JP2002244329A - 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 with a resin layer excellent in toner cleaning performance and stability to the burr 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 with the resin layer on an electrically conductive substrate, the resin layer contains a resin having an organic polymer component and a siloxane condensate component and an electric charge transporting compound, and the siloxane condensate component of the resin is formed using a silane compound having at least an epoxy group or its ring opened group.

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.

Further, since such a protective layer is a high-order crosslinked resin layer peculiar to a siloxane-based resin, it becomes a protective layer having a strong elastic behavior. The problem is often that the torque between the cleaning blade and the cleaning blade increases, and the cleaning performance of the toner and the stability of the cleaning blade against turning up decrease. 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. In an electrophotographic photoreceptor having a resin layer on a conductive support, the resin layer contains a resin having an organic polymer component and a siloxane condensate component, a charge transporting compound, and the siloxane condensate component of the resin is at least epoxy. An electrophotographic photosensitive member formed using a silane compound having a group or a ring-opening group thereof.

[0010] 2. 2. The electrophotographic photoreceptor according to item 1, wherein the mass ratio of the organic polymer component to the siloxane condensate component in the resin layer is 1: 0.1 to 10.

3. The siloxane condensate is formed using a silane compound having an epoxy group or its ring-opening group and another silane compound, and the mass ratio of both is 1: 0.0
3. The electrophotographic photoreceptor according to the above 1 or 2, wherein the number is from 1 to 100.

4. 4. The electrophotographic photoconductor according to any one of the above items 1 to 3, wherein the organic polymer component is a vinyl resin component.

5. 5. The electrophotographic photoreceptor according to the item 4, wherein the vinyl resin component is an acrylic polymer.

6. The electrophotographic photoreceptor according to any one of the above items 1 to 5, wherein the resin layer contains an antioxidant.

[0015] 7. 7. The electrophotographic photoconductor according to any one of items 1 to 6, wherein the resin layer is a protective layer.

8. In a method for producing an electrophotographic photosensitive member having a resin layer on a conductive support, the resin layer comprises an organic polymer having a silyl group in a side chain and a silane compound having at least an epoxy group or a ring-opening group thereof, and a charge transporting property. A method for producing an electrophotographic photoreceptor, wherein the method is formed by applying a coating solution containing a compound, followed by curing.

9. In the method for producing an electrophotographic photoreceptor having a resin layer on a conductive support, the resin layer is an organic compound having a siloxane condensate formed on at least an epoxy group or a silane compound having a ring-opening group in a side chain. A method for producing an electrophotographic photoreceptor, wherein the method is formed by applying a coating solution containing a polymer and a charge transporting compound, followed by curing.

10. The method for producing an electrophotographic photoreceptor according to the above item 9, wherein the coating solution contains a silane compound.

11. The method for producing an electrophotographic photosensitive member according to any one of the above items 8 to 10, wherein the coating liquid contains a metal chelate compound.

[12] When the content of the metal chelate compound in the coating liquid is 0.
12. The method for producing an electrophotographic photoreceptor as described in 11 above, wherein the content is from 0.01 to 20% by mass.

13. (11) or (12), wherein the metal chelate compound is an aluminum chelate.
3. The method for producing an electrophotographic photoreceptor according to item 1.

14. 13. The method for producing an electrophotographic photosensitive member according to the above item 11 or 12, wherein the metal chelate compound is a titanium chelate.

[15] 8. An image forming method using the electrophotographic photoreceptor according to any one of the above items 1 to 7, through at least a charging step, an image exposing step, a developing step, and a cleaning step.

16. An image forming apparatus using the image forming method described in 15 above.

17. 17. The process cartridge used in the image forming apparatus according to 16 above, wherein the electrophotographic photosensitive member according to any one of 1 to 7 above, and any one of a charger, an image exposing unit, a developing unit, and a cleaning unit. Are integrated with each other so as to be freely inserted into and removed from the image forming apparatus.

Hereinafter, the present invention will be described in detail. The resin layer of the present invention contains a resin having an organic polymer component and a siloxane condensate component.

The organic polymer component constituting the resin is a polymer component composed of organic monomer units.
The organic monomer unit means, for example, a monomer unit constituting a vinyl resin, a polyester resin, a polycarbonate resin, or the like. In the resin of the present invention, the organic polymer component is chemically bonded to the siloxane condensate component and the charge transporting structural component, and is homogenized. Here, the chemical bond includes a covalent bond, a hydrogen bond, and an ionic bond generated by a chemical reaction.

In order to introduce an organic polymer component into the resin of the present invention, a vinyl resin having a silyl group on the side chain of the organic polymer component or a vinyl resin having a siloxane condensate component already formed on the side chain. Can be used.

The method for producing the silyl group-containing vinyl resin used in the present invention is not particularly limited. For example, it may be obtained by once introducing a silyl group after obtaining a vinyl resin, or by polymerizing a vinyl compound having a silyl group with various vinyl compounds. Specifically, the silyl group-containing vinyl resin may be produced, for example, by reacting (a) a hydroxysilane compound with a vinyl resin having a carbon-carbon double bond, and (b) the following general formula (1) );

[0030]

Embedded image

(Wherein R ³ is a hydrogen atom, having 1 to 10 carbon atoms)
R ⁴ is an organic group having a polymerizable double bond, X is a halogen atom, an alkoxy group, an acyloxy group, an aminooxy group, a phenoxy group, and n is 1 to 3 Is an integer. ) And various vinyl compounds may be polymerized.

Here, examples of the hydroxysilane compound used in the production method shown in (a) above include halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldiethoxysilane; Alkoxysilanes such as methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane and triethoxysilane; methyldiacetoxysilane;
Acetoxysilanes such as phenyldiacetoxysilane and triacetoxysilane; methyldiaminoxysilane,
Examples include aminosilanes such as triaminoxysilane, dimethylaminoxysilane, and triaminosilane. These hydroxysilane compounds can be used alone or in combination of two or more.

The vinyl resin used in the production method shown in (a) is not particularly limited, except for the vinyl resin containing a hydroxyl group. For example, methyl (meth) acrylate, (meth) acryl Ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid esters such as cyclohexyl (meth) acrylate; (meth) acrylic acid, itaconic acid,
Carboxylic acids such as fumaric acid and acid anhydrides such as maleic anhydride; epoxy compounds such as glycidyl (meth) acrylate; amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether;
(Meth) acrylamide, itaconic diamide, α-ethylacrylamide, crotonamide, fumaric diamide, maleic diamide, N-butoxymethyl (meth)
Amide compounds such as acrylamide; vinyl resins obtained by polymerizing or copolymerizing one or more vinyl compounds selected from the group consisting of acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate and the like are preferable. .

On the other hand, in the production method shown in (b)
Silane compounds include silyl groups, especially hydrolyzable
Having a silyl group having the following various vinyl compounds and
The compound is not particularly limited as long as it is a polymerizable compound.
H_Two= CHSi (CH_Three) (OCH_Three)_Two, CH_Two= CHS
i (OCH_Three)_Three, CH_Two= CHSi (CH_Three) Cl_Two, C
H_Two= CHSiCl_Three, CH_Two= CHCOO (CH_Two)_TwoS
i (CH_Three) (OCH_Three)_Two, CH_Two= CHCOO (C
H_Two)_TwoSi (OCH_Three)_Three, CH_Two= CHCOO (CH_Two)
_ThreeSi (CH_Three) (OCH_Three)_Two, CH_Two= CHCOO (C
H_Two)_ThreeSi (OCH_Three) _Three, CH_Two= CHCOO (CH_Two)
_TwoSi (CH_Three) Cl_Two, CH_Two= CHCOO (CH_Two)_TwoS
iCl_Three, CH_Two= CHCOO (CH_Two)_ThreeSi (CH_Three)
Cl_Two, CH_Two= CHCOO (CH_Two)_ThreeSiCl_Three, CH_Two
= C (CH_Three) COO (CH_Two)_TwoSi (CH_Three) (OCH
_Three)_Two, CH_Two= C (CH_Three) COO (CH_Two)_TwoSi (OC
H_Three)_Three, CH_Two= C (CH_Three) COO (CH_Two)_ThreeSi (C
H_Three) (OCH_Three)_Two, CH_Two= C (CH_Three) COO (C
H_Two)_ThreeSi (OCH_Three)_Three, CH_Two= C (CH_Three) COO
(CH_Two)_TwoSi (CH_Three) Cl_Two, CH_Two= C (CH_Three) C
OO (CH_Two)_TwoSiCl_Three, CH_Two= C (CH_Three) COO
(CH_Two)_ThreeSi (CH_Three) C_l2, CH_Two= C (CH_Three) C
OO (CH_Two)_ThreeSiCl_Three,

[0035]

Embedded image

And the like. These silane compounds can be used alone or in combination of two or more.

As the various vinyl compounds used in the production method shown in (b), the vinyl compounds exemplified in the description of the vinyl resin used in the production method (a) can be used. However, besides these examples,
Vinyl compounds containing a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyvinyl ether, N-methylolacrylamide, and the like can be given. These vinyl compounds can be used alone or in combination of two or more.

Synthesis of Silyl Group-Containing Vinyl Resin (A) As monomers, 65 parts of methyl methacrylate, 35 parts of n-butyl acrylate, γ-methacryloxypropyltrimethoxysilane (KBM503: manufactured by Shin-Etsu Chemical Co., Ltd.) 2
0 parts and 16 parts of 2-hydroxyethyl methacrylate were mixed and dissolved in 130 parts of isopropyl alcohol, and stirred at 80 ° C. A solution obtained by dissolving 4 parts of azobisisobutyronitrile in 10 parts of tetrahydrofuran was added dropwise and reacted for 4 hours to obtain a silyl group-containing vinyl resin (A) having a solid concentration of 50%.

Synthesis of Silyl Group-Containing Vinyl Resin (B) As monomers, 65 parts of methyl methacrylate, 35 parts of n-butyl acrylate, γ-methacryloxypropyltrimethoxysilane (KBM503: manufactured by Shin-Etsu Chemical Co., Ltd.) 2
0 parts, 10 parts of N-methylolacrylamide and 6 parts of acrylic acid were mixed and dissolved in 130 parts of isopropyl alcohol, and stirred at 80 ° C. A solution obtained by dissolving 4 parts of azobisisobutyronitrile in 10 parts of xylene was added dropwise and reacted for 4 hours to obtain a silyl group-containing vinyl resin (B) having a solid concentration of 50%.

In the vinyl resin having a siloxane condensate component in the side chain, the silyl group-containing vinyl resin is reacted with the silane compound in the side chain to form a siloxane condensate in the side chain of the vinyl resin. I can do it.

The polymerization degree of the silyl group-containing vinyl resin used in the present invention is not particularly limited, but is preferably from 100 to 500.

The siloxane condensate component of the present invention has a structure in which a plurality of siloxane bonds are three-dimensionally connected.

The siloxane condensate of the present invention is characterized by being formed using a silane compound having at least an epoxy group or a ring-opening group thereof.

That is, when the resin layer of the present invention having a siloxane condensate formed using a silane compound having an epoxy group or a ring-opening group thereof is used as a surface layer of an electrophotographic photosensitive member, Improves abrasion resistance and does not cause image blur in high-humidity environment or low-humidity environment.

The silane compounds having an epoxy group or a ring-opening group thereof preferably used in the present invention include (3-glycidoxypropyl) trimethoxysilane and 2- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3- (Glycidoxypropyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, diethoxy-3
-Glycidoxypropylmethylsilane and the like.

In order to form the siloxane condensate component of the present invention, a polycondensation is formed by using a silane compound represented by the following general formula (2) in addition to the silane compound having an epoxy group or a ring-opening group thereof. Is preferred.

Formula (2) 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. Wherein n is an integer of 0 to 3) Z in the general formula (2) 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, 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-acryloxypropyl, and γ- (Meth) acryloyl group of methacryloxypropyl, γ-
Hydroxy groups such as hydroxypropyl and 2,3-dihydroxypropyloxypropyl, vinyl groups such as vinyl and propenyl, mercapto groups such as γ-mercaptopropyl, γ-aminopropyl, N-β (aminoethyl) -γ
Amino-containing groups such as -aminopropyl, halogen-containing groups such as γ-chloropropyl, 1,1,1-trifluoropropyl, nonafluorohexyl, and perfluorooctylethyl; and other nitro and cyano-substituted alkyl groups. Can be. 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.

In producing the siloxane resin of the present invention, the silane compound represented by the general formula (2)
When more than one kind is used, R of each silane compound may be the same or different.

Specific examples of the silane compound represented by the general formula (2) 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 where 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-bromopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, 3-aminopropyltriethoxysilane , Methyltriisopropenoxysilane, 3-methacryloxypropyltrimethoxysilane, decyltrichlorosilane, bis (ethylmethylketoxime) methoxymethylsilane, 3-morpholinopropyltrimethoxysilane, 3-piperazinopropyltrimethoxysilane Methyltripropoxysilane, methyltris (2-methoxyethoxysilane), 2- (2-aminoethylthioethyl) triethoxysilane, 3- [2- (2-aminoethylaminoethyl (No) propyl] triethoxysilane, tris (1-methylvinyloxy) vinylsilane, triisopropoxyvinylsilane, tris (2-methoxyethoxy) vinylsilane, diisopropoxyethylmethylketoximemethylsilane, 3-piperidinopropyltrimethoxy Silane, pentyltriethoxysilane, 4
-Chlorophenyltriethoxysilane, phenyltriethoxysilane, bis (ethylmethylketoxime) methylisopropoxysilane, bis (ethylmethylketoxime) -2-methoxyethoxymethylsilane, 3- (2
-Methylpiperidinopropyl) trimethoxysilane, 3
-Cyclohexylaminopropyltrimethoxysilane,
O, O'-diethyl-S- (2-triethoxysilylethyl) dithiophosphate, benzyltriethoxysilane, 6-triethoxysilyl-2-norbornene,
-Benzylaminopropyltrimethoxysilane, methyltris (ethylmethylketoxime) silane, bis (ethylmethylketoxime) butoxymethylsilane, methyltris (N, N-diethylaminoxy) silane, tetradecyltrichlorosilane, octyltriethoxysilane, phenyl Tris (2-methoxyethoxy) silane,
3- (vinylbenzylaminopropyl) trimethoxysilane, N- (3-triethoxysilylpropyl) -p-
Nitrobenzamide, 3- (vinylbenzylaminopropyl) triethoxysilane, octadecyltrichlorosilane, dodecyltriethoxysilane, docosyltrichlorosilane, octadecyltriethoxysilane, dimethyloctadecyl-3-trimethoxylsilylpropylammonium chloride, 1,2- Bis (methyldichlorosilyl) ethane and the like can be mentioned.

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, 3- (3-acetoxypropylthio) propyldimethoxymethylsilane, dimethoxymethyl-3-piperidinopropylsilane, dipropoxyethylmethylketoximemethylsilane, diphenyldichlorosilane, diphenyldifluorosilane, diphenylsilanediol, dihexyldichlorosilane, Bis (ethylmethylketoxime) methylpropoxysilane, dimethoxymethyl-3- (4-methylpiperidinopropyl)
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 silane compound used as a raw material of the siloxane-based resin having a crosslinked structure is generally such that when the number (4-n) of hydrolyzable groups bonded to a silicon atom is 3, the silane compound is The polymerization reaction 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 resin layer of the present invention contains a resin having an organic polymer component and a siloxane condensate component. These resins in the resin layer are mutually bonded by a chemical bond, and the entire resin layer has a crosslinked structure. It is formed with a resin layer having.

The ratio of the organic polymer component to the siloxane condensate component in the resin layer of the present invention is 1
It is preferable that the siloxane condensate component is constituted with a compounding ratio of 0.25 to 4. 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. Also, if the compounding ratio of the siloxane condensate component is small, the electrophotographic characteristics (charging, sensitivity, residual potential characteristics, etc.) during repeated use are degraded, while if too large, the film strength is reduced.

The siloxane condensate component is preferably formed in a weight ratio of the silane compound having an epoxy group or a ring-opening group thereof to another silane compound of 1: 0.01 to 100. Further, the mass ratio is from 1: 1 to 20
Is preferred.

The resin layer of the present invention preferably contains a charge transporting compound. Here, the charge transporting compound is a compound having a property of having electron or hole drift mobility, and as another definition, Time-Of-Fli
It is a compound capable of obtaining a detection current due to charge transport by a known method such as the ght method capable of detecting charge transport performance.

As the charge transporting compound (CTM), for example, as the hole transporting type CTM, there may be mentioned 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
And compounds such as -vinylcarbazole, poly-1-vinylpyrene, and poly-9-vinylanthracene.

On the other hand, as electron transport type CTM, 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 compounds such as 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and melitic acid.

Examples of the charge transporting compound preferably used in the resin layer of the present invention are described below.

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The compounding amount of the charge transporting compound contained in the resin layer of the present invention is preferably such that the ratio of the charge transporting compound to the total mass of the resin layer is 1: 0.01 to 10:10. If the mass ratio of the charge transporting compound is small, the electrophotographic characteristics (charging, sensitivity, residual potential characteristics, etc.) during repeated use deteriorate,
On the other hand, if it is too large, the film strength decreases.

The thickness of the resin layer of the present invention is 0.03 to 30 μm.
m, preferably 0.03 to 10 μm, most preferably 0.1 to 5 μm. In particular, when the resin layer of the present invention is used as a protective layer, the thickness is 0.03 to 1
It is desirable that the thickness be 0 μm, preferably 0.1 to 5 μm. When the resin layer of the present invention is used as the protective layer, even if the protective layer has such a relatively large thickness, without lowering electrostatic characteristics such as sensitivity and residual potential, which have conventionally been a problem, The abrasion resistance, the cleaning performance of the toner, and the stability of the cleaning blade against turning up can be improved. Further, a clear image can be obtained even in a high humidity environment.

The above 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 silane compound on the particle surface. Examples of the reactive compound group include a hydroxyl group and an amino group. By using a metal oxide particle having such a reactive group, a siloxane condensed component of the resin of the present invention and a composite resin layer in which the surface of the metal oxide particle is chemically bonded to form a resin layer. 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 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, hindered phenol means 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).

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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The following compounds are commercially available antioxidants, 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 is formed by applying a coating solution containing an organic polymer having a silyl group on the side chain and a silane compound having at least an epoxy group or its ring-opening group onto the photosensitive layer and then curing the coating solution. can do.

The resin layer of the present invention is obtained by applying a coating solution containing an organic polymer having a siloxane condensate in a side chain formed by using a silane compound having at least an epoxy group or its ring-opening group onto the photosensitive layer. After that, it can also be formed by curing.

Specifically, a coating solution obtained by mixing a vinyl resin having a silyl group in the side chain with at least a silane compound having an epoxy group or a ring-opening group thereof may be applied and cured. A vinyl-based resin having a silyl group and a silane compound having at least an epoxy group or its ring-opening group are mixed, a siloxane condensate is previously formed on the side chain of the vinyl-based resin, and then a coating liquid mixed with the silane compound is applied.
It may be cured.

By the curing, the siloxane condensate becomes 3
Dimensionally, the siloxane condensate and the silyl group-containing vinyl resin are chemically bonded via the silyl group and the reactive group, thereby providing a resin layer having good abrasion resistance, adhesion to the photosensitive layer, and cleaning properties. Is formed.

In any of the above production methods, the compounding ratio of the silane compound, siloxane condensate, and vinyl resin having a silyl group as the raw materials in the coating solution is determined by the organic polymer component and siloxane condensate component in the obtained resin layer. Any ratio may be used as long as the compounding ratio of the silane compound and the silyl group-containing vinyl resin is within the above range.
A compounding ratio of 0:25 to 400 is preferred.

The silane compound is preferably blended in a weight ratio of the silane compound having an epoxy group or a ring-opening group thereof to another silane compound of 1: 0.01 to 100. Further, the compounding ratio is preferably from 1: 1 to 20 in terms of mass ratio.

In order to promote the reaction between the silane compound and the silyl group-containing vinyl resin, 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) is obtained by hydrolyzing the silane compound and the silyl group-containing vinyl resin and / or
Alternatively, it is considered that the compound promotes the partial condensation reaction 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 (7), (8) and (9), or partial hydrolysates of these compounds.

Formula (7) Zr (OR_Five)_p(R₆COCHCOR₇)_4-p General formula (8) Ti (OR_Five)_q(R₆COCHCOR₇)_4-q General formula (9) Al (OR_Five)_r(R₆COCHCOR₇)_3-r R in general formulas (7), (8) and (9)_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 amount of the metal chelate compound (III) added is
The compounding amount based on the total mass of the coating solution solids (the coating solution solids are components remaining after drying the coating solution) such as a silane compound, a siloxane condensate, and a silyl group-containing vinyl resin is 0.01 to 20%. %, Preferably 0.5 to 20% by weight. Metal chelate compound (III)
If the amount is too small, three-dimensionalization of the resin layer may not be achieved, while if too large, the pot life of the coating liquid is deteriorated.

The curing conditions after applying the coating solution for the resin layer depend on the reactivity of the silane compound used.
It is preferable to carry out drying at 0 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 preferable. The amount of the organic solvent to be used is not limited to the amount of the silane compound, but is adjusted according to the purpose of use.

As the solvent for accelerating the curing reaction, a solvent for uniformly dissolving the silane compound and the silyl group-containing vinyl resin 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, that is, methanol, ethanol, n-propanol, iso-propanol, n-butanol, 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,

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Mercaptide-type organotin compounds such as

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Sulfide-type organotin compounds 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 relative to 100 parts by mass of the solid content of the coating solution (the solid content means a 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 resin layer coating solution 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 can be added when preparing the surface protective solution of the present invention and / or at an appropriate stage after the preparation.

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 of the present invention means a cylindrical support necessary for forming an image endlessly by rotating, and has a straightness of 0.1 mm or less and a runout of 0.1 mm or less. Conductive supports in the range 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 such as aluminum or nickel, 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 may be provided between the conductive support and the photosensitive layer.

In the present invention, in order to improve the adhesiveness between the conductive support and the photosensitive layer or to prevent charge injection from the support, an intermediate layer (below the support) 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 or 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 generation material (CGM), a known charge generation material (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 The charge transport layer contains a charge transport material (CTM: same as the charge transport compound) 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 a photoreceptor, a photoreceptor having the most preferred layer constitution of the present invention can be obtained.

The solvent or dispersion medium used for forming the intermediate layer, photosensitive layer, etc. of the present invention includes n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, and the like.
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-trichloroethane, trichloroethylene, tetrachloroethane, tetrahydrofuran, dioxolan,
Examples thereof include dioxane, methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, and methyl cellosolve. Although the present invention is not limited to these, 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.

Next, 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 step), which applies uniform charging to 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 step) 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 of the present invention is to uniformly charge the surface of the photoreceptor by the charger 52, and to carry out the image-exposed region, that is, the exposed portion potential (exposed portion region) of the photoreceptor. 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 step)
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 includes, for example, a carrier having ferrite as a core and an insulating resin coated around the core, a coloring agent such as carbon black, a charge control agent, and a low molecular weight of the present invention. The toner comprises toner in which silica, titanium oxide, or the like is externally added to colored particles made of polyolefin. The developer is transported to a developing area with the layer thickness regulated by a transport amount regulating member, and development is performed. At this time, usually, the photosensitive drum 50
The development is performed by applying a DC bias and an AC bias voltage if necessary between the developing sleeve 541 and the developing sleeve 541. The developer is developed in a state of contact or non-contact with the photoconductor. In order to measure the potential of the photoconductor, the potential sensor 547 is used as shown in FIG.
As described above.

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 step) 58 for applying a charge having a polarity opposite to that of the toner.

Next, the recording paper P is separated from the separation electrode (separation step) 5.
9, the toner is removed from the peripheral surface of the photosensitive drum 50, conveyed to a fixing device (fixing step) 60, and heated and pressed by the heat roller 601 and the pressure roller 602 to fuse the toner, and then the discharge roller 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 step) 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, facsimile and the like.

[0144]

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 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 material having a diameter of 100 mm was used. It was applied on a support having a dry 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 charge generation layer having a dry film thickness of 0.2 μm.

<Charge Transport Layer> Charge transport material (T-18) 225 g Polycarbonate (viscosity average molecular weight 30,000) 300 g Antioxidant (Exemplified Compound 1-3) 6 g Dichloromethane 2,000 ml was mixed and dissolved, and the charge transport layer was dissolved. A coating solution was prepared. 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> Silyl Group-Containing Vinyl Resin (A) 100 g Methyltrimethoxysilane 70 g 3-glycidoxypropyltrimethoxysilane 30 g 2-butyl alcohol 100 g Butyl cellosolve 75 g Di-i-propoxy After 10 g of ethyl acetoacetate aluminum was mixed and stirred well, 30 g of pure water was added dropwise with stirring and reacted at 60 ° C. for 4 hours. Next, the mixture was cooled to room temperature, and 10 g of a 2-propyl alcohol solution of dioctyltin dimaleate ester (solid content: 15% by mass) and 50 g of a charge transporting compound (T-18) were added and stirred to prepare a coating solution. . This coating solution was used to form a resin layer having a dry film thickness of 3 μm on the charge transporting layer by a circular amount control type coating device, and was heated and cured at 120 ° C. for 1 hour to obtain an organic polymer component and a siloxane condensate of the present invention. Photoconductor 1 provided with a resin having a component and a resin layer containing a charge transporting compound was prepared.

Preparation of Photoreceptor 2 The photoreceptor 1 of the present invention was prepared in the same manner as the photoreceptor 1 except that the charge transporting compound in the protective layer was changed to the exemplified compound (T-20) instead of the exemplified compound (T-18). Photoconductor 2 provided with a resin layer containing a resin having an organic polymer component and a siloxane condensate component and a charge transporting compound was prepared.

Preparation of Photoreceptor 3 Titanium chelate (TC) was used in photoreceptor 1 in place of dioctyltin dimaleate ester as a curing agent in the protective layer.
-750: manufactured by Matsumoto Pharmaceutical Co., Ltd.), and a photoconductor 3 provided with a resin layer containing a resin having an organic polymer component and a siloxane condensate component of the present invention and a charge transporting compound was prepared.

Preparation of Photoreceptor 4 The same procedure as in Photoreceptor 1 was conducted except that 2- (3,4-epoxycyclohexyl) trimethoxysilane was used instead of 3-glycidoxypropyltrimethoxysilane. Photoconductor 4 provided with a resin layer containing a resin having a polymer component and a siloxane condensate component and a charge transporting compound was prepared.

Preparation of Photoreceptor 5 Photoreceptor 1 was prepared in the same manner up to the charge transport layer.

<Protective Layer: Resin Layer of the Present Invention> Methyltrimethoxysilane 70 g 3-glycidoxypropyltrimethoxysilane 30 g 2-propanol 50 g 3% acetic acid 10 g was mixed, and the mixture was stirred at 50 ° C. for 24 hours. An oligomerization solution of trimethoxysilane and 3-glycidoxypropyltrimethoxysilane was prepared.

The above oligomerization solution 160 g Tetramethoxysilane 10 g Silyl group-containing vinyl resin (A) (solid content: 50% by mass) 60 g Charge transporting compound (T-18) 40 g Antioxidant (Exemplified compound 2-1) 2 g 2-propanol 100 g 2-butanone 100 g Aluminum chelate A (W) (manufactured by Kawaken Chemical Co., Ltd.) 10 g was mixed to prepare a coating solution for a protective layer. This coating solution was used to form a protective layer having a dry film thickness of 2 μm on the charge transporting layer by a circular quantity controlling type coating device, and was heated and cured at 120 ° C. for 1 hour to obtain an organic polymer component and a siloxane condensate of the present invention. Photoreceptor 5 provided with a resin having a component and a resin layer containing a charge transporting compound was prepared.

Comparative Example Preparation of Photoconductor 6 <Protective Layer: Comparative Resin Layer> Photoconductor 1 was the same as Photoconductor 1 except that the charge transporting compound (T-18) in the protective layer was omitted.
In the same manner as in the above, a photoreceptor 6 having a resin layer outside the present invention was produced.

Preparation of Photoreceptor 7 Photoreceptor 1 was prepared in the same manner up to the charge transport layer.

<Protective Layer: Comparative Resin Layer> Silyl Group-Containing Vinyl Resin (A) 100 g Methyltrimethoxysilane 100 g Charge Transporting Compound (T-18) 6 g Antioxidant (Exemplified Compound 2-1) 3 g 2-propanol 115 g Hardener HPC404 (manufactured by JSR) 15 g was mixed to prepare a coating liquid for a protective layer. A 2 μm-thick protective layer was formed on the charge transporting layer by a circular amount-regulating type coating apparatus on the charge transporting layer, and was heated and cured at 120 ° C. for 1 hour. (Without using a silane compound).

Preparation of Photoreceptor 8 Photoreceptor 1 was prepared in the same manner up to the charge transport layer.

<Protective Layer: Comparative Resin Layer> Silicone Hard Coating Agent (KP-81: manufactured by Shin-Etsu Chemical Co., Ltd.) 182 g Charge-transporting compound (T-18) 15 g Antioxidant (Exemplified Compound 2-1) 75 g 2-propanol 75 g 3% acetic acid 5 g were mixed to prepare a coating solution for a protective layer. This coating solution was used to form a protective layer having a dry film thickness of 2 μm on the charge transporting layer by a circular amount control type coating apparatus, and was cured by heating at 120 ° C. for 1 hour. (No component) was prepared.

Preparation of Photoreceptor 9 Photoreceptor 1 was prepared in the same manner up to the charge transport layer.

<Protective Layer: Comparative Resin Layer> Polycarbonate (Z300: manufactured by Mitsubishi Gas Chemical Company) 660 g Charge transporting compound (T-18) 360 g Antioxidant (Exemplary Compound 2-1) 18 g Phenyltrimethoxysilane 33 g Hydrochloric acid (1 g) and 1,3-dioxolan (2,800 ml) were mixed to prepare a coating solution for a protective layer. A protective layer having a dry film thickness of 5 μm was formed on the charge transport layer by a circular amount control type coating apparatus on the charge transport layer, and was heated and cured at 120 ° C. for 1 hour. Photoconductor 9 having a resin layer was produced.

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 to A4 neutral paper. Environmental conditions are considered to be the most severe high temperature and high humidity environment (30 ° C, 80% R
H), 200,000 copies were made continuously, and evaluation was performed using a halftone, solid white image, and solid black image. The evaluation criteria are shown below.

Evaluation Criteria Image density (measured using Macbeth RD-918).
The measurement was made at a relative reflection density where the reflection density of the paper was "0".
Evaluation was made at the initial stage and after 200,000 copies. ◎: Black solid image density of 1.2 or more ○: Black solid image density of less than 1.2 to 1.0 ×: Black solid image density of less than 1.0 Resolution (determined by the ease of distinguishing character images) : No difference between initial and resolution after 200,000 copies △: Slight reduction in resolution after 200,000 copies ×: Remarkable reduction in resolution after 200,000 copies Cleaning properties (100,000, 150,000, and 200,000) After the copying is completed, 10 continuous copies are made on A3 paper, and the determination is made based on whether or not cleaning failure has occurred in the solid white portion. : Slippage of toner occurs on less than 100,000 sheets. Blade turning (determined by occurrence of blade turning during 200,000 copies) ：: No blade turning until copying of 200,000 sheets ○: Minor bleeding before copying of 200,000 sheets Over head portion curling occurred ×: 200,000 copies using one or more blade curling occurrence cleaning blade starting torque 200,000 after copying drum cartridge during the torque gauge which is 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 photoreceptor film thickness reduction was determined by calculating the difference between the average film thickness of the photoreceptor measured at the start of the actual printing evaluation and at the end of 200,000 copies.

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 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 a carrier coated with an insulating resin using ferrite as a core, a coloring agent such as carbon black using a styrene acrylic resin as a main material, a charge control agent, and a low molecular weight of the present invention. A toner developer in which silica, titanium oxide and the like were externally added to colored particles made of polyolefin was used.

Transfer conditions Transfer pole; corona charging system Cleaning conditions Hardness 70 °, rebound resilience 34%, thickness 2
(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).

Table 1 shows the results of the evaluation.

[0172]

[Table 1]

As is clear from Table 1, the photoreceptors 1 to 5 having the resin layer (protective layer) of the present invention have image characteristics such as image density and resolution, cleaning properties, cleaning characteristics such as blade turning, and film thickness wear. The amount has been improved with a balance. On the other hand, in the photoreceptor 6 out of the present invention, the charge transport property of the protective layer (the resin layer having no charge generating compound) is not sufficient, and the residual density is increased, so that the image density is reduced and the starting torque is large. The blade is turning over.

In the photoreceptor 7 (a resin layer not using a silane compound having an epoxy group) outside the present invention, the image density,
Although there is no problem in the resolution, there is a problem in the cleaning property, and the thickness loss is larger than that of the photoreceptor in the present invention.

Further, in the photoreceptor 8 (resin layer having no organic polymer component) outside the present invention, although the thickness is reduced, the starting torque is high, cleaning failure occurs, and blade turning occurs.

The photoreceptors 1 to 5 of the present invention have remarkably improved film thickness reduction as compared with the photoreceptor 9 using a protective layer of a polycarbonate resin other than the present invention.

[0177]

As is evident from the above examples, the photoreceptor having the resin layer (protective layer) of the present invention and the method for producing the same can provide abrasion resistance against abrasion with a cleaning blade and the like, and repetition. Electrophotographic characteristics (charge, sensitivity, residual potential characteristics, etc.) during use have been improved.
An image forming method, an image forming apparatus, and a process cartridge having excellent toner cleaning performance and stability against turning of a cleaning blade can be provided.

[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 (72) Inventor Akihiko Itami 2970 Ishikawacho, Hachioji-shi, Tokyo Konica Corporation F-term (reference) 2H068 AA03 AA04 BA05 BA12 BA13 BA57 BA58 BB06 BB33

Claims (17)

[Claims] 1. An electrophotographic photosensitive member having a resin layer on a conductive support, wherein the resin layer contains a resin having an organic polymer component and a siloxane condensate component, and a charge transporting compound, and the siloxane condensation of the resin is carried out. An electrophotographic photoreceptor wherein the body component is formed using a silane compound having at least an epoxy group or a ring-opening group thereof. 2. The electrophotographic photoreceptor according to claim 1, wherein the mass ratio of the organic polymer component to the siloxane condensate component in the resin layer is 1: 0.1 to 10. 3. The siloxane condensate is formed using a silane compound having an epoxy group or a ring-opening group thereof and another silane compound, and the mass ratio of both is 1: 0.01.
The electrophotographic photosensitive member according to claim 1, wherein the number is from 100 to 100. 4. The electrophotographic photosensitive member according to claim 1, wherein the organic polymer component is a vinyl resin component. 5. The electrophotographic photoreceptor according to claim 4, wherein said vinyl resin component is an acrylic polymer. 6. The electrophotographic photosensitive member according to claim 1, wherein the resin layer contains an antioxidant. 7. The electrophotographic photosensitive member according to claim 1, wherein the resin layer is a protective layer. 8. A method for producing an electrophotographic photoreceptor having a resin layer on a conductive support, wherein the resin layer comprises an organic polymer having a silyl group in a side chain and a silane compound having at least an epoxy group or a ring-opening group thereof. A method for producing an electrophotographic photoreceptor, which is formed by applying a coating solution containing a charge transporting compound and then curing the coating solution. 9. A method for producing an electrophotographic photosensitive member having a resin layer on a conductive support, wherein the resin layer comprises a siloxane condensate formed using a silane compound having at least an epoxy group or a ring-opening group thereof. A method for producing an electrophotographic photoreceptor, which is formed by applying a coating solution containing an organic polymer having a side chain and a charge transporting compound and then curing the coating solution. 10. The method according to claim 9, wherein the coating solution contains a silane compound. 11. The method according to claim 8, wherein the coating solution contains a metal chelate compound. 12. The content of the metal chelate compound in the coating solution is preferably 0.03% based on the total weight of the coating solution solids.
The method for producing an electrophotographic photosensitive member according to claim 11, wherein the content is 1 to 20% by mass. 13. The method according to claim 11, wherein the metal chelate compound is an aluminum chelate.
3. The method for producing an electrophotographic photoreceptor according to item 1. 14. The method according to claim 11, wherein the metal chelate compound is a titanium chelate. 15. An image forming method using the electrophotographic photoreceptor according to claim 1 through at least a charging step, an image exposing step, a developing step, and a cleaning step. 16. An image forming apparatus using the image forming method according to claim 15. 17. A process cartridge used in the image forming apparatus according to claim 16, wherein
Wherein the electrophotographic photosensitive member according to any one of the above, and any one of a charger, an image exposure device, a developing device, and a cleaning device are integrally combined, and are configured to be freely inserted into and removed from the image forming apparatus. A process cartridge.