JP2002244327A - Electrophotographic photoreceptor, method for manufacturing electrophotographic photoreceptor, image forming method, image forming device and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high durability in which the wear resistance characteristics against friction with a cleaning blade or the like and the electrophotographic characteristics (characteristics of electrification, sensitivity, residual potential or the like) for repeated use are improved, and to provide a method for manufacturing the electrophotographic photoreceptor, an image forming method which uses the electrophotographic photoreceptor, an image forming device and a process cartridge. SOLUTION: In the electrophotographic photoreceptor having a resin layer formed on a conductive supporting body, the resin layer contains a block copolymer of a phenoxy resin and a siloxane condensation product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, a method of manufacturing an electrophotographic photosensitive member, an image forming method using the electrophotographic photosensitive member, an image forming apparatus, and a process cartridge.

[0002]

2. Description of the Related Art In recent years, as an electrophotographic photosensitive member (hereinafter, also simply referred to as a photosensitive member), an organic electrophotographic photosensitive member containing an organic photoconductive material (hereinafter, also referred to as an organic photosensitive member) is most widely used. Organic photoreceptors are advantageous over other photoreceptors in that they are easy to develop materials for various exposure light sources from visible light to infrared light, that they can select materials that do not pollute the environment, and that they have low manufacturing costs. However, the drawback is that the mechanical strength is weak, and the photoreceptor surface is likely to be degraded or damaged during copying or printing a large number of sheets.

In order to satisfy the above-mentioned various required characteristics, various studies have been made so far.

[0004] As a problem for improving the durability of the organic photoreceptor as described above, there has been a strong demand for suppressing the abrasion of a cleaning blade or the like due to abrasion. As an approach therefor, techniques such as providing a high-strength protective layer on the surface of the photoreceptor have been studied. For example, JP-A-6
JP-A-118681 reports that a colloidal silica-containing curable siloxane resin is used as a surface layer of a photoreceptor. However, a siloxane bond (Si-O-
In a protective layer made of only silica formed by repeating three-dimensionally (Si bond), cracks (cracks) are generated on the surface, adhesion to the photosensitive layer is deteriorated, and electrostatic characteristics of the photosensitive layer are reduced. Was a problem.

As an attempt to improve abrasion resistance and adhesion to a photosensitive layer, an organic-inorganic hybrid polymer having both properties of an organic polymer and a crosslinked siloxane component has been proposed. For example, JP-A-2000-22172
No. 3 discloses a protective layer containing a polymer in which polysiloxane and a silyl group-containing vinyl resin are chemically bonded as a protective layer of an electrophotographic photosensitive member. However, the photoreceptor having such a protective layer has improved mechanical abrasion resistance, but has insufficient electrophotographic properties upon repeated use, and is liable to cause fogging and image blur. A photoreceptor having a layer was not suitable as the most widely used electrophotographic photoreceptor such as the Carlson process.

Therefore, as a protective layer of an electrophotographic photoreceptor which simultaneously satisfies mechanical abrasion resistance and electrophotographic characteristics during repeated use, the present researchers have a charge transporting performance imparting group,
In addition, a siloxane-based resin layer having a crosslinked structure has been proposed as a protective layer of a photoreceptor (Japanese Patent Application No. 11-70308).
issue). The photoreceptor having this protective layer has improved friction resistance and electrophotographic characteristics (charge, sensitivity, residual potential characteristics, etc.) upon repeated use, which have been important issues in the past, and is a highly durable organic electrophotographic photoreceptor. Has sufficient practicality.
However, this protective layer also forms a high-order crosslinked resin specific to a siloxane-based resin, so that the protective layer becomes a protective layer having a strong elasticity. When a cleaning device using blade cleaning is used, the photosensitive member and the cleaning blade In many cases, problems such as an increase in the torque between the toners and a decrease in toner cleaning performance and stability of the cleaning blade against turning are likely to occur. Further, a problem that the resolution of an image is significantly reduced in a high-humidity environment as compared with a conventional organic photoreceptor has been clarified.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been developed in consideration of the abrasion resistance against rubbing with a cleaning blade and the like, and the electrophotographic characteristics (charging, sensitivity, residual potential) when repeatedly used. To provide a highly durable electrophotographic photoreceptor having improved properties and the like, and to provide a photoreceptor having a protective layer excellent in toner cleaning performance and stability against turning of a cleaning blade. An object of the present invention is to provide a photoreceptor having a protective layer capable of obtaining a clear image even in an environment, and a method for producing the electrophotographic photoreceptor, an image forming method using the electrophotographic photoreceptor, and an image forming method. An object of the present invention is to provide a forming apparatus and a process cartridge.

[0008]

That is, the object of the present invention is achieved by the following constitutions.

1. An electrophotographic photoreceptor comprising a resin layer provided on a conductive support, wherein the resin layer contains a block copolymer of a phenoxy resin and a siloxane condensate.

[0010] 2. An electrophotographic photoreceptor comprising a resin layer provided on a conductive support, wherein the resin layer is a block copolymer of a phenoxy resin and a siloxane condensate, and has a resin structure in which the entire resin layer is crosslinked. Electrophotographic photoreceptor.

3. The resin layer is formed by reacting at least one selected from an organosilicon compound represented by the following general formula (1), a hydrolyzate of the organosilicon compound, and a condensate of the organosilicon compound with a phenoxy resin. 3. The electrophotographic photosensitive member according to the above 1 or 2, wherein

Formula (1) R _n Si (Z) _4-n (wherein, R represents an organic group in which carbon is directly bonded to silicon in the formula, and Z represents a hydroxyl group or a hydrolyzable group. 3. n is an integer of 0 to 3.) 4. The electrophotographic photoconductor according to the item 3, wherein an organic silicon compound having at least n = 0 is used as the organic silicon compound.

5. 5. The electrophotographic photoreceptor according to any one of items 1 to 4, wherein the phenoxy resin is represented by the general formula (A).

6. 6. The electrophotographic photosensitive member according to any one of the above items 1 to 5, wherein the resin layer has a charge transporting group as a partial structure.

[0015] 7. Wherein the siloxane condensate has a charge transporting group as a partial structure.
8. The electrophotographic photosensitive member according to any one of the above.

8. 8. The electrophotographic photoreceptor according to the above item 6 or 7, wherein the partial structure of the charge transporting group is formed by a reaction between an organosilicon compound and a reactive charge transporting compound.

9. 9. The electrophotographic photoreceptor as described in 8 above, wherein the reactive charge transporting compound has a molecular weight of 100 to 700.

10. The electrophotographic photoreceptor according to the above item 9, wherein the reactive charge transporting compound has a molecular weight of 100 to 450.

11. The electrophotographic photoreceptor according to any one of Items 1 to 10, wherein the resin layer contains an antioxidant.

[12] Any one of the above items 1 to 11, wherein the resin layer contains a metal chelate compound
13. The electrophotographic photoreceptor according to item 6.

13. 13. The electrophotographic photoreceptor as described in 12 above, wherein the content of the metal chelate compound is 0.01 to 20% by mass based on the total solid mass of the resin layer.

14. (12) or (13), wherein the metal chelate compound is an aluminum chelate.
2. The electrophotographic photoreceptor of claim 1.

[15] 14. The electrophotographic photoreceptor as described in 12 or 13, wherein the metal chelate compound is a titanium chelate.

16. The electrophotographic photoreceptor according to any one of Items 1 to 15, wherein the resin layer is a surface layer.

17. In an electrophotographic photoreceptor having a resin layer provided on a conductive support, the resin layer comprises an organosilicon compound represented by the general formula (1), a hydrolyzate of the organosilicon compound, and an organic silicon compound. A method for producing an electrophotographic photoreceptor, comprising applying a coating solution containing at least one selected from condensates and a phenoxy resin, followed by curing.

18. 18. The method for producing an electrophotographic photosensitive member according to the above 17, wherein the phenoxy resin is represented by the general formula (A).

19. 19. The method for producing an electrophotographic photosensitive member according to the above item 17 or 18, wherein the coating solution contains a reactive charge transporting compound.

20. 20. The method for producing an electrophotographic photoreceptor as described in 19 above, wherein the reactive charge transporting compound has a hydroxyl group as a reactive group.

21. The above 19, wherein the reactive charge transporting compound has a silyl group as a reactive group.
3. The method for producing an electrophotographic photoreceptor according to item 1.

22. 19. The method according to the above 19, wherein the reactive charge transporting compound has a plurality of reactive groups in a molecule.
22. The method for producing an electrophotographic photosensitive member according to any one of items 21 to 21.

23. Wherein the reactive charge transporting compound has a molecular weight of 100 to 700.
23. The method for producing an electrophotographic photosensitive member according to any one of 22.

24. The method for producing an electrophotographic photoreceptor according to the above item 23, wherein the reactive charge transporting compound has a molecular weight of 100 to 450.

25. 25. The method for producing an electrophotographic photosensitive member according to any one of 17 to 24, wherein the coating solution contains a metal chelate compound.

26. The method for producing an electrophotographic photoreceptor according to the above item 25, wherein the content of the metal chelate compound is 0.01 to 20% by mass relative to the total solid content of the coating solution.

27. Wherein the metal chelate compound is an aluminum chelate.
3. The method for producing an electrophotographic photoreceptor according to item 1.

28. 27. The method for producing an electrophotographic photosensitive member according to the above item 25 or 26, wherein the metal chelate compound is a titanium chelate.

29. 17. An image forming method, wherein an image is formed by using the electrophotographic photosensitive member according to any one of the items 1 to 16 through at least a charging step, an image exposing step, a developing step, and a cleaning step.

30. 17. An image forming apparatus, wherein an image is formed by using the electrophotographic photosensitive member according to any one of 1 to 16 through at least a charging unit, an image exposing unit, a developing unit, and a cleaning unit.

31. 31. The process cartridge used in the image forming apparatus according to 30 above, wherein
The electrophotographic photoreceptor according to any one of the above, and any one of a charging unit, an image exposing unit, a developing unit, and a cleaning unit are integrally combined, and are configured to be able to be taken in and out of the image forming apparatus. A process cartridge comprising:

Hereinafter, the present invention will be described in detail. The resin layer of the present invention is a layer formed by using a resin on a conductive support, and does not directly relate to the function of the resin layer.

In the present invention, the phenoxy resin is a polymer in which β-hydroxypropyl ether of bisphenols is a repeating unit.

The phenoxy resin used in the present invention is preferably a phenoxy resin represented by the general formula (A). Among these, specific compound examples are shown below, but the present invention is not limited to these compound examples.

[0043]

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[0044]

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The phenoxy resin of the present invention may be a one-component phenoxy resin or a multi-component phenoxy resin. Further, a plurality of phenoxy resins may be mixed and used.

Furthermore, the phenoxy resin before polycondensation with the siloxane condensate has a number molecular weight of 2,000 to 30,000.
Is preferable, and 2,000 to 20,000 is most preferable. When the molecular weight is less than 2,000, film properties such as abrasion resistance of the resin layer after the polycondensation are likely to be insufficient, and 3
When it is larger than 000, it is difficult to sufficiently achieve the smoothness of the resin layer.

In the present invention, the resin layer forms a block copolymer of a phenoxy resin and a siloxane condensate by reacting a hydroxyl group of the phenoxy resin with a hydrolysis product of an organosilicon compound or a siloxane condensate. By further promoting the reaction of the copolymer, a resin structure in which the entire resin layer is crosslinked is formed. In forming the block copolymer, the presence of a reactive charge transporting compound forms a charge transporting group in a part (partial structure) of the resin structure, has a crosslinked structure, and has a charge transporting property. A resin layer having a structure can be formed, and a resin layer having both mechanical strength such as abrasion resistance and electrophotographic characteristics can be obtained.

Here, the block copolymer is defined by a generally known concept, that is, a copolymer composed of a phenoxy resin and a siloxane condensate each bonded to a certain degree in a homopolymer state. It is.

Here, the reaction of the present invention means a chemical reaction such as a condensation reaction, a polycondensation reaction or a cross-linking reaction, and as a result, a reaction for forming a chemical bond such as a covalent bond, an ionic bond or a hydrogen bond. .

That is, the resin layer of the present invention forms a silane-modified phenoxy resin by reacting a hydroxyl group of the phenoxy resin with an organosilicon compound of the following general formula (1), a hydrolysis product of the organosilicon compound, or a siloxane condensate. Is formed, followed by the reaction between the silane-modified phenoxy resin and the organosilicon compound, forming a block copolymer of the phenoxy resin and the siloxane condensate, and further promoting the reaction between the block copolymers. In addition, a resin layer having strong abrasion resistance and the like formed by bonding the entire resin layer in a cross-linked structure is formed.
Here, the siloxane condensate is a siloxane bond (Si-
(O-Si bond) three-dimensionally repeated.

Formula (1) R _n Si (Z) _4-n (wherein, R represents an organic group in which carbon is directly bonded to silicon in the formula, and Z represents a hydroxyl group or a hydrolyzable group. N in the general formula (1) is a hydrolyzable group, and is a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, or a butoxy group. Methoxyethoxy group, halogen atom and the like. Examples of the organic group in which carbon is directly bonded to silicon represented by R include alkyl groups such as methyl, ethyl, propyl and butyl, aryl groups such as phenyl, tolyl, naphthyl and biphenyl, γ-glycidoxypropyl, β An epoxy-containing group such as-(3,4-epoxycyclohexyl) ethyl, a (meth) acryloyl group of γ-acryloxypropyl and γ-methacryloxypropyl,
hydrous groups such as γ-hydroxypropyl and 2,3-dihydroxypropyloxypropyl, vinyl groups such as vinyl and propenyl, mercapto groups such as γ-mercaptopropyl, γ-aminopropyl, N-β (aminoethyl)-
Examples include amino-containing groups such as γ-aminopropyl, halogen-containing groups such as γ-chloropropyl, 1,1,1-trifluoropropyl, nonafluorohexyl, and perfluorooctylethyl, and other nitro and cyano-substituted alkyl groups. be able to. When _n of R _n is 2 or 3, the plurality of organic groups bonded to the same silicon atom may be the same as each other;
It may be different.

When two or more organosilicon compounds represented by the above general formula (1) are used in producing the siloxane condensate component of the present invention, R of each organosilicon compound may be the same or different. You may.

Specific examples of the organosilicon compound represented by the general formula (1) include the following compounds.

That is, examples of compounds in which n is 0 include tetrachlorosilane, diethoxydichlorosilane, tetramethoxysilane, phenoxytrichlorosilane, tetraacetoxysilane, tetraethoxysilane, tetraallyloxysilane, tetrapropoxysilane, and tetraisopropoxy. Silane, tetrakis (2-methoxyethoxy) silane, tetrabutoxysilane, tetraphenoxysilane,
Examples include tetrakis (2-ethylbutoxy) silane and tetrakis (2-ethylhexyloxy) silane.

Examples of the compound wherein n is 1 include trichlorosilane, chloromethyltrichlorosilane, methyltrichlorosilane, 1,2-dibromoethyltrichlorosilane,
Vinyltrichlorosilane, 1,2-dichloroethyltrichlorosilane, 1-chloroethyltrichlorosilane, 2
-Chloroethyltrichlorosilane, ethyltrichlorosilane, 3,3,3-trifluoropropyltrichlorosilane, 2-cyanoethyltrichlorosilane, allyltrichlorosilane, 3-bromopropyltrichlorosilane,
Chloromethyltrimethoxysilane, 3-chloropropyltrichlorosilane, n-propyltrichlorosilane, ethoxymethyldichlorosilane, dimethoxymethylchlorosilane, trimethoxysilane, 3-cyanopropyltrichlorosilane, n-butyltrichlorosilane, isobutyltrichlorosilane, chloro Methyltriethoxysilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, pentyltrichlorosilane, trimethoxyvinylsilane, ethyltrimethoxysilane, 3,
3,4,4,5,5,6,6,6-nonafluorohexyltrichlorosilane, 4-chlorophenylchlorosilane, phenyltrichlorosilane, cyclohexyltrichlorosilane, hexyltrichlorosilane, tris (2-
Chloroethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, 2-cyanoethyltrimethoxysilane, triethoxychlorosilane, 3-chloropropyltrimethoxysilane, triethoxysilane, 3-
Mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, benzyltrichlorosilane,
p-tolyltrichlorosilane, 6-trichlorosilyl-
2-norbornene, 2-trichlorosilyl norbornene, methyltriacetoxysilane, heptyltrichlorosilane, chloromethyltriethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, methyltris (2-aminoethoxy) silane, β-phenethyltrichlorosilane, Triacetoxyvinylsilane, 2-
(4-cyclohexylethyl) trichlorosilane, ethyltriacetoxysilane, 3-trifluoroacetoxypropyltrimethoxysilane, octyltrichlorosilane, triethoxyvinylsilane, ethyltriethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane , Chloromethylphenylethyltrichlorosilane, 2-phenylpropyltrichlorosilane, 4-
Chlorophenyltrimethoxysilane, phenyltrimethoxysilane, nonyltrichlorosilane, 2-cyanoethyltriethoxysilane, allyltriethoxysilane, 3
-Allylthiopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, propyltriethoxysilane, hexyltri Methoxysilane, 3-aminopropyltriethoxysilane, methyltriisopropenoxysilane, 3-methacryloxypropyltrimethoxysilane, decyltrichlorosilane, bis (ethylmethylketoxime) methoxymethylsilane, 3-morpholinopropyltrimethoxysilane , 3-piperazinopropyltrimethoxysilane, methyltripropoxysilane, methyltris (2-methoxyethoxysilane), 2- (2-aminoethylthioethyl) triethoxysilane 3- [2- (2-aminoethyl-aminoethyl amino) propyl] triethoxysilane, tris (1-methylvinyloxy) vinylsilane, 2
-(3,4-epoxycyclohexylethyl) trimethoxysilane, triisopropoxyvinylsilane, tris (2-methoxyethoxy) vinylsilane, diisopropoxyethylmethylketoximemethylsilane, 3-piperidinopropyltrimethoxysilane, pentyltri Ethoxysilane, 4-chlorophenyltriethoxysilane,
Phenyltriethoxysilane, bis (ethylmethylketoxime) methylisopropoxysilane, bis (ethylmethylketoxime) -2-methoxyethoxymethylsilane, 3- (2-methylpiperidinopropyl) trimethoxysilane, 3-cyclohexyl Aminopropyltrimethoxysilane, O, O'-diethyl-S- (2-triethoxysilylethyl) dithiophosphate, benzyltriethoxysilane, 6-triethoxysilyl-2-norbornene, 3-benzylaminopropyltrimethoxysilane , Methyltris (ethylmethylketoxime) silane, bis (ethylmethylketoxime) butoxymethylsilane, methyltris (N, N-diethylaminoxy) silane, tetradecyltrichlorosilane, octyltriethoxysilane, Phenyltris (2-methoxyethoxy) silane, 3- (vinylbenzylaminopropyl) trimethoxysilane, N- (3-triethoxysilylpropyl) -p-nitrobenzamide, 3- (vinylbenzylaminopropyl) triethoxysilane, Examples include octadecyltrichlorosilane, dodecyltriethoxysilane, docosyltrichlorosilane, octadecyltriethoxysilane, dimethyloctadecyl-3-trimethoxylsilylpropylammonium chloride, and 1,2-bis (methyldichlorosilyl) ethane.

Examples of compounds in which n is 2 include chloromethylmethyldichlorosilane, dimethyldichlorosilane, ethyldichlorosilane, methylvinyldichlorosilane, ethylmethyldichlorosilane, dimethoxymethylsilane, dimethoxydimethylsilane, divinyldichlorosilane, methyl- 3,3,3-trifluoropropyldichlorosilane, allylmethyldichlorosilane, 3-chloropropylmethyldichlorosilane, diethyldichlorosilane, methylpropyldichlorosilane, diethoxysilane, 3-cyanopropylmethyldichlorosilane, butylmethyldichlorosilane , Bis (2-chloroethoxy) methylsilane, diethoxymethylsilane, phenyldichlorosilane, diallyldichlorosilane, dimethoxymethyl-3,
3,3-trifluoropropylsilane, methylpentyldichlorosilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxysilane, diethoxydimethylsilane, dimethoxy-3-mercaptopropylmethylsilane, 3,3,4,4 5,5,6,6,6-nonafluorohexylmethyldichlorosilane, methylphenyldichlorosilane, diacetoxymethylvinylsilane, cyclohexylmethyldichlorosilane, hexylmethyldichlorosilane, diethoxymethylvinylsilane,
Hexylmethyldichlorosilane, diethoxymethylvinylsilane, phenylvinyldichlorosilane, 6-methyldichlorosilyl-2-norbornene, 2-methyldichlorosilylnorbornene, 3-methacryloxypropylmethyldichlorosilane, diethoxydivinylsilane, heptylmethyldichlorosilane , Dibutyldichlorosilane,
Diethoxydiethylsilane, dimethyldipropoxysilane, 3-aminopropyldiethoxymethylsilane, 3-
(2-aminoethylaminopropyl) dimethoxymethylsilane, allylphenyldichlorosilane, 3-chloropropylphenyldichlorosilane, methyl-β-phenethyldichlorosilane, dimethoxymethylphenylsilane,
2- (4-cyclohexenylethyl) methyldichlorosilane, methyloctyldichlorosilane, diethoxyethylmethylketoximemethylsilane, 2- (2-aminoethylthioethyl) diethoxymethylsilane, O, O '
-Diethyl-S- (2-trimethylsilylethyl) dithiophosphate, O, O'-diethyl-S- (2-trimethoxysilylethyl) dithiophosphate, t-
Butylphenyldichlorosilane, 3-methacryloxypropyldimethoxymethylsilane, 3- (3-cyanopropylthiopropyl) dimethoxymethylsilane, 3- (2
-Acetoxyethylthiopropyl) dimethoxymethylsilane, dimethoxymethyl-2-piperidinoethylsilane, dimethoxymethyl-3-piperazinopropylsilane, dibutoxydimethylsilane, dimethoxy-3- (2
-Ethoxyethylthiopropyl) methylsilane, 3-dimethylaminopropyldiethoxymethylsilane, diethyl-2-trimethylsilylmethylthioethylphosphite, diethoxymethylphenylsilane, decylmethyldichlorosilane, bis (ethylmethylketoxime) ethoxymethylsilane, Diethoxy-3-glycidoxypropylmethylsilane, 3- (3-acetoxypropylthio) propyldimethoxymethylsilane, dimethoxymethyl-3-piperidinopropylsilane, dipropoxyethylmethylketoximemethylsilane, diphenyldichlorosilane, diphenyl Difluorosilane, diphenylsilanediol, dihexyldichlorosilane, bis (ethylmethylketoxime) methylpropoxysilane, dimethoxymethyl-3 (4-piperidino-propyl)
Silane, dodecylmethyldichlorosilane, dimethoxydiphenylsilane, dimethoxyphenyl-2-piperidinoethoxysilane, dimethoxymethyl-3- (3-phenoxypropylthiopropyl) silane, diacetoxydiphenylsilane, diethoxydiphenylsilane, diethoxydodecyl Examples include methylsilane, methyloctadecyldichlorosilane, diphenylmethoxy-2-piperidinoethoxysilane, docosylmethyldichlorosilane, and diethoxymethyloctadecylsilane.

The organosilicon compound used as a raw material of the siloxane condensate component having a crosslinked structure generally has a number of hydrolyzable groups (4-
n): That is, when n is 3, the polymerization reaction of the organosilicon compound is suppressed. When n is 0, 1 or 2, a polymerization reaction easily occurs. In particular, when n is 1 or 0, the crosslinking reaction can be advanced to a high degree. Therefore, by controlling these, it is possible to control the storability of the obtained coating layer liquid and the hardness of the coating film. In the present invention, among these organosilicon compounds, a tetrafunctional organosilicon compound with n = 0 is particularly preferred, and the use amount of the tetrafunctional organosilicon compound is preferably 20% or more based on the whole organosilicon compound.

Since the resin layer of the present invention has a charge transporting group as a partial structure of the resin structure, it can have electrophotographic characteristics such as sensitivity characteristics and charging characteristics as an electrophotographic photosensitive member. In order to incorporate the charge transporting group into the resin structure, a reactive charge transporting compound is present during the polycondensation described above, that is, during the polycondensation using the phenoxy resin and the organosilicon compound of the general formula (1). This is achieved by advancing a polycondensation reaction including a reactive charge transporting compound.

The charge transporting group of the present invention is a structural unit having the property of having electron or hole drift mobility or a charge transporting compound residue.
It is a structural unit or a charge transporting compound residue from which a detection current due to charge transport can be obtained by a known method capable of detecting charge transport performance such as a me-Of-Flight method.

Here, the reactive charge transporting compound means the above-mentioned organosilicon compound or a charge transporting compound having a reactive group capable of chemically bonding to the phenoxy resin. Hereinafter, the reactive charge transporting compound will be described. Incidentally, the charge transporting compound may be hereinafter referred to as CTM.

Examples of the reactive charge transporting compound include a charge transporting compound having a hydroxyl group, a mercapto group, an amino group and a silyl group.

The charge transporting compound having a hydroxyl group is represented by the following general formula (2). Formula _{(2) X- (R 7 -OH} ) m wherein, X: charge transport group, R _7: a single bond, a substituted or unsubstituted alkylene group, an arylene group, m: is an integer from 1 to 5 .

Among them, the following are typical ones. For example, a triarylamine-based compound has a triarylamine structure such as triphenylamine as a charge transporting group = X, and has an alkylene or arylene group extended from a carbon atom constituting X or extended from X. A compound having a hydroxyl group through the intermediate is preferably used.

Next, a synthesis example of a charge transporting compound having a hydroxyl group will be described. Synthesis of Compound B-1

[0065]

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Step A In a four-headed kolben equipped with a thermometer, a cooling tube, a stirrer, and a dropping funnel, 49 g of the compound (1) and phosphorus 184 chloride were added.
g was added and dissolved by heating. 117 g of dimethylformamide was gradually added dropwise from the dropping funnel.
The mixture was kept at ９５95 ° C. and stirred for about 15 hours. Next, the reaction solution was gradually poured into a large excess of warm water, and then slowly cooled while stirring.

The precipitated crystals were filtered and dried, and then purified by adsorption of impurities using silica gel or the like and recrystallization with acetonitrile to obtain Compound (2). Yield 30
g. Step B 30 g of compound (2) and 100 ml of ethanol were charged into a kolben and stirred. After gradually adding 1.9 g of sodium borohydride, the solution was kept at 40 to 60 ° C. and stirred for about 2 hours. Next, the reaction solution was gradually poured into about 300 ml of water, and stirred to precipitate crystals. After filtration, the resultant was sufficiently washed with water and dried to obtain a compound (3). The yield was 30 g.

The charge transporting compound having a mercapto group is represented by the following general formula (3). X- (R ₈ -SH) _m wherein X: a charge transporting group, R ₈ : a single bond, a substituted or unsubstituted alkylene, an arylene group, and m: an integer of 1 to 5.

The charge transporting compound having an amine group is represented by the following general formula (4). X- (R ₉ -NR ₁₀ H) _m wherein X: charge transporting group, R ₉ : single bond, substituted, unsubstituted alkylene, substituted, unsubstituted arylene group, R ₁₀ : A hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, m: an integer of 1 to 5;

Among the charge transporting compounds having an amino group, in the case of a primary amine compound (—NH ₂ ), two hydrogen atoms may react with an organosilicon compound and be linked to a siloxane structure. In the case of a secondary amine compound (—NHR ₁₀ ), one hydrogen atom reacts with the organosilicon compound, and R ₁₀ may be a group remaining as a side chain or a group that causes a cross-linking reaction. It may be a compound residue.

Further, the charge transporting compound having a silyl group is represented by the following general formula (5). Formula (5) B - in _{- (R 1 -Si (R 11} ) 3-a (R 12) a) n -type, B is a charge transport group, R ₁₁ is a hydrogen atom, a substituted or unsubstituted R ₁₂ represents an alkyl group or an aryl group;
Represents a hydrolyzable group or a hydroxyl group, and R ₁ represents a substituted or unsubstituted alkylene group. a represents an integer of 1 to 3, and n represents an integer.

Representative examples of the general formulas (2) to (5) are shown below.

[0073]

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[0074]

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[0075]

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[0076]

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The reactive charge transporting compound of the present invention is preferably a compound having a plurality of reactive groups in the same molecule. As a result, the reactivity of the reactive charge transporting compound with the organosilicon compound is improved, and the resin layer of the present invention has good charge transporting properties.

The charge transporting group of the present invention indicates a chemical structural component corresponding to the charge transporting group X in the general formulas (2) to (5). Specific examples of the compound structure of the charge transporting group X include, for example, oxazole,
Oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidin, styryl, hydrazone, benzidine, pyrazoline, stilbene compound, amine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine, aminostilbene,
Examples include groups having a chemical structure such as poly-N-vinylcarbazole, poly-1-vinylpyrene, and poly-9-vinylanthracene.

On the other hand, electron transport type CTM includes succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, nitrobenzene, dinitrobenzene, trinitrobenzene, Tetranitrobenzene, nitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bromanyl, benzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4'-dinitrobenzophenone, 4-nitrobenzalmalonedinitrile, α-cyano-β- (p-cyanophenyl) -2-
(P-chlorophenyl) ethylene, 2,7-dinitrofluorene, 2,4,7-trinitrofluorenone, 2,
4,5,7-tetranitrofluorenone, 9-fluorenylidenedicyanomethylenemalononitrile, polynitro-9-fluoronylidenedicyanomethylenemalonodinitrile, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3, Examples include groups having a chemical structure such as 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and melitic acid.

The molecular weight of the reactive charge transporting compound used in the present invention is preferably 700 or less and 100 or more. 70
By using a reactive charge transporting compound of 0 or less,
It is possible to form a resin layer that has a small residual electric charge, good electrophotographic properties, and excellent cleaning properties. Further, a reactive charge transporting compound having a molecular weight of 450 or less and 100 or more is preferable.

The above-mentioned charge transporting group X is shown as a monovalent group in the above formula, but the reactive charge transporting compound to be reacted with the organosilicon compound and the siloxane condensate component is 2
When it has two or more reactive functional groups, it may be bonded as a divalent or higher crosslink group in the resin, or may be bonded simply as a pendant group.

The ratio of the charge transporting group to the total mass of the phenoxy resin component and the siloxane condensate component in the resin layer of the present invention is preferably from 1: 0.01 to 10:10. When the compounding ratio of the charge transporting group is small, electrophotographic characteristics (charging, sensitivity, residual potential characteristics and the like) during repeated use are deteriorated, and when it is large, the film strength is reduced.

The ratio of the phenoxy resin component, the siloxane condensate component, and the charge transporting group in the resin layer of the present invention is such that the ratio of the phenoxy resin component to the siloxane condensate component is 0.25.
And a charge transporting group of 0.02 to 50. If the compounding ratio of the siloxane condensate component is small, the film strength is reduced, while if it is too large, the cleaning property is deteriorated and the blade is easily turned up. Further, the adhesiveness to the lower photosensitive layer is deteriorated. When the compounding ratio of the charge transporting group is small, electrophotographic characteristics (charging, sensitivity, residual potential characteristics and the like) during repeated use are deteriorated, and when it is large, the film strength is reduced.

The above-mentioned resin layer may contain metal oxide particles as long as the effects of the present invention are not impaired. By blending the metal oxide particles, the wear resistance of the resin layer of the present invention can be further improved, and the cleaning performance of the toner and the stability of the cleaning blade against turning up can be improved.

The primary particle diameter of the metal oxide particles is 5 nm to
Preferably it is 500 nm. These metal oxide particles are usually synthesized by a liquid phase method and can be obtained as colloid particles. Examples of metal atoms include Si, T
i, Al, Cr, Zr, Sn, Fe, Mg, Mn, N
i, Cu and the like.

The metal oxide particles preferably have a compound group reactive with the organosilicon compound on the particle surface. As the reactive compound group,
Examples include a hydroxyl group and an amino group. By using metal oxide particles having such a reactive group, the present invention forms a composite resin layer in which the surface of the siloxane condensate component and the metal oxide particles are chemically bonded, and is used for blade cleaning and the like. It is possible to form a resin layer having good electrophotographic properties, which is not easily worn by abrasion. The amount is preferably 0.1 to 30% by mass of the total mass of the resin layer. If the amount of these components exceeds 30% by mass, the cleaning performance deteriorates, and the image in a high humidity environment deteriorates.

Further, organic fine particles and the like may be blended in the resin layer. By blending these, the surface energy of the resin layer can be reduced and the cleaning characteristics can be improved. As organic fine particles, fluorine resin,
Silicone resins, acrylic resins, olefin resins and the like are mentioned, and particularly preferable ones are fluorine resins such as polytetrafluoroethylene and polyvinyldene fluoride and olefin resins such as polyethylene and polypropylene. Organic fine particles may be used alone or in combination of two or more.

As the size of the organic fine particles, the average volume particle size or the maximum length of the projected image of the particles is 0.01 to 1.
It is desirably 0 μm, preferably 0.01 to 0.3 μm. The compounding amount of the organic fine particles is 0.1% of the total mass of the resin layer.
1-30 mass% is preferable. If the amount of these components exceeds 30% by mass, the sensitivity of the photoreceptor decreases, and the residual potential of the photoreceptor increases during repeated use, causing fog.

Further, an antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure can be added to the resin layer in the present invention.
This is effective in improving the potential stability and image quality when the environment changes.

Here, the hindered phenol refers to compounds having a branched alkyl group at the ortho position to the hydroxyl group of the phenol compound and derivatives thereof (however, the hydroxyl group may be modified to alkoxy).

Examples of the hindered amine include compounds having an organic group represented by the following structural formula.

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R ₁₃ in the formula is a hydrogen atom or a monovalent organic group,
R ₁₄ , R ₁₅ , R ₁₆ and R _{17 each} represent an alkyl group, and R ₁₈ represents a hydrogen atom, a hydroxyl group or a monovalent organic group.

Examples of the antioxidant having a hindered phenol partial structure include, for example, JP-A-1-118137 (P.
7 to P14), but the present invention is not limited thereto.

Examples of the antioxidant having a hindered amine partial structure include, for example, JP-A-1-118138 (P7-
The compounds described in P9) may also be mentioned, but the present invention is not limited thereto.

The following are examples of typical antioxidant compounds.

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Examples of commercially available antioxidants include the following compounds, for example, “Irganox 107
6, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076, 3,5-di-t-butyl- 4
-Hydroxybiphenyl "or more hindered phenols," Sanol LS2626 "," Sanol LS76 "
5 "," Sanol LS2626 "," Sanol LS77 "
0 "," Sanol LS744 "," Tinuvin 144 ",
“Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”, “Mark LA6”
8 "," mark LA63 "or more hindered amine-based,
"SUMILIZER TPS", "SUMILIZER TP-D" or higher thioether, "Mark 2112", "Mark PE"
P-8 "," Mark PEP-24G "," Mark PEP "
-36 "," Mark 329K "," Mark HP-10 "
The phosphite type is mentioned above. Among these, hindered phenol and hindered amine antioxidants are particularly preferred. It is preferable to use 0.1 to 10 parts by mass of the antioxidant based on 100 parts by mass of the total solid content of the resin layer.

Next, a method for manufacturing the resin layer will be described. In the present invention, the resin layer may be formed by any method as long as the resin layer as described above is formed. Hereinafter, a typical method for producing the resin layer of the present invention will be described.

The resin layer of the present invention comprises at least one selected from the group consisting of the organosilicon compound represented by the general formula (1), a hydrolyzate of the organosilicon compound and a condensate of the organosilicon compound, and a phenoxy resin Can be formed by applying a coating solution containing the above on a conductive support or the like and then curing the coating solution.

It is preferable that a reactive charge transporting compound is contained in the coating solution, and that the curing including the reactive charge transporting compound proceeds.

Specifically, a coating solution in which a phenoxy resin is mixed with an organosilicon compound and a reactive charge transporting compound may be applied and cured, or the phenoxy resin and the organosilicon compound may be mixed and then modified with silane beforehand. After forming a phenoxy resin, a coating solution mixed with an organosilicon compound, a siloxane condensate, a reactive charge transporting compound, or the like may be applied and cured.

Here, the curing of the present invention means that a chemical reaction between phenoxy resins or between the phenoxy resin and an organosilicon compound, a reactive charge transporting compound or the like proceeds, and the coating solution is gelled and dried. It means that a resin layer is formed.

Specifically, a coating solution in which a phenoxy resin is mixed with an organosilicon compound and a reactive charge transporting compound may be applied and cured. Alternatively, the phenoxy resin and the organosilicon compound may be mixed, and the phenoxy resin may be mixed in advance. A siloxane condensate may be formed at the terminal, and then a coating solution mixed with an organosilicon compound and a reactive charge transporting compound may be applied and cured.

By the curing, the polycondensation of the phenoxy resin and siloxane and the reaction with the reactive charge transporting compound proceed. That is, a siloxane condensate, a phenoxy resin, and a reactive charge transporting compound are chemically bonded via a hydroxyl group or a reactive group, and further, a crosslinking reaction proceeds in the entire resin layer, thereby causing abrasion resistance and photosensitivity. A resin layer having good adhesion to the layer and good cleaning properties is formed.

By the curing, the polycondensation of the copolymer of the phenoxy resin and the siloxane condensate proceeds, and a resin structure having a charge transporting group as a partial structure of the resin and a three-dimensional resin layer as a whole is formed. As a result, a resin layer having good electrophotographic properties, good abrasion resistance, good adhesion to the photosensitive layer and good cleaning properties is formed.

Next, an example of a specific method for preparing a coating solution will be described. After adding the organosilicon compound represented by the general formula (1) and a necessary amount of water to the phenoxy resin solution,
Stir at room temperature to 60 ° C for 0 minutes to 24 hours. At this time, hydrochloric acid, acetic acid, acidic catalysts such as p-toluenesulfonic acid and sodium hydroxide, triethylamine, piperidine,
It is preferable to use a basic catalyst such as 1,8-diazabicyclo (5,4,0) -7-undecene or an organic tin catalyst such as dibutyltin dilaurate or tin octylate. Further, a required amount of water and the above-mentioned catalyst may be added to the organosilicon compound represented by the general formula (1), and the mixture may be stirred and partially condensed in advance, followed by adding a phenoxy resin solution to cause a reaction. When the phenoxy resin and the organosilicon compound are mixed, the hydroxyl group of the phenoxy resin and the hydrolyzable silyl group chemically react to form a covalent bond. This silane-modified phenoxy resin is coated on a photosensitive layer together with an organosilicon compound, a siloxane condensate, a reactive charge-transporting compound, and various additives as necessary, and is hydrolyzed and polycondensed to form a three-dimensional structure. Thus, a block cured film of the phenoxy resin and the siloxane condensate is obtained.

In any of the above production methods, the mixing ratio of the organosilicon compound, the siloxane condensate or the phenoxy resin as the raw materials and the reactive charge transporting compound in the coating solution is determined based on the phenoxy resin component, siloxane It is sufficient that the compounding ratio of the condensate component and the charge transporting structural component is within the above-mentioned range. For example, when the compound of the general formula (1) is used as the organosilicon compound,
The mass ratio of the organosilicon compound, the phenoxy resin, and the reactive charge transporting compound is 100: 25 to 400: 1 to 1000.
Is preferred.

In order to accelerate the reaction of the organosilicon compound, the phenoxy resin and the reactive charge transporting compound, it is preferable to add a metal chelate compound in the coating solution or during the process of forming the coating solution. Here, the metal chelate compound is a chelate compound of a metal selected from the group of zirconium, titanium and aluminum (hereinafter, referred to as metal chelate compound (III)). Metal chelate compound (III)
It is considered that the compound promotes the hydrolysis and / or partial condensation reaction between the organosilicon compound and the phenoxy resin and the reactive charge transporting compound, and promotes the formation of a three-component co-condensate.

Examples of such a metal chelate compound (III) include compounds represented by the general formulas (6), (7) and (8), or partial hydrolysates of these compounds.

Formula (6) Zr (OR_Five)_p(R₆COCHCOR₇)_4-p General formula (7) Ti (OR_Five)_q(R₆COCHCOR₇)_4-q General formula (8) Al (OR_Five)_r(R₆COCHCOR₇)_3-r R in general formulas (6), (7) and (8)_FiveAnd R
₆Are each independently a monovalent hydrocarbon having 1 to 6 carbon atoms
Groups, specifically, ethyl group, n-propyl group, i-pro
Pill group, n-butyl group, sec-butyl group, t-butyl
Group, n-pentyl group, n-hexyl group, cyclohexyl
Group, phenyl group, etc.,₇Is R_FiveAnd R ₆the same as
In addition to the monovalent hydrocarbon group having 1 to 6 carbon atoms,
16 alkoxy groups, specifically, a methoxy group, an ethoxy group
Si group, n-propoxy group, i-propoxy group, n-buto
Xyl group, sec-butoxy group, t-butoxy group, lauri
A ruoxy group, a stearyloxy group and the like. Also, p
And q are integers of 0 to 3, and r is an integer of 0 to 2.

Specific examples of such a metal chelate compound (III) include zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), and zirconium n-butoxytris (ethyl). Acetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium,
Zirconium chelate compounds such as tetrakis (acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium; di-i-propoxybis (ethylacetoacetate) titanium, di-
titanium chelate compounds such as i-propoxybis (acetylacetate) titanium and di-i-propoxybis (acetylacetone) titanium; aluminum di-i-propoxyethylacetoacetate, aluminum di-i-propoxyacetylacetonate, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (ethylacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetate Aluminum chelate compounds such as natobis (ethylacetoacetate) aluminum and the like. Of these compounds, tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titanium, di-i
-Aluminum propoxy-ethyl acetoacetate,
Tris (ethyl acetoacetate) aluminum is preferred. These metal chelate compounds (III) can be used alone or in combination of two or more.

The addition amount of the metal chelate compound (III)
The amount of the solid content of the coating solution such as the organosilicon compound, the siloxane condensate or the phenoxy resin, and the reactive charge transporting compound (the solid content of the coating solution is a component remaining after drying the coating solution) is 0 based on the total mass The amount is 0.01 to 20% by mass, preferably 0.5 to 20% by mass. If the amount of the metal chelate compound (III) is too small, the resin layer resin may not be three-dimensionally formed, while if it is too large, the pot life of the coating liquid is deteriorated.

The curing conditions after the application of the coating solution for the resin layer depend on the reactivity of the phenoxy resin, the organosilicon compound and the like to be used, but the drying is carried out at 60 to 150 ° C. for 30 minutes to 6 hours. Preferably.

It is preferred that a necessary amount of a water component is present in the resin layer coating solution in order to promote the hydrolysis of the organosilicon compound. This water component may be present as an acid solution or an alkali solution.

In order to accelerate the curing reaction of the coating solution for the resin layer, it is preferable that an organic solvent is present. As the organic solvent usable here, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable. The amount of the organic solvent used is not limited to the amount of the organosilicon compound, but is adjusted according to the purpose of use.

As the solvent for accelerating the curing reaction, a solvent capable of uniformly dissolving an organosilicon compound, a phenoxy resin, and a charge transporting compound having a reactive group is preferably used. As these solvents, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are used, and particularly preferred are the solvents exemplified below.

Examples of alcohol solvents include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, Examples include triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl acetate.

As the ketone solvent, ketone solvents such as ethyl methyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, acetone and cyclohexanone are preferably used.

Further, hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and n-hexane; carbon tetrachloride, chloroform, dichloromethane, chloroethane,
Dichloroethane, chlorobenzene, dichlorobenzene,
Halogenated hydrocarbon solvents such as trichlorobenzene; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethyl ether and dibutyl ether; ethyl acetate, n-propyl acetate and n-acetic acid
Ester solvents such as -butyl and propylene carbonate, and the like, but are not limited thereto.

These organic solvents can be used alone or in combination of two or more. The method for adding the organic solvent is not particularly limited, and the organic solvent can be added at the time of preparing the resin layer coating solution of the present invention and / or at an appropriate stage after the preparation.

A curing accelerator can be further added to the resin layer coating solution, if necessary.

As the curing accelerator, naphthenic acid, octyl
Alkaline such as luic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid
Li metal salts; such as sodium hydroxide and potassium hydroxide
Lucari compound: alkyl titanic acid, phosphoric acid, p-toluene
Acidic compounds such as enesulfonic acid and phthalic acid; ethylene
Diamine, hexanediamine, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Piperidine, piperazine, metaphenylenediamine, di
Aminodiphenylmethane, diaminodiphenylsulfo
Epoxy such as ethanol, ethanolamine and triethylamine
Various modified amines, γ-A
Minopropyltriethoxysilane, γ- (2-amino
Tyl) -aminopropyltrimethoxysilane, γ- (2
-Aminoethyl) -aminopropylmethyldimethoxy
Orchid, γ-anilinopropyltrimethoxysilane, etc.
Amine compounds, (C_FourH₉)_TwoSn (OCOC
₁₁H_{twenty three})_Two, (C_FourH₉)_TwoSn (OCOCH = CHCOO
CH_Three)_Two, (C_FourH₉)_TwoSn (OCOCH = CHCOO
C_FourH₉)_Two, (C₈H₁₇)_TwoSn (OCOC₁₁H_{twenty three})_Two,
(C₈H₁₇)_TwoSn (OCOCH = CHCOOCH_Three)_Two,
(C₈H₁₇)_TwoSn (OCOCH = CHCOOC
_FourH₉)_Two, (C₈H₁₇)_TwoSn (OCOCH = CHCOO
C₈H₁₇)_Two, Sn (OCOCC₈H₁₇)_Two, Such as carbo
Acid-type organotin compounds; (C_FourH₉) _TwoSn (SCH_TwoCO
O)_Two, (C_FourH₉)_TwoSn (SCH_TwoCOOC₈H₁₇)_Two,
(C₈H₁₇)_TwoSn (SCH_TwoCOO)_Two, (C₈H₁₇)_TwoS
n (SCH_TwoCH_TwoCOO)_Two, (C₈H₁₇)_TwoSn (SC
H_TwoCOOCH_TwoCH_TwoOCOCH_TwoS)_Two, (C₈H₁₇)_Two
Sn (SCH_TwoCOOCH_TwoCH_TwoCH_TwoCH_TwoOCOCH_Two
S)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC₈H₁₇)_Two,
(C₈H₁₇)_TwoSn (SCH_TwoCOOC₁₂H_{twenty five})_Two,

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Mercaptide-type organotin compounds such as

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A sulfide type organotin compound such as (C)
_{4 H 9) 2 SnO, (} C 8 H 17) 2 SnO, (C 4 H 9) 2 Sn
Organic tin compounds such as reaction products of organic tin oxides such as O, (C ₈ H ₁₇ ) ₂ SnO and ester compounds such as ethyl silicate, ethyl silicate 40, dimethyl maleate, diethyl maleate and dioctyl phthalate; methyl Acid anhydrides such as nadic anhydride and methyltetrahydroanhydride are used.

The amount of the curing accelerator added in the coating solution is 0.1 to 20 parts by mass per 100 parts by mass of the solid content of the coating solution (the solid content means the component remaining after drying in the components of the coating solution).
It is parts by mass, preferably 0.5 to 100 parts by mass. If these amounts are too small, the strength of the film may be reduced, while if too large, the pot life of the coating liquid deteriorates.

Further, the above-mentioned coating solution can be added with the above-mentioned metal oxide particles, organic fine particles and antioxidant as required, to prepare the resin layer of the present invention.

Next, the structure of the photoconductor of the present invention other than the resin layer will be described. The photoreceptor having the resin layer of the present invention can be applied to an inorganic photoreceptor using selenium, amorphous silicon, or the like. However, for the purpose of the present invention, an organic electrophotographic photoreceptor (also referred to as an organic photoreceptor) is used. It is preferable to apply a resin layer. In the present invention, the organic photoreceptor means an electrophotographic photoreceptor constituted by providing an organic compound with one of a charge generation function and a charge transport function indispensable for the configuration of the electrophotographic photoreceptor, It includes all known organic electrophotographic photosensitive members such as a photosensitive member composed of a known organic charge generating substance or organic charge transporting substance, and a photosensitive member composed of a polymer complex having a charge generating function and a charge transporting function.

The layer constitution of the organic photoreceptor is not particularly limited, but an intermediate layer, a charge generation layer, a charge transport layer, or a charge generation / charge transport layer (function of charge generation and charge transport) may be provided on a conductive support. Is well known, and a layer structure in which a protective layer is further provided thereon is well known. The resin layer of the present invention can be applied to each of the above-described layers. Although it is possible, it is particularly preferable to adopt a configuration in which the resin layer of the present invention is applied to the protective layer constituting the surface layer.

Conductive Support The conductive support used for the photoreceptor of the present invention may be either a sheet or a cylinder. However, in order to design an image forming apparatus compactly, a cylindrical conductive support is used. Supports are preferred.

The cylindrical conductive support means a cylindrical support necessary for forming an image endlessly by rotating, and has a straightness of 0.1 mm or less and a run-out of 0.1 mm.
Conductive supports in the following ranges are preferred. Exceeding the ranges of the roundness and the shake make it difficult to form a good image.

As the conductive material, a metal drum of aluminum, nickel, or the like, a plastic drum on which aluminum, tin oxide, indium oxide, or the like is deposited, or a paper or plastic drum coated with a conductive substance can be used. The conductive support preferably has a specific resistance of 10 ³ Ωcm or less at room temperature.

The conductive support used in the present invention may have a surface on which a sealed alumite film is formed. The alumite treatment is usually performed in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid, and sulfamic acid, but anodizing treatment in sulfuric acid gives the most preferable result. In the case of the anodic oxidation treatment in sulfuric acid, the sulfuric acid concentration is preferably 100 to 200 g / L, the aluminum ion concentration is 1 to 10 g / L, the liquid temperature is about 20 ° C., and the applied voltage is preferably about 20 V. It is not limited. The average thickness of the anodic oxide coating is usually 2
0 μm or less, particularly preferably 10 μm or less.

Intermediate Layer In the present invention, an intermediate layer having a barrier function may be provided between the conductive support and the photosensitive layer.

In the present invention, in order to improve the adhesion between the conductive support and the photosensitive layer or to prevent charge injection from the support, an intermediate layer (below the lower layer) is provided between the support and the photosensitive layer. (Including a subbing layer). Examples of the material for the intermediate layer include polyamide resins, vinyl chloride resins, vinyl acetate resins, and copolymer resins containing two or more of the repeating units of these resins. Among these undercoating resins, a polyamide resin is preferable as a resin capable of reducing an increase in residual potential due to repeated use. The thickness of the intermediate layer using these resins is 0.01 to 0.5 μm.
Is preferred.

The intermediate layer most preferably used in the present invention is an intermediate layer using a curable metal resin obtained by thermosetting an organic metal compound such as a silane coupling agent and a titanium coupling agent. The thickness of the intermediate layer using a curable metal resin is preferably 0.1 to 2 μm.

Photosensitive Layer The photosensitive layer of the photoreceptor of the present invention may have a single-layered structure in which a charge generation function and a charge transport function are provided in one layer on the intermediate layer. It is preferable to adopt a configuration in which the functions of the layers are separated into a charge generation layer (CGL) and a charge transport layer (CTL). By adopting a configuration in which functions are separated, an increase in residual potential due to repeated use can be controlled to be small, and other electrophotographic characteristics can be easily controlled according to the purpose. In the photoreceptor for negative charging, a charge generation layer (C
GL) and a charge transport layer (CTL) thereon. In the case of a positively charged photoreceptor, the order of the layer configuration is opposite to that of the negatively charged photoreceptor. The most preferred photosensitive layer structure of the present invention is a negatively charged photosensitive member having the function-separated structure.

The structure of the photosensitive layer of the function-separated negatively charged photosensitive member will be described below. Charge generation layer The charge generation layer contains a charge generation material (CGM). As other substances, a binder resin and other additives may be contained as necessary.

As the charge generating substance (CGM), a known charge generating substance (CGM) can be used. For example, phthalocyanine pigments, azo pigments, perylene pigments, azurenium pigments, and the like can be used. Among them, CGM that can minimize the increase in residual potential due to repeated use
Has a steric and potential structure capable of forming a stable aggregation structure among a plurality of molecules, and specifically includes CGM of a phthalocyanine pigment and a perylene pigment having a specific crystal structure. For example, Bragg angle 2θ for Cu-Kα ray
CGM such as titanyl phthalocyanine having a maximum peak at 27.2 ° and benzimidazole perylene having a maximum peak at 2θ of 12.4 have almost no deterioration due to repeated use, and the residual potential increase can be reduced.

When a binder is used as a dispersion medium for CGM in the charge generation layer, a known resin can be used as the binder, but the most preferred resin is a formal resin, a butyral resin, a silicone resin, a silicone-modified butyral resin, a phenoxy resin. Resins. The ratio between the binder resin and the charge generating substance is preferably from 20 to 600 parts by mass per 100 parts by mass of the binder resin. By using these resins, the increase in residual potential due to repeated use can be minimized. The thickness of the charge generation layer is preferably from 0.01 μm to 2 μm.

Charge Transport Layer The charge transport layer contains a charge transport material (CTM) and a binder resin for dispersing the CTM and forming a film. As other substances, additives such as antioxidants may be contained as necessary.

As the charge transport material (CTM), a known charge transport material (CTM) can be used. For example, triphenylamine derivatives, hydrazone compounds, styryl compounds, benzidine compounds, butadiene compounds and the like can be used. These charge transport materials are usually dissolved in a suitable binder resin to form a layer. Among these, the CTM that can minimize the increase in residual potential due to repeated use has a high mobility and a characteristic in which the ionization potential difference with the CGM to be combined is 0.5 (eV) or less, and is preferably 0. .25 (eV) or less.

The ionization potential of CGM and CTM is measured with a surface analyzer AC-1 (manufactured by Riken Keiki Co., Ltd.).

Examples of the resin used for the charge transport layer (CTL) include polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, and alkyd. Resins, polycarbonate resins, silicone resins, melamine resins, and copolymer resins containing two or more of the repeating units of these resins. In addition to these insulating resins, poly-
A high-molecular organic semiconductor such as N-vinylcarbazole may be used.

The most preferred binder for these CTLs is a polycarbonate resin. Polycarbonate resins are most preferred for improving the dispersibility and electrophotographic properties of CTM. The ratio of the binder resin to the charge transporting material is preferably from 10 to 200 parts by mass per 100 parts by mass of the binder resin. The thickness of the charge transport layer is preferably from 10 to 40 μm.

Protective Layer By providing the resin layer of the present invention as a protective layer on the surface of the photoreceptor, a photoreceptor having the most preferred layer constitution of the present invention can be obtained.

Solvents or dispersion media used for forming layers such as the intermediate layer and the photosensitive layer include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-
Dimethylformamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-
Examples include trichloroethane, trichloroethylene, tetrachloroethane, tetrahydrofuran, dioxolan, dioxane, methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve and the like. The present invention is not limited to these, but dichloromethane, 1,2
-Dichloroethane, methyl ethyl ketone and the like are preferably used. In addition, these solvents can be used alone or as a mixed solvent of two or more kinds.

The coating method for producing the electrophotographic photosensitive member of the present invention includes dip coating, spray coating,
A coating method such as a circular amount control type coating is used, but the coating process on the upper layer side of the photosensitive layer is performed by spray coating or a circular amount control type in order to minimize dissolution of the lower layer film and to achieve a uniform coating process. A typical example is a circular slide hopper type. It is preferable to use a coating method such as coating. It is most preferable that the resin layer of the present invention employs the above-mentioned circular amount control type coating processing method. The circular amount control type coating is described in detail in, for example, JP-A-58-189061.

FIG. 1 is a sectional view of an image forming apparatus as an example of the image forming method of the present invention. In FIG. 1, reference numeral 50 denotes a photoreceptor drum (photoreceptor) serving as an image carrier, which is a photoreceptor having an organic photosensitive layer applied on the drum and a resin layer of the present invention provided thereon. It is driven and rotated clockwise. 52
Is a scorotron charger (charging means) for uniformly charging the peripheral surface of the photosensitive drum 50 by corona discharge. Prior to the charging by the charger 52, in order to eliminate the history of the photoconductor in the previous image formation, exposure by the pre-charging exposure unit 51 using a light emitting diode or the like may be performed to remove the charge on the peripheral surface of the photoconductor.

After the photosensitive member is uniformly charged, an image exposing device (image exposing means) 53 performs image exposure based on an image signal. The image exposure device 53 in this figure uses a laser diode (not shown) as an exposure light source. Rotating polygon mirror 53
1. The light on the photosensitive drum is scanned by the light whose optical path is bent by the reflection mirror 532 via the fθ lens and the like, and an electrostatic latent image is formed.

Here, the reversal development is to uniformly charge the surface of the photoreceptor by the charger 52, and to develop a region where the image exposure has been performed, that is, an exposed portion potential (exposed portion region) of the photoreceptor in a developing step (means).
Is an image forming method for visualizing the image. On the other hand, the unexposed portion potential is not developed by the developing bias potential applied to the developing sleeve 541.

The electrostatic latent image is then developed (developing means)
Developed at. A developing device 54 containing a developer including a toner and a carrier is provided on the periphery of the photoreceptor drum 50, and development is performed by a developing sleeve 541 that contains a magnet and rotates while holding the developer. The inside of the developing device 54 is composed of developer stirring / conveying members 544 and 543, a conveyance amount regulating member 542, and the like. The developer is agitated and conveyed to be supplied to the developing sleeve. Controlled by member 542. The transport amount of the developer varies depending on the linear velocity of the applied electrophotographic photosensitive member and the specific gravity of the developer, but is generally 20 to 200 m.
g / cm ² .

The developer is composed of, for example, a carrier having ferrite as a core and an insulating resin coated around the core, a colorant such as carbon black, a charge control agent, and a low molecular weight polyolefin using the above-mentioned styrene acrylic resin as a main material. The developer is made up of a toner in which silica, titanium oxide, or the like is externally added to the colored particles. The developer is transported to the development area with the layer thickness regulated by the transport amount regulating member, and is developed. At this time, development is usually performed by applying a DC bias voltage between the photosensitive drum 50 and the developing sleeve 541 and, if necessary, an AC bias voltage. The developer is developed in a state of contact or non-contact with the photoconductor.
The potential measurement of the photoconductor is performed by providing a potential sensor 547 above the developing position as shown in FIG.

After the image is formed, the recording paper P is fed to the transfer area by the rotation of the paper feed roller 57 at the time when the transfer timing is adjusted.

In the transfer area, the toner on the photoreceptor is transferred to the fed recording paper P by a transfer electrode (transfer means) 58 which applies a charge of the opposite polarity to the toner.

Next, the recording paper P is separated from the separation electrode (separation means) 5.
9, the toner is removed from the peripheral surface of the photosensitive drum 50, conveyed to a fixing device (fixing unit) 60, and heated and pressed by the heat roller 601 and the pressure roller 602 to fuse the toner and then discharge the paper 61. Is discharged out of the apparatus via The transfer electrode 58 and the separation electrode 59 are retracted and separated from the peripheral surface of the photosensitive drum 50 after the recording paper P has passed to prepare for the formation of the next toner image.

On the other hand, the photosensitive drum 50 from which the recording paper P has been separated removes and cleans the residual toner by pressing the blade 621 of the cleaning device (cleaning means) 62.
Upon receiving the charge elimination by the pre-charge exposure unit 51 and the charging by the charger 52 again, the image forming process starts.

Reference numeral 70 denotes a detachable process cartridge in which a photosensitive member, a charger, a transfer device, a separator, and a cleaning device are integrated.

The image forming method and the image forming apparatus of the present invention are generally applicable to electrophotographic apparatuses such as electrophotographic copying machines, laser printers, LED printers, and liquid crystal shutter printers. , Light printing, plate making and facsimile.

[0165]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto. In the description, “parts” means “parts by mass”.

Example 1 Photoconductor 1 was prepared as follows.

<Undercoat layer> Titanium chelate compound (TC-750, manufactured by Matsumoto Pharmaceutical Co., Ltd.) 30 g Silane coupling agent (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) 17 g 2-propanol 150 ml The above-mentioned coating solution is used to form a cylindrical conductive material having a diameter of 100 mm. It was applied to a support having a thickness of 0.5 μm.

<Charge Generating Layer> Y-type titanyl phthalocyanine (Titanyl phthalocyanine having a maximum peak at 27.2 degrees at a Bragg angle of 2θ (± 0.2) in Cu-Kα characteristic X-ray diffraction spectrum measurement) 60 g Silicone-modified A butyral resin (X-40-1211M: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2000 ml was mixed and dispersed using a sand mill for 10 hours to prepare a charge generation layer coating solution. This coating solution was applied on the undercoat layer by a dip coating method to form a 0.2 μm-thick charge generation layer.

<Charge Transport Layer> Charge transport material (N- (4-methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine) 225 g Polycarbonate (viscosity average molecular weight 30,000) 300 g 6 g of an antioxidant (exemplary compound 1-3) and 2,000 ml of dichloromethane were mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a dry film thickness of 20 μm.

<Protective Layer (Resin Layer of the Present Invention)> Phenoxy resin (Exemplary compound (A-1): PAPHEN PHEN)
OXY RESIN PKHJ; Phenoxy As
manufactured by Sociates Inc. (number average molecular weight 16000) 50
Was dissolved in 500 parts of 1,4 dioxane, 100 parts of tetramethoxysilane partially hydrolyzed condensate (M silicate 51 manufactured by Tama Chemical Industry Co., Ltd.) and 2.5 parts of dibutyltin dilaurate as a catalyst were added. The mixture was stirred for 2 hours to obtain an alkoxysilane-modified phenoxy resin solution. Here, the reactive charge transporting compound (exemplified compound (B-
1)) 40 parts, 2 parts of an antioxidant (exemplary compound 2-1),
4 parts of aluminum chelate A (W) (manufactured by Kawaken Chemical Co., Ltd .: aluminum trisacetylacetonate) was added to prepare a coating solution for a surface protective layer. This coating solution was applied onto the charge transport layer by a circular amount-regulating coating device,
C .; heat-cured for 90 minutes to form a surface protective layer of a block copolymer of a phenoxy resin and a siloxane condensate having a thickness of 3.0 μm and a cross-linked resin structure, thereby producing Photoreceptor 1.

Example 2 A phenoxy resin and siloxane condensation were carried out in the same manner as in Example 1 except that the reactive charge transporting compound in the protective layer was replaced with the exemplary compound (Si-1) instead of the exemplary compound B-1. Photoreceptor 2 was prepared which was a block copolymer and had a surface protective layer having a crosslinked resin structure.

Example 3 Example 1 was repeated except that titanium chelate (TC-750: manufactured by Matsumoto Pharmaceutical Co., Ltd .: diisopropoxytitanium bisethylacetoacetate) was used in place of aluminum chelate A (W) as the curing agent in the protective layer. Similarly, a photoreceptor 3 having a surface protective layer of a block copolymer of a phenoxy resin and a siloxane condensate and having a crosslinked resin structure was produced.

Example 4 A charge transport layer was prepared in the same manner as in Example 1.

<Protective Layer (Resin Layer of the Present Invention)> Phenoxy resin (PAPHEN PHENOXY RESIN P)
KHJ; manufactured by Phenoxy Associates
50 parts of (number average molecular weight 16000) is dissolved in 500 parts of 1,4-dioxane, 50 parts of tetramethoxysilane and 50 parts of methyltrimethoxysilane are added, and the mixture is stirred at room temperature for 2 hours to obtain an alkoxysilane-modified phenoxy resin solution. Was. Here, the reactive charge transporting compound (exemplified compound (B-
1)) 40 parts, 2 parts of an antioxidant (exemplary compound 2-1),
4 parts of aluminum chelate A (W) (manufactured by Kawaken Chemical Co., Ltd.) was added to prepare a coating solution for a surface protective layer. This coating solution is applied on the charge transport layer by a circular amount-regulating type coating device, and is cured by heating at 110 ° C. for 90 minutes to form a block copolymer of a phenoxy resin and a siloxane condensate having a thickness of 3.0 μm, And a surface protective layer having a crosslinked resin structure is formed,
Was prepared.

Example 5 A charge transport layer was prepared in the same manner as in Example 1.

<Protective layer (resin layer of the present invention)> 80 parts of methyltrimethoxysilane, 20 parts of 3-glycidoxypropyltrimethoxysilane, 25 parts of water, and 0.25 part of acetic acid
The mixture was stirred at 0 ° C. for 2 hours to obtain an alkoxysilane partially hydrolyzed condensate. Next, a phenoxy resin (PAPHEN)
Phenoxy Resin PKHJ; Phenox
y Associates company number average molecular weight 1600
0) 50 parts are dissolved in 500 parts of 1,4-dioxane,
The above alkoxysilane partially hydrolyzed condensate was added and stirred at room temperature for 2 hours. Here, 40 parts of a reactive charge transporting compound (exemplified compound B-1), 2 parts of an antioxidant (exemplified compound 2-1), and 4 parts of aluminum chelate A (W) (manufactured by Kawaken Chemical Co., Ltd.) were added. A coating solution for a surface protective layer was prepared.
This coating solution was applied onto the charge transport layer by a circular amount-regulating coating apparatus, and was cured by heating at 110 ° C. for 90 minutes, and was a block copolymer of a phenoxy resin and a siloxane condensate having a thickness of 3.0 μm, In addition, a surface protective layer having a cross-linked resin structure was formed, and photoreceptor 5 was produced.

Comparative Example 1 A charge transport layer was prepared in the same manner as in Example 1.

<Protective layer> 10 parts of tetramethoxysilane,
90 parts of methyltrimethoxysilane, 25 parts of water, and acetic acid 0.1 part.
Two parts were stirred at 70 ° C. for 2 hours to obtain an alkoxysilane partially hydrolyzed condensate. Here, 40 parts of a reactive charge transporting compound (exemplified compound B-1), 2 parts of an antioxidant (exemplified compound 2-1), and 4 parts of aluminum chelate A (W) (manufactured by Kawaken Chemical Co., Ltd.) were added. A coating solution for a surface protective layer was prepared.
This coating solution is applied on the charge transport layer by a circular amount-regulating type coating device, and is heated and cured at 110 ° C. for 90 minutes to form a surface protective layer of a siloxane-based resin having a thickness of 3.0 μm. No. 6 was produced.

Comparative Example 2 A photoreceptor 7 was prepared in the same manner as in Example 1 except that the surface protective layer was not provided.

Evaluation Konica 7 digital copier manufactured by Konica Corporation was used as the evaluation machine.
075 (including a process employing a corona charging, laser exposure, reversal development, electrostatic transfer, nail separation, blade cleaning, and cleaning auxiliary brush roller), the photoconductors 1 to 7 were mounted on the copying machine and evaluated. The cleaning performance and image evaluation are as follows: character images with a pixel ratio of 7%, portrait photos,
An original image in which a solid white image and a solid black image were each equally divided into quarters was copied to A4 neutral paper. Environmental conditions are considered to be the most severe high temperature and high humidity environment (30 ° C, 80% R
In H), 200,000 copies were continuously made to evaluate a halftone, a solid white image, and a solid black image. The thickness loss of the photoreceptor is calculated from the difference between the initial film thickness and the film thickness after 200,000 copies, and the cleaning property is about 100, 150,000, and 200,000 copies. Ten continuous copies of the original image having a ratio of white image 1 were made, and the occurrence of cleaning failure in a solid white portion was determined. Blade turning was determined by the presence or absence of occurrence during 200,000 copies. After the completion of 200,000 copies, the starting torque of the blade was measured.

The image density was measured by the relative reflection density using RD-918 manufactured by Macbeth Co., Ltd., and the initial image was evaluated on the image after 100,000 or 200,000 copies.

Evaluation Criteria Image density (measured using Macbeth RD-918).
A: The reflection density of the paper was measured as a relative reflection density of "0". ◎: Good from 1.2 to 200,000 sheets from the initial stage, good. ：: Practical from less than 1.2 to 1.0 from the initial stage to 200,000 sheets. Non-problematic level ×: An image less than 1.0 is generated, which is a problem in practical use Resolution (determined by the easiness of discrimination of character images) ○: No difference between initial and resolution after 200,000 copies △: Halftone There is a slight decrease in the resolution after 200,000 copies of the image. ×: A noticeable decrease in the resolution after 200,000 copies. Cleanability (After 100,000, 150,000, and 200,000 copies, 10 continuous copies are made on A3 paper. Judgment based on whether or not cleaning failure has occurred on solid white areas) ◎: No slippage occurred on 200,000 sheets ○: No slippage occurred up to 150,000 sheets ×: Slippage occurred on less than 100,000 sheets Blade turning over (occurred during 200,000 copies) The number of times ◎: No blade turning up to 200,000 sheets ○: Minor partial turning up during 200,000 copies ×: One or more blade turning up during 200,000 copies Measurement of starting torque of cleaning blade After 200,000 copies A torque gauge (MODEL 6) connected to the drum shaft of the copying machine using the drum cartridge of
(BTG: manufactured by TOHNICHI) was rotated to measure the starting torque. The measurement was performed five times, and the average value was adopted.

Photoreceptor Film Thickness Wear Amount The difference between the average thickness of the photoreceptor measured at the start of the actual image evaluation and at the end of 200,000 copies was determined as the thickness loss.

Method of Measuring Film Thickness The film thickness of the photosensitive layer is measured at random at 10 locations of uniform thickness, and the average value is defined as the film thickness of the photosensitive layer. The film thickness measuring device is an eddy current type film thickness measuring device EDDY560C (HELMUT
FISCER GMBTE CO), and the difference between the thicknesses of the photosensitive layers before and after the actual printing test is defined as the thickness loss.

Other Evaluation Conditions The other evaluation conditions using the digital copying machine Konica 7075 were set as follows.

Charging conditions: Charger: Scorotron charger, initial charging potential was -750
V Exposure conditions Exposure amount is set so that the exposed portion potential is -50V.

Developing conditions DC bias; -550 V The developer is composed of a carrier coated with an insulating resin with ferrite as a core, a styrene acrylic resin as a main material, a colorant such as carbon black, a charge control agent, and a low molecular weight polyolefin. A toner developer in which silica, titanium oxide, or the like is externally added to the colored particles is used. Transfer conditions Transfer pole; corona charging system Cleaning conditions Hardness 70 °, rebound resilience 34%, thickness 2 in cleaning section
(Mm), a cleaning blade having a free length of 9 mm was abutted in the counter direction by a weight load method so as to have a linear pressure of 20 (N / m).

The evaluation results are shown in Table 1.

[0189]

[Table 1]

As is clear from Table 1, the photoconductors 1 to 5 having the resin layer of the present invention in the protective layer have image characteristics such as image density and resolution which are lower than those of the photoconductor 6 having the protective layer outside the present invention. Since the cleaning blade is good and the starting torque of the cleaning blade is small, the cleaning properties such as the cleaning property and the turning up of the blade are improved. It is also found that the photoreceptor 7 without the protective layer according to the present invention has a large thickness loss and low durability.

[0191]

As is clear from the above examples, by using the photoreceptor having the resin layer of the present invention, abrasion resistance against abrasion with a cleaning blade and the like, and electrophotographic characteristics (charge, The present invention provides an image forming method, an image forming apparatus, and a process cartridge which are improved in toner cleaning performance and stability against turning of a cleaning blade by using the photoreceptor. it can.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an image forming apparatus as an example of an image forming method of the present invention.

[Explanation of symbols]

 Reference Signs List 50 photoconductor drum (or photoconductor) 51 pre-charging exposure unit 52 charger 53 image exposure device 54 developing device 541 developing sleeve 543, 544 developer stirring and conveying member 547 potential sensor 57 paper feed roller 58 transfer electrode 59 separation electrode (separation) Device) 60 fixing device 61 paper discharge roller 62 cleaning device 70 process cartridge

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/05 102 G03G 5/05 102 5/07 103 5/07 103

Claims (31)

[Claims] 1. An electrophotographic photoreceptor comprising a resin layer provided on a conductive support, wherein the resin layer contains a block copolymer of a phenoxy resin and a siloxane condensate. . 2. An electrophotographic photoreceptor comprising a resin layer provided on a conductive support, wherein the resin layer is a block copolymer of a phenoxy resin and a siloxane condensate, and has a resin structure in which the entire resin layer is crosslinked. An electrophotographic photosensitive member comprising: 3. The phenoxy resin, wherein the resin layer comprises at least one selected from an organosilicon compound represented by the following general formula (1), a hydrolyzate of the organosilicon compound, and a condensate of the organosilicon compound. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is formed by the following reaction. General formula (1) R _n Si (Z) _4-n (wherein, R represents an organic group in which carbon is directly bonded to silicon in the formula, Z represents a hydroxyl group or a hydrolyzable group, and n represents An integer from 0 to 3) 4. The electrophotographic photoconductor according to claim 3, wherein at least n = 0 is used as said organosilicon compound. 5. The phenoxy resin represented by the following general formula (A)
5. The method according to claim 1, wherein:
13. The electrophotographic photoreceptor according to item 6. Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 carbon atoms
To 12 substituted or unsubstituted aryloxy groups, and a and b are each independently an integer of 0 to 4. R
_When there are a plurality of R ₃ and R ₄ , they may be the same or different. R ₁ and R ₂ may be linked to form a substituted or unsubstituted cyclo ring having 5 to 7 carbon atoms). 6. The electrophotographic photosensitive member according to claim 1, wherein the resin layer has a charge transporting group as a partial structure. 7. The siloxane condensate has a charge transporting group as a partial structure.
8. The electrophotographic photosensitive member according to any one of the above. 8. The electrophotographic photosensitive member according to claim 6, wherein the partial structure of the charge transporting group is formed by a reaction between an organosilicon compound and a reactive charge transporting compound. 9. The electrophotographic photosensitive member according to claim 8, wherein the reactive charge transporting compound has a molecular weight of 100 to 700. 10. The electrophotographic photoreceptor according to claim 9, wherein the reactive charge transporting compound has a molecular weight of 100 to 450. 11. The electrophotographic photosensitive member according to claim 1, wherein the resin layer contains an antioxidant. 12. The method according to claim 1, wherein the resin layer contains a metal chelate compound.
13. The electrophotographic photoreceptor according to item 6. 13. The electrophotographic photoconductor according to claim 12, wherein the content of the metal chelate compound is 0.01 to 20% by mass based on the total solid content of the resin layer. 14. The metal chelate compound is an aluminum chelate.
2. The electrophotographic photoreceptor of claim 1. 15. The electrophotographic photoreceptor according to claim 12, wherein the metal chelate compound is a titanium chelate. 16. The electrophotographic photosensitive member according to claim 1, wherein the resin layer is a surface layer. 17. An electrophotographic photoreceptor comprising a conductive support and a resin layer provided on a conductive support, wherein the resin layer has the general formula (1)
Is formed by applying a coating solution containing at least one selected from an organosilicon compound represented by the formula, a hydrolyzate of the organosilicon compound and a condensate of the organosilicon compound, and a phenoxy resin, followed by curing. A method for producing an electrophotographic photoreceptor. 18. The method according to claim 17, wherein the phenoxy resin is represented by the general formula (A). 19. The method for producing an electrophotographic photoreceptor according to claim 17, wherein the coating solution contains a reactive charge transporting compound. 20. The method according to claim 19, wherein the reactive charge transporting compound has a hydroxyl group as a reactive group. 21. The reactive charge transporting compound having a silyl group as a reactive group.
3. The method for producing an electrophotographic photoreceptor according to item 1. 22. The reactive charge transporting compound having a plurality of reactive groups in a molecule.
22. The method for producing an electrophotographic photosensitive member according to any one of items 21 to 21. 23. The reactive charge transporting compound having a molecular weight of 100 to 700.
23. The method for producing an electrophotographic photosensitive member according to any one of 22. 24. The method according to claim 23, wherein the reactive charge transporting compound has a molecular weight of 100 to 450. 25. The method according to claim 17, wherein the coating solution contains a metal chelate compound. 26. The method according to claim 25, wherein the content of the metal chelate compound is 0.01 to 20% by mass based on the total solid content of the coating solution. . 27. The metal chelate compound is an aluminum chelate.
3. The method for producing an electrophotographic photoreceptor according to item 1. 28. The method according to claim 25, wherein the metal chelate compound is a titanium chelate. 29. An image is formed by using the electrophotographic photosensitive member according to claim 1 through at least a charging step, an image exposure step, a developing step, and a cleaning step. Image forming method. 30. An image is formed by using the electrophotographic photoreceptor according to claim 1 through at least a charging unit, an image exposing unit, a developing unit, and a cleaning unit. Image forming apparatus. 31. A process cartridge used in the image forming apparatus according to claim 30, wherein
7. The electrophotographic photoreceptor according to any one of the above items 6 and one of a charging unit, an image exposing unit, a developing unit, and a cleaning unit are integrally combined with each other so that the unit can be inserted into and removed from the image forming apparatus. A process cartridge characterized in that it has been made.