JP2006161029A - Organic-inorganic hybrid material, method for producing the same, polymer for hybrid material, electrophotographic receptor, process cartridge, image forming device and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic hybrid material having charge-transfer function and excellent abrasion resistance and mechanical and useful as an electrophotographic receptor, a raw material for the hybrid material, an electrophotographic receptor produced by using the hybrid material, having excellent scratch resistance and abrasion resistance and capable of forming a high-quality image over a long period, a process cartridge produced by using the receptor, an image forming device containing the process cartridge, and an image forming method. <P>SOLUTION: The organic-inorganic hybrid material is produced by synthesizing a polymer for the hybrid material containing a metal alkoxide group bonded to an organic component of a polymer composed of a polycarbonate constitution unit having charge transfer function and subjecting the hybrid material having the metal alkoxide group to hydrolysis and polycondensation. The electrophotographic receptor is formed by using the hybrid material as the surface layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic-inorganic hybrid material useful for various organic electronic devices, particularly an electrophotographic photoreceptor, a method for producing the organic-inorganic hybrid material, a polymer for hybrid material, and an electron using the organic-inorganic hybrid material. The present invention relates to a photographic photosensitive member (hereinafter also referred to as “photosensitive member”, “electrostatic latent image carrier”, and “image carrier”), a process cartridge, an image forming apparatus, and an image forming method.

Recently, in a plastic composite material, an organic-inorganic hybrid material in which an inorganic component is dispersed in an organic polymer matrix on a nano scale has attracted attention and has been actively studied. In such an organic-inorganic hybrid material, studies are being made to draw out the excellent features of the inorganic component and to develop synergistic effects. Also in the field of electrophotographic photoreceptors, functional organic-inorganic hybrid materials that take advantage of the characteristics of inorganic materials are also attracting attention.
In recent years, organic photoconductors (OPCs) instead of inorganic photoconductors are often used in copiers, facsimiles, laser printers, and their combined machines because they have good performance and various advantages. The reasons why OPC is frequently used in this way are, for example, (1) optical characteristics such as the light absorption wavelength range and the amount of absorption, and (2) electrical characteristics such as high sensitivity and stable charging characteristics. (3) Wide range of material selection, (4) Ease of manufacturing, (5) Low cost, (6) Non-toxicity and other advantages and advantages.

Under such circumstances, as the size of the image forming apparatus is reduced, the diameter of the photoconductor is reduced, and the demand for high-speed and maintenance-free machines is added, so that the photoconductor is highly durable. ing.
However, since the surface layer of the organic photoreceptor is composed mainly of a low molecular charge transport material and an inert polymer, it is generally soft, and when used repeatedly in an electrophotographic process, it depends on a developing system and a cleaning system. There is a drawback that wear is likely to occur due to a mechanical load. Further, in order to achieve high image quality, it is necessary to improve the cleaning property as the toner particles are made smaller. As a countermeasure, it is inevitable to raise the contact pressure by increasing the rubber hardness of the cleaning blade, which is a factor that promotes wear of the photoreceptor. Such abrasion of the photoconductor deteriorates electrical characteristics such as sensitivity deterioration and chargeability, and causes an abnormal image such as a decrease in image density and background stains. Furthermore, scratches where wear has occurred locally cause streak-like stain images due to poor cleaning. At present, the life of the photoreceptor is limited by the wear and scratches, and has been replaced.

As described above, in the electrophotographic image forming method, efforts are being made to improve the durability of the organic photoreceptor, which is the main member, that is, to extend the life. Until now, the lifetime of organic photoreceptors has been deteriorated due to electrostatic factors due to repeated use, scratches on the surface caused by paper, cleaning blades, separation nails, etc. coming into contact with the photoreceptor surface, and wear depending on the mechanical strength of the photosensitive layer. It has been influenced by. In recent years, electrostatic durability has been improved by improving the photosensitive material, but regarding mechanical strength, a material that surpasses polycarbonate used as a binder for the surface layer has not been found, and it is still effective. At present, few technical means have been proposed.
Therefore, in order to increase the durability of the organic photoreceptor, it is indispensable to reduce the amount of wear described above, and this is the most pressing issue in the field.

  Therefore, as a technique for improving the abrasion resistance of the photosensitive layer, for example, (a) a method using a curable binder for the surface layer (see Patent Document 1), (b) a method using a polymer type charge transport material (patent) (See Reference 2), (c) a method of dispersing an inorganic filler in the surface layer (see Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7, Patent Literature 8, and Patent Literature 9). Proposed.

  However, those using the curable binder (a) have poor compatibility with the charge transport material, or the residual potential increases due to impurities such as polymerization initiators and unreacted residues, resulting in a decrease in image density. It tends to occur. In addition, those using the polymer type charge transport material (b) and those containing the inorganic filler (c) can be improved to some extent, but are required for organic photoreceptors. The durability has not been fully satisfied. In addition, in the case where the inorganic filler (c) is dispersed, since there is no direct bond between 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 It tends to occur easily, and light scattering of the inorganic filler is unavoidable, so it is difficult to realize high image quality. Therefore, the technologies (a), (b), and (c) described above are sufficiently satisfactory for the overall durability including the electrical durability and mechanical durability required for the organic photoreceptor. is not.

Further, as an approach for improving the durability of the organic photoreceptor, methods for improving the mechanical strength by adding silica particles to the surface layer of the photoreceptor have been proposed (Patent Document 10, Patent Document 11, and Patent). Reference 12). In addition, hydrophobic silica particles obtained by treating the silica particles with a silane coupling agent or the like are included in the outermost surface layer of the photoconductor to increase the mechanical strength of the photoconductor and increase lubricity. A method for obtaining a durable photoconductor has been proposed (see Patent Document 13, Patent Document 14, and Patent Document 15).
However, in these methods, since it is necessary to keep the particle size of the silica particles at a certain size or more in order to provide the adhesion between the silica particles and the binder, the particle size is inevitably increased. When the particle size increases, the roughness of the surface increases. For example, there is a problem that cleaning failure occurs due to damage to the edge portion of the cleaning blade, and sufficient durability cannot be obtained.

  In order to improve wear resistance and scratch resistance, a method of hydrolyzing or polycondensing alkoxysilane or the like in the presence of a polycarbonate resin has been proposed (see Patent Document 16). According to this proposed method, the size of the silica component in the product can be reduced, but since the content of the silica component is small, the characteristics of the inorganic material have not been fully exploited.

Furthermore, a method for obtaining an organic-inorganic hybrid polymer material from a terminal silyl-modified polycarbonate has been proposed (see Patent Document 17). In addition, a method for obtaining an organic-inorganic hybrid material by hydrolyzing or polycondensing a polymer having a polycarbonate and / or polyarylate moiety as a main skeleton and a metal alkoxide group as a functional group has been proposed. (See Patent Document 18).
However, when these organic-inorganic hybrid polymer materials are used in an organic photoreceptor, it is necessary to add a low-molecular charge transport material, which impairs the characteristics of the organic-inorganic hybrid material, -There exists a fault that the synergistic characteristic expression as an inorganic hybrid material is scarce.

In addition, an electrophotographic photosensitive member is proposed which has at least a photosensitive layer on a support, and the uppermost layer of the photosensitive layer contains a polymer charge transport material, an inorganic filler, and acryl-modified polyorganosiloxane fine particles ( (See Patent Literature 19 and Patent Literature 20). These proposals describe the use of an aromatic polycarbonate resin synthesized from a diol having charge transport ability as a polymer charge transport material.
The dispersion of the inorganic filler in this manner has a certain effect of improving the abrasion resistance, but does not have a direct bond between the inorganic filler and the binder. However, the actual situation is that the performance is not sufficiently satisfactory.

JP 56-48637 A JP-A 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 56-117245 A JP-A-63-91666 JP-A-1-205171 JP-A-57-176057 JP 61-117558 A Japanese Patent Laid-Open No. 3-155558 JP 2000-105474 A JP 2002-241383 A JP-A-11-209596 Japanese Patent No. 3368415 JP 2003-98710 A

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention relates to an organic-inorganic hybrid material having a charge transport function excellent in abrasion resistance and mechanical strength, useful for various organic electronic devices, in particular, an electrophotographic photosensitive member, and a hybrid material for forming the organic-inorganic hybrid material. An electrophotographic photosensitive member capable of forming a high-quality image over a long period of time by using an organic-inorganic hybrid material while providing a combination and a manufacturing method, It is an object of the present invention to provide a used process cartridge, an image forming apparatus equipped with the process cartridge, and an image forming method.

  As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, a polymer for hybrid having a metal alkoxide group bonded to a polymer organic component having a structural unit having a charge transport function is hydrolyzed or polycondensed. Thus, it was found that an organic-inorganic hybrid material having a charge transport function was obtained, and that the above problems were solved.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> An organic-inorganic hybrid material characterized in that a polymer organic component having a charge transport function and a metal alkoxide compound are bonded and integrated with each other.
<2> The organic-inorganic hybrid material according to <1>, wherein the polymer organic component contains a structural unit represented by the following structural formula (I).
However, in the structural formula (I), R ¹ represents any ^one of a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Ar ¹ represents an aryl group which may have a substituent. Ar ² and Ar ³ may be the same as or different from each other, and represent an arylene group that may have a substituent.
<3> The organic-inorganic hybrid material according to <2>, wherein the structural unit represented by the structural formula (I) is a structural unit represented by the following structural formula (II).
However, in the structural formula (II), Ar ² , Ar ³ , and Ar ⁴ may be the same as or different from each other and represent an arylene group that may have a substituent. R ¹⁷ and R ¹⁸ may be the same as or different from each other, and each may have an acyl group that may have a substituent, an alkyl group that may have a substituent, and a substituent. It represents any of the aryl groups that may have.
<4> The organic-inorganic hybrid material according to <2>, wherein the structural unit represented by the structural formula (I) is a structural unit represented by the following structural formula (III).
However, in the structural formula (III), R ¹⁷ and R ¹⁸ represent the same meaning as described above.
<5> The organic-inorganic hybrid material according to <1>, wherein the polymer organic component contains a structural unit represented by the following structural formula (IV).
However, in the structural formula (IV), Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ may be the same as or different from each other, and may represent an arylene group which may have a substituent. To express. Ar ⁷ represents an aryl group which may have a substituent. Z represents an arylene group and —Ar ¹⁰ —Za—Ar ¹⁰ — (wherein Ar ¹⁰ represents an arylene group which may have a substituent. Za represents any of O, S, and an alkylene group. Represents one of the following. R and R ′ may be the same as or different from each other, and each represents a linear or branched alkylene group. n represents 0 or 1.
<6> The organic-inorganic hybrid material according to <5>, wherein the structural unit represented by the structural formula (IV) is a structural unit represented by the following structural formula (V).
However, in the structural formula (V), Ra, Rb, Rc and Rd may be the same as or different from each other and represent an alkyl group which may have a substituent. Ar ⁷ , Z, R, R ′ and n represent the same meaning as described above.
<7> The organic-inorganic hybrid material according to any one of <1> to <6>, wherein the polymer organic component further contains a structural unit represented by the following structural formula (VI).
In the structural formula (VI), X represents an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, a divalent group formed by linking these, and the following structural formula (VI -1) and the following structural formula (VI-2).
However, in the structural formulas (VI-1) and (VI-2), R ² , R ³ , R ⁴ , and R ⁵ may be the same as or different from each other, an alkyl group, Represents 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 an integer of 0 to 3. Y represents a single bond, a linear alkylene group having 2 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —, —CO—, and the following structural formula (VI-3) to It represents one selected from (VI-11).
In Structural Formula, Z ₁ and Z ₂ each represents any one of divalent groups, and arylene groups aliphatic.
However, in the structural formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same as or different from each other, a hydrogen atom, a halogen atom Represents 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 . R ¹³ and R ¹⁴ may be the same as or different from each other, and each represents a single bond or an alkylene group having 1 to 4 carbon atoms. R ¹⁵ and R ¹⁶ may be the same as or different from each other, and each represents an alkyl group having 1 to 5 carbon atoms or an aryl group. e represents an integer of 0 to 4, f represents an integer of 0 to 20, and g represents an integer of 0 to 2000.
<8> Configuration represented by Structural Formula (VI), where k is the composition ratio of the structural unit represented by any one of Structural Formulas (I), (II), (III), (IV), and (V) When the composition ratio of the unit is j, the organic-inorganic hybrid material according to any one of <1> to <7>, which satisfies the following formula: 0 <k / (k + j) ≦ 1.
<9> The organic-inorganic hybrid material according to any one of <1> to <8>, wherein the polymer organic component has a number average molecular weight of 400 to 40,000.
<10> The organic-inorganic hybrid material according to any one of <1> to <9>, wherein the metal alkoxide compound is represented by the following structural formula (VII).
_{^{R 19 p A m M (R}} "X ') n ··· structural formula (VII)
In the Structural Formula ^{(VII), R 19} represents an alkyl group having 1 to 5 carbon atoms. A represents a C1-C4 alkoxy group. M represents any of Si, Ti, and Zr. R ″ represents any one of an alkylene group having 2 to 4 carbon atoms and an alkylidene group. X ′ represents any one selected from an isocyanate group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. P represents an integer of 0 to 3. m and n each represents an integer of 1 to 3.
<11> The organic-inorganic hybrid material according to <10>, wherein M is Si.
<12> A polymer having a structural unit represented by the following structural formula (I) and a metal alkoxide compound represented by the following structural formula (VII), and a metal alkoxide group in the polymer. It is a polymer for hybrid materials characterized by having.
However, in the structural formula (I), R ¹ represents any ^one of a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Ar ¹ represents an aryl group which may have a substituent. Ar ² and Ar ³ may be the same as or different from each other, and represent an arylene group that may have a substituent.
_{^{R 19 p A m M (R}} "X ') n ··· structural formula (VII)
In the Structural Formula ^{(VII), R 19} represents an alkyl group having 1 to 5 carbon atoms. A represents a C1-C4 alkoxy group. M represents any of Si, Ti, and Zr. R ″ represents any one of an alkylene group having 2 to 4 carbon atoms and an alkylidene group. X ′ represents any one selected from an isocyanate group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. P represents an integer of 0 to 3. m and n each represents an integer of 1 to 3.
<13> The polymer for hybrid materials according to <12>, which has a molecular structure represented by the following structural formula (VIII).
In Structural Formula (VIII), Ar ¹ , Ar ² , Ar ³ , R ¹ , R ″, M, A, R ¹⁹ , p and m represent the same meaning as described above. E represents —NH—. Or -O-, L represents the number of repeating units in parentheses.
<14> The polymer for hybrid materials according to <12>, which has a molecular structure represented by the following structural formula (IX).
In Structural Formula (IX), Ar ¹ , Ar ² , Ar ³ , R ¹ , R ″, M, A, R ¹⁹ , p and m have the same meaning as described above. E represents —NH—. Or -O-, L represents the number of repeating units in parentheses.
<15> A polymer having a structural unit represented by the following structural formula (IV) and a metal alkoxide compound represented by the following structural formula (VII), and a metal alkoxide group in the polymer. It is a polymer for hybrid materials characterized by having.
However, in the structural formula (IV), Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ may be the same as or different from each other, and may represent an arylene group which may have a substituent. To express. Ar ⁷ represents an aryl group which may have a substituent. Z represents an arylene group and —Ar ¹⁰ —Za—Ar ¹⁰ — (wherein Ar ¹⁰ represents an arylene group which may have a substituent. Za represents any of O, S, and an alkylene group. Represents one of the following. R and R ′ may be the same as or different from each other, and each represents a linear or branched alkylene group. n represents 0 or 1.
_{^{R 19 p A m M (R}} "X ') n ··· structural formula (VII)
In the Structural Formula ^{(VII), R 19} represents an alkyl group having 1 to 5 carbon atoms. A represents a C1-C4 alkoxy group. M represents any of Si, Ti, and Zr. R ″ represents any one of an alkylene group having 2 to 4 carbon atoms and an alkylidene group. X ′ represents any one selected from an isocyanate group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. P represents an integer of 0 to 3. m and n each represents an integer of 1 to 3.
<16> The polymer for hybrid materials according to <15>, which has a molecular structure represented by the following structural formula (X).

In Structural Formula (X), R ¹⁹ , A, M, R ″, Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , n, and p represent the same meaning as described above. , -NH-, or -O-, L represents the number of repeating units in parentheses.
<17> The polymer for hybrid materials according to <15>, which has a molecular structure represented by the following structural formula (XI).
However, in the structural formula (XI), R ¹⁹ , A, M, R ″, Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Z, X, n, and p have the same meaning as described above. E represents —NH— or —O—, and L represents the number of repeating units in parentheses.
<18> The polymer for hybrid materials according to any one of <12> to <17>, wherein M is Si.
<19> A method for producing an organic-inorganic hybrid material, wherein the metal alkoxide group in the polymer for a hybrid material according to any one of <12> to <18> is hydrolyzed or polycondensed.
<20> An electrophotographic photoreceptor, wherein the surface layer contains the organic-inorganic hybrid material according to any one of <1> to <11>.
<21> The electrophotographic photosensitive member according to <20>, wherein the electrophotographic photosensitive member is a laminated structure including a support and at least a charge generation layer, a charge transport layer, and a surface layer in this order on the support.
<22> After providing a layer containing the polymer for hybrid materials according to any one of <12> to <18> on the support, the polymer for hybrid materials is hydrolyzed or polycondensed to form an organic material. -A method for producing an electrophotographic photosensitive member, comprising at least a surface layer forming step of forming a surface layer containing an inorganic hybrid material.
<23> The electrophotographic photosensitive member according to any one of <20> to <21>, and at least one unit selected from a charging unit, a developing unit, a transfer unit, a cleaning unit, and a discharging unit. The process cartridge is detachable from the main body of the image forming apparatus.
<24> The electrophotographic photosensitive member according to any one of <20> to <21>, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrophotographic photosensitive member, and the electrostatic latent image And developing means for developing a visible image by using toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium. An image forming apparatus characterized by the above.
<25> An electrostatic latent image forming step of forming an electrostatic latent image on the electrophotographic photosensitive member according to any one of <20> to <21>, and developing the electrostatic latent image using toner. And an image forming method comprising: a developing step for forming a visible image in the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium. It is.

The organic-inorganic hybrid material of the present invention is formed by combining a polymer organic component having a charge transport function and a metal alkoxide compound with each other. By using the organic-inorganic hybrid material of the present invention, the level of mechanical durability, which has been a factor impeding the high durability of conventional electrophotographic photoreceptors, can be greatly improved, and scratch resistance, It is possible to provide an electrophotographic photosensitive member that is excellent in abrasion and can stably obtain a high-density and high-quality image throughout use over a long period of use.
By using the electrophotographic photosensitive member of the present invention configured as described above, it is possible to provide an image forming method, an image forming apparatus, and a process cartridge that can realize high image quality over a long period of time.

  According to the present invention, conventional problems can be solved, and a polymer for a hybrid material having a metal alkoxide group bonded to a polymer organic component having the above structural unit is hydrolyzed and polycondensed, whereby organic-inorganic Organic-inorganic hybrid material that exhibits the characteristics of the components and has a charge transport function with excellent properties such as wear resistance, mechanical strength, rigidity, heat resistance, surface hardness, weather resistance, chemical resistance, and contamination resistance , And a method for producing the organic-inorganic hybrid material, a polymer for hybrid material, an electrophotographic photosensitive member using the organic-inorganic hybrid material, and the electrophotographic photosensitive member mounted thereon, A process cartridge, an image forming apparatus, and an image forming method capable of forming an image can be provided.

(Organic-inorganic hybrid material)
The organic-inorganic hybrid material of the present invention is formed by combining a polymer organic component having a charge transport function and a metal alkoxide compound with each other.

-Polymer organic component-
The polymer organic component preferably contains a structural unit represented by any one of the following structural formula (I) and the following structural formula (IV).
However, in the structural formula (I), R ¹ represents any ^one of a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Ar ¹ represents an aryl group which may have a substituent. Ar ² and Ar ³ may be the same as or different from each other, and represent an arylene group that may have a substituent.

However, in the structural formula (IV), Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ may be the same as or different from each other, and may represent an arylene group which may have a substituent. To express. Ar ⁷ represents an aryl group which may have a substituent. Z represents an arylene group and —Ar ¹⁰ —Za—Ar ¹⁰ — (wherein Ar ¹⁰ represents an arylene group which may have a substituent. Za represents any of O, S, and an alkylene group. Represents one of the following. R and R ′ may be the same as or different from each other, and each represents a linear or branched alkylene group. n represents 0 or 1.

<Structural Unit Represented by Structural Formula (I)>

The alkyl group of R ¹ represented by the structural formula (I) is preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and these alkyl groups further include a fluorine atom and a cyano group. , A phenyl group or a phenyl group substituted with a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms may be contained. Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2 -Cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.

Examples of the aryl group of R ¹ include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a pyrenyl group, a fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, and a chrysenyl group. Fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, thienyl group, benzothienyl group, furyl group, benzofuranyl group, carbazolyl group, pyridinyl group, pyrrolidyl group, oxazolyl group, etc. . These have the above-described alkyl group, alkoxy group having the above-described alkyl group, halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, and amino group represented by the following structural formula as a substituent. Also good.
In Structural Formula, R ¹⁹ and R ²⁰ represents may be the same as each other or different, an alkyl group, as defined R ^1, the aryl group as defined by R ^1, R ¹⁹ and R ²⁰ may form a ring together, or may form a ring together with a carbon atom on the aryl group. Specific examples thereof include a piperidino group, a morpholino group, and a urolidyl group.

Examples of the aryl group of Ar ¹ include a group represented by the following structural formula (XII), pyrrole, pyrazole, imidazole, triazole, dioxazole, indole, isoindole, benzimidazole, benzotriazole, benzoisoxazine, carbazole, phenoxy. Examples thereof include monovalent groups derived from a heterocyclic group having an amine structure such as sazine. These may have an alkyl group, an aryl group, or a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom defined by R ¹ as a substituent.
However, in the structural formula (XII), R ²¹ and R ²² may be the same as or different from each other, and each represents an acyl group, an alkyl group, or an aryl group. Ar ¹¹ represents an arylene group. h represents an integer of 1 to 3.

Examples of the acyl group of R ²¹ and R ²² in the structural formula (XII) include an acetyl group, a propionyl group, and a benzoyl group.
The alkyl group for R ²¹ and R ²² is the same as the alkyl group defined for R ¹ .
Examples of the aryl group of R ²¹ and R ²² include a group represented by the following structural formula (XIII) in addition to the aryl group defined by R ¹ .
However, in the structural formula (XIII), B is any selected from —O—, —S—, —SO—, —SO ₂ —, —CO—, and a divalent group represented by the following structural formula. Represents R ²³ represents any one of a hydrogen atom, an alkyl group defined by R ¹ , an alkoxy group, a halogen atom, an aryl group defined by R ¹ , an amino group, a nitro group, and a cyano group.
However, in the above formula, R ²⁴ represents a hydrogen atom, an alkyl group as defined R ^1, and represents any of the defined aryl group R ^1. i represents an integer of 1 to 12, and j represents an integer of 1 to 3.

Examples of the alkoxy group of R ²³ in the structural formula (XIII) include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and t- Examples include butoxy group, 2-hydroxyethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
Examples of the halogen atom for R ²³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The amino group of R ²³ represents an amino group defined as a substituent for the aryl group of R ¹ .

Examples of the arylene group of Ar ¹⁰ in the structural formula (XII) include a divalent group derived from the aryl group defined by R ¹ .

Ar ² and Ar ³ in the structural formula (I) represent an arylene group, and examples thereof include a divalent group derived from the aryl group defined by R ¹ .
Although the structural unit of the structural formula (I) has been described above, the same symbols have the same definition in other structural formulas.

As the structural unit represented by the structural formula (I), either a structural unit represented by the following structural formula (II) or a structural unit represented by the following structural formula (III) is preferable.
However, in the structural formula (II), Ar ² , Ar ³ , and Ar ⁴ may be the same as or different from each other and represent an arylene group that may have a substituent. R ¹⁷ and R ¹⁸ may be the same as or different from each other, and each may have an acyl group that may have a substituent, an alkyl group that may have a substituent, and a substituent. It represents any of the aryl groups that may have.

However, in the structural formula (III), R ¹⁷ and R ¹⁸ may be the same as or different from each other, and may have an acyl group or a substituent that may have a substituent. It represents either an alkyl group which may be substituted or an aryl group which may have a substituent.

As R ¹⁷ and R ¹⁸ in the structural formulas (II) and (III), those similar to R ²¹ and R ^{22 in} the structural formula (XII) can be used.

<Structural Unit Represented by Structural Formula (IV)>

Ar ⁷ in the structural formula (IV) represents an aryl group, for example, a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, a pyrenyl group, a fluorenyl group, a 9,9-dimethyl-2-fluorenyl group, an azulenyl group, Anthryl, triphenylenyl, chrycenyl, fluorenylidenephenyl, 5H-dibenzo [a, d] cycloheptenylidenephenyl, thienyl, benzothienyl, furyl, benzofuranyl, carbazolyl, pyridinyl, pyrrolidyl Group, oxazolyl group and the like. These may have an alkyl group or an alkoxy group having this alkyl group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, or an amino group represented by the following structural formula as a substituent.
In Structural Formula, R ¹⁹ and R ²⁰ represents may be the same as each other or different, an alkyl group, as defined R ^1, the aryl group as defined by R ^1, R ¹⁹ and R ²⁰ may form a ring together, or may form a ring together with a carbon atom on the aryl group. Specific examples thereof include a piperidino group, a morpholino group, and a urolidyl group.
The alkyl group is a linear or branched alkyl group having 1 to 5 carbon atoms, and these alkyl groups are further a fluorine atom, a cyano group, a phenyl group, a halogen atom, or a linear or branched group having 1 to 5 carbon atoms. It may contain a phenyl group substituted with a chain alkyl group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-cyanoethyl group Benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group and the like.

Ar ⁴ , Ar ⁶ , Ar ⁸ , and Ar ⁹ in the structural formula (IV) may be the same as or different from each other, represent an arylene group, and represent an aryl group represented by Ar ⁷ above. Divalent group to be derived.
Examples of the arylene group include phenylene, naphthylene, biphenylylene, terphenylylene, pyrene-1,6-diyl, fluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, and thiophene-2,5. -Diyl, furan-2,5-diyl, N-ethylcarbazole-3,6-diyl and the like may be mentioned, and these may have an alkyl group, an alkoxy group and a halogen atom as a substituent.

Z in the structural formula (IV) represents an arylene group and —Ar ¹⁰ —Za—Ar ¹⁰ — (wherein Ar ¹⁰ represents an arylene group which may have a substituent. Za represents O, S, And any one of alkylene groups).
Ar ^{10 in} Z includes phenylene, naphthylene, biphenylylene, terphenylylene, and the like, and these may have an alkyl group, an alkoxy group, or a halogen atom as a substituent.

R and R ′ in the structural formula (IV) may be the same as or different from each other, and represent a linear or branched alkylene group.
n represents 0 or 1.

As the structural unit represented by the structural formula (IV), a structural unit represented by the following structural formula (V) is preferable.
However, in the structural formula (V), Ra, Rb, Rc and Rd may be the same as or different from each other, and represent an alkyl group. Ar ⁷ , Z, R, R ′ and n are the same as defined above.

  Ra, Rb, Rc and Rd in the structural formula (V) are linear or branched alkyl groups having 1 to 5 carbon atoms, and these alkyl groups are further fluorine atom, cyano group, phenyl group, halogen atom or It may contain a phenyl group substituted with a linear or branched alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2 -A cyanoethyl group, a benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, etc. are mentioned.

In addition to the structural unit represented by any one of the structural formula (I) and the structural formula (IV), the polymer organic component further contains a structural unit represented by the following structural formula (VI). It is preferable.
In the structural formula (VI), X represents an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, a divalent group formed by linking these, and the following structural formula (VI -1) and the following structural formula (VI-2).
However, in the structural formulas (VI-1) and (VI-2), R ² , R ³ , R ⁴ , and R ⁵ may be the same as or different from each other, an alkyl group, Represents 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 an integer of 0 to 3. Y represents a single bond, a linear alkylene group having 2 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —, —CO—, and the following structural formula (VI-3) to It represents one selected from (VI-11).
However, _{Z 1} and _{Z 2} represent a divalent group, or an arylene group aliphatic.
However, in the structural formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same as or different from each other, a hydrogen atom, a halogen atom Represents 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 . R ¹³ and R ¹⁴ may be the same as or different from each other, and each represents a single bond or an alkylene group having 1 to 4 carbon atoms. R ¹⁵ and R ¹⁶ may be the same as or different from each other, and each represents an alkyl group having 1 to 5 carbon atoms or an aryl group. e represents an integer of 0 to 4, f represents an integer of 0 to 20, and g represents an integer of 0 to 2000.

  The present invention relates to an organic-inorganic hybrid material in which a polymer organic component having a structural unit represented by any one of the structural formulas (I) and (IV) and a component composed of a metal oxide are combined together. The hybrid material hydrolyzes the metal alkoxide group of the polymer for hybrid material, that is, the metal alkoxide group bonded to the polymer organic component comprising the structural unit represented by the structural formula (I) or (IV). And obtained by polycondensation.

The polymer for hybrid materials is obtained by reacting at least a polymer organic component having a polycarbonate structure having a charge transport function and a metal alkoxide compound having a functional group reactive with the functional group in the polymer organic component. Obtained by bonding.
The composition ratio of the structural unit (polymer organic component) represented by any one of the structural formulas (I), (II), (III), (IV), and (V) is k, and the structural formula (VI ), The ratio of k to the total composition ratio (k + j) is preferably 0 <k / (k + j) ≦ 1, 3 <k / (k + j) ≦ 1 is more preferable. When the k / (k + j) is 0.3 or less, the content of the charge transport component is decreased, and thus the obtained hybrid material may not be able to satisfy sufficient electrical characteristics.

  The number average molecular weight of the polymer organic component is preferably 400 to 40,000, more preferably 1000 to 10,000. When the number average molecular weight is less than 400, the obtained hybrid material may lack polymer characteristics, and when it exceeds 40,000, the number of metal alkoxide groups bonded to the polymer organic component decreases. In some cases, the obtained hybrid material cannot sufficiently bring out the characteristics of the inorganic material.

  The polymer organic component having the charge transporting structural unit preferably has at least one, preferably two or more functional groups in the molecule. Such a functional group is not particularly limited as long as it can react with the functional group of the metal alkoxide, and can be appropriately selected according to the purpose. For example, a hydroxyl group, an amino group, a carboxyl group, a thiol group Alkenyl group, alkynyl group, acid halogen group, acid ester group, formyl group, halogen group, epoxy group, isocyanate group and the like. Among these, a functional group having active hydrogen such as a hydroxyl group, an amino group, and a carboxyl group is preferable, and a hydroxyl group is particularly preferable.

  The polymer organic component containing a polycarbonate structure having a 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 can do.

  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).

  In the case of producing a polymer organic component containing a polycarbonate structure having a charge transport function by the above known method (hereinafter sometimes abbreviated as “polycarbonate resin”), the following structural formulas (1), (2), and (3 ) Represented by the following structural formula (1) or more of the diols having the charge transporting ability represented by the formula (1) or one or more of the diols having the charge transporting ability represented by the following structural formulas (4) and (5) By using the diol represented by 6), a copolymer having improved mechanical properties and the like can be obtained.

However, in the structural formula (1), R ¹ represents any ^one of a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Ar ¹ represents an aryl group which may have a substituent. Ar ² and Ar ³ may be the same as or different from each other, and represent an arylene group that may have a substituent.

However, in the structural formula (2), Ar ² , Ar ³ , and Ar ⁴ may be the same as or different from each other and represent an arylene group. R ¹⁷ and R ¹⁸ may be the same as or different from each other, and each represents an acyl group, an alkyl group, or an aryl group.

However, in the structural formula (3), R ¹⁷ and R ¹⁸ may be the same as or different from each other, and represent any of an acyl group, an alkyl group, and an aryl group.

In the structural formula (4), Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ may be the same as or different from each other, an arylene group, Ar 7 is an aryl group, and Z is an arylene group. or ^{-Ar 10 -Za-Ar} 10 - (provided that, ^{Ar 10} is an arylene group, Za represents O, S or alkylene group). R and R ′ represent a linear or branched alkylene group. n represents 0 or 1.
However, in the structural formula (5), Ra, Rb, Rc and Rd may be the same as or different from each other, and represent an alkyl group. Ar ⁷ represents an arylene group. Z, R, R ′ and n are the same as in the above structural formula (4).

In the structural formula (6), X represents an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, a divalent group formed by linking these, and the following structural formula (7 ) And the following structural formula (8).
However, in the structural formulas (7) and (8), R ² , R ³ , R ⁴ , and R ⁵ may be the same or different from each other, and may be an alkyl group, an aryl group, or Represents a halogen atom. a and b are each independently an integer of 0 to 4; c and d are each independently an integer of 0 to 3. Y represents a single bond, a linear alkylene group having 2 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —, —CO—, and the following formulas (3) to (11): )

However, in the formula, Z ¹ and Z ² represents a divalent group or an arylene group aliphatic. R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same or different from each other, and may be a hydrogen atom, a halogen atom, or a carbon number of 1 to 5. Represents an alkyl group, an alkoxy group having 1 to 5 carbon atoms, or an aryl group, and R ⁶ and R ⁷ may combine to form a carbocyclic or heterocyclic ring having 6 to 12 carbon atoms; R ⁶ and R ⁷ may form a carbocycle or a heterocycle together with R ² and R ³ , R ¹³ and R ¹⁴ represent a single bond or an alkylene group having 1 to 4 carbon atoms, R ¹⁵ and R ¹⁶ may be the same as or different from each other, and represents any one of an alkyl group having 1 to 5 carbon atoms and an aryl group. e represents an integer of 0 to 4, f represents an integer of 0 to 20, and g represents an integer of 0 to 2000.

Examples of the diol when X in the structural formula (6) is an aliphatic divalent group or a cycloaliphatic divalent group include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polytetramethylene ether. Glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, neopentyl glycol, 2-ethyl-1, 6-hexanediol, 2-methyl-1,3-propanediol, 2-ethyl 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane-1,4-dimethanol, 2,2-bis (4 -Hydroxycyclohexyl) propane, xylylenediol, 1,4-bis (2-hydroxyethyl) benzene, 1,4-bis (3-hydroxypropyl) benzene, 1,4-bis (4-hydroxybutyl) benzene, 1 , 4-bis (5-hydroxypentyl) benzene, 1,4-bis (6-hydroxyhexyl) benzene, isophoronediol and the like.
Moreover, as a case where X is an aromatic divalent group, a divalent group derived from an aryl group defined in Ar ⁷ in the structural formula (4) can be exemplified.

In addition, as Y in the structural formula (7), as a specific example of a divalent group composed of one or more alkylene groups having 1 to 10 carbon atoms and one or more oxygen atoms and sulfur atoms, OCH ₂ CH ₂ O, OCH ₂ CH ₂ OCH ₂ CH ₂ O, OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ O, OCH ₂ CH ₂ CH ₂ O, OCH ₂ CH ₂ CH ₂ CH ₂ O, OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O, OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O, CH ₂ O, CH ₂ CH ₂ O, CHEtOCHEtO, CHCH ₃ O, SCH ₂ OCH ₂ S, CH _{2 OCH 2, OCH 2 OCH 2} O, SCH 2 CH 2 OCH 2 OCH 2 CH 2 S, OCH 2 CHCH 3 OCH 2 CHCH 3 O, SC _{2 S, SCH 2 CH 2 S} , SCH 2 CH 2 CH 2 S, SCH 2 CH 2 CH 2 CH 2 S, SCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 S, SCH 2 CH 2 SCH 2 CH 2 S , SCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ S and the like.
In addition, examples of the substituent that modifies the branched alkylene group having 2 to 12 carbon atoms include an aryl group and a halogen atom.
Among these, the alkyl group and aryl group are the same as the alkyl group and aryl group defined in the present specification. Further, when Z ¹ and Z ² are an aliphatic divalent group, a divalent group obtained by removing a hydroxy group from a diol when X is an aliphatic divalent group or a cycloaliphatic divalent group is Can be mentioned. Examples of the case where Z ¹ and Z ² are arylene groups include divalent groups derived from aryl groups defined in the present invention.

  Specific examples of preferable diol when X in the structural formula (6) is an aromatic divalent group include bis (4-hydroxyphenyl) methane, bis (2-methyl-4-hydroxyphenyl) methane, Bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis (4-hydroxyphenyl) -1,1-dimethylpropane, 2,2-bis ( 4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 1,1 Bis (4-hydroxyphenyl) -2-methylpropane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4- Hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) Butane, 2,2-bis (4-hydroxyphenyl) nonane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2 -Bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2- (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) Propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo- 4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxy) Phenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis ( 4-hydroxyphenyl) cycloheptane, 2,2-bis (4-hydroxyphenyl) norbornane, 2,2-bis (4-hydroxyphenyl) adamantane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3 , 3′-dimethyldiphenyl ether, ethylene glycol bis (4-hydroxypheny ) Ether, 1,3-bis (4-hydroxyphenoxy) benzene, 1,4-bis (3-hydroxyphenoxy) benzene, 4,4′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′- Dihydroxydiphenyl sulfide, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfoxide 4,4′-dihydroxydiphenylsulfone, 3,3′-dimethyl-4,4′-dihydroxydiphenylsulfone, 3,3′-diphenyl-4,4′-dihydroxydiphenylsulfone, 3,3′-dichloro-4 , 4'-dihydroxydiphenylsulfone, bis (4-hydroxyphene E) ketone, bis (3-methyl-4-hydroxyphenyl) ketone, 3,3,3 ′, 3′-tetramethyl-6,6′-dihydroxyspiro (bis) indane, 3,3 ′, 4,4 '-Tetrahydro-4,4,4', 4'-tetramethyl-2,2'-spirobis (2H-1-benzopyran) -7,7'-diol, trans-2,3-bis (4-hydroxy Phenyl) -2-butene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, 1,6-bis (4-hydroxyphenyl) -1,6- Xanthedione, α, α, α ′, α′-tetramethyl-α, α′-bis (4-hydroxyphenyl) -p-xylene, α, α, α ′, α′-tetramethyl-α, α′- Bis (4-hydroxyphenyl) -m- Xylene, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathiin, 9,10-dimethyl-2,7-dihydroxyphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, 4,4′-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 2,7-dihydroxypyrene, hydroquinone, resorcin, 4-hydroxyphenyl-4-hydroxybenzoate, ethylene glycol-bis (4 -Hydroxybenzoate), diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate), p-phenylene-bis (4-hydroxybenzoate), 1,6-bi (4-hydroxybenzoyloxy) -1H, 1H, 6H, 6H-perfluorohexane, 1,4-bis (4-hydroxybenzoyloxy) -1H, 1H, 4H, 4H-perfluorobutane, 1,3-bis (4-hydroxyphenyl) tetramethyldisiloxane, phenol-modified silicone oil, and the like.

  Although the structural formulas (1) and (4) have been described above, the same symbols have the same definition in other structural formulas.

  One or more diols having a charge transport ability represented by the structural formulas (1), (2), and (3), or a charge transport ability represented by the structural formulas (4) and (5). The ratio of one or more diols having a diol and the diol represented by the structural formula (6) in combination can be selected from a wide range depending on the desired properties.

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, a diol having a charge transport ability represented by the structural formulas (1), (2), and (3), or a diol having a charge transport ability represented by the structural formulas (4) and (5) And the diol represented by the structural formula (6) are mixed uniformly from the beginning and subjected to a condensation reaction with phosgene, the structural formulas (1), (2), and (3) are represented. Or a random copolymer comprising the structural units represented by the structural formulas (4) and (5) and the structural unit represented by the structural formula (6).
Furthermore, 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 structural formula (6) and the charge represented by the structural formula (1), (2), (3), (4) or (5) By performing a condensation reaction with a diol having a transport ability, an alternating copolymer composed of repeating units represented by the following structural formula (9), (10), (11), (12), or (13) is obtained. It is done.

In the Structural Formula ^{(9), R 1, Ar} 1, Ar 2, Ar 3, and X represent the same meaning as above. n represents a polymerization degree and represents an integer of 2 to 5,000.

However, in the structural formula (10), Ar ² , Ar ³ , Ar ⁴ , R ¹⁷ , R ¹⁸ , and X represent the same meaning as described above. n represents a polymerization degree and represents an integer of 2 to 5,000.

However, in said structural formula (11), R < ¹⁷ > R <^18> and X represent the same meaning as the above. n represents a polymerization degree and represents an integer of 2 to 5,000.
However, in the structural formula (12), Ar ⁵ , Ar ⁶ , Ar ⁸ , and Ar ⁹ may be the same as or different from each other and represent an arylene group. Ar ⁷ represents an aryl group. Z represents an arylene group or —Ar ¹⁰ —Za—Ar ¹⁰ — (wherein Ar ¹⁰ represents an arylene group, Za represents O, S or an alkylene group). R and R ′ may be the same as or different from each other, and each represents a linear or branched alkylene group. n represents 0 or 1. n 'represents a polymerization degree and represents an integer of 2 to 5,000.

However, in the structural formula (13), Ra, Rb, Rc and Rd may be the same as or different from each other, and represent an alkyl group. Ar ³ represents an arylene group. Z, R, R ′ and n represent the same meaning as in the structural formula (4). n 'represents a polymerization degree and represents an integer of 2 to 5,000.

In this case, conversely, bischloroformate derived from a diol having a charge transporting ability represented by the structural formula (1), (2), (3), (4), or (5), and the structure Similarly, by the condensation reaction with the diol represented by the formula (6), the alternating unit consisting of repeating units represented by the structural formula (9), (10), (11), (12), or (13) A copolymer is obtained.
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 a 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. A mixture is mentioned. 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, There are compounds having an amide group. 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, benzyltriphenyl Suphonium chloride, 4-methylpyridine, 1-methylimidazole, 1,2-dimethylimidazole, 3-methylpyridazine, 4,6-dimethylpyrimidine, 1-cyclohexyl-3,5-dimethylpyrazole, 2,3,5 Examples include 6-tetramethylpyrazine.

  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 higher.

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.
As the deoxidizer in this case, for example, tertiary amines such as trimethylamine, triethylamine, and tripropylamine, and pyridine are used.
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 composed of a polycarbonate resin having at least one, preferably two or more functional groups in the molecule obtained by the above various methods, and a functional group reactive with the functional group in the polymer organic component. By reacting and bonding the metal alkoxide, a polymer for a hybrid material having a metal alkoxide group bonded to the polymer organic component can be obtained.

<Metal alkoxide compound>
Examples of the metal alkoxide include compounds represented by the following structural formula (b).
AoM: Structural formula (b)
However, in the structural formula (b), Ao preferably has 1 to 8 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms. Examples of M include Si, Ti, Zr, Fe, Cu, Sn, B, Al, Ge, Ce, and Ta, and Si, Ti, and Zr are particularly preferable.

Examples of the metal alkoxide compound represented by the structural formula (b) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane; tetrapropoxy titanium, tetraisopropoxy titanium, tetraisopropoxy zirconium, Examples thereof include metal alkoxides such as tetrapropoxyzirconium, tetrabutoxytin, tetraisopropoxytin, and triisopropoxyaluminum.
The metal alkoxide compound 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.

Moreover, as said metal alkoxide compound, the compound represented by following structural formula (VII) is suitable.
^{_{R 19 p A m M (R}} "X ') n ··· structural formula (VII)
In the Structural Formula ^{(VII), R 19} represents an alkyl group having 1 to 5 carbon atoms. A represents a C1-C4 alkoxy group. M represents any of Si, Ti, and Zr. R ″ represents any one of an alkylene group having 2 to 4 carbon atoms and an alkylidene group. X ′ represents any one selected from an isocyanate group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. P represents an integer of 0 to 3. m and n each represents an integer of 1 to 3.

  The metal element 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, it is easy to synthesize the polymer for hybrid materials in the present invention, and the resulting polymer has chemical stability. Alternatively, the polymer for hybrid materials has appropriate reactivity (temperature, time, etc.). For example, an organic-inorganic hybrid material can be obtained by easily hydrolyzing and polycondensing (sol-gel reaction) the polymer. The cured polymer can have electrical, mechanical, physical and other properties useful for organic electronic devices, particularly electrophotographic photoreceptors. Moreover, the raw material of a metal alkoxide can be selected widely like the following example, and can also be used properly according to the objective.

  The metal alkoxide represented by the structural formula (VII) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include monoisocyanate trialkoxymetals, monoisocyanate dialkoxymetals, and monoisocyanates. Monoalkoxymetals, diisocyanatealkoxymetals, triisocyanatealkoxymetals, metal alkoxides having an epoxy group as a functional group, alkylalkoxysilanes having an epoxy group as a functional group, metal alkoxides having an acid halide as a functional group, Or the alkoxysilane etc. which have an amino group and a mercapto group as a functional group are mentioned.

  Examples of the monoisocyanate trialkoxymetals include 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 2-isocyanateethyltriethoxysilane, 2-isocyanateethyltripropoxyzirconium, 2-isocyanateethyltributoxy. Examples include tin.

  Examples of the monoisocyanate dialkoxymetals include 3-isocyanatepropylethyldiethoxysilane, 3-isocyanatepropylethyldiisopropoxytitanium, 2-isocyanateethylethyldipropoxyzirconium, 2-isocyanateethylmethyldibutoxytin, and isocyanate. Examples thereof include methyldimethoxyaluminum.

  Examples of the monoisocyanate monoalkoxymetals include 3-isocyanatepropyldiethylethoxysilane, 3-isocyanatopropyldimethylisopropoxytitanium, 2-isocyanatoethyldiethylpropoxyzirconium, 2-isocyanatoethyldimethylbutoxytin, and isocyanatomethylmethylmethoxyaluminum. Etc.

Examples of the diisocyanate alkoxymetals include di (3-isocyanatepropyl) diethoxysilane, di (3-isocyanatepropyl) methylisopropoxytitanium, and the like.
Examples of the triisocyanate alkoxymetals include ethoxysilane triisocyanate.

  Examples of the metal alkoxide having an epoxy group as a functional group include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxy. Propyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, γ-glycidoxypropyltriisopropoxy Titanium, γ-glycidoxypropylmethyl diisopropoxytitanium, γ-glycidoxypropyldimethylisopropoxytitanium, 3,4-epoxybutyltripropoxyzirconium, 3,4-epoxybutylmethyldipropoxyzirconium, 3,4- D Carboxybutyl dimethylpropoxy zirconium, beta-(3,4-epoxycyclohexyl) ethyl triethoxy tin, and the like.

  Examples of the alkylalkoxysilanes having the alkoxy group as a functional group include methyltrimethoxysilane, ethyltriethoxysilane, isopropyltriisopropoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diisopropyldiisopropoxysilane, and trimethylmethoxy. Examples include silane, triethylethoxysilane, triisopropylisopropoxysilane, and the like.

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

  The polymer for hybrid materials in the present invention containing the structural unit having the charge transport function includes a polymer organic component comprising a polycarbonate resin having at least one, preferably two or more functional groups in the molecule, and a polymer. It is obtained by reacting a metal alkoxide having a functional group having reactivity with a functional group in the organic component. In the reaction, a catalyst can also be used. Specific examples of the reaction between the polymer organic component and the metal alkoxide will be described below.

  Polymers made of polycarbonate resin having functional groups having active hydrogen such as hydroxyl group, amino group, carboxyl group, and thiol group, and functional groups such as isocyanate group, epoxy group, carboxyl group, acid halide group, and acid anhydride group Is reacted in a solvent, preferably in an inert gas atmosphere. Any solvent may be used as long as it can well dissolve both the polymer and the metal alkoxide.

In general, a metal alkoxide solution or a metal alkoxide 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 may be used as it is, and may be transferred to the next step sol-gel reaction shown below, or the reaction solution may be concentrated or poured into a large amount of poor solvent to precipitate the reaction product. And after performing treatments such as washing, purification, and drying, a sol-gel reaction may be performed using the treatment.

An organic-inorganic hybrid material having a charge transport function can be obtained by the production method of hydrolyzing and polycondensing a polymer for hybrid material having a metal alkoxide group bonded to a polymer organic component in the present invention by a sol-gel reaction. This product may be either dissolved in the reaction solution immediately after preparation or isolated.
Hydrolysis and polycondensation by the sol-gel method means that a polymer for a hybrid material having a metal alkoxide group in the molecule is reacted with water to convert the alkoxy group to a hydroxyl group (hydroxy metal group: for example, —Si ( OH) ₃ ), and the hydroxyl group is simultaneously polycondensed by dehydration reaction or dealcoholization reaction with adjacent molecules to form an inorganic covalent bond, that is, a metal oxide bond, and a three-dimensional crosslinking reaction. Point to.

As a supply source of water used for the hydrolysis reaction, an amount necessary for converting all alkoxy groups in the polymer for hybrid materials to be converted into hydroxyl groups may be added separately, or in the reaction system. You may carry out by using the water | moisture content contained or making the water | moisture content in air | atmosphere absorbed.
The reaction conditions for hydrolysis and polycondensation 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, and p-toluenesulfonic acid, or a basic catalyst such as sodium hydroxide, potassium hydroxide, ammonia, triethylamine, and piperidine may be used. Furthermore, when the condensation reaction is advanced to make the cross-linking stronger, it is preferable to perform heat treatment at 50 to 400 ° C. for about 5 minutes to 48 hours. The obtained reaction solution can be used as it is as a coating solution for a photoreceptor described later.

  As described above, an organic-inorganic hybrid material in which an organic component obtained by hydrolysis and polycondensation of a polymer for hybrid material and an inorganic component are integrally bonded is three-dimensionally crosslinked, The characteristics of organic and inorganic materials are manifested, and excellent properties such as wear resistance, mechanical strength, rigidity, surface hardness, and heat resistance are exhibited.

  The organic-inorganic hybrid material having a charge transport function in the present invention (hereinafter abbreviated as “charge transporting organic-inorganic hybrid material”) has been described above, but the surface layer of the photosensitive layer formed on the support. However, an embodiment of an electrophotographic photoreceptor constituted mainly using this organic-inorganic hybrid material will be described below.

In the method for producing an electrophotographic photoreceptor of the present invention, a layer containing the polymer for hybrid material of the present invention is provided on a support, and then the polymer for hybrid material is hydrolyzed or polycondensed to form an organic- It includes at least a surface layer forming step for forming a surface layer containing an inorganic hybrid material, and further includes other steps as necessary.
The surface layer is formed by applying a coating liquid containing a polymer for a hybrid material having a metal alkoxide group bonded to the above-described polymer organic component onto a support, and hydrolyzing and polycondensing the metal alkoxide group to be cured. Formed by. The layer structure and formation method of the photoreceptor will be described later.

  The said coating liquid is diluted with a solvent as needed, and is apply | coated. Solvents used in this case 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 thickness, and is appropriately selected. The coating operation can be performed using a dip coating method, spray coating, bead coating, ring coating method, or the like.

After coating the coating liquid by the above various coating operations, a cross-linking reaction is performed by a sol-gel method to form a surface layer of a charge transporting organic-inorganic hybrid material. The conditions are 50 to 250 ° C. Heat treatment is preferably performed for about 5 minutes to 24 hours. If it is less than 50 degreeC, reaction rate is slow and reaction does not complete | finish completely. When the temperature is higher than 250 ° C., the reaction proceeds non-uniformly and a large strain tends to be 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. For example, the prepared coating solution is applied by spraying or the like onto a photoreceptor in which an undercoat layer, a charge generation layer, and the charge transport layer are sequentially laminated on a support such as an aluminum cylinder. Thereafter, 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 obtain the photoreceptor of the present invention.
Before applying a coating liquid containing a polymer having a charge transporting function to which a metal alkoxide group is bonded, a small amount of an acidic catalyst is added, so that the water is added at room temperature to 100 ° C. for about 0.5 to 24 hours. The decomposition reaction can be promoted, and crosslinking can be facilitated.

  By hydrolyzing and polycondensing the polymer for hybrid materials, it is excellent in mechanical strength such as abrasion resistance and scratch resistance, and also in heat resistance, surface hardness, weather resistance, chemical resistance, stain resistance, etc. A photoreceptor surface layer is formed. The thickness of the photoreceptor surface layer in the present invention varies depending on the layer structure of the photoreceptor, as will be described later.

(Electrophotographic photoreceptor)
In the electrophotographic photosensitive member of the present invention, the surface layer contains the organic-inorganic hybrid material of the present invention, and further has other configurations as necessary.

The electrophotographic photoreceptor has at least a photosensitive layer on a support, and the entire photosensitive layer may be a surface layer, or may have a surface layer on the photosensitive layer.
In the case where the photosensitive layer comprises a charge generation layer having a charge generation function and a charge transport layer having a charge transport material function, the entire charge transport layer may be a surface layer, and the charge transport layer You may have a surface layer on it.

Here, FIG. 1A and FIG. 1B are schematic cross-sectional views showing an example of the layer structure of the electrophotographic photoreceptor having a single layer structure of the present invention.
1A and 1B, a photosensitive layer 2 having a single layer structure having a charge generation function and a charge transport function at the same time is provided on a support 1. Reference numerals 3 and 3 ′ denote layers having a charge generation function and a charge transport function.
FIG. 1A shows the case where the surface layer 4 formed of the organic-inorganic hybrid material is the entire photosensitive layer 2, and FIG. 1B shows the surface layer 4 formed of the organic-inorganic hybrid material being the surface of the photosensitive layer 2. The case where it is a part is shown.

2A and 2B are schematic cross-sectional views showing an example of a layer structure of an electrophotographic photosensitive member having a laminated structure according to the present invention.
2A and 2B, on the support 1, a photosensitive layer 6 having a laminated structure in which a charge generation layer 5 having a charge generation function and a charge transport layer 7 or 7 'having a charge transport material function are laminated. Is provided.
FIG. 2A shows a case where the surface layer formed of the organic-inorganic hybrid material is the entire charge transport layer 7, and FIG. 2B shows that the surface layer 8 formed of the organic-inorganic hybrid material is the charge transport layer 7 ′. It shows the case of the surface portion.

-Support-
Examples of the 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, or tin oxide and indium oxide. Metal oxide coated with film or cylindrical plastic or paper by vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel, etc. It is possible to use a tube which has been subjected to surface treatment such as super finishing or polishing. Further, for example, endless nickel belts and endless stainless steel belts disclosed in JP-A-52-36016 can also be used as the 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 support of the present invention.
Examples of the conductive powder used 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. Is mentioned.
The binder resin used simultaneously 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, ethyl cellulose, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin , Urethane resins, phenol resins, alkyd resins, and other thermoplastic, thermosetting resins, and photocurable resins.
The conductive layer can be provided by dispersing and applying the conductive powder and the binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, toluene and the like.

  Further, a heat shrinkable tube in which the conductive powder is previously 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 using can be used favorably as the support of the present invention.

<Photosensitive layer>
The photosensitive layer may have a laminated structure or a single layer structure. In the case of a laminated structure, as shown in FIGS. 2A and 2B, the photosensitive layer is composed of a charge generation layer having a charge generation function and a charge transport layer having a charge transport function. As shown in FIGS. 1A and 1B, in the case of a single layer structure, the photosensitive layer is composed of layers having a charge generation function and a charge transport function at the same time. Hereinafter, the photosensitive layer having a multilayer structure and the photosensitive layer having a single layer structure will be described.

[When photosensitive layer is laminated]
-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 can be used in combination as necessary. As the charge generation material, inorganic materials and organic materials can be used.

  Examples of the inorganic material include crystalline selenium, amorphous-selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compound, and amorphous-silicon. In amorphous-silicon, a dangling bond terminated with a hydrogen atom or a halogen atom, or doped with a boron atom or a phosphorus atom is preferably used.

  The organic material is not particularly limited and may be appropriately selected from known materials according to the purpose. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid Methine pigment, azo pigment having carbazole skeleton, azo pigment having triphenylamine skeleton, azo pigment having diphenylamine skeleton, azo pigment having dibenzothiophene skeleton, azo pigment having fluorenone skeleton, azo pigment having oxadiazole skeleton, Azo pigment having bis stilbene skeleton, azo pigment having distyryl oxadiazole skeleton, azo pigment having distyryl carbazole skeleton, perylene pigment, anthraquinone pigment, polycyclic quinone pigment, quinoneimine pigment, diphenylmethane pigment Triphenylmethane pigments, benzoquinone pigments, naphthoquinone pigments, cyanine pigments, azomethine pigments, indigoid pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  The binder resin used as needed for the charge generation layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin Resins, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, polyacrylamide, and the like can be given. These binder resins can be used alone or as a mixture of two or more.

  Further, as the binder resin of the charge generation layer, in addition to the binder resin described above, a polymer charge transport material having a charge transport function, for example, an arylamine skeleton, a benzidine skeleton, a hydrazone skeleton, a carbazole skeleton, a stilbene skeleton, a 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 in the charge transporting polymer material include, for example, JP-A-01-001728, JP-A-01-009964, JP-A-01-013061, and JP-A-01-019049. JP, 01-241559, JP, 04-01627, JP, 04-175337, JP, 04-183719, JP, 04-2225014, JP, 04-230767, Japanese Laid-Open Patent Publication Nos. 04-320420, 05-232727, 05-310904, 06-234836, 06-234837, 06-234838, 06 -234839, JP-A-06-234840, JP-A-06-234841 JP-A 06-239049, JP-A 06-236050, JP-A 06-236051, JP-A 06-295077, JP-A 07-056374, JP 08-176293, JP 08-208820, JP 08-21640, JP 08-253568, JP 08-269183, JP 09-062019, JP 09-038883, JP JP-A 09-71642, JP-A 09-87376, JP-A 09-104746, JP 09-110974, JP 09-110976, JP 09-157378, JP 09-09. No. 221544, JP 09-227669 A, JP 09-23536 A JP-A 09-241369, JP-A 09-268226, JP-A 09-272735, JP-A 09-302084, JP-A 09-302085, JP-A 09-328539. And the like.
Specific examples of the latter polymer material having a polysilane skeleton include, for example, JP-A 63-285552, JP-A 05-19497, JP-A 05-70595, and JP-A 10-73944. Examples include polysilylene polymers described in publications and the like.

  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 electron transport materials and hole transport materials.

-Electron transport material-
The electron transport material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include chloroanil, bromoanil, 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-trinitrodibenzothiophene-5,5-dioxide, and diphenoquinone derivatives. These electron transport materials can be used alone or as a mixture of two or more.

-Hole transport material-
Examples of the hole transporting material include the electron donating materials shown 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 Examples of materials known as methane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and other hole transport materials It is done. These hole transport materials can be used alone or as a mixture of two or more.

The method for forming the charge generation layer is broadly classified into a vacuum thin film preparation method and a casting method using a solution (for example, a 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 inorganic material or the organic material is formed well. it can.
In the case of the casting method, the inorganic or organic charge generating material may be combined with a binder resin, if necessary, with tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclopentanone, anisole. Disperse in a solvent such as xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate using a ball mill, attritor, sand mill, bead mill, etc. can do. Moreover, leveling agents, such as a dimethyl silicone oil and a methylphenyl silicone oil, can be added as needed. The application can be performed by dip coating, spray coating, bead coating, ring coating, or the like.
The thickness of the charge generation layer is preferably from 0.01 to 5 μm, more preferably from 0.05 to 2 μm.

-Charge transport layer-
The charge transport layer is a layer having a so-called charge transport function, and the surface layer formed of the organic-inorganic hybrid material composed of the structural unit having the charge transport function of the present invention is useful as the charge transport layer.
When the surface layer formed of the organic-inorganic hybrid material is the entire charge transport layer, a polymer for hybrid material having a metal alkoxide group bonded to the polymer organic component in the present invention is included on the charge generation layer. The surface layer of the organic-inorganic hybrid material is formed by applying a coating liquid to be applied, drying as necessary, and performing a sol-gel reaction (crosslinking reaction) by heating.
10-30 micrometers is preferable and, as for the thickness of the said surface layer, 10-25 micrometers is more preferable. If the thickness is less than 10 μm, a sufficient charging potential may not be maintained. If the thickness exceeds 30 μm, peeling from the lower layer may easily occur due to volume shrinkage during curing.

  Further, when the surface layer formed of the organic-inorganic hybrid material is the surface portion of the charge transport layer and the charge transport layer has a laminated structure, the lower layer portion of the laminated structure in the charge transport layer has a charge transport function. First, a first charge transport layer is formed by dissolving or dispersing the binder resin in a suitable solvent and applying and drying the charge resin on the charge generation layer. In the present invention, a coating liquid containing a polymer for a hybrid material having a metal alkoxide group bonded to a polymer organic component in the present invention is applied, dried as necessary, and then subjected to a sol-gel reaction (crosslinking reaction) by heating. Thus, a surface layer (second charge transport layer) made of an organic-inorganic hybrid material is formed.

As the charge transport material used in the lower layer portion, 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 a polymer charge transport material is particularly useful because the solubility of the lower layer during coating of the surface layer can be reduced.
Examples of the binder resin include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, poly Vinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin And thermoplastic or thermosetting resins such as urethane resin, phenol resin, and alkyd resin.
The amount of the charge transport material is preferably 20 to 300 parts by mass and more preferably 40 to 150 parts by mass with respect to 100 parts by mass 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 layer portion of the charge transport layer in the above laminated structure, the same solvent as that for the charge generation layer can be used, but those that dissolve the charge transport material and the binder resin well are suitable. . These solvents may be used alone or in combination of two or more. In addition, the same coating method as that for the charge generation layer can be used to form the lower layer portion of the charge transport layer. If necessary, a plasticizer and a leveling agent can be added.

  As the plasticizer that can be used in combination with the lower layer portion of the 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 of the plasticizer used is the binder resin 100. 0-30 mass parts is preferable with respect to mass parts.

Examples of the leveling agent that can be used in the lower layer portion of the 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. The amount used is preferably 0 to 1 part by mass with respect to 100 parts by mass of the binder resin.
5-40 micrometers is preferable and, as for the thickness of the lower layer part of the said charge transport layer, 10-30 micrometers is more preferable.

  The thickness of the surface layer formed from the polymer for hybrid materials of the present invention formed on the lower layer portion (first charge transport layer) of the laminated structure in the charge transport layer is preferably 1 to 20 μm. 10 μm is more preferable. When the thickness is less than 1 μm, the durability varies due to thickness unevenness, and when it exceeds 20 μm, the entire thickness of the charge transport layer is increased and the reproducibility of the image is reduced due to the diffusion of charges.

<Single layer photosensitive layer>
The photosensitive layer having a single layer structure has a layer structure having a charge generation function and a charge transport function at the same time, and the organic-inorganic hybrid material comprising the structural unit having the charge transport function of the present invention is useful as a photosensitive layer having a single layer structure. Used.
As described in the method for forming the charge generation layer, a coating solution containing both the charge generation material and the polymer for hybrid material having a metal alkoxide group bonded to the polymer organic component of the present invention is prepared. A surface layer containing an organic-inorganic hybrid material is formed by applying the solution on a conductive support, drying it as necessary, and heating it.
The charge generation material may be prepared by dispersing in advance together with a solvent and adding it to the surface layer coating solution containing the polymer for hybrid material. 10-30 micrometers is preferable and, as for the thickness of the said surface layer, 10-25 micrometers is more preferable. When the thickness is less than 10 μm, a sufficient charging potential may not be maintained. When the thickness exceeds 30 μm, peeling from the conductive substrate or the undercoat layer may easily occur due to volume shrinkage during curing.

In addition, when the surface layer formed of the organic-inorganic hybrid material of the present invention is a surface portion of a photosensitive layer having a single layer structure, the lower layer portion in the photosensitive layer having a single layer structure includes a charge generating material having a charge generating function. It can be formed by dissolving or dispersing a charge transport material having a charge transport function and a binder resin in an appropriate solvent, and applying and drying the solution. Moreover, a plasticizer, a leveling agent, etc. can also be added as needed. Here, the charge generation material dispersion method, charge generation material, charge transport material, plasticizer, leveling agent and the like can be the same as those already described in the charge generation layer and charge transport layer.
As the binder resin, in addition to the binder resin previously mentioned in the section of the charge transport layer, a binder resin mentioned in the charge generation layer may be mixed and used. In addition, the polymer charge transport materials listed above can also be used, which is useful in that contamination of the lower photosensitive layer composition into the surface layer can be reduced. The thickness of the lower layer portion of the photosensitive layer is preferably 5 to 30 μm, and more preferably 10 to 25 μm.

In order to form the organic-inorganic hybrid material of the present invention on the surface portion of the photosensitive layer having the single layer structure, a polymer for hybrid materials having a metal alkoxide group bonded to the polymer organic component of the present invention is contained as described above. What is necessary is just to apply | coat a coating liquid and to harden | cure (crosslink) by heating after drying as needed.
1-20 micrometers is preferable and, as for the thickness of the said surface layer, 2-10 micrometers is more preferable. If the thickness is less than 1 μm, uneven durability may occur due to uneven thickness.
In addition, the charge generation material contained in the photosensitive layer having a single layer structure is preferably 1 to 30% by mass with respect to the total amount of the photosensitive layer, and the binder resin contained in the lower layer portion of the photosensitive layer is 20 to 80% of the total amount. The mass% is preferable, and the charge transport material is preferably 10 to 70 parts by mass.

  In the electrophotographic photoreceptor of the present invention, when the surface layer composed of an organic-inorganic hybrid material is the surface portion of the photosensitive layer, the purpose is to suppress mixing of lower layer components into the surface layer or to improve the adhesion to the lower layer. For this purpose, an intermediate layer can be provided. By this intermediate layer, for example, the composition of the lower photosensitive layer can be prevented from being mixed into the outermost surface layer to inhibit the curing reaction, or the surface layer can be prevented from being uneven. . Alternatively, the adhesion between the lower photosensitive layer and the surface layer can be improved.

  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 as described above is employed. The thickness of the intermediate layer is suitably about 0.05 to 2 μm.

  In the electrophotographic photoreceptor of the present invention, an undercoat layer can be provided between the support and the photosensitive layer. In general, the undercoat layer is composed mainly of a resin. Therefore, considering that the photosensitive layer is applied and formed on the undercoat layer using a solvent, the resin used for the undercoat layer 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 resins, phenol resins, and alkyd-melamine resins. And curable resins that form a three-dimensional network structure, such as epoxy resins.
In addition, for the purpose of preventing moire and reducing residual potential, the undercoat layer is added with a fine powder pigment of a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide or the like. Also good.

The undercoat layer can be formed using an appropriate solvent and coating method as in the above-described 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. As the undercoat layer, an Al ₂ O ₃ provided by anodic oxidation, an organic substance such as polyparaxylylene (parylene), or an inorganic substance such as SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ is vacuum thin film. Those provided by the preparation method can also be used favorably. In addition, a known material for the undercoat layer can be used.
The thickness of the undercoat layer is preferably 0 to 5 μm.

  In addition, in the electrophotographic photoreceptor of the present invention, in order to improve environmental resistance, the surface layer, the photosensitive layer, the charge generation layer, the charge transport layer, the intermediate layer are especially used for the purpose of preventing a decrease in sensitivity and an increase in residual potential. An antioxidant can be added to each layer such as a layer and an undercoat layer.

Examples of the antioxidant include phenolic compounds, paraphenylenediamines, organic sulfur compounds, and organic phosphorus compounds.
Examples of the phenol compound include 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-t-butylphenol), 2,2'-methylene-bis- (4-ethyl- 6-t-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-hydroxy Ben ) Benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3 ′) -T-butylphenyl) butyric acid] cricol ester, tocopherols and the like.
Examples of the paraphenylenediamines include N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl- Examples include p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine, and the like.
Examples of the hydroquinones include 2,5-di-t-octyl hydroquinone, 2,6-didodecyl hydroquinone, 2-dodecyl hydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methyl. Examples include hydroquinone and 2- (2-octadecenyl) -5-methylhydroquinone.
Examples of the organic sulfur compounds include dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like. .
Examples of the organic phosphorus compounds include triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.
These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
There is no restriction | limiting in particular in the addition amount of the said antioxidant, Although it can select suitably according to the objective, 0.01-10 mass% is preferable with respect to the total mass of the layer to add.

(Image forming method and image forming apparatus)
The image forming apparatus of the present invention comprises at least an electrophotographic photosensitive member, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and other components appropriately selected as necessary. Means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.
The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrophotographic photosensitive member.
The material, shape, structure, size, etc. of the electrophotographic photosensitive member (photosensitive member) are not particularly limited, and can be appropriately selected from known ones. The shape is preferably a drum shape. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon or the like is preferable in terms of long life.
The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrophotographic photosensitive member and then performing imagewise exposure, and can be performed by the electrostatic latent image forming unit. it can. The electrostatic latent image forming means includes at least a charger that uniformly charges the surface of the electrophotographic photosensitive member and an exposure device that exposes the surface of the electrophotographic photosensitive member imagewise.
The charging can be performed, for example, by applying a voltage to the surface of the electrophotographic photosensitive member using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.
The exposure can be performed, for example, by exposing the surface of the electrophotographic photosensitive member imagewise using the exposure device.
The exposure device is not particularly limited as long as the surface of the electrophotographic photosensitive member charged by the charger can be exposed like an image to be formed, and can be appropriately selected according to the purpose. However, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, an optical backside system that performs imagewise exposure from the backside of the electrophotographic photosensitive member may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the developer of the present invention, and can be appropriately selected from known ones. For example, the developer of the present invention is accommodated. And a developer having at least a developer capable of applying the developer to the electrostatic latent image in a contact or non-contact manner, and a developer equipped with the developer-containing container of the present invention is more preferable. .
The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multicolor developing unit. Well, for example, a developer having a stirrer for charging the developer by frictional stirring and a rotatable magnet roller is preferable.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrophotographic photosensitive member (photosensitive member), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrophotographic photosensitive member (photosensitive member). As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrophotographic photosensitive member (photosensitive member).

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the electrophotographic photoreceptor (photoreceptor) with the transfer charger using the visible image, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
The transfer means (the primary transfer means and the secondary transfer means) includes a transfer device that peels and charges the visible image formed on the electrophotographic photosensitive member (photosensitive member) to the recording medium side. It is preferable to have at least. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrophotographic photosensitive member, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrophotographic photosensitive member. For example, a neutralization lamp is preferably used. Can be mentioned.

The cleaning step is a step of removing the toner remaining on the electrophotographic photosensitive member, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrophotographic photosensitive member, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling process is a process of recycling the developer removed by the cleaning process to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.

  The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Here, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG.
FIG. 3 is a schematic diagram illustrating a configuration example of the image forming apparatus according to the present invention.
In FIG. 3, a charging charger 233 is used as means for charging the photoconductor 231 on average. 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 235 is used to form an electrostatic latent image on the uniformly charged photoreceptor 231. As the light source, all light emitters 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.

  A developing unit 236 is used to visualize the electrostatic latent image formed on the photoconductor 231. 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, the transfer charger 210 is used to transfer the toner image visualized on the photosensitive member 231 onto the transfer member 239. In addition, a pre-transfer charger 237 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.

  As means for separating the transfer member 239 from the photosensitive member 231, a separation charger 211 and a separation claw 212 are used. 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 211, the charging means can be used.

  Next, a fur brush 214 and a cleaning blade 215 are used to clean the toner remaining on the photoreceptor 231 after the transfer. Further, a pre-cleaning charger 213 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 charge eliminating unit is used for the purpose of removing the latent image on the photoconductor 231 as necessary. As the charge removal means, a charge removal lamp 232 and a charge removal charger are used, and the exposure light source and charging means can be used respectively.
In addition, known processes can be used for reading, feeding, fixing, and ejecting documents that are not close to the photosensitive member 231.

  In addition, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 5 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and an exposure unit. An exposure device 30, a developing device 40 as the developing unit, an intermediate transfer member 50, a cleaning device 60 as the cleaning unit having a cleaning blade, and a static elimination lamp 70 as the static elimination unit.

The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is formed between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is arranged between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.
The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoreceptor 10.

  In the image forming apparatus 100 shown in FIG. 5, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 6 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 5, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is directly opposed, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 6, the same components as those in FIG. 5 are denoted by the same reference numerals.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 7 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15, and 16 and can be rotated clockwise in FIG. 7. An intermediate transfer body cleaning device 17 for removing residual toner on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

Next, formation of a full color image (color copy) using the tandem image forming apparatus will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.
When a start switch (not shown) is pressed, when a document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem image forming apparatus. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each of the image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 8), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, and the toner image is an intermediate transfer member. The image forming apparatus includes a transfer charger 62 for transferring the image onto 0, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the paper discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  With the image forming apparatus and the image forming method using the electrophotographic photosensitive member of the present invention, it is possible to form a high-quality image over a long period of time. Further, the apparatus can be miniaturized.

(Process cartridge)
The image forming means in the present invention 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. Also good. FIG. 4 is a schematic diagram illustrating a configuration example of a process cartridge that is detachable from the image forming apparatus according to the present invention.
The process cartridge incorporates the photosensitive member 101 and includes at least one unit selected from a charging unit 102, a developing unit 104, a transfer unit 108, a cleaning unit 107, and a charge eliminating unit (not shown). The apparatus (part) is supported by the image forming apparatus and is detachable from the main body of the image forming apparatus.

The apparatus and image forming process illustrated in FIG. 4 will be described.
In FIG. 4, an electrostatic latent image corresponding to the exposure image is formed on the surface of the photoconductor 101 by charging by the charging unit 102 and exposure by the exposure unit 103 while rotating in the direction of the arrow. The toner is developed by the developing means 104, and the toner development is transferred to the transfer member 105 by the transfer means 108 and printed out. The surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and is further neutralized by a neutralizing unit (not shown), and the same operation is repeated again.

A process in which the electrophotographic photosensitive member of the present invention and at least one unit selected from a charging unit, a developing unit, a transfer unit, a cleaning unit, and a neutralizing unit are integrally supported and detachable from the main body of the image forming apparatus. By using the cartridge, the image forming apparatus can be made compact, and simple and steady maintenance work can be performed. Furthermore, it is possible to easily replace parts and to stabilize the image quality. In addition, it is possible to restore the original high-quality image simply by replacing the process cartridge.
By mounting the process cartridge on an image forming apparatus and repeatedly performing at least charging, image exposure, development, and transfer, high-quality and stable image formation can be achieved over a long period of time.

  As is apparent from the above description, the electrophotographic photosensitive member of the present invention is not only used 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. It can also be used widely.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “part” represents “part by mass”, and “%” represents “mass%”.

(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 The solution was stirred and dissolved in 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, dried, and charged with a hydroxyl group-containing charge transporting polymer (polymer) containing the polymer structural units shown in Table 1 below. Combined No. 1) was obtained.
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 2,200 in terms of number average molecular weight. The infrared absorption spectrum is shown in FIG. Table 1 shows the structural units of the polymer and the results of elemental analysis.

(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- Add 3.87 g (0.008 mol) of bis (4-tolyl) amine, 2.74 g (0.012 mol) of 2,2-bis (4-hydroxyphenyl) propane, 2.5 ml of dehydrated pyridine and 40 ml of dehydrated dichloromethane. The solution was stirred and dissolved in 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 over 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, dried, and charged with a hydroxyl group-containing charge transporting polymer (heavy polymer) containing the polymer structural units shown in Table 1 below. Combined No. 2) was obtained.
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 3,400 in terms of number average molecular weight. The structural units of the polymer and the results of elemental analysis are shown in Table 1.

(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, dried, and charged with a hydroxyl group-containing charge transporting polymer (polymer) containing the polymer structural units shown in Table 1 below. Combined No. 3) was obtained.
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 2,500 in terms of number average molecular weight. The structural units of the polymer and the results of elemental analysis are shown in Table 1.

(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. Subsequently, it was washed with ion exchange water. The obtained solution was dropped into 1.5 l of methanol to precipitate a yellow product, dried, and charged with a hydroxyl group-containing charge transporting polymer (polymer) containing the polymer structural units shown in Table 1 below. Combined No. 4) was obtained.
The obtained polymer no. When the molecular weight of No. 4 was measured by gel permeation chromatography (GPC), the molecular weight in terms of polystyrene was 4,500 in terms of number average molecular weight. The structural units of the polymer and the results of elemental analysis are shown in Table 1.

(Production Example 5)
-Charge transporting polymer having a hydroxyl group: Polymer No. 5-
In a 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube, and dropping funnel, N, N′-bis {3-methyl-4 [2- (4-hydroxy) phenethyl]} phenyl-4 -Methylbiphenyl-4'-amine (synthesized according to JP-A No. 2002-249472), 12.08 g (0.02 mol), dehydrated pyridine 2.5 ml, and dehydrated dichloromethane 40 ml were added and stirred under a nitrogen gas stream. Dissolved. 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 the stirring was stopped, the reaction solution was washed with a 2% aqueous hydrochloric acid solution and washed with ion-exchanged water.
The obtained solution was dropped into 1.5 L of methanol to precipitate a yellow product, dried, and charged with a hydroxyl group-containing charge transporting polymer (heavy polymer) containing the polymer structural units shown in Table 1 below. Combined No. 5) was obtained.
The obtained polymer no. When the molecular weight of 5 was measured by gel permeation chromatography (GPC), the molecular weight in terms of polystyrene was 3,200 in terms of number average molecular weight. The structural units of the polymer and the results of elemental analysis are shown in Table 1.

(Production Example 6)
-Charge transporting polymer having a hydroxyl group: Polymer No. 6-
In a 200 ml four-necked flask equipped with a stirrer, thermometer, silica gel tube, and dropping funnel, N, N′-bis {3-methyl-4 [2- (4-hydroxy) phenethyl]} phenyl-4 4-methylbiphenyl-4′-amine (synthesized according to JP-A-2002-249472) 4.83 g (0.008 mol), 1,1-bis (4-hydroxyphenyl) cyclohexane 3.22 g (0.012 mol) Then, 2.5 ml of dehydrated pyridine and 40 ml of dehydrated dichloromethane 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, dried, and charged with a hydroxyl group-containing charge transporting polymer (polymer) containing the polymer structural units shown in Table 1 below. Combined No. 6) was obtained.
The obtained polymer no. When the molecular weight of 6 was measured by gel permeation chromatography (GPC), the molecular weight in terms of polystyrene was 3,000 in terms of number average molecular weight. Table 1 shows the structural units of the polymer and the results of elemental analysis.

Example 1
-Polymer No. Introduction of alkoxysilyl group into 1
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into No. 1 (polymer No. 1 for hybrid materials).
First, charge transporting polymer No. 1 having a hydroxyl group is used. 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.

(Example 2)
-Polymer No. Introduction of alkoxysilyl group into 2
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into No. 2 (polymer No. 2 for hybrid material).
First, charge transporting polymer No. 1 having a hydroxyl group is used. 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. As a result of measurement by GPC, the product had a number average molecular weight of 4,000.

(Example 3)
-Polymer No. Introduction of alkoxysilyl group into 3
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into 3 (polymer No. 3 for hybrid material).
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. As a result of measurement by GPC, the product had a number average molecular weight of 3,000.

Example 4
-Polymer No. Introduction of alkoxysilyl group into 4
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into 4 (polymer No. 4 for hybrid material).
First, charge transporting polymer No. 1 having a hydroxyl group is used. 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 5,100.

(Example 5)
-Polymer No. Introduction of alkoxysilyl group into 5
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into No. 5 (polymer No. 5 for hybrid material).
Charge transporting polymer No. having a hydroxyl group 5 (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. Further, as a result of measurement by GPC, the product had a number average molecular weight of 3,700.

(Example 6)
-Polymer No. Introduction of alkoxysilyl group into 6
Alkoxysilylation of the synthesized charge transporting polymer having a hydroxyl group was carried out as follows. An alkoxysilyl group was introduced into 6 (polymer No. 6 for hybrid material).
Charge transporting polymer No. having a hydroxyl group 6 (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 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 3,500.

  Next, the synthesized polymer for hybrid material No. 1-No. 6, each constituent layer was formed by the following procedure to prepare an electrophotographic photosensitive member.

(Example 7)
The surface of an aluminum (Al) support having an outer diameter of 30 mm is coated by the dipping method using the prepared coating liquid for the undercoat layer according to the following formulation so that the thickness after drying becomes 3.5 μm. An undercoat layer was formed.

<Coating liquid for undercoat layer>
・ Alkyd resin (Beckosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.) ... 6 parts ・ Melamine resin (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.) ... 4 parts ・ Titanium oxide (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.) ・ ・ ・ 40 parts ・ Methyl ethyl ketone ・ ・ ・ 50 parts

  Next, the support on which the undercoat layer has been formed is dip-coated using a charge generation layer coating solution prepared according to the following formulation, and then dried by heating to generate a 0.2 μm thick charge on the undercoat layer. A layer was formed.

<Coating liquid for charge generation layer>
-Bisazo pigment represented by the following structural formula (13): 2.5 parts
・ Polyvinyl butyral (XYHL, manufactured by UCC): 0.5 part ・ Cyclohexanone: 200 parts ・ Methyl ethyl ketone: 80 parts

  Next, a charge transport layer having a thickness of 22 μm was formed on the formed charge generation layer by dip coating using a charge transport layer coating solution prepared according to the following formulation, followed by heating and drying.

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

  Next, spray coating is performed on the charge transport layer using an organic-inorganic hybrid surface layer coating solution prepared according to the following formulation, and heat treatment is performed at 130 ° C. for 30 minutes to form a crosslinked surface layer having a thickness of 4.0 μm. To prepare an electrophotographic photosensitive member.

-Preparation of coating solution for organic-inorganic hybrid surface layer-
After dissolving 2.0 parts of the alkoxysilylated charge transporting polymer (hybrid material polymer No. 1) obtained in Example 1 in 20 parts of tetrahydrofuran, 0.10 parts of 1N hydrochloric acid water was added. The mixture was vigorously stirred at room temperature for 1 hour to prepare an organic-inorganic hybrid surface layer coating solution.

(Example 8)
In Example 7, the organic-inorganic hybrid surface layer coating liquid material (polymer No. 1 for hybrid material) was used as the polymer No. 1 for hybrid material obtained in Example 2. An electrophotographic photosensitive member was produced in the same procedure and configuration as in Example 7 except that the number was changed to 2. The thickness of the crosslinked surface layer was 4.0 μm.

Example 9
Instead of the organic-inorganic hybrid surface layer coating solution material (polymer No. 1 for hybrid material) used in Example 7, the polymer No. for hybrid material obtained in Example 3 was used. An electrophotographic photosensitive member was produced in the same procedure and configuration as in Example 7 except that No. 3 was used. The thickness of the crosslinked surface layer was 4.0 μm.

(Example 10)
In Example 7, the organic-inorganic hybrid surface layer coating solution material (hybrid material polymer No. 1) was mixed with the hybrid material polymer No. 1 obtained in Example 4. An electrophotographic photosensitive member was produced in the same procedure and configuration as in Example 7, except that the number was changed to 4. The thickness of the crosslinked surface layer was 4.0 μm.

(Example 11)
In Example 7, the organic-inorganic hybrid surface layer coating solution material (hybrid material polymer No. 1) was mixed with the hybrid material polymer No. 1 obtained in Example 5. An electrophotographic photosensitive member was produced in the same manner as in Example 7 except that it was changed to 5. The thickness of the crosslinked surface layer was 4.0 μm.

(Example 12)
In Example 7, the organic-inorganic hybrid surface layer coating solution material (hybrid material polymer No. 1) was mixed with the hybrid material polymer No. 1 obtained in Example 6. An electrophotographic photosensitive member was produced in the same manner as in Example 7 except that it was changed to 6. The thickness of the crosslinked surface layer was 4.0 μm.

(Comparative Example 1)
In Example 7, instead of the organic-inorganic hybrid surface layer coating liquid material (polymer No. 1 for hybrid material), the number average molecular weight of 80,000 synthesized with reference to the method described in Japanese Patent No. 3368415 In the same manner as in Example 7, except that a surface layer coating solution obtained by dissolving 5 parts of a charge transporting polymer (polymer having the same structural unit as in Production Example 1) in 100 parts of tetrahydrofuran was used. A photoconductor was prepared. The thickness of the surface layer was 4.0 μm.

(Comparative Example 2)
In Example 7, instead of the organic-inorganic hybrid surface layer coating liquid material (polymer No. 1 for hybrid material), the number average molecular weight of 90,000 synthesized with reference to the method described in Japanese Patent No. 3368415 In the same manner as in Example 7, except that a surface layer coating solution obtained by dissolving 5 parts of a charge transporting polymer (polymer having the same constitutional unit as in Production Example 3) in 100 parts of tetrahydrofuran was used. A photoreceptor was prepared. The thickness of the surface layer was 4.0 μm.

(Comparative Example 3)
In Example 7, instead of the organic-inorganic hybrid surface layer coating liquid material (polymer No. 1 for hybrid material), a solution having the following composition was used as a reference with reference to the method described in JP-A-2000-105474. An electrophotographic photosensitive member was produced in the same manner as in Example 7 except that it was used as a layer coating solution. The thickness of the crosslinked surface layer was 4.0 μm.
[Solution composition]
・ Polycarbonate (Z300, manufactured by Mitsubishi Gas Chemical Co., Ltd.) ... 6.6g
-Charge transport compound represented by the following structural formula: 4.2 g
・ Tetraethoxysilane 0.33g
・ Dichloromethane ... 30g

<Evaluation>
About each produced electrophotographic photosensitive member, using an imgio MF2200 remodeling machine manufactured by Ricoh Co., Ltd. (using a 655 nm semiconductor laser as an image exposure light source), 150,000 sheets were passed through an actual machine (A4 size, manufactured by NBS Ricoh, (MyPaper, charging potential at start: −700 V) was performed, and the amount of wear, the in-machine potential, and the image characteristics (image density, streak image) were evaluated. The results are shown in Table 2, Table 3, and Table 4. The in-machine potential represents the surface potential (dark portion potential) of the photosensitive member before exposure and the surface potential (light portion potential) of the photosensitive member after exposure.
In image evaluation, image density and streak image evaluation criteria are as follows.
[Evaluation criteria for image density]
○: Good, Δ: Slightly decreased image density, ×: Low image density [Evaluation criteria for streak images]
○: Good, Δ: Locally generated, ×: Generated on the entire image

From the results of Table 2, Table 3, and Table 4, as shown in Examples 7 to 12, by using the organic-inorganic hybrid material composed of the structural unit having the charge transport function of the present invention, 150,000 actual machines Even after the paper was passed, all of the wear amount, the in-machine potential, and the image characteristics showed good values, and high-density and high-quality images were stably obtained throughout.
On the other hand, since Comparative Example 1 did not contain an inorganic component, the amount of wear was large, and the surface layer disappeared by 50,000 sheets, making subsequent evaluation impossible. Since Comparative Example 2 also did not contain an inorganic component, the amount of wear was large, and the surface layer disappeared by 100,000 sheets, making subsequent evaluation impossible. Further, Comparative Example 3 is a crosslinked film formed by simply mixing a low molecular charge transport material having no reactivity into polycarbonate, and therefore, as in Comparative Examples 1 and 2, the wear amount is large and low molecular weight. There was also a reduction in image density due to the deposition of charge transport material. By 50,000 sheets, the potential of the exposed area became so large that subsequent evaluation became impossible.
From the above results, by using the surface layer formed of the organic-inorganic hybrid material composed of the structural unit having the charge transport function of the present invention, it is excellent in scratch resistance and abrasion resistance, and good image formation can be maintained for a long time. It has been found that a long-life and high-performance photoconductor can be provided. In addition, it has been found that the image forming process, the image forming apparatus, and the process cartridge for the image forming apparatus using the photoconductor of the present invention have a high durability level, high quality, and high reliability.

  The electrophotographic photosensitive member using the organic-inorganic hybrid material of the present invention is not only used in an electrophotographic copying machine, but also in electrophotographic application fields such as a laser beam printer, a CRT printer, an LED printer, a liquid crystal printer, and a laser plate making. Can also be used widely.

FIG. 1A is a schematic cross-sectional view showing an example of a layer structure of an electrophotographic photoreceptor having a single layer structure of the present invention. FIG. 1B is a schematic cross-sectional view showing another example of the layer structure of the electrophotographic photoreceptor having a single layer structure of the present invention. FIG. 2A is a schematic cross-sectional view showing an example of a layer structure of an electrophotographic photosensitive member having a laminated structure according to the present invention. FIG. 2B is a schematic cross-sectional view showing another example of the layer structure of the electrophotographic photosensitive member having the laminated structure of the present invention. FIG. 3 is a schematic diagram illustrating a configuration example of the image forming apparatus according to the present invention. FIG. 4 is a schematic diagram illustrating a configuration example of a process cartridge that is detachable from the image forming apparatus according to the present invention. FIG. 5 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 6 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 7 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention (tandem color image forming apparatus). FIG. 8 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG. FIG. 9 is an infrared absorption spectrum diagram of the polymer of Production Example 1. 10 is a ¹ H-NMR spectrum of the polymer of Example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support body 2 Photosensitive layer 3 Layer which has a charge generation function and a charge transport function 3 'Layer which has a charge generation function and a charge transport function 4 Surface layer (organic-inorganic hybrid material)
5 Photosensitive layer 6 Charge generation layer 7 Charge transport layer 7 'Charge transport layer 8 Surface layer (organic-inorganic hybrid material)
10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 discharger 70 discharger lamp 80 transfer roller 90 cleaning device 95 transfer paper 100 image forming apparatus 101 photoconductor 102 charging means 103 exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developer 121 Heating roller 122 Fixing roller 123 Fixing belt 124 Pressure roller 125 Heating source 126 Clear Ninging roller 127 Temperature sensor 130 Document table 142 Paper feeding roller 143 Paper bank 144 Paper feeding cassette 145 Separating roller 146 Paper feeding path 147 Conveying roller 148 Paper feeding path 150 Copier main body 200 Paper feeding table 210 Transfer charger 211 Separating charger 212 Separating claw 213 Charger before cleaning 214 Fur brush 215 Cleaning blade 231 Photoconductor 232 Static elimination lamp 233 Charge charger 234 Eraser 235 Image exposure unit 236 Development unit 237 Pre-transfer charger 238 Registration roller 239 Transfer paper 241 Photosensitive drum 242 Charging device 243 Exposure 244 Development device 245 Transfer body 246 Transfer device 247 Cleaning blade 300 Scanner 400 Automatic document feeder (ADF)

Claims (25)

  An organic-inorganic hybrid material, wherein a polymer organic component having a charge transport function and a metal alkoxide compound are bonded together and integrated. The organic-inorganic hybrid material according to claim 1, wherein the polymer organic component contains a structural unit represented by the following structural formula (I).
However, in the structural formula (I), R ¹ represents any ^one of a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Ar ¹ represents an aryl group which may have a substituent. Ar ² and Ar ³ may be the same as or different from each other, and represent an arylene group that may have a substituent. The organic-inorganic hybrid material according to claim 2, wherein the structural unit represented by the structural formula (I) is a structural unit represented by the following structural formula (II).
However, in the structural formula (II), Ar ² , Ar ³ , and Ar ⁴ may be the same as or different from each other and represent an arylene group that may have a substituent. R ¹⁷ and R ¹⁸ may be the same as or different from each other, and each may have an acyl group that may have a substituent, an alkyl group that may have a substituent, and a substituent. It represents any of the aryl groups that may have. The organic-inorganic hybrid material according to claim 2, wherein the structural unit represented by the structural formula (I) is a structural unit represented by the following structural formula (III).
However, in the structural formula (III), R ¹⁷ and R ¹⁸ represent the same meaning as described above. The organic-inorganic hybrid material according to claim 1, wherein the polymer organic component contains a structural unit represented by the following structural formula (IV).
However, in the structural formula (IV), Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ may be the same as or different from each other, and may represent an arylene group which may have a substituent. To express. Ar ⁷ represents an aryl group which may have a substituent. Z represents an arylene group and —Ar ¹⁰ —Za—Ar ¹⁰ — (wherein Ar ¹⁰ represents an arylene group which may have a substituent. Za represents any of O, S, and an alkylene group. Represents one of the following. R and R ′ may be the same as or different from each other, and each represents a linear or branched alkylene group. n represents 0 or 1. The organic-inorganic hybrid material according to claim 5, wherein the structural unit represented by the structural formula (IV) is a structural unit represented by the following structural formula (V).
However, in the structural formula (V), Ra, Rb, Rc and Rd may be the same as or different from each other and represent an alkyl group which may have a substituent. Ar ⁷ , Z, R, R ′ and n represent the same meaning as described above. The organic-inorganic hybrid material according to any one of claims 1 to 6, wherein the polymer organic component further contains a structural unit represented by the following structural formula (VI).
In the structural formula (VI), X represents an aliphatic divalent group, a cycloaliphatic divalent group, an aromatic divalent group, a divalent group formed by linking these, and the following structural formula (VI -1) and the following structural formula (VI-2).
However, in the structural formulas (VI-1) and (VI-2), R ² , R ³ , R ⁴ , and R ⁵ may be the same as or different from each other, an alkyl group, Represents 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 an integer of 0 to 3. Y represents a single bond, a linear alkylene group having 2 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —, —CO—, and the following structural formula (VI-3) to It represents one selected from (VI-11).
In Structural Formula, Z ₁ and Z ₂ each represents any one of divalent groups, and arylene groups aliphatic.
However, in the structural formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may be the same as or different from each other, a hydrogen atom, a halogen atom Represents 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 . R ¹³ and R ¹⁴ may be the same as or different from each other, and each represents a single bond or an alkylene group having 1 to 4 carbon atoms. R ¹⁵ and R ¹⁶ may be the same as or different from each other, and each represents an alkyl group having 1 to 5 carbon atoms or an aryl group. e represents an integer of 0 to 4, f represents an integer of 0 to 20, and g represents an integer of 0 to 2000.   The composition ratio of the structural unit represented by Structural Formula (VI) is represented by k, where k is the composition ratio of the structural unit represented by Structural Formula (I), (II), (III), (IV), or (V). The organic-inorganic hybrid material according to claim 7, wherein a ratio of j satisfies the following formula: 0 <k / (k + j) ≦ 1.   The organic-inorganic hybrid material according to claim 1, wherein the polymer organic component has a number average molecular weight of 400 to 40,000. The organic-inorganic hybrid material according to any one of claims 1 to 9, wherein the metal alkoxide compound is represented by the following structural formula (VII).
_{^{R 19 p A m M (R}} "X ') n ··· structural formula (VII)
In the Structural Formula ^{(VII), R 19} represents an alkyl group having 1 to 5 carbon atoms. A represents a C1-C4 alkoxy group. M represents any of Si, Ti, and Zr. R ″ represents any one of an alkylene group having 2 to 4 carbon atoms and an alkylidene group. X ′ represents any one selected from an isocyanate group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. P represents an integer of 0 to 3. m and n each represents an integer of 1 to 3.   The organic-inorganic hybrid material according to claim 10, wherein M is Si. A polymer having a structural unit represented by the following structural formula (I) is reacted with a metal alkoxide compound represented by the following structural formula (VII), and the polymer has a metal alkoxide group. A polymer for hybrid materials.
However, in the structural formula (I), R ¹ represents any ^one of a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Ar ¹ represents an aryl group which may have a substituent. Ar ² and Ar ³ may be the same as or different from each other, and represent an arylene group that may have a substituent.
_{^{R 19 p A m M (R}} "X ') n ··· structural formula (VII)
In the Structural Formula ^{(VII), R 19} represents an alkyl group having 1 to 5 carbon atoms. A represents a C1-C4 alkoxy group. M represents any of Si, Ti, and Zr. R ″ represents any one of an alkylene group having 2 to 4 carbon atoms and an alkylidene group. X ′ represents any one selected from an isocyanate group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. P represents an integer of 0 to 3. m and n each represents an integer of 1 to 3. The polymer for hybrid materials according to claim 12, which has a molecular structure represented by the following structural formula (VIII).
In Structural Formula (VIII), Ar ¹ , Ar ² , Ar ³ , R ¹ , R ″, M, A, R ¹⁹ , p and m represent the same meaning as described above. E represents —NH—. Or -O-, L represents the number of repeating units in parentheses. The polymer for hybrid materials according to claim 12, which has a molecular structure represented by the following structural formula (IX).
In Structural Formula (IX), Ar ¹ , Ar ² , Ar ³ , R ¹ , R ″, M, A, R ¹⁹ , p and m have the same meaning as described above. E represents —NH—. Or -O-, L represents the number of repeating units in parentheses. A polymer having a structural unit represented by the following structural formula (IV) is reacted with a metal alkoxide compound represented by the following structural formula (VII), and the polymer has a metal alkoxide group. A polymer for hybrid materials.
However, in the structural formula (IV), Ar ⁵ , Ar ⁶ , Ar ⁸ and Ar ⁹ may be the same as or different from each other, and may represent an arylene group which may have a substituent. To express. Ar ⁷ represents an aryl group which may have a substituent. Z represents an arylene group and —Ar ¹⁰ —Za—Ar ¹⁰ — (wherein Ar ¹⁰ represents an arylene group which may have a substituent. Za represents any of O, S, and an alkylene group. Represents one of the following. R and R ′ may be the same as or different from each other, and each represents a linear or branched alkylene group. n represents 0 or 1.
_{^{R 19 p A m M (R}} "X ') n ··· structural formula (VII)
In the Structural Formula ^{(VII), R 19} represents an alkyl group having 1 to 5 carbon atoms. A represents a C1-C4 alkoxy group. M represents any of Si, Ti, and Zr. R ″ represents any one of an alkylene group having 2 to 4 carbon atoms and an alkylidene group. X ′ represents any one selected from an isocyanate group, an epoxy group, a carboxyl group, an acid halogen group, and an acid anhydride group. P represents an integer of 0 to 3. m and n each represents an integer of 1 to 3. The polymer for hybrid materials according to claim 15, which has a molecular structure represented by the following structural formula (X).

In Structural Formula (X), R ¹⁹ , A, M, R ″, Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , n, and p represent the same meaning as described above. , -NH-, or -O-, L represents the number of repeating units in parentheses. The polymer for hybrid materials according to claim 15, which has a molecular structure represented by the following structural formula (XI).
However, in the structural formula (XI), R ¹⁹ , A, M, R ″, Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Z, X, n, and p have the same meaning as described above. E represents —NH— or —O—, and L represents the number of repeating units in parentheses.   The polymer for hybrid materials according to any one of claims 12 to 17, wherein M is Si.   A method for producing an organic-inorganic hybrid material, wherein the metal alkoxide group in the polymer for hybrid materials according to any one of claims 12 to 18 is hydrolyzed or polycondensed.   An electrophotographic photoreceptor, wherein the surface layer contains the organic-inorganic hybrid material according to claim 1.   21. The electrophotographic photosensitive member according to claim 20, wherein the electrophotographic photosensitive member has a laminated structure having a support and at least a charge generation layer, a charge transport layer, and a surface layer in this order on the support.   A layer containing the polymer for a hybrid material according to any one of claims 12 to 18 is provided on a support, and then the polymer for a hybrid material is hydrolyzed or polycondensed to contain an organic-inorganic hybrid material. A method for producing an electrophotographic photosensitive member, comprising at least a surface layer forming step of forming a surface layer to be formed.   An image forming apparatus comprising: the electrophotographic photosensitive member according to any one of claims 20 to 21; 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 which is detachable from the main body.   An electrophotographic photosensitive member according to any one of claims 20 to 21, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrophotographic photosensitive member, and developing the electrostatic latent image using toner. And at least developing means for forming a visible image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. apparatus. An electrostatic latent image forming step of forming an electrostatic latent image on the electrophotographic photosensitive member according to any one of claims 20 to 21, and developing the electrostatic latent image with toner to form a visible image An image forming method comprising: a developing step for transferring; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium.