus.

The image forming process by the apparatus illustrated in FIG. 6 is performed as follows.
First, while rotating in the direction of the arrow, the photosensitive member (101) is charged by the charging means (102) and exposed by the exposure means (103) to form an electrostatic latent image corresponding to the exposed image on the surface. The electrostatic latent image is developed with toner by the developing means (104), and the toner development is transferred to the transfer body (105) by the transfer means (106) and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by a cleaning unit (107), and is further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  According to the process cartridge of the present invention, the characteristics of the surface layer containing an organic-inorganic hybrid material as a constituent material are exhibited, and a stable and high-quality image can be obtained even after repeated use. Can be facilitated.

  As is apparent from the above description, the electrophotographic photosensitive member of the present invention can be used not only in electrophotographic copying machines but also in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making. Can also be used widely.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to this.
First, a charge transporting polymer having a hydroxyl group shown in the following Production Examples 1 to 4 (corresponding to the “polymer organic component” described in the embodiment) is synthesized, and then a metal alkoxide (a) is used for this. Then, an alkoxysilyl group was introduced to synthesize a charge transporting polymer having a metal alkoxide group shown in Production Examples 5 to 8 (corresponding to the “hybrid polymer having a metal alkoxide group” described in the embodiment). The obtained charge transporting polymer having a metal alkoxide group was used in the production of the photoreceptors of Examples and Comparative Examples. In the examples and comparative examples, “parts” are all “parts by weight”.

(Production Example 1)
<Charge transporting polymer having a hydroxyl group: Polymer No. 1>
In a 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel, N- {4- [2,2-bis (4-hydroxyphenyl) vinyl] phenyl} -N, N-bis ( 4-Tolyl) amine 3.87 g (0.008 mol), 2,2-bis (4-hydroxyphenyl) propane 2.74 g (0.012 mol), dehydrated pyridine 2.5 ml and dehydrated dichloromethane 40 ml were charged with nitrogen. The mixture was dissolved by stirring under a gas stream. A solution in which 1.48 g (5.0 mmol) of bis (trichloromethane) carbonate, which is a phosgene trimer, was dissolved in 20 ml of dehydrated dichloromethane in 20 minutes while maintaining the internal temperature at 3 ° C. with a water bath and stirring vigorously. The reaction was carried out for 3 hours while keeping the internal temperature at 4 ° C. After stopping the stirring, the reaction solution was washed with a 2% hydrochloric acid aqueous solution and then washed with ion-exchanged water. The obtained solution was dropped into 1.5 l of methanol to precipitate a yellow product and dried to obtain a charge transporting polymer (polymer No. 1) having a hydroxyl group shown in Table 1 below. .
The obtained polymer no. When the molecular weight of 1 was measured by gel permeation chromatography (GPC), the molecular weight in terms of polystyrene was 2200 in terms of number average molecular weight. An infrared absorption spectrum is shown in FIG. The structural units of the polymer and the results of elemental analysis are shown in Table 1 below.

(Production Example 2)
<Charge transporting polymer having a hydroxyl group: Polymer No. 2>
In a 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel, N- {4- [2,2-bis (4-hydroxyphenyl) vinyl] phenyl} -N, N-bis ( 4-Tolyl) amine 3.87 g (0.008 mol), 2,2-bis (4-hydroxyphenyl) propane 2.74 g (0.012 mol), dehydrated pyridine 2.5 ml and dehydrated dichloromethane 40 ml were charged with nitrogen. The mixture was dissolved by stirring under a gas stream. A solution in which 1.78 g (6.0 mmol) of bis (trichloromethane) carbonate, which is a phosgene trimer, was dissolved in 20 ml of dehydrated dichloromethane in 20 minutes while maintaining the internal temperature at 3 ° C. with a water bath and stirring vigorously. The reaction was carried out for 3 hours while keeping the internal temperature at 4 ° C. After stopping the stirring, the reaction solution was washed with a 2% hydrochloric acid aqueous solution and then washed with ion-exchanged water. The obtained solution was dropped into 1.5 l of methanol to precipitate a yellow product and dried to obtain a charge transporting polymer (polymer No. 2) having a hydroxyl group shown in Table 1 below. .
The obtained polymer no. When the molecular weight of 2 was measured by gel permeation chromatography (GPC), the molecular weight in terms of polystyrene was 3400 in terms of number average molecular weight. The structural units of the polymer and the results of elemental analysis are shown in Table 1 below.

(Production Example 3)
<Charge transporting polymer having a hydroxyl group: Polymer No. 3>
In a 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel, N- {4- [2,2-bis (4-hydroxyphenyl) vinyl] phenyl} -N, N-bis ( 4-Tolyl) amine (9.96 g, 0.02 mol), dehydrated pyridine (2.5 ml), and dehydrated dichloromethane (40 ml) were added and dissolved by stirring under a nitrogen gas stream. A solution in which 1.48 g (5.0 mmol) of bis (trichloromethane) carbonate, which is a phosgene trimer, was dissolved in 20 ml of dehydrated dichloromethane in 20 minutes while maintaining the internal temperature at 3 ° C. with a water bath and stirring vigorously. The reaction was carried out for 3 hours while keeping the internal temperature at 4 ° C. After stopping the stirring, the reaction solution was washed with a 2% hydrochloric acid aqueous solution and then washed with ion-exchanged water. The obtained solution was dropped into 1.5 l of methanol to precipitate a yellow product and dried to obtain a charge transporting polymer (polymer No. 3) having a hydroxyl group shown in Table 1 below. .
The obtained polymer no. When the molecular weight of No. 3 was measured by gel permeation chromatography (GPC), the molecular weight in terms of polystyrene was 2500 in terms of number average molecular weight. The structural units of the polymer and the results of elemental analysis are shown in Table 1 below.

(Production Example 4)
<Charge transporting polymer having a hydroxyl group: Polymer No. 4>
In a 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube and dropping funnel, N- {4- [2,2-bis (4-hydroxyphenyl) vinyl] phenyl} -N, N-bis ( 4-Tolyl) amine (9.96 g, 0.02 mol), dehydrated pyridine (2.5 ml), and dehydrated dichloromethane (40 ml) were added and dissolved by stirring under a nitrogen gas stream. A solution in which 1.78 g (6.0 mmol) of bis (trichloromethane) carbonate, which is a phosgene trimer, was dissolved in 20 ml of dehydrated dichloromethane in 20 minutes while maintaining the internal temperature at 3 ° C. with a water bath and stirring vigorously. The reaction was carried out for 3 hours while keeping the internal temperature at 4 ° C. After stopping the stirring, the reaction solution was washed with a 2% hydrochloric acid aqueous solution and then washed with ion-exchanged water. The obtained solution was dropped into 1.5 l of methanol to precipitate a yellow product and dried to obtain a charge transporting polymer (polymer No. 4) having a hydroxyl group shown in Table 1 below. .
The obtained polymer no. When the molecular weight of 4 was measured by gel permeation chromatography (GPC), the molecular weight in terms of polystyrene was 4500 in terms of number average molecular weight. The structural units of the polymer and the results of elemental analysis are shown in Table 1 below.

(Production Example 5)
<Charge transporting polymer having metal alkoxide group: Hybrid polymer No. 1>
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into 1 to synthesize a charge transporting polymer (hybrid polymer No. 1) having a metal alkoxide group.
Charge transporting polymer No. having a hydroxyl group 1 (3.5 g) was dissolved in 25 ml of chloroform. Next, 0.6 g of 3-isocyanatopropyltriethoxysilane (IPTES) was added to this solution, heated under reflux for 10 hours, and then cooled to room temperature. This reaction solution was dropped into methanol to precipitate the reaction product. The precipitate was filtered off, washed with methanol, and dried under reduced pressure.
The measurement result by ¹ H-NMR of the obtained product is shown in FIG. As a result of the measurement, it was confirmed that alkoxysilyl groups were introduced at both ends of the product. As a result of measurement by GPC, the product had a number average molecular weight of 2,700.

(Production Example 6)
<Charge transporting polymer having metal alkoxide group: Hybrid polymer No. 2>
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into 2 to synthesize a charge transporting polymer (hybrid polymer No. 2) having a metal alkoxide group.
Charge transporting polymer No. having a hydroxyl group 2 (3.5 g) was dissolved in 25 ml of chloroform. Next, 0.5 g of 3-isocyanatopropyltriethoxysilane (IPTES) was added to this solution, heated under reflux for 10 hours, and then cooled to room temperature. This reaction solution was dropped into methanol to precipitate the reaction product. The precipitate was filtered off, washed with methanol, and dried under reduced pressure.
The product was confirmed by introduction of alkoxysilyl groups at both ends by ¹ H-NMR. Moreover, the number average molecular weight of the product was 4000 as a result of the measurement by GPC.

(Production Example 7)
<Charge transporting polymer having metal alkoxide group: Hybrid polymer No. 3>
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into 3 to synthesize a charge transporting polymer (hybrid polymer No. 3) having a metal alkoxide group.
Charge transporting polymer No. having a hydroxyl group 3 (3.5 g) was dissolved in 25 ml of chloroform. Next, 0.6 g of 3-isocyanatopropyltriethoxysilane (IPTES) was added to this solution, heated under reflux for 10 hours, and then cooled to room temperature. This reaction solution was dropped into methanol to precipitate the reaction product. The precipitate was filtered off, washed with methanol, and dried under reduced pressure.
The product was confirmed by introduction of alkoxysilyl groups at both ends by ¹ H-NMR. Moreover, the number average molecular weight of the product was 3000 as a result of the measurement by GPC.

(Production Example 8)
<Charge transporting polymer having metal alkoxide group: Hybrid polymer No. 4>
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into 4 to synthesize a charge transporting polymer (hybrid polymer No. 4) having a metal alkoxide group.
Charge transporting polymer No. having a hydroxyl group 4 (3.5 g) was dissolved in 25 ml of chloroform. Next, 0.5 g of 3-isocyanatopropyltriethoxysilane (IPTES) was added to this solution, heated under reflux for 10 hours, and then cooled to room temperature. This reaction solution was dropped into methanol to precipitate the reaction product. The precipitate was filtered off, washed with methanol, and dried under reduced pressure.
The product was confirmed by introduction of alkoxysilyl groups at both ends by ¹ H-NMR. As a result of measurement by GPC, the product had a number average molecular weight of 5100.

Example 1
An undercoat layer, a charge generation layer, a charge transport layer, and a surface layer were formed in this order on an Al support by the following procedure to produce the electrophotographic photoreceptor of Example 1.
First, an undercoat layer coating solution was formed on an Al support (outer diameter 30 mmφ) by dipping so that the film thickness after drying was 3.5 μm by an immersion method. .

<Coating liquid for undercoat layer>
Alkyd resin (Beccosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals): 6 parts Melamine resin (Super Becamine G-821-60, manufactured by Dainippon Ink and Chemicals): 4 parts Titanium oxide (CR-EL: Ishihara) Industry): 40 parts Methyl ethyl ketone: 50 parts

  On the formed undercoat layer, dip coating was performed using a charge generation layer coating liquid having the following formulation, followed by heating and drying to form a charge generation layer having a thickness of 0.2 μm.

<Coating liquid for charge generation layer>
Bisazo pigment represented by the following structural formula (12): 2.5 parts Polyvinyl butyral (XYHL, manufactured by UCC): 0.5 part Cyclohexanone: 200 parts Methyl ethyl ketone: 80 parts

  On the formed charge generation layer, dip coating was performed using a charge transport layer coating liquid having the following formulation, followed by drying by heating to form a charge transport layer having a thickness of 22 μm.

<Coating liquid for charge transport layer>
Bisphenol N type polycarbonate: 10 parts Low molecular charge transport material represented by the following structural formula (13): 10 parts Tetrahydrofuran: 80 parts Tetrahydrofuran solution of 1% silicone oil (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.2 parts

  Further, spray coating is performed on the charge transport layer using the organic-inorganic hybrid surface layer coating solution prepared below, and a surface layer having a thickness of 4.0 μm is formed by heat treatment at 130 ° C. for 30 minutes. Thus, an electrophotographic photosensitive member of Example 1 was obtained. The surface layer contains, as a constituent material, an organic-inorganic hybrid material in which an alkoxide group of an alkoxysilylated charge transporting polymer and a tetramethoxysilane oligomer MKC silicate are crosslinked and integrated by hydrolysis and polycondensation.

<Organic-inorganic hybrid surface layer coating solution>
1.8 parts of charge transporting polymer (hybrid polymer No. 1) having a metal alkoxide group obtained in Production Example 5 and 0.2 part of tetramethoxysilane oligomer MKC silicate MS-56 (TMOS) manufactured by Mitsubishi Chemical Corporation After being dissolved in 20 parts of tetrahydrofuran, 0.10 parts of 1N hydrochloric acid water was added and then vigorously stirred at room temperature for 1 hour to prepare an organic-inorganic hybrid surface layer coating solution.

(Example 2)
The hybrid polymer No. used in the organic-inorganic hybrid surface layer coating solution in Example 1 was used. 1 is a hybrid polymer No. 1 obtained in Production Example 6. An electrophotographic photoreceptor of Example 2 was produced in the same manner as Example 1 except that the number was changed to 2. The film thickness of the surface layer was 4.0 μm.

(Example 3)
The hybrid polymer No. used in the organic-inorganic hybrid surface layer coating solution in Example 1 was used. 1 is a hybrid polymer No. 1 obtained in Production Example 7. An electrophotographic photoreceptor of Example 3 was produced in the same manner as Example 1 except that the number was changed to 3. The film thickness of the surface layer was 4.0 μm.

Example 4
The hybrid polymer No. used in the organic-inorganic hybrid surface layer coating solution in Example 1 was used. 1 is a hybrid polymer No. 1 obtained in Production Example 8. An electrophotographic photosensitive member of Example 4 was produced in the same manner as in Example 1 except that the number was changed to 4. The film thickness of the surface layer was 4.0 μm.

(Comparative Example 1)
An electrophotographic photosensitive member of Comparative Example 1 was prepared in the same manner as in Example 1 except that the surface layer composed of the organic-inorganic hybrid in Example 1 was not formed.

(Comparative Example 2)
An electrophotographic photoreceptor of Comparative Example 2 was produced in the same manner as in Example 1 except that the following surface layer coating solution was used instead of the organic-inorganic hybrid surface layer coating solution used in Example 1.

<Surface layer coating solution>
The surface layer coating was conducted by dissolving 5 parts of a charge transporting polymer having a number average molecular weight of 80,000 having the same constitutional unit as in Production Example 1 synthesized according to the method described in Japanese Patent No. 3368415 in 100 parts of tetrahydrofuran. Liquid.

(Comparative Example 3)
The electrophotographic photoreceptor of Comparative Example 3 was the same as Example 1 except that the following organic-inorganic hybrid surface layer coating solution was used instead of the organic-inorganic hybrid surface layer coating solution used in Example 1. Was made.

<Organic-inorganic hybrid surface layer coating solution>
After dissolving 2.0 parts of the charge transporting polymer (hybrid polymer No. 4) having a metal alkoxide group obtained in Production 8 in 20 parts of tetrahydrofuran, adding 0.10 parts of 1N hydrochloric acid water, The mixture was vigorously stirred for 1 hour to obtain an organic-inorganic hybrid surface layer coating solution.

[Evaluation of surface pure water contact angle and universal hardness]
The surface pure water contact angle and universal hardness (HM) of each electrophotographic photoreceptor obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated by the following measuring methods. The evaluation results are shown in Table 2 below.

<Measuring method of surface pure water contact angle>
It measured using AUTOMATIC CONTACT ANGLE METER (KYOWA INTERFACE SCIENCE Co. LTD).

<Measurement method of HM>
The surface hardness of the above photoconductor is determined by a microhardness test system, Fischerscope H-100
HM (universal hardness calculated considering the ridgeline at the tip of the Vickers indenter) was measured by (Fischer Instruments Co., Ltd.).
Measurement conditions Test method: Load unloading repetition (once) test Number of tests: 5 times for each photoconductor Indenter: Vickers indenter Maximum load: 9.8 mN
Load (unloading) time: 30 seconds Holding time: 5 seconds

  As can be seen from Table 2, the photoreceptor of the present invention has higher water repellency and higher surface hardness than the comparative example. That is, the organic-inorganic hybrid material forming the surface layer of the photoconductor of the present invention has a large amount of Si-based inorganic component and sufficiently exhibits its characteristics.

[Real machine paper test]
The electrophotographic photoreceptors obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were converted into 150,000 using a Ricoh imagio MF2200 remodeling machine (using a 655 nm semiconductor laser as an image exposure light source) and a Ricoh polymerized toner. An actual sheet passing test (A4, MyPaper manufactured by NBS Ricoh, charge potential at start-700 V) was performed, and the wear characteristics, the in-machine potential, and the image characteristics (image density, streak image) in a predetermined number of sheets were evaluated. The polymerized toner can be obtained by a technique described in JP-A No. 2003-131430. The results are shown in Tables 3, 4 and 5 below.

The image density in Table 5 and the evaluation criteria for the streak image are as follows.
Image density: ○ → Good, △ → Slightly reduced image density, × → Lower image density Line image: ○ → Good, △ → Locally generated, × → Generated over the entire image

As can be seen from the evaluation results in Tables 3, 4 and 5, Comparative Example 1 was not provided with a protective layer, so the surface was soft and the wear was severe, and the evaluation was interrupted in the initial stage. In the case of Comparative Example 2, since the surface of the photoreceptor does not contain an inorganic component, the wear amount is large, the surface water repellency is poor, and a streak image is generated due to poor cleaning from the beginning. The evaluation was interrupted because the surface layer disappeared. In the case of Comparative Example 3, an organic-inorganic hybrid material having a charge transport function is used for the surface layer. However, since the content of the inorganic component is small, the surface water repellency is insufficient, and the streak image is caused by poor cleaning. Was generated on the whole surface, so the evaluation was interrupted.
On the other hand, in the case of a photoreceptor provided with a surface layer composed of the organic-inorganic hybrid material of the present invention, the content of the inorganic component in the surface layer is large, and the surface hardness, mechanical strength and inorganic properties of the inorganic component are large. The components (Si-based components) such as water repellency are fully exhibited, and all exhibit good wear characteristics, in-machine potential, and image characteristics (image density, streak image). That is, the photoreceptor of the present invention can cope with the reduction of the diameter of the photoreceptor and the spheroidization of the toner particles, and a high-density and high-quality image can be stably obtained even during high-speed printing and repeated use.
From the above results, the electrophotographic photosensitive member of the present invention is greatly improved in the surface hardness, water repellency, scratch resistance, and abrasion resistance of the surface layer, and the decrease in chargeability is suppressed, so that it can be used repeatedly for a long time. In contrast, an image free from a decrease in image density, background stain, streak-like stain, or the like can be stably obtained. If this photoreceptor is used in an image forming apparatus, a high-quality image can be stably obtained. Further, if it is incorporated in a process cartridge, it is possible to achieve compactness and ease of maintenance work while realizing high image quality.

FIG. 2 is a schematic cross-sectional view showing an example of the configuration of an electrophotographic photoreceptor in which a single-layer photosensitive layer including a charge generation material and a charge transport material is provided on a conductive support in the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the configuration of an electrophotographic photoreceptor in which a multilayered photosensitive layer including a charge generation material and a charge transport material is provided on a conductive support in the present invention. FIG. 5 is a schematic cross-sectional view showing another configuration example of an electrophotographic photoreceptor in which a multilayered photosensitive layer including a charge generation material and a charge transport material is provided on a conductive support in the present invention. FIG. 6 is a schematic cross-sectional view showing still another structural example of an electrophotographic photosensitive member in which a multilayered photosensitive layer including a charge generating material and a charge transporting material is provided on a conductive support in the present invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention. It is a schematic block diagram which shows an example of the process cartridge in this invention. 2 is an infrared absorption spectrum diagram of a charge transporting polymer (polymer No. 1) having a hydroxyl group synthesized in Production Example 1. FIG. 6 is a ¹ H-NMR spectrum diagram of a charge transporting polymer (hybrid polymer No. 1) having a metal alkoxide group synthesized in Production Example 5. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger 4 Eraser 5 Image exposure part 6 Developing unit 7 Pre-transfer charger 8 Registration roller 9 Transfer body 10 Transfer charger 11 Separation charger 12 Separation claw 13 Pre-cleaning charger 14 Fur brush 15 Cleaning blade 20 Conductivity Support 21 Photosensitive layer 22 Surface layer 30 Conductive support 31 Photosensitive layer 31a Lower photosensitive layer 31b Upper photosensitive layer 32 Surface layer 40 Conductive support 41 Charge generation layer 42 Charge transport layer 43 Photosensitive layer 44 Surface layer 50 Conductive support Body 51 Charge generation layer 52a Lower charge transport layer 52b Upper charge transport layer 53 Photosensitive layer 54 Surface layer 101 Photoconductor 102 Charging means 103 Exposure means 104 Development means 105 Transfer body 106 Transfer means 107 Cleaning means

Claims (12)

In an electrophotographic photosensitive member comprising a charge generating material and a charge transporting material on a conductive support, a photosensitive layer consisting of a single layer or multiple layers is provided, and the outermost layer of the photosensitive layer is configured as a surface layer.
The surface layer is
(1) a hybrid polymer having a structural unit mainly represented by the following general formula (I) and having a metal alkoxide group as a functional group;
(2) a metal alkoxide compound;
An electrophotographic photoreceptor comprising an organic-inorganic hybrid material in which the two are combined and integrated as a constituent material.

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, or an aryl group. Ar ¹ represents an aryl group, and Ar ² and Ar ³ represent an arylene group.) The electrophotographic photoreceptor according to claim 1, wherein the structural unit represented by the general formula (I) is represented by the following general formula (II).

(In the formula, Ar ² , Ar ³ and Ar ⁴ represent an arylene group. R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group and aryl group.) The electrophotographic photoreceptor according to claim 2, wherein the structural unit represented by the general formula (II) is represented by the following general formula (III).

(In the formula, R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group, and aryl group.) The hybrid polymer contains the structural unit represented by the following general formula (IV) together with the structural unit represented by the general formula (I), and the composition of the structural unit represented by the general formula (I) The ratio of the composition ratio k to the total composition ratio (k + j) is 0 <k / (k + j) ≦ 1, where k is the ratio and j is the composition ratio of the structural unit represented by the following general formula (IV). The electrophotographic photoreceptor according to claim 1, wherein:

[Wherein, X is an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, or a divalent group formed by linking these, or the following formula (1) or (2),

(Wherein R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group, an aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, and c and d are each independently integers of from 0 to 3, Y is a single bond, a straight-chain alkylene group having 2 to 12 carbon atoms, -O -, - S -, - SO-, SO 2 -, - CO- Or the following formulas (3) to (11),

Z ¹ and Z ^{2 each} represent an aliphatic divalent group or an arylene group, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, Represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group, and R ⁶ and R ⁷ are bonded to form a carbocyclic or heterocyclic ring having 6 to 12 carbon atoms. R ⁶ and R ⁷ may form a carbocyclic or heterocyclic ring together with R ² and R ^3, and R ¹³ and R ¹⁴ are a single bond or an alkylene group having 1 to 4 carbon atoms. R ¹⁵ and R ¹⁶ each independently represents an alkyl group having 1 to 5 carbon atoms or an aryl group, e is an integer of 0 to 4, f is an integer of 0 to 20, and g is an integer of 0 to 2000. Represents. ). ] The electrophotographic photoreceptor according to claim 4, wherein the structural unit represented by the general formula (I) is represented by the following general formula (II).

(In the formula, Ar ² , Ar ³ and Ar ⁴ represent an arylene group. R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group and aryl group.) 6. The electrophotographic photoreceptor according to claim 5, wherein the structural unit represented by the general formula (II) is represented by the following general formula (III).

(In the formula, R ¹⁷ and R ¹⁸ represent the same or different acyl group, alkyl group, and aryl group.)   The organic-inorganic hybrid material is integrated by crosslinking by hydrolysis and polycondensation of a metal alkoxide group of a hybrid polymer and a metal alkoxide compound. Electrophotographic photoreceptor.   The electron according to any one of claims 1 to 7, wherein each metal element in the metal alkoxide group and the metal alkoxide compound of the hybrid polymer is at least one element selected from Si, Ti, and Zr. Photoconductor for photography.   9. The electrophotographic photoreceptor according to claim 8, wherein each metal element in the metal alkoxide group and the metal alkoxide compound of the hybrid polymer is Si.   An image forming method, wherein at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to claim 1.   An image forming apparatus comprising at least the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transferring unit. 10. An electrophotographic photosensitive member according to claim 1, and at least one means selected from a charging means, a developing means, a transfer means, a cleaning means, and a charge eliminating means, and is detachable from an image forming apparatus main body. Process cartridge characterized by that.

Images