JP2002196523A - Electrophotographic photoreceptor, method for producing the same, image forming method, image forming device and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having a protective layer excellent in toner cleaning performance and stability to the curling-up of a cleaning blade and to provide a method for producing the photoreceptor, an image forming method, an image forming device and a process cartridge. SOLUTION: In the electrophotographic photoreceptor obtained by disposing a resin layer on an electrically conductive substrate, the resin layer contains a resin having a polycarbonate component, a siloxane condensation component and an electric charge transporting structural component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photosensitive member, a method of manufacturing an electrophotographic photosensitive member, and an image forming method, an image forming apparatus, and a process cartridge using the electrophotographic photosensitive member.

[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 photosensitive member having a resin layer provided on a conductive support, wherein the resin layer contains a resin having a polycarbonate component, a siloxane condensate component, and a charge transporting structural component. body.

[0010] 2. The ratio (M ₁ / M ₂ ) of the total number of moles of monomer units M _{1 of the} polycarbonate component to the total number of moles M ₂ of the charge transporting structural component (M ₁ / M ₂ ) is 0.01 to 10; Electrophotographic photoreceptor.

3. The electrophotographic photosensitive member according to the 2 wherein M ₁ / M ₂ is characterized in that 0.1 to 1.5.

4. The electrophotographic photoreceptor according to any one of the above items 1 to 3, wherein the resin layer contains an antioxidant.

5. 5. The electrophotographic photoconductor according to any one of the items 1 to 4, wherein the resin layer is a protective layer.

6. 5. The electrophotographic photosensitive member according to any one of items 1 to 4, wherein the resin layer is a surface layer.

[0015] 7. In a method for producing an electrophotographic photoreceptor comprising a resin layer provided on a conductive support, the resin layer comprises a coating solution containing a polycarbonate having a silyl group in a side chain, an organosilicon compound and a reactive charge transporting compound. A method for producing an electrophotographic photosensitive member, which is formed by applying and then curing.

8. In the method for producing an electrophotographic photosensitive member having a resin layer provided on a conductive support, the resin layer was coated with a coating solution containing a polycarbonate having a siloxane condensate group in a side chain and a reactive charge transporting compound. A method for producing an electrophotographic photoreceptor, wherein the method is formed by curing afterwards.

9. 9. The method for producing an electrophotographic photoreceptor according to the above item 8, wherein the coating liquid further contains an organosilicon compound.

10. In the method for producing an electrophotographic photosensitive member having a resin layer provided on a conductive support, after applying a coating solution containing a polycarbonate having a silyl group in a side chain, an organosilicon compound and a reactive charge transporting compound, A method for producing an electrophotographic photosensitive member, comprising forming a resin layer containing a resin having a polycarbonate component, a siloxane condensate component, and a charge transporting structural component by curing.

11. In a method for producing an electrophotographic photosensitive member having a resin layer provided on a conductive support, a coating solution containing a polycarbonate having a siloxane condensate group in a side chain and a reactive charge transporting compound is applied, and then cured. Forming a resin layer containing a resin having a polycarbonate component, a siloxane condensate component, and a charge transporting structural component.

[12] The method for producing an electrophotographic photoreceptor according to the above item 11, wherein the coating solution further contains an organosilicon compound.

13. The method for producing an electrophotographic photosensitive member according to any one of the above items 7 to 12, wherein the coating liquid contains a metal chelate compound.

14. When the content of the metal chelate compound in the coating liquid is 0.
14. The method for producing an electrophotographic photoreceptor as described in 13 above, wherein the content is 0.01 to 20% by mass.

[15] 15. The method for producing an electrophotographic photosensitive member according to 13 or 14, wherein the metal chelate compound is an aluminum chelate compound.

16. The above 13 or 14, wherein the metal chelate compound is a titanium chelate compound.
3. The method for producing an electrophotographic photoreceptor according to item 1.

17. Wherein the reactive charge transporting compound contains a hydroxyl group as a reactive group.
17. The method for producing an electrophotographic photoreceptor according to any one of items 16.

18. (7) The reactive charge-transporting compound contains a silyl group as a reactive group.
17. The method for producing an electrophotographic photoreceptor according to any one of items 16 to 16.

19. Wherein the reactive charge transporting compound has a plurality of reactive groups in the molecule.
19. The method for producing an electrophotographic photosensitive member according to any one of 18.

20. 20. The method for producing an electrophotographic photosensitive member according to any one of 7 to 19 above, wherein the reactive charge transporting compound has a molecular weight of 100 or more and 700 or less.

21. 21. The method for producing an electrophotographic photosensitive member according to any one of the items 7 to 20, wherein the reactive charge transporting compound has a molecular weight of 100 or more and 450 or less.

22. 7. An image forming method, wherein an image is formed using the electrophotographic photosensitive member according to any one of 1 to 6 through a charging step, an image exposing step, a developing step, and a cleaning step.

23. 7. An image forming apparatus, wherein an image is formed by using the electrophotographic photoreceptor according to any one of 1 to 6, via a charging unit, an image exposing unit, a developing unit, and a cleaning unit.

24. In the process cartridge used in the image forming apparatus, the electrophotographic photosensitive member according to any one of 1 to 6, wherein at least one of a charger, an image exposing device, a developing device, and a cleaning device is integrally combined. A process cartridge which can be taken in and out of the image forming apparatus.

Hereinafter, the present invention will be described in detail. The resin of the resin layer of the present invention has a polycarbonate component, a siloxane condensate component, and a charge transporting structural component.

The polycarbonate component constituting the resin is a polymer having a carbonate structure (—OCOO—). In the present invention, the monomer unit of the polycarbonate component means a unit of each of the carbonate structural units. This polycarbonate component in the resin layer of the present invention,
It is chemically dispersed with the siloxane condensate component and the charge transporting structural component and is uniformly dispersed. Here, the chemical bond includes a covalent bond, a hydrogen bond, and an ionic bond.

In order to introduce a polycarbonate component into the resin layer of the present invention, a polycarbonate resin having a silyl group in a side chain or a polycarbonate resin having a siloxane condensate component already formed in a side chain can be used.

The method for producing a polycarbonate having a silyl group in a side chain used in the present invention is not particularly limited. For example, it may be obtained by introducing a silyl group after obtaining polycarbonate once, or by copolymerizing a phenol having a silyl group with various phenol compounds. For example, a polycarbonate having a silyl group in a side chain is described in JP-A-2000-221721.

The siloxane condensate component can be introduced into the side chain by subjecting a polycarbonate having a silyl group to the side chain to a hydrolytic condensation reaction with a silane compound in a polar solvent in the presence of water. . Here, examples of the silane compound include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; and alkoxysilanes such as methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane, and triethoxysilane. Silanes; acetoxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, and triacetoxysilane;
Examples include aminosilanes such as methyldiaminoxysilane, triaminoxysilane, dimethylaminoxysilane, and triaminosilane. These silane compounds can be used alone or in combination of two or more.

The degree of polymerization of the polycarbonate having a silyl group in the side chain used in the present invention is not particularly limited.
It is desirably about 500.

The total number of moles of the monomer units of the polycarbonate component of the present invention is based on the raw material components at the time of polycarbonate synthesis,
For example, it can be calculated from the number of moles of the bisphenol component.
It can also be calculated using the average polymerization degree of the polycarbonate in the resin layer coating liquid.

The polycarbonate component of the present invention may be any polycarbonate component having a silyl group in the side chain and having the above-mentioned carbonate structure. In particular, a silyl group may be added to the side chain selected from the following structural group A. It is preferable to have a carbonate structure.

[0041]

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In the formula, R ³ represents an alkyl group or an aryl group which may be substituted; R ⁴ represents an alkyl group which may be substituted; R ^{5 to} R ^{12 each} represent a hydrogen atom; Represents a group and a halogen atom. Y represents a group having a divalent bonding terminal. p represents 0 or 1. m is 0 <m
Represents an integer of ≤8, and n represents an integer of 0≤n≤2.

Y is a group having a divalent bonding terminal, and particularly preferably has a structure represented by the following structural group B.

[0044]

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In the formula, R ¹⁵ and R ^{16 each} represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. t represents an integer of 1 ≦ t ≦ 8.

Specific examples of the structure group A include the following structures, for example.

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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The siloxane condensate component of the present invention has a structure in which a plurality of siloxane bonds are three-dimensionally connected,
It has a structure represented by the following general formula (1) in which an organic silicon compound is polycondensed.

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. Where n is an integer of 0 to 3) Z 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. 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 − (3,
Epoxy-containing groups such as 4-epoxycyclohexyl) ethyl and the like; hydric acid groups such as (meth) acryloyl-containing γ-acryloxypropyl and γ-methacryloxypropyl; γ-hydroxypropyl and 2,3-dihydroxypropyloxypropyl; Vinyl-containing groups such as vinyl and propenyl,
a mercapto-containing group such as γ-mercaptopropyl, an amino-containing group such as γ-aminopropyl, N-β (aminoethyl) -γ-aminopropyl, γ-chloropropyl, 1,1,1
-Halogen-containing groups such as trifluorofluoropropyl, nonafluorohexyl, and perfluorooctylethyl; and other nitro and cyano-substituted alkyl groups. R
_{When n} of n is 2 or 3, the plurality of organic groups bonded to the same silicon atom may be the same or 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 the compound 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 compounds 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 wherein 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 for the siloxane condensate component having a crosslinked structure generally has a number of hydrolyzable groups (4-
When n in 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.

The charge-transporting structural component of the present invention is a structural unit having the property of having electron or hole drift mobility,
Alternatively, a charge transporting compound residue, or as another definition, a structural unit capable of obtaining a detection current due to charge transport by a known method capable of detecting charge transport performance such as a Time-Of-Flight method, or charge transport. Is a compound residue.

In order to introduce the charge transporting structural component into the resin layer of the present invention, an organic silicon compound and a reactive charge transporting compound are used, and the charge transporting structural component can be incorporated into the siloxane condensate component. . Here, the reactive charge transporting compound means the organic silicon compound or the charge transporting compound having a reactive group capable of chemically bonding to the side chain silyl group of polycarbonate. Hereinafter, the reactive charge transporting compound will be described.

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

The charge transporting compound having a hydroxyl group is represented by the following general formula (2). X- (R ₇ -OH) _m wherein X: a charge-transporting structural group, R ₇ : a single bond, a substituted or unsubstituted alkylene group, an arylene group, m: an integer of 1 to 5 is there.

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

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

[0067]

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Step A In a four-headed kolben equipped with a thermometer, a condenser, 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.

After the precipitated crystals were filtered and dried, they were 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 structural group having an alkoxy group bonded to a carbon atom, R ₈ : a single bond, a substituted or unsubstituted alkylene, an arylene group, 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: a charge-transporting structural group having an alkoxy group bonded to a carbon atom, R ₉ : a single bond, substituted, unsubstituted alkylene, substituted An unsubstituted arylene group, R _{10 is a} hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and m is 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 that remains as a branch or a group that causes a cross-linking reaction, and includes a charge transport material. 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 group containing a structural unit having charge transportability, R ₁₁ is a hydrogen atom , A substituted or unsubstituted alkyl group or an aryl group, R ₁₂ 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.

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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 structural component of the present invention refers to a chemical structural component corresponding to the charge transporting structural group X in the general formulas (2) to (5). As a specific compound structure of the charge transporting structural group X, for example, as a hole transporting type CTM, xazole, oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidin, styryl, hydrazone, benzidine,
Pyrazoline, stilbene compound, amine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine, aminostilbene, poly-N-vinylcarbazole, poly-1-
Compounds having a chemical structure such as vinylpyrene and poly-9-vinylanthracene are exemplified.

On the other hand, 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 thereof include compounds having a chemical structure such as 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and melitic acid.

The reactive charge transporting compound used in the present invention has a molecular weight of 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 charge transporting performance-imparting 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 or the siloxane condensate component has two or more reactive charge transporting compounds. When it has a functional group, it may be bonded as a divalent or higher crosslink group in the resin, or may be bonded simply as a pendant group.

The total number of moles of the charge transporting component of the present invention means the total number of moles of the reactive charge transporting compound used for forming the resin layer of the present invention.

In the present invention, the ratio (M ₁ / M ₂ ) of the total mole number M ₁ of the monomer units of the polycarbonate component to the total mole number M ₂ of the charge transporting structural component in the resin layer is preferably 0.01 to 10. And M ₁ / M ₂ is preferably 0.1 to 1.5,
0.3-1.5 is most preferred.

When M ₁ / M ₂ is in the range of 0.01 to 10,
A clear and good density image can be obtained, and the toner has good film properties with good cleaning properties.

The resin layer of the present invention comprises a polycarbonate component,
It contains a siloxane condensate component and a resin having a charge transporting structural component, but these resins in the resin layer are mutually bonded by a chemical bond, and the entire resin layer is formed of a resin layer having a crosslinked structure. ing.

The ratio of the charge transporting structural component to the total mass of the polycarbonate 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 blending ratio of the charge transporting structural component is small, the electrophotographic characteristics (charging, sensitivity, residual potential characteristics, etc.) during repeated use are degraded, while when it is too large, the film strength is reduced.

The polycarbonate component of the resin layer of the present invention,
The ratio of the siloxane condensate component and the charge transporting structural component is such that the ratio of the siloxane condensate component is 0.25 to 4 and the charge transporting structural component is 0.02 to 50 with respect to the polycarbonate component 1. preferable. 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 blending ratio of the charge transporting structural component is small, the electrophotographic characteristics (charging, sensitivity, residual potential characteristics, etc.) during repeated use are degraded, while when it is too large, the film strength is reduced.

The thickness of the resin layer of the present invention is 0.03 to 10 μm.
m, preferably 0.1 to 5 μm.
In the present invention, even if the film thickness of the resin layer is relatively large as described above, the wear resistance, the toner cleaning performance and The stability against turning of the cleaning blade can be improved. Further, a clear image can be obtained even in a high humidity environment.

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 metal oxide particles have a primary particle size of 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 diameter or the maximum length of the particle projected image 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 an ortho position to the hydroxyl group of the phenol compound and derivatives thereof (however, the hydroxyl group may be modified to alkoxy).

[0098] Examples of the hindered amine include compounds having an organic group represented by the following structural formula.

[0099]

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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.

[0104]

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[0105]

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[0106]

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[0107]

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The following compounds may be used as antioxidants in commercial products, 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 can be formed by applying a coating solution containing a polycarbonate having a silyl group in a side chain, an organosilicon compound, and a reactive charge transporting compound onto the photosensitive layer, followed by curing. it can.

The resin layer of the present invention may also be formed by applying a coating solution containing a polycarbonate having a siloxane condensate group in a side chain and a reactive charge transporting compound onto the photosensitive layer and then curing the coating solution. Can be.

More specifically, a coating solution obtained by mixing a polycarbonate having a silyl group in the side chain with an organosilicon compound and a reactive charge transporting compound may be applied and cured. A polycarbonate and an organosilicon compound may be mixed to form a siloxane condensate on the side chain of the polycarbonate in advance, and then a coating solution mixed with the organosilicon compound and the reactive charge transport compound may be applied and cured.

By the curing, the siloxane condensate becomes 3
Dimensionalized, a siloxane condensate and a polycarbonate having a silyl group in the side chain, and a reactive charge transporting compound are chemically bonded via a silyl group or a reactive group, thereby providing abrasion resistance and a photosensitive layer. A resin layer having good adhesion and cleaning properties is formed.

In any of the above-mentioned production methods, the compounding ratio of the organosilicon compound as the raw material, the polycarbonate having a siloxane condensate group or a silyl group in the side chain, and the reactive charge transporting compound in the coating liquid is determined by the resin layer obtained. The proportion of the polycarbonate component, the siloxane condensate component, and the charge transporting structural component in the composition may be any ratio that falls within the above range. For example, when the compound of the general formula (1) is used as the organosilicon compound, The mass ratio of the organic silicon compound, the polycarbonate having a silyl group in the side chain, and the reactive charge transporting compound is preferably from 100: 25 to 400: 1 to 1,000.

In order to accelerate the reaction between the organosilicon compound, the polycarbonate having a silyl group in the side chain, 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)). The metal chelate compound (III) promotes the hydrolysis and / or partial condensation reaction between the organosilicon compound and the polycarbonate having a silyl group in the side chain, and the reactive charge transporting compound, and forms a three-component co-condensate. It is thought to act to promote formation.

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 solid content of the coating solution such as an organosilicon compound, a polycarbonate having a siloxane condensate group or a silyl group in a side chain, and a reactive charge transporting compound (the solid content of the coating solution is a component remaining after drying the coating solution). The compounding amount is 0.
The amount is from 0.01 to 20% by mass, preferably from 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 liquid for the resin layer depend on the reactivity of the organosilicon compound used, but it is preferable to carry out drying at 60 to 150 ° C. for 30 minutes to 6 hours. .

In order to accelerate these curing reactions, 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 suitable. 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 polycarbonate having a silyl group in a side chain, 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 the alcohol solvent include alcohols having 1 to 4 carbon atoms, ie, methanol, ethanol, n-propanol, iso-propanol, n-butanol and is
o-Butanol, sec-butanol and tert-butanol are preferably used.

As the non-alcohol solvent, ketone solvents such as ethyl methyl ketone, methyl isopropyl ketone and methyl isobutyl ketone are preferably used.

A curing accelerator can be further added to the above 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, d
Hardness of tanolamine, triethylamine, epoxy resin
Various modified amines used as an agent, γ-aminopro
Piltriethoxysilane, γ- (2-aminoethyl)-
Aminopropyltrimethoxysilane, γ- (2-amino
Ethyl) -aminopropylmethyldimethoxysilane, γ
-Amines such as anilinopropyltrimethoxysilane
Compound, (C_FourH₉)_TwoSn (OCOC₁₁H_{twenty three})_Two, (C_Four
H₉)_TwoSn (OCOCH = CHCOOCH_Three)_Two, (C_Four
H₉)_TwoSn (OCOCH = CHCOOC_FourH₉)_Two, (C₈
H₁₇)_TwoSn (OCOC₁₁H _{twenty three})_Two, (C₈H₁₇)_TwoSn
(OCOCH = CHCOOCH_Three)_Two, (C₈H₁₇)_TwoSn
(OCOCH = CHCOOC_FourH₉)_Two, (C₈H₁₇)_TwoS
n (OCOCH = CHCOOC₈H₁₇)_Two, Sn (OCO
CC₈H₁₇)_TwoCarboxylic acid type organotin compounds such as
(C_FourH₉)_TwoSn (SCH_TwoCOO)_Two, (C_FourH₉)_TwoSn
(SCH_TwoCOOC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SC
H_TwoCOO)_Two, (C₈H₁₇)_TwoSn (SCH _TwoCH_TwoCO
O)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOCH_TwoCH_TwoO
COCH_TwoS)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC
H_TwoCH_TwoCH_TwoCH_TwoOCOCH_TwoS)_Two, (C₈H₁₇)_TwoS
n (SCH_TwoCOOC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (S
CH_TwoCOOC₁₂H_{twenty five})_Two,

[0127]

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Mercaptide-type organotin compounds such as

[0129]

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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. 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.

In the present invention, an organic solvent can be used in order to adjust the total solid content of the coating solution for the resin layer and also adjust the viscosity. As such an organic solvent, it is preferable to use an organic solvent such as alcohols, aromatic hydrocarbons, ethers, ketones and esters. As the alcohols, for example, monovalent or divalent
Alcohols, specifically 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, 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, ethylene glycol monoethyl ether acetate and the like. Among them, monovalent saturated aliphatic alcohols having 1 to 8 carbon atoms are preferred. Specific examples of the aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of the ethers include tetrahydrofuran and dioxane, and specific examples of the esters. Examples include ethyl acetate, n-propyl acetate, n-butyl acetate, propylene carbonate and the like. 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.

Next, the structure of the photoreceptor 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 may be a charge generation layer, a charge transport layer, or a charge generation / charge transport layer (a layer having functions of charge generation and charge transport in the same layer).
And the like, and a resin layer of the present invention coated thereon as a protective 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 rotation, 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 a 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 / 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 can 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-layer 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 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, and 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 Charge transport layer: The charge transport layer contains a charge transport material (CTM) and a binder resin for dispersing the CTM to form 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 unit (image exposing means) 53 performs image exposure based on the 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 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 by a developing device (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 a ferrite core 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 applicable to general electrophotographic apparatuses such as electrophotographic copying machines, laser printers, LED printers, and liquid crystal shutter printers. , Light printing, plate making and facsimile.

[0166]

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 Preparation of Photoconductor 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 Using the above coating solution, a cylindrical conductive support having a diameter of 100 mm. It was applied to a thickness of 0.5 μm on the top. <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 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 generating 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 substance (N- (4-methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine) 225 g Polycarbonate (viscosity average molecular weight 30,000) 300 g Antioxidant (Exemplified Compound 1-3) 6 g of dichloromethane 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. <Resin Layer> Polycarbonate (1) having a silyl group in the side chain (weight average molecular weight 8500) (polycarbonate (1) below) 30 g methyltrimethoxysilane 120 g 1% acetic acid aqueous solution 30 g 1,3-dioxolane 100 g was mixed, Heat and stir for 48 hours at a temperature of
A hydrolysis-condensation reaction between a polycarbonate having a silyl group in a side chain and methyltrimethoxysilane was performed to obtain an oligomerization solution.

Next, the following components were added to the obtained oligomerized solution, and the mixture was further stirred at room temperature for 12 hours.

Reactive charge transporting compound (exemplified compound (B-1): molecular weight 305) 60 g Antioxidant (exemplified compound 2-1) 3 g Curing agent aluminum chelate A (W) (manufactured by Kawaken Chemical Co., Ltd.) 4 g 1 , 3-dioxolane 150 g This photo-conductor 1 was prepared by forming a 2 μm-thick resin layer on the above-mentioned charge transporting layer by a circular amount-regulating type coating apparatus and heating and curing at 120 ° C. for 1 hour. . The ratio of the total number of moles of monomer units M ₁ of the polycarbonate component in the resin layer of the photoreceptor 1 to the total number of moles M ₂ of the charge transporting structural component (M ₁ /
M ₂₎ was 0.45.

[0170]

Embedded image

Preparation of Photoreceptor 2 In the photoreceptor 1, polycarbonate as a resin layer coating solution
The amount of (1) was increased from 30 g to 60 g with methyltrimethoxy.
The amount of silane is increased from 120 g to 90 g,
The compound was converted from the exemplified compound B-1 to the exemplified compound Si-1 (min.
Photoreceptor 2 was fabricated in the same manner except that
did. Model of polycarbonate component in the resin layer of photoconductor 2
Nomer unit total mole number M₁And total moles of charge transporting structural components
Number M_TwoRatio (M ₁/ M_Two) Was 1.46.

Preparation of Photoconductor 3 Photoconductor 3 was prepared in the same manner as photoconductor 1, except that acetylacetone trisbutoxyzirconium (manufactured by Matsumoto Pharmaceutical Co.) was used as a curing agent in the resin layer.

Preparation of Photoconductor 4 Photoconductor 4 was prepared in the same manner as photoconductor 1, except that titanium chelate (TC-750: manufactured by Matsumoto Pharmaceutical Co., Ltd.) was used as a curing agent in the resin layer.

Preparation of Photoreceptor 5 In the photoreceptor 1, instead of the polycarbonate (1) having a silyl group on the side chain in the resin layer, the polycarbonate (2) having a silyl group on the side chain (weight average molecular weight 12,000: the above polycarbonate ( Photoconductor 5 was prepared in the same manner except that 2)) was used. The ratio (M ₁ / M ₂ ) of the total mole number M ₁ of the monomer units of the polycarbonate component to the total mole number M ₂ of the charge transporting structural component in the resin layer of the photoreceptor 5 was 0.41.

Preparation of Photoreceptor 6 Photoreceptor 6 was prepared in the same manner as for Photoreceptor 1, except that the reactive charge transporting compound (Exemplary Compound B-1) in the resin layer was omitted. The ratio (M ₁ / M ₂ ) of the total mole number M ₁ of the monomer unit of the polycarbonate component to the total mole number M ₂ of the charge transporting structural component in the resin layer of the photoconductor 6 is a value (infinity) larger than 10 (infinity). .

Preparation of Photoreceptor 7 A photoreceptor 1 was prepared in the same manner up to the charge transport layer. <Resin Layer> Silicone hard coat agent (KP-851: manufactured by Shin-Etsu Chemical Co., Ltd.) 182 g Reactive charge transporting compound (Exemplary Compound (B-1)) 15 g Antioxidant (Exemplary Compound 2-1) 0.75 g 2- 75 g of propanol and 5 g of 3% acetic acid were mixed to prepare a coating solution for a resin layer. This coating solution was coated on the charge transport layer with a circular amount-regulating coating device to form a resin layer having a dry film thickness of 2 μm, and was heated and cured at 120 ° C. for 1 hour to form a siloxane resin layer. Was prepared. The ratio (M ₁ / M ₂ ) of the total mole number M ₁ of the monomer unit of the polycarbonate component to the total mole number M ₂ of the charge transporting structural component in the resin layer of the photoconductor 7 is 0.

Evaluation A Konica Digital Copier Konica 7 was used as an 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 on A4 neutral paper. Copying conditions are considered to be the most severe in a high-temperature and high-humidity environment (30 ° C, 80%
(RH), 200,000 copies were made continuously, and a halftone, a solid white image, and a solid black image were evaluated. 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 as follows. 10 copies of the original image were continuously copied, and the determination was made based on whether or not cleaning failure occurred in the solid white portion. The blade turn is 2
The number of occurrences during the 10,000 copies was counted. 20
After 10,000 copies, the starting torque of the blade was measured. The absolute reflection density was measured using RD-918 manufactured by Macbeth Co., Ltd., and comparison was made between the initial image and the image after 100,000 sheets. Further, for fog, a solid white image was used, and the relative reflection density was set to RD-918 manufactured by Macbeth Co., Ltd. with the reflection density of the paper being “0”.
Was used to compare the initial density and the density after 100,000 copies.

Evaluation Criteria Image density (measured using Macbeth RD-918).
測定: 1.2 or more: good ○: less than 1.2 to 1.0: no practical problem x: less than 1.0: practical Problematic level of resolution (determined by the easiness of discrimination of character images) ○: No difference between initial and resolution after 200,000 copies △: Minor decrease in resolution after 200,000 copies in halftone image ×: 200,000 There is a noticeable decrease in the resolution after copying. Cleanability (A3 after 100,000 and 200,000 copies)
(Continuous copying of 10 sheets is performed on paper, and judgment is made based on whether or not cleaning failure has occurred on the solid white area.) ◎: No pass-through occurred on 200,000 sheets ○: No pass-through occurred on 100,000 sheets ×: Pass-through occurred on less than 100,000 sheets Blade turning (judging the number of occurrences during 200,000 copies by counting) ◎: No occurrence up to 200,000 sheets ○: Minor partial turning up ×: Blade turning up Measurement of starting torque of cleaning blade Drum cartridge after 200,000 copies Torque gauge connected to the drum shaft of the copier body (MODEL 6
(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 Amount The wear amount was determined by calculating the difference between the average film thickness of the photoreceptor measured at the start of the actual image evaluation and at the end of 200,000 copies, and used as the film thickness loss amount.

Method for Measuring Film Thickness The film thickness of the photosensitive layer is measured at random at 10 places with a uniform film 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 above 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 using 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 (g / cm).

The evaluation results are shown in Table 1.

[0184]

[Table 1]

As is clear from Table 1, the photoreceptors 1 to 5 having the resin layer of the present invention are compared with the photoreceptors 6 and 7 outside the present invention.
Although the thickness loss is slightly reduced, the image characteristics such as image density and resolution, and the cleaning characteristics such as cleaning properties and blade turn-up are improved. The smaller size than the bodies 6 and 7 also indicates that the cleaning characteristics are stable.

[0186]

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 5/05 101 G03G 5/05 101 104 104B

Claims (24)

[Claims] 1. An electrophotographic photoreceptor comprising a resin layer provided on a conductive support, wherein the resin layer contains a resin having a polycarbonate component, a siloxane condensate component and a charge transporting structural component. Electrophotographic photosensitive member. _2. The ratio (M ₁ / M ₂ ) of the total number of moles of monomer units M _{1 of the} polycarbonate component to the total number of moles M ₂ of charge transporting structural components is from 0.01 to 10. The electrophotographic photosensitive member according to claim 1. 3. The electrophotographic photoconductor according to claim 2, wherein M ₁ / M ₂ is 0.1 to 1.5. 4. The electrophotographic photoreceptor according to claim 1, wherein the resin layer contains an antioxidant. 5. The electrophotographic photosensitive member according to claim 1, wherein the resin layer is a protective layer. 6. The electrophotographic photosensitive member according to claim 1, wherein the resin layer is a surface layer. 7. A method for producing an electrophotographic photoreceptor comprising a resin layer provided on a conductive support, wherein the resin layer comprises a polycarbonate having a silyl group in a side chain, an organosilicon compound and a reactive charge transporting compound. A method for producing an electrophotographic photoreceptor, which is formed by applying and then curing a coating solution contained therein. 8. A method for producing an electrophotographic photoreceptor comprising a resin layer provided on a conductive support, wherein the resin layer contains a polycarbonate having a siloxane condensate group in a side chain and a reactive charge transporting compound. A method for producing an electrophotographic photoreceptor, which is formed by applying a coating liquid and then curing the coating liquid. 9. The method according to claim 8, wherein the coating solution further contains an organosilicon compound. 10. A method for producing an electrophotographic photoreceptor comprising a resin layer provided on a conductive support, wherein the coating solution contains a polycarbonate having a silyl group in a side chain, an organosilicon compound and a reactive charge transporting compound. A method for producing an electrophotographic photosensitive member, comprising forming a resin layer containing a resin having a polycarbonate component, a siloxane condensate component, and a charge transporting structural component by applying and curing the resin. 11. A method for producing an electrophotographic photoreceptor comprising a resin layer provided on a conductive support, wherein a coating liquid containing a polycarbonate having a siloxane condensate group in a side chain and a reactive charge transporting compound is applied. After curing,
A method for producing an electrophotographic photosensitive member, comprising forming a resin layer containing a resin having a polycarbonate component, a siloxane condensate component, and a charge transporting structural component. 12. The method according to claim 11, wherein the coating liquid further contains an organosilicon compound. 13. The method according to claim 7, wherein the coating liquid contains a metal chelate compound. 14. The content of the metal chelate compound in the coating solution is preferably 0.03% by weight based on the total weight of the coating solution solids.
The method for producing an electrophotographic photosensitive member according to claim 13, wherein the content is 1 to 20% by mass. 15. The method according to claim 13, wherein the metal chelate compound is an aluminum chelate compound. 16. The metal chelate compound according to claim 13, wherein the metal chelate compound is a titanium chelate compound.
3. The method for producing an electrophotographic photoreceptor according to item 1. 17. The reactive charge-transporting compound contains a hydroxyl group as a reactive group.
17. The method for producing an electrophotographic photoreceptor according to any one of items 16. 18. The method according to claim 7, wherein the reactive charge transporting compound contains a silyl group as a reactive group.
17. The method for producing an electrophotographic photoreceptor according to any one of items 16 to 16. 19. The method according to claim 7, wherein the reactive charge transporting compound has a plurality of reactive groups in a molecule.
19. The method for producing an electrophotographic photosensitive member according to any one of 18. 20. The method for producing an electrophotographic photosensitive member according to claim 7, wherein the reactive charge transporting compound has a molecular weight of 100 or more and 700 or less. 21. The method for producing an electrophotographic photosensitive member according to claim 7, wherein the reactive charge transporting compound has a molecular weight of 100 or more and 450 or less. 22. An image forming method using the electrophotographic photosensitive member according to claim 1 through a charging step, an image exposing step, a developing step, and a cleaning step. Method. 23. An image forming method using the electrophotographic photoreceptor according to claim 1 through a charging unit, an image exposing unit, a developing unit, and a cleaning unit. apparatus. 24. A process cartridge used in the image forming apparatus, wherein the electrophotographic photosensitive member according to claim 1 is used, and at least one of a charging device, an image exposing device, a developing device, and a cleaning device. A process cartridge, wherein one is integrally combined and can be taken in and out of the image forming apparatus.