JP2002311627A - Electrophotographic photoreceptor, image forming method, image forming device and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having good potential stability and not causing image defects such as black spots and to provide an image forming method using the electrophotographic photoreceptor, an image forming device and a process cartridge. SOLUTION: In the electrophotographic photoreceptor having a photosensitive layer on an electrically conductive substrate by way of a middle layer, the middle layer contains a binder resin and n-type semiconductive fine particles subjected to a plurality of surface treatments including the final surface treatment with a reactive organosilicon compound and the surface layer of the photosensitive layer contains a resin having an organic polymer component, a siloxane condensate component and an electric charge transporting structure component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used in the field of copying machines and printers, and to 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.

[0003] As a problem for improving the durability of the organic photoreceptor, 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 characteristics 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. The 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 both mechanical abrasion resistance and electrophotographic characteristics upon 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). A photoreceptor having this protective layer has been improved in the conventional abrasion resistance characteristics and electrophotographic characteristics (charging, sensitivity, residual potential characteristics, etc.) upon repeated use, which have been important issues, and is sufficient as a highly durable organic photoreceptor. Has practicality. However, the photoreceptor having this protective layer still has the following problems in digital electrophotographic image formation.

That is, in the digital type electrophotographic image forming, a reversal developing method (developing method for developing an exposed portion) is generally used. A phenomenon in which toner adheres to a portion where an image is to be formed as a white background portion to cause fogging, and occurrence of black spots due to a local defect of the photoconductor are known.

When the photoreceptor having the siloxane-based resin layer as a protective layer is combined with a photoreceptor layer formed of a phthalocyanine-based pigment or the like, the charging potential immediately after resuming the image formation for a certain period of time and then resuming the image formation is reduced. There is a problem that the charge potential is lower than the charge potential after the second time. This phenomenon causes a copy image formed on the first rotation of the photoreceptor to be clearly inferior to that after the second rotation, particularly in reversal development. The image defect is conspicuous and serious because it originally appears as toner fog on a white background.

Further, the photoreceptor using the siloxane-based resin layer as a protective layer cannot sufficiently suppress the occurrence of black spots in a high-temperature and high-humidity environment. In addition, the charge potential tends to decrease under a high-temperature and high-humidity environment due to a hydrophilic group (eg, a hydroxyl group) remaining in the siloxane bond. 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 also become apparent.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor having good potential stability and free from image defects such as black spots in view of the above-mentioned problems of the prior art. More specifically, the present invention provides an electrophotographic photosensitive member that does not generate image defects such as black spots and has good potential stability even when used repeatedly, and an image forming method, an image forming apparatus, and a process cartridge using the electrophotographic photosensitive member. It is in.

[0010]

The object of the present invention has been attained by adopting the following photoreceptor constitution to solve the above problems as a result of studying each layer constituting the photoreceptor.

1. In an electrophotographic photoreceptor having a photosensitive layer on a conductive support via an intermediate layer, the intermediate layer is subjected to a plurality of surface treatments, and the final surface treatment is performed using a reactive organosilicon compound. Wherein the surface layer of the photosensitive layer contains a resin having an organic polymer component, a siloxane condensate component and a charge transport structure component. Photoreceptor.

2. 2. The electrophotographic photoreceptor according to the above 1, wherein the siloxane condensate component is formed using an organosilicon compound having at least an epoxy group or a ring-opening group thereof.

3. 3. The electrophotographic photoreceptor according to the above item 1 or 2, wherein the reactive organic silicon compound is methyl hydrogen polysiloxane.

4. 3. The electrophotographic photoreceptor according to the above item 1 or 2, wherein the reactive organic silicon compound is an organic silicon compound represented by the general formula (1).

[0015] 5. 5. The electrophotographic photoreceptor according to the above item 4, wherein R in the general formula (1) is an alkyl group having 4 to 8 carbon atoms.

6. In an electrophotographic photoreceptor having a photosensitive layer on a conductive support via an intermediate layer, the intermediate layer is subjected to a plurality of surface treatments, and the final surface treatment is performed using a reactive organic titanium compound. Wherein the surface layer of the photosensitive layer contains a resin having an organic polymer component, a siloxane condensate component and a charge transport structure component. Photoreceptor.

[7] In an electrophotographic photoreceptor having a photosensitive layer on a conductive support via an intermediate layer, the intermediate layer is subjected to a plurality of surface treatments, and the final surface treatment is performed using a reactive organic zirconium compound. Wherein the surface layer of the photosensitive layer contains a resin having an organic polymer component, a siloxane condensate component and a charge transport structure component. Photoreceptor.

[8] The electrophotographic photoreceptor according to the above item 6 or 7, wherein the siloxane condensate component is formed using an organosilicon compound having at least an epoxy group or a ring-opening group thereof.

9. 9. The electron according to any one of 1 to 8, wherein at least one of the plurality of surface treatments is a surface treatment of at least one of alumina, silica, and zirconia. Photoreceptor.

[10] The electrophotography according to any one of the above items 1 to 5, wherein the N-type semiconductor fine particles are subjected to a surface treatment with at least silica or alumina, and then subjected to a surface treatment with a reactive organic silicon compound. Photoconductor.

11. 7. The electrophotographic photoreceptor according to the above item 6, wherein the N-type semiconductor fine particles are subjected to a surface treatment with at least silica or alumina, and then subjected to a surface treatment with a reactive organic titanium compound.

12. 8. The electrophotographic photoreceptor according to the item 7, wherein the N-type semiconductor fine particles are subjected to a surface treatment using at least silica or alumina, and then subjected to a surface treatment using a reactive organic zirconium compound.

13. The electrophotographic photoreceptor according to any one of the above items 1 to 12, wherein the N-type semiconductor fine particles are titanium oxide particles.

14. 14. The electrophotographic photoreceptor according to any one of the items 1 to 13, wherein the N-type semiconductive fine particles have a rutile crystal type.

[15] 15. The electrophotographic photoreceptor according to any one of the items 1 to 14, wherein the N-type semiconductive fine particles have a number average primary particle size of 10 nm or more and 200 nm or less.

16. In an electrophotographic photoreceptor having a photosensitive layer on a conductive support via an intermediate layer, the intermediate layer is
It contains titanium oxide particles surface-treated with a reactive organic silicon compound having a fluorine atom and a binder resin, and the surface layer of the photosensitive layer contains an organic polymer component, a siloxane condensate component, and a charge transport structure component. An electrophotographic photoreceptor characterized by containing a resin having the same.

17. 17. The electrophotographic photoreceptor as described in 16 above, wherein the siloxane condensate component is formed using an organosilicon compound having at least an epoxy group or a ring-opening group thereof.

18. 18. The electrophotographic photoreceptor according to the above item 16 or 17, wherein the number average primary particle diameter of the titanium oxide particles is 10 nm or more and 200 nm or less.

19. 19. The electrophotographic photoconductor according to any one of items 1 to 18, wherein the binder resin of the intermediate layer is a polyamide resin.

20. In an image forming method in which at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and a cleaning unit are provided around an electrophotographic photosensitive member, and the image forming method for repeatedly forming an image, the electrophotographic photosensitive member is An image forming method, comprising the electrophotographic photoreceptor according to any one of the preceding claims.

21. An image forming apparatus using the image forming method according to the above item 20.

22. The process cartridge used in the image forming apparatus according to the item 21, wherein at least
20. An electrophotographic photosensitive member according to any one of the above items 19 and at least one of a charger, an image exposure device, a developing device, a transfer device, and a cleaning device, which are integrally formed so as to be able to be taken in and out of the image forming apparatus. Process cartridge characterized by being done.

Hereinafter, the present invention will be described in detail. The electrophotographic photoreceptor of the present invention is characterized in that an intermediate layer provided between a conductive support and a photosensitive layer contains N-type semiconductor fine particles subjected to a specific surface treatment and a binder resin. The surface treatment of the N-type semiconductor particles is performed a plurality of times, and the last one of the plurality of times is a surface treatment using a reactive organosilicon compound. What is to be characterized in that it is a surface treatment using a reactive organosilicon compound having a fluorine atom, a plurality of times surface treatment is performed, and the last surface treatment of the plurality of times surface treatment is Characterized in that it is a surface treatment using a reactive organic titanium compound,
And a plurality of surface treatments is performed, and the last of the plurality of surface treatments is a surface treatment using a reactive organic zirconium compound.

An intermediate layer is provided between the conductive support and the photosensitive layer by containing N-type semiconductor fine particles which have been subjected to any one of these four surface treatments. Providing a layer containing an organic polymer component, a siloxane condensate component, and a resin having a charge transport structure component, wherein the siloxane condensate component is formed using an organosilicon compound having at least an epoxy group or a ring-opening group thereof. Thereby, the occurrence of black spots can be significantly suppressed without deteriorating electrophotographic characteristics such as an increase in residual charge and a decrease in charging potential, and furthermore, it has been found that the occurrence of moiré due to laser exposure can be improved. .

Further, in the present invention, it has been found that it is particularly preferable to use titanium oxide fine particles as the N-type semiconductive fine particles.

Hereinafter, the surface treatment of the N-type semiconductor fine particles and titanium oxide used in the present invention will be described in detail.

The N-type semiconductive fine particles used in the present invention are fine particles having a property of using a conductive carrier as an electron. That is, the property of making the conductive carrier an electron is as follows.
By incorporating the N-type semiconductive fine particles into an insulating binder, it is possible to efficiently block holes from being injected from the substrate, and to exhibit a property of not blocking the electrons from the photosensitive layer. Say.

Specific examples of the N-type semiconductive fine particles include fine particles of titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ) and the like.
Particularly, titanium oxide is preferably used.

The average particle size of the N-type semiconductor fine particles used in the present invention is 10 nm or more in number average primary particle size.
nm or less, more preferably 10 nm or less.
nm to 100 nm, particularly preferably 15 nm to 50 n
m.

When the value of the number average primary particle size is within the above range,
The intermediate layer using the semiconductive fine particles can make the dispersion in the layer dense, and has a sufficient potential stability and a function to prevent occurrence of black spots.

The number average primary particle diameter of the N-type semiconductive fine particles is, for example, in the case of titanium oxide, magnified 10000 times by transmission electron microscopy, and 100 particles are randomly observed as primary particles. It is measured as the number average diameter of Feret diameter by analysis.

The shape of the N-type semiconductor fine particles used in the present invention includes dendrites, needles, and particles. The N-type semiconductor fine particles having such a shape are, for example, titanium oxide particles. The crystal form includes an anatase type, a rutile type, an amorphous type, and the like. Any of the crystal types may be used, or two or more types may be mixed and used. Among them, the rutile type is best.

One of the surface treatments performed on the N-type semiconductor fine particles of the present invention is that a plurality of surface treatments are performed, and the last one of the plurality of surface treatments is a reactive organosilicon. A surface treatment using a compound is performed. Further, among the plurality of surface treatments, at least one surface treatment performs at least one or more surface treatments selected from alumina, silica, and zirconia, and finally, a surface treatment using a reactive organosilicon compound. Is preferably performed.

The alumina treatment, the silica treatment, and the zirconia treatment mean that alumina, silica,
Alternatively, it refers to a treatment for depositing zirconia, and the alumina, silica, and zirconia deposited on these surfaces include hydrates of alumina, silica, and zirconia. Further, the surface treatment of the reactive organosilicon compound means to use the reactive organosilicon compound in the treatment solution.

As another method of the surface treatment performed on the N-type semiconductive fine particles of the present invention, the surface treatment is performed a plurality of times, and in the plurality of the surface treatments, the last surface treatment is performed. The surface treatment is performed using a reactive organic titanium compound or a reactive organic zirconium compound. In the plurality of surface treatments, at least one surface treatment performs at least one kind of surface treatment selected from alumina, silica, and zirconia as described above, and finally, the reactive organic titanium compound or the reactive organic titanium compound. It is preferable to perform a surface treatment using an organic zirconium compound.

As described above, by performing the surface treatment of the N-type semiconductor fine particles such as titanium oxide particles at least twice, the surface of the N-type semiconductor fine particles is uniformly coated (treated). When the treated N-type semiconductive fine particles are used for the intermediate layer, the dispersibility of the N-type semiconductive fine particles such as titanium oxide particles in the intermediate layer is good, and good image defects such as black spots are not generated. A photoreceptor can be obtained.

The surface treatment may be performed a plurality of times by subjecting the surface treatment to alumina and silica, and then to the surface treatment using a reactive organosilicon compound. Those that perform a surface treatment using a titanium compound or a reactive organic zirconium compound are particularly preferable.

The above-mentioned treatment of alumina and silica may be carried out simultaneously, but it is particularly preferred to carry out the alumina treatment first and then the silica treatment. In the case where alumina and silica are respectively treated, the amount of alumina and silica to be treated is preferably larger than that of alumina.

The surface treatment of the N-type semiconductor fine particles such as titanium oxide with a metal oxide such as alumina, silica, and zirconia can be performed by a wet method. For example, N-type semiconductive particles having been subjected to silica or alumina surface treatment can be prepared as follows.

When titanium oxide particles are used as the N-type semiconductive fine particles, titanium oxide particles (number average primary particle diameter: 50
nm) at a concentration of 50 to 350 g / L in water to form an aqueous slurry, to which a water-soluble silicate or a water-soluble aluminum compound is added. Thereafter, neutralization is performed by adding an alkali or an acid to deposit silica or alumina on the surface of the titanium oxide particles. Subsequently, filtration, washing and drying are performed to obtain a target surface-treated titanium oxide. When sodium silicate is used as the water-soluble silicate, it can be neutralized with an acid such as sulfuric acid, nitric acid or hydrochloric acid.
On the other hand, when aluminum sulfate is used as the water-soluble aluminum compound, it can be neutralized with an alkali such as sodium hydroxide or potassium hydroxide.

The amount of the metal oxide in the above surface treatment is as follows:
0.1 to 50 parts by mass, more preferably 1 to 10 parts by mass of metal oxide is used with respect to 100 parts by mass of the N-type semiconductive fine particles such as titanium oxide particles in the charged amount at the time of the surface treatment. . In the case of the above-mentioned treatment with alumina and silica, for example, in the case of titanium oxide particles, it is preferable to use 1 to 10 parts by mass for 100 parts by mass of titanium oxide particles, and it is preferable that the amount of silica is larger than that of alumina.

The surface treatment using a reactive organic silicon compound, which is performed after the surface treatment of the metal oxide, is preferably performed by the following wet method.

That is, the titanium oxide treated with the metal oxide is added to a solution in which the reactive organosilicon compound is dissolved or suspended in an organic solvent or water, and the solution is stirred for several minutes to one hour. I do. In some cases, the liquid is subjected to a heat treatment, filtered, etc., and then dried to obtain titanium oxide particles whose surface is coated with an organosilicon compound. Note that the reactive organic silicon compound may be added to a suspension in which titanium oxide is dispersed in an organic solvent or water.

In the present invention, the fact that the surface of the titanium oxide particles is coated with the reactive organosilicon compound is as follows.
Photoelectron spectroscopy (ESCA), Auger electron spectroscopy (Au
ger) is confirmed by combining surface analysis methods such as secondary ion mass spectrometry (SIMS) and diffuse reflection FI-IR.

The amount of the reactive organosilicon compound used in the surface treatment is such that the amount of the reactive organosilicon compound is 0 with respect to 100 parts by mass of the titanium oxide treated with the metal oxide at the amount charged during the surface treatment. 0.1 to 50 parts by mass, more preferably 1 to 10 parts by mass. If the surface treatment amount is less than the above range, the surface treatment effect is not sufficiently provided, and the dispersibility and the like of the titanium oxide particles in the intermediate layer deteriorate.
Further, when the ratio exceeds the above range, electrophotographic characteristics are degraded, and as a result, a residual potential rises and a charged potential lowers.

The reactive organosilicon compound used in the present invention includes an organosilicon compound represented by the following general formula (2), and is a compound that undergoes a condensation reaction with a reactive group such as a hydroxyl group on the surface of titanium oxide. If present, it is not limited to the following compounds.

Formula (2) (R) _n -Si- (X) _4-n (wherein Si is a silicon atom, R is an organic group in which carbon is directly bonded to the silicon atom, and X is Represents a hydrolyzable group, and n represents an integer of 0 to 3.) In the organosilicon compound represented by the general formula (2), R
Organic groups in the form of carbon directly bonded to silicon represented by, methyl, ethyl, propyl, butyl, pentyl,
Alkyl groups such as hexyl, octyl and dodecyl, aryl groups such as phenyl, tolyl, naphthyl and biphenyl, and γ
Epoxy-containing groups such as glycidoxypropyl, β- (3,4-epoxycyclohexyl) ethyl, (meth) acryloyl-containing γ-acryloxypropyl and γ-methacryloxypropyl, γ-hydroxypropyl, 2, 3
-A hydroxyl group such as dihydroxypropyloxypropyl,
Vinyl, vinyl-containing groups such as propenyl, mercapto-containing groups such as γ-mercaptopropyl, γ-aminopropyl, N-
amino-containing groups such as β (aminoethyl) -γ-aminopropyl; halogen-containing groups such as γ-chloropropyl, 1,1,1-trifluoropropyl, nonafluorohexyl, and perfluorooctylethyl; and other nitro and cyano groups And substituted alkyl groups. Examples of the hydrolyzable group for X include methoxy, ethoxy and other alkoxy groups, halogen groups,
An acyloxy group is exemplified.

The organosilicon compound represented by the general formula (2) may be used alone or in combination of two or more.

When the specific compound of the organosilicon compound represented by the general formula (2) is 2 or more, a plurality of R
May be the same or different. Similarly, when n is 2 or less, a plurality of Xs may be the same or different. When two or more organosilicon compounds represented by the general formula (2) are used, R and X may be the same or different between the respective compounds.

Examples of the compound in which n is 0 include the following compounds. Tetrachlorosilane, diethoxydichlorosilane, tetramethoxysilane, phenoxytrichlorosilane, tetraacetoxysilane, tetraethoxysilane, tetraallyloxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrakis (2-methoxyethoxy) silane, tetrabutoxysilane , Tetraphenoxysilane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane and the like.

Examples of the compound in which n is 1 include the following compounds. That is, trichlorosilane, methyltrichlorosilane, vinyltrichlorosilane, ethyltrichlorosilane, allyltrichlorosilane, n-propyltrichlorosilane, n-butyltrichlorosilane, chloromethyltriethoxysilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, Trimethoxyvinylsilane, ethyltrimethoxysilane, 3,3,4
4,5,5,6,6,6-nonafluorohexyltrichlorosilane, phenyltrichlorosilane, 3,3,3-
Trifluoropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, triethoxysilane, 3
-Mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, benzyltrichlorosilane, methyltriacetoxysilane, chloromethyltriethoxysilane, ethyltriacetoxysilane, phenyltrimethoxysilane, 3-allylthiopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-methacryloxypropyltrimethoxysilane, bis (ethylmethylketoxime) methoxymethylsilane, pentyltriethoxysilane, octyl Triethoxysilane, a dodecyloxy triethoxy silane and the like.

Examples of the compound in which n is 2 include the following compounds. Dimethyldichlorosilane, dimethoxymethylsilane, dimethoxydimethylsilane, methyl-3,
3,3-trifluoropropyldichlorosilane, diethoxysilane, diethoxymethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxysilane, diethoxydimethyl Silane, dimethoxy-3-mercaptopropylmethylsilane, 3,3
4,4,5,5,6,6,6-nonafluorohexylmethyldichlorosilane, methylphenyldichlorosilane,
Diacetoxymethylvinylsilane, diethoxymethylvinylsilane, 3-methacryloxypropylmethyldichlorosilane, 3-aminopropyldiethoxymethylsilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, t-butylphenyldichlorosilane,
3-methacryloxypropyldimethoxymethylsilane,
3- (3-cyanopropylthiopropyl) dimethoxymethylsilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, dimethoxymethyl-2-
Piperidinoethylsilane, dibutoxydimethylsilane,
3-dimethylaminopropyldiethoxymethylsilane,
Diethoxymethylphenylsilane, diethoxy-3-glycidoxypropylmethylsilane, 3- (3-acetoxypropylthio) propyldimethoxymethylsilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxymethyloctadecylsilane and the like. Can be

Examples of the compound wherein n is 3 include the following compounds. Trimethylchlorosilane, methoxytrimethylsilane, ethoxytrimethylsilane, methoxydimethyl-3,3,3-trifluoropropylsilane, 3-
Chloropropylmethoxydimethylsilane, methoxy-3
-Mercaptopropylmethylmethylsilane.

The organosilicon compound represented by the general formula (2) is preferably an organosilicon compound represented by the general formula (1).

In the organosilicon compound represented by the general formula (1), more preferably, an organosilicon compound in which R is an alkyl group having 4 to 8 carbon atoms is preferable. Examples include n-butylsilane, trimethoxy i-butylsilane, trimethoxyhexylsilane, and trimethoxyoctylsilane.

A preferred reactive organosilicon compound used in the final surface treatment is a hydrogen polysiloxane compound. The hydrogen polysiloxane compound having a molecular weight of 1,000 to 20,000 is generally easily available, and has a good black spot prevention function. Particularly, when methyl hydrogen polysiloxane is used for the final surface treatment, a good effect can be obtained.

Another one of the surface treatments of the titanium oxide of the present invention is titanium oxide particles which have been subjected to a surface treatment with a fluorine atom-containing organosilicon compound. The surface treatment using the organosilicon compound having a fluorine atom is preferably performed by the above-mentioned wet method.

That is, the above-mentioned organosilicon compound having a fluorine atom is dissolved or suspended in an organic solvent or water, untreated titanium oxide is added thereto, and such a solution is stirred for several minutes to one hour. After the mixture is subjected to a heat treatment in some cases, it is dried through a step such as filtration, and the surface of the titanium oxide is coated with an organosilicon compound having a fluorine atom. The organic silicon compound having a fluorine atom may be added to a suspension in which titanium oxide is dispersed in an organic solvent or water.

The fact that the titanium oxide surface is coated with an organosilicon compound having a fluorine atom is as follows.
Photoelectron spectroscopy (ESCA), Auger electron spectroscopy (Au
ger) can be confirmed compositely using a surface analyzer such as secondary ion mass spectrometry (SIMS) or diffuse reflection FI-IR.

The fluorine-containing organosilicon compound used in the present invention includes 3,3,4,4,5,5,5
6,6,6-nonafluorohexyltrichlorosilane,
3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldichlorosilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,4,4,5 , 5,6,6
6-nonafluorohexylmethyldichlorosilane and the like.

In the present invention, the surface treatment finally performed on the N-type semiconductor fine particles described above may be performed by using a reactive organic titanium compound or a reactive organic zirconium compound. The surface treatment method is performed by a method according to the surface treatment method using the above reactive organosilicon compound.

The fact that the surface of the N-type semiconductor fine particles is coated with a reactive organic titanium compound or a reactive organic zirconium compound is confirmed by photoelectron spectroscopy (ESC).
(A), Auger electron spectroscopy (Auger), secondary ion mass spectroscopy (SIMS), and surface analysis such as diffuse reflection FI-IR are used in a complex manner to confirm the results with high accuracy.

Specific reactive organic titanium compounds used for the surface treatment of the N-type semiconductive fine particles include metal alkoxide compounds such as tetrapropoxytitanium and tetrabutoxytitanium, diisopropoxytitanium bis (acetylacetate), and the like. Metal chelate compounds such as diisopropoxytitanium bis (ethylacetoacetate), diisopropoxytitanium bis (lactate), dibutoxytitanium bis (octylene glycolate), diisopropoxytitanium bis (triethanolaminate) and the like. . Examples of the reactive organic zirconium compound include metal alkoxide compounds such as tetrabutoxyzirconium and butoxyzirconium tri (acetylacetate) and metal chelate compounds.

Next, N-type semiconductive fine particles such as the above-mentioned surface-treated titanium oxide particles (hereinafter also referred to as surface-treated N-type semiconductive fine particles. The structure of the intermediate layer using particles (also referred to as surface-treated titanium oxide) will be described.

The intermediate layer of the present invention is formed by dispersing a liquid obtained by dispersing a surface-treated N-type semiconductor fine particle such as a surface-treated titanium oxide obtained by performing the surface treatment a plurality of times together with a binder resin in a solvent. It is produced by coating on a support.

The intermediate layer of the present invention is provided between the conductive support and the photosensitive layer to improve the adhesion between the conductive support and the photosensitive layer and to function as a barrier to prevent charge injection from the support. Have. Examples of the binder resin for the intermediate layer include thermosetting resins such as polyamide resin, vinyl chloride resin, vinyl acetate resin, polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl alcohol resin and melamine resin, epoxy resin, and alkyd resin, and these resins. And copolymer resins containing two or more of the above repeating units. Among these binder resins, polyamide resins are particularly preferable, and alcohol-soluble polyamides such as copolymerization and methoxymethylol are particularly preferable.

The amount of the surface-treated N-type semiconductive fine particles of the present invention dispersed in the binder resin is, for example, in the case of surface-treated titanium oxide, 10 to 10,000 parts by mass with respect to 100 parts by mass of the binder resin. Parts, preferably 50 to
It is 1,000 parts by mass. By using the surface-treated titanium oxide in this range, the dispersibility of the titanium oxide can be kept good, and a good intermediate layer free of black spots can be formed.

The thickness of the intermediate layer of the present invention is 0.5 to 15 μm.
Is preferred. By using the film thickness in the above-mentioned range, an intermediate layer having good electrophotographic characteristics without black spots can be formed.

The coating solution for the intermediate layer prepared for forming the intermediate layer of the present invention is a surface-treated N
It is composed of a mold semiconductive fine particle, a binder resin, a dispersion solvent and the like. As the dispersion solvent, the same solvent as that used for producing other photosensitive layers is appropriately used.

That is, n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N are used as solvents or dispersion media for forming the intermediate layer, photosensitive layer and other layers of the present invention. -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, dioxane, methanol, ethanol,
Butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve and the like.

The solvent for the coating liquid for the intermediate layer is not limited to these, but methanol, ethanol, butanol, 1-propanol, isopropanol and the like are preferably used. In addition, these solvents can be used alone or as a mixed solvent of two or more kinds.

As the solvent for coating the intermediate layer, it is preferable to use a mixed solvent of methanol and straight-chain alcohol having high resin solubility in order to prevent drying unevenness during coating of the intermediate layer. The ratio of the volume ratio of the linear alcohol to the methanol is 0.05 to 0.
A mixture of 6 is preferred. By using the coating solvent as a mixed solvent in this manner, the evaporation rate of the solvent is appropriately maintained, and the occurrence of image defects due to uneven drying during coating can be suppressed.

As a dispersing means of the surface-treated titanium oxide used for preparing the coating liquid for the intermediate layer, any dispersing means such as a sand mill, a ball mill and an ultrasonic dispersing means may be used.

Coating processing methods for manufacturing the electrophotographic photoreceptor of the present invention including the intermediate layer include dip coating,
Coating methods such as spray coating and circular amount control type coating are used, but the coating process on the upper layer side of the photosensitive layer is performed by spray coating or circular coating to minimize the dissolution of the lower layer film and to achieve uniform coating processing. It is preferable to use a coating method such as a regulated type (a typical example is a circular slide hopper type). The spray coating is described in, for example,
No. 90250 and JP-A-3-269238, and the circular amount-control type coating is described in detail, for example, in JP-A-58-189061.

Next, the surface layer of the present invention will be described.
The surface layer of the present invention contains an organic polymer component, a siloxane condensate component, and a resin having a charge transport structure 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.

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 (3) );

[0089]

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(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.

Here, examples of the hydroxysilane compound used in the production method shown in the above (a) 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 groups include, especially,
Various vinyl compounds described below having a silyl group
There is no particular limitation as long as the monomer can be polymerized with, for example,
If CH_Two= CHSi (CH_Three) (OCH_Three)_Two, CH_Two=
CHSi (OCH_Three)_Three, CH_Two= CHSi (CH_Three) Cl
_Two, CH_Two= CHSiCl_Three, CH_Two= CHCOO (C
H_Two)_TwoSi (CH_Three) (OCH _Three)_Two, CH_Two= CHCOO
(CH_Two)_TwoSi (OCH_Three)_Three, CH_Two= CHCOO (C
H_Two)_ThreeSi (CH_Three) (OCH_Three)_Two, CH_Two= CHCOO
(CH_Two)_ThreeSi (OCH _Three)_Three, CH_Two= CHCOO (C
H_Two)_TwoSi (CH_Three) Cl_Two, CH_Two= CHCOO (C
H_Two)_TwoSiCl_Three, CH_Two= CHCOO (CH_Two)_ThreeSi
(CH_Three) Cl_Two, CH_Two= CHCOO (CH_Two)_ThreeSiC
l_Three, CH_Two= C (CH_Three) COO (CH_Two)_TwoSi (C
H_Three) (OCH_Three)_Two, CH_Two= C (CH_Three) COO (C
H_Two)_TwoSi (OCH_Three) _Three, CH_Two= C (CH_Three) COO
(CH_Two)_ThreeSi (CH_Three) (OCH_Three)_Two, CH_Two= C (C
H_Three) COO (CH_Two)_ThreeSi (OCH_Three)_Three, CH_Two= C
(CH_Three) COO (CH_Two)_TwoSi (CH_Three) Cl_Two, CH_Two
= C (CH_Three) COO (CH_Two)_TwoSiCl_Three, CH_Two= C
(CH_Three) COO (CH_Two)_ThreeSi (CH_Three) C_l2, CH_Two
= C (CH_Three) COO (CH_Two)_ThreeSiCl_Three,

[0094]

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And the like. These silane monomers 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% by mass.

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 dropped and reacted for 4 hours to obtain a silyl group-containing vinyl resin (B) having a solid concentration of 50% by mass.

The vinyl resin having a siloxane condensate component in the side chain is obtained by reacting the vinyl resin having a silyl group in the side chain with an organosilicon compound to form a siloxane condensate on the side chain of the vinyl resin. Can be formed.

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 preferably formed using an organosilicon 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 an organosilicon compound having an epoxy group or its ring-opening group is used as a surface layer of an electrophotographic photosensitive member, Improve the wear resistance of
In addition, image blur does not occur in a high humidity environment or a low humidity environment.

The organosilicon compound having an epoxy group or a ring-opening group thereof preferably used in the present invention includes (3-
Glycidoxypropyl) trimethoxysilane, 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, in addition to the above-mentioned organosilicon compound having an epoxy group or a ring-opening group thereof, the organosilicon compound represented by the general formula (2) and the specific examples thereof can be used. It is preferable to form a polycondensation by using the compounds in combination.

The organosilicon compound of the general formula (2) used as a raw material of the siloxane-based resin having a crosslinked structure generally has n of the number (4-n) of hydrolyzable groups bonded to silicon atoms. At 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 charge-transporting structural group exhibiting the property of having electron or hole drift mobility. Another definition is Time-Of-F.
It is a charge transporting structural group capable of obtaining a detection current due to charge transport by a known method capable of detecting charge transport performance such as a light method.

In order to introduce a charge transporting structural component into the resin of the present invention, an organic silicon compound and a reactive charge transporting compound can be used, and the charge transporting structural component can be incorporated into a siloxane condensate. 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 the organic polymer. 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 (4). 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.

[0111] Among them, representative ones are as follows. 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

[0113]

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

The precipitated crystals were filtered and dried, and then purified by adsorption of impurities using silica gel or the like and recrystallization using 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 (5). X- (R ₈ -SH) _m wherein X is a charge transporting structural group, R _{8 is a} single bond, a substituted or unsubstituted alkylene or arylene group, and m is an integer of 1 to 5. .

The charge transporting compound having an amine group is represented by the following general formula (6). X- (R ₉ -NR ₁₀ H) _m wherein X: charge-transporting structural group, R ₉ : single bond, substituted, unsubstituted alkylene, substituted, unsubstituted arylene group, R ₁₀ : A hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, m: an integer of 1 to 5.

Among the charge transporting compounds having an amino group, in the case of a primary amine compound (—NH ₂ ), two hydrogen atoms may react with an organosilicon compound and be linked to a siloxane structure. In the case of a secondary amine compound (—NHR ₁₀ ), one hydrogen atom reacts with the organosilicon compound, and R ₁₀ may be a group 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 (7). X-(— R ₁ —Si (R ₁₁ ) _3-a (R ₁₂ ) _a ) _{n In the} formula, X is a charge transporting structural group, 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 (4) to (7) are shown below.

[0121]

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[0122]

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[0123]

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[0124]

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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 surface layer of the present invention has good charge transporting properties.

The charge transporting structural component of the resin of the present invention refers to a chemical structural component corresponding to the charge transporting structural group X in the general formulas (4) to (7). 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, The chemical structure of pyrazoline, stilbene compound, amine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine, aminostilbene, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene Groups.

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 include groups having a chemical structure such as 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and melitic acid.

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

In the above formula, the charge transporting structural group X is 1
Although it is shown as a valence group, when the reactive charge transporting compound to be reacted with the organosilicon compound and the siloxane condensate component has two or more reactive functional groups, It may be joined as a crosslink group, or may be joined simply as a pendant group.

The surface layer of the present invention contains a resin having an organic polymer component, a siloxane condensate component and a charge transporting structural component. These resins in the surface layer are mutually bonded by a chemical bond. The whole is formed of a surface layer having a crosslinked structure.

The ratio of the charge transporting structural component to the total weight of the organic polymer component and the siloxane condensate component in the surface 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.) at the time of repeated use are deteriorated.

The ratio of the organic polymer component, the siloxane condensate component and the charge transporting structural component in the surface layer of the present invention is such that the ratio of the organic polymer component 1 to the siloxane condensate component 0.2
Preferably, the composition ratio is 5 to 4, and the charge transporting structural component is 0.02 to 50. When the compounding ratio of the siloxane condensate component is small, the film strength is reduced, while when 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.) at the time of repeated use are deteriorated.

The siloxane condensate component is preferably formed at a mass ratio of the organosilicon compound having an epoxy group or its ring-opening group to the other organosilicon compound of 1: 0.01 to 100. Further, the mass ratio is 1:
A ratio of 1 to 20 is preferred.

The thickness of the surface 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 surface layer of the present invention is used as a protective layer, the protective layer has a thickness of 0.0
It is desirably 3 to 10 μm, preferably 0.1 to 5 μm. When a protective layer is used as the surface layer of the present invention, even if the thickness of the protective layer is relatively large, without lowering electrostatic characteristics such as sensitivity and residual potential, which have been a problem in the past. 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-mentioned surface layer may contain metal oxide particles as long as the effects of the present invention are not impaired. By incorporating the metal oxide particles, the wear resistance of the surface layer of the present invention can be further improved, and the cleaning performance of the toner and the stability of the cleaning blade against turning up can be improved.

The primary particle diameter of the metal oxide particles is from 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 having a reactivity with the organosilicon compound on the particle surface. As the reactive compound group,
Examples include a hydroxyl group and an amino group. By using a metal oxide particle having such a reactive group, a siloxane condensation component of the resin of the present invention and a surface layer in which the surface of the metal oxide particle is chemically bonded to form a complex surface layer are formed. It is possible to form a surface 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 surface layer. If the amount of these components exceeds 30% by mass, the cleaning performance deteriorates, and the image in a high humidity environment deteriorates.

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

As the size of the organic fine particles, the average volume particle size or the maximum length of the projected image of the particles is 0.01 to 1.
It is desirably 0 μm, preferably 0.01 to 0.3 μm. The compounding amount of the organic fine particles is 0.1% of the total mass of the surface layer.
1-30 mass% is preferable. If the content 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 surface layer in the present invention.
This is effective in improving the potential stability and image quality when the environment changes.

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

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

[0143]

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In the formula, R ₁₃ 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 antioxidants 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.

[0148]

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[0149]

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[0150]

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[0151]

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Examples of commercially available antioxidants include the following compounds, for example, “Irganox 107
6, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076, 3,5-di-t-butyl- 4
-Hydroxybiphenyl "or more hindered phenols," Sanol LS2626 "," Sanol LS76 "
5 "," Sanol LS2626 "," Sanol LS77 "
0 "," Sanol LS744 "," Tinuvin 144 ",
“Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”, “Mark LA6”
8 "," mark LA63 "or more hindered amine-based,
"SUMILIZER TPS", "SUMILIZER TP-D" or higher thioether type, "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. The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total solid content of the surface layer.

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

The surface layer of the present invention is formed by applying a coating solution containing an organic polymer having a silyl group in a side chain, an organosilicon compound and a reactive charge transporting compound onto the photosensitive layer and then curing the coating solution. Can be. In particular, it is preferable to use an organosilicon compound having at least an epoxy group or its ring-opening group in the organosilicon compound.

The surface layer of the present invention contains at least an organic polymer having a side chain of a siloxane condensate formed using an organosilicon compound having an epoxy group or its ring-opening group, and a reactive charge transporting compound. It can also be formed by applying a coating liquid on the photosensitive layer and then curing.

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

By this curing, the siloxane condensate becomes 3
The siloxane condensate, the silyl group-containing vinyl resin, and the reactive charge transporting compound are chemically bonded via the silyl group and the reactive group, thereby providing abrasion resistance and adhesion to the photosensitive layer. In addition, a surface layer having good cleaning characteristics is formed.

In any of the above production methods, the compounding ratio of the organic silicon compound, the siloxane condensate, the vinyl resin having a silyl group, and the reactive charge transporting compound as the raw materials in the coating solution is as follows. It is sufficient that the compounding ratio of the organic polymer component, the siloxane condensate component, and the charge transporting structural component is within the above range. For example, an organic silicon compound, a silyl group-containing vinyl resin, and a reactive charge transporting compound Is 100: 25 to 400: 1 to 10.
A mixing ratio of 00 is preferred.

The organosilicon compound is preferably blended in a weight ratio of the organosilicon compound having an epoxy group or its ring-opening group to the other organosilicon 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 of the organosilicon compound, the silyl group-containing vinyl resin and the reactive charge transporting compound, it is preferable to add a metal chelate compound in the coating solution or during the process of forming the coating solution. Here, the metal chelate compound is a chelate compound of a metal selected from the group of zirconium, titanium and aluminum (hereinafter, referred to as metal chelate compound (III)). The metal chelate compound (III) promotes the hydrolysis and / or partial condensation reaction of the organosilicon compound with the silyl group-containing vinyl resin and the reactive charge transporting compound to form a three-component co-condensate. It is thought to have a promoting effect.

Examples of such a metal chelate compound (III) include compounds represented by the general formulas (8), (9) and (10), or partial hydrolysates of these compounds.

General formula (8) Zr (OR ₅ ) _p (R ₆ COCHCOR ₇ ) _4-p General formula (9) Ti (OR ₅ ) _q (R ₆ COCHCOR ₇ ) _4-q General formula (10) Al ( OR ₅ ) _r (R ₆ COCHCOR ₇ ) _3-r R ₅ and R ₆ in the general formulas (8), (9) and (10)
Is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms,
Specifically, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group,
n-pentyl group, n-hexyl group, cyclohexyl group,
A phenyl group or the like; R ₇ is a monovalent hydrocarbon group having 1 to 6 carbon atoms similar to R ₅ and R ₆ ,
An alkoxy group, specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, a lauryloxy group, a stearyloxy group, etc. . Further, p and q are integers of 0 to 3, and r is an integer of 0 to 2.

Specific examples of such 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)
Coating solution solids (organic silicon compounds, siloxane condensates, silyl group-containing vinyl resins, reactive charge transporting compounds, etc.) (based on the total mass of coating solution solids are the components remaining after drying the coating solution) The amount is such that the amount is 0.01 to 20% by mass, preferably 0.5 to 20% by mass. If the amount of the metal chelate compound (III) is too small, the three-dimensional surface layer may not be achieved. On the other hand, if the amount is too large, the pot life of the coating solution is deteriorated.

The curing conditions after the application of the coating solution for the surface 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, an organic solvent is preferably 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 the organic silicon compound, the silyl group-containing vinyl resin, and the 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, 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 surface layer coating solution, if necessary.

[0171] As the curing accelerator, naphthenic acid,
Alkaline such as luic acid, nitrous acid, sulfurous acid, aluminate, carbonic acid
Li metal salts; sodium hydroxide, potassium hydroxide, etc.
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
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, Such as mercaptide organics
Compound; (C_FourH₉)_TwoSnO, (C₈H₁₇)_TwoSnO,
(C_FourH₉)_TwoSnO, (C₈H₁₇)_TwoOrganic materials such as SnO
Oxide and ethyl silicate, ethyl silicate 4
0, dimethyl maleate, diethyl maleate, phthalate
Reaction products with ester compounds such as dioctyl acid
And the like are used.

The amount of the curing accelerator added in the coating solution is 0.1 to 20 parts by mass per 100 parts by mass of the solid content of the coating solution (the solid content means 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.

The surface layer of the present invention can be prepared by adding the above-mentioned metal oxide particles, organic fine particles, and antioxidants to the coating solution as required.

In the present invention, an organic solvent can be used to adjust the total solid content of the surface 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 the organic solvent 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 photoreceptor of the present invention other than the intermediate layer and the surface layer will be described. The photoreceptor 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 applied to the intermediate layer and the surface of the present invention. Preferably, a layer is applied.

In the present invention, the organic photoreceptor means an electrophotographic photoreceptor constituted by giving an organic compound at least one of a charge generation function and a charge transport function which are essential for the constitution of the electrophotographic photoreceptor. Further, it includes all known organic electrophotographic photosensitive members such as a photosensitive member composed of a known organic charge generating substance or an 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 the functions of charge generation and charge transport in the same layer).
It is preferable to adopt a configuration in which a photosensitive layer such as described above and a surface layer are coated thereon. Further, since the surface layer of the present invention has a function of a protective layer and a function of transporting charges, it may be used instead of the charge transporting layer.

The specific constitution of the photosensitive member preferably used in the present invention will be described below. Conductive Support As the conductive support used in the photoreceptor of the present invention, any of a sheet shape and a cylindrical shape may be used, but in order to design the image forming apparatus compactly, the cylindrical conductive support is used. Is more preferred.

The cylindrical conductive support of the present invention means a cylindrical support necessary for forming an image endlessly by rotation, 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 anodic oxidation treatment in sulfuric acid, it is preferable that the sulfuric acid concentration is 100 to 200 g / l, the aluminum ion concentration is 1 to 10 g / l, the liquid temperature is around 20 ° C., and the applied voltage is about 20 V. It is not limited. The average thickness of the anodic oxide coating is usually 2
It is preferably 0 μm or less, particularly preferably 10 μm or less.

Intermediate Layer In the present invention, the above-mentioned intermediate layer having a barrier function is provided between the conductive support and the photosensitive layer.

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, the 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, a phenoxy resin. Resins. The ratio between the binder resin and the charge generating substance is preferably from 20 to 600 parts by mass per 100 parts by mass of the binder resin. By using these resins, the increase in residual potential due to repeated use can be minimized. The thickness of the charge generation layer is preferably from 0.01 μm to 2 μm.

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

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

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

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

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

Surface Layer By providing the siloxane-based resin layer of the present invention as the surface layer of the photoconductor, a photoconductor having the most preferred layer configuration of the present invention can be obtained.

Although the most preferred layer configuration of the photoreceptor of the present invention has been described above, other layer configurations of the photoreceptor may be used in the present invention.

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 surface layer of the present invention applied thereon. It is driven and rotated clockwise. 52
Is a scorotron charger (charging means) for uniformly charging the peripheral surface of the photosensitive drum 50 by corona discharge. Prior to the charging by the charger 52, in order to eliminate the history of the photoconductor in the previous image formation, exposure by the pre-charging exposure unit 51 using a light emitting diode or the like may be performed to remove the charge on the peripheral surface of the photoconductor.

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

Here, the reversal development of the present invention means that the surface of the photosensitive member is uniformly charged by the charger 52, and the region where image exposure has been performed, that is, the exposed portion potential (exposed portion region) of the photosensitive member is developed. 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 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 and the like, and a low molecular weight of the present invention. The toner is composed of a toner in which silica, titanium oxide, or the like is externally added to colored particles of polyolefin, and the developer is transported to a development area with the layer thickness regulated by a transport amount regulating member, where 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 means) 58 for applying 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 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 electrophotographic apparatuses in general, such as electrophotographic copying machines, laser printers, LED printers, and liquid crystal shutter printers. , Light printing, plate making and facsimile.

[0205]

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”.

Preparation of Coating Liquid for Intermediate Layer Coating liquids for the intermediate layer of each Example and Comparative Example were prepared as follows.

(Preparation of Intermediate Layer Coating Solution 1) 1 part by mass of polyamide resin CM8000 (manufactured by Toray Industries, Inc.), titanium oxide SMT
3 parts by weight of 500SAS (first time: silica / alumina treatment, second time: methylhydrogenpolysiloxane treatment: manufactured by Teica), 3 parts by weight of methanol and 10 parts by weight of methanol were added to the same vessel, and dispersed using an ultrasonic homogenizer. Application liquid 1 was prepared.

(Preparation of Intermediate Layer Coating Solutions 2 to 7) Intermediate layer coating solution except that titanium oxide and its surface treatment and particle size, binder resin, titanium oxide / binder resin mass ratio and solvent were as shown in Table 1. In the same manner as in Example 1, intermediate layer coating solutions 2 to 7 were prepared.

(Preparation of Intermediate Layer Coating Solution 8) Titanium oxide MT
Intermediate layer coating liquid 8 was prepared in the same manner as intermediate layer coating liquid 1 except that the second surface treatment of 500SA (primary treatment was silica / alumina treatment) was performed with diisopropoxytitanium bis (acetyl acetate).

(Preparation of Intermediate Layer Coating Solution 9) Titanium oxide MT
Intermediate layer coating liquid 9 was prepared in the same manner as intermediate layer coating liquid 1 except that the second surface treatment of 500SA (primary treatment was silica / alumina treatment) was performed with butoxyzirconium tri (acetyl acetate).

(Preparation of Intermediate Layer Coating Solutions 10 to 12: Comparative Example) Titanium oxide and its surface treatment and particle size, binder resin, titanium oxide / binder resin mass ratio, and type of solvent were as shown in Table 1. Other than that, the intermediate layer coating liquids 10 to 12 were prepared in the same manner as the intermediate layer coating liquid 1.

(Preparation of Coating Solution 13 for Intermediate Layer: Comparative Example) Coating solution 13 for intermediate layer was prepared by dissolving 1 part by mass of polyamide resin CM8000 (manufactured by Toray Industries, Ltd.) and 10 parts by mass of methanol.

[0213]

[Table 1]

In Table 1, those described in the column of primary treatment are substances precipitated on the surface of the titanium oxide particles after the primary treatment.
Those described in the secondary treatment column indicate substances used in the secondary treatment.

Preparation of Photoreceptor 1 <Intermediate Layer> An intermediate layer coating solution 1 was formed on a cylindrical aluminum substrate.
Was applied by dip coating to form an intermediate layer with a dry film thickness of 4 μm.

<Charge Generation Layer> Y-type titanyl phthalocyanine (the maximum peak angle of X-ray diffraction by Cu-Kα characteristic X-ray is 27.3 at 2θ) 60 g Silicon-modified butyral resin (X-40-1211M: manufactured by Shin-Etsu Chemical Co., Ltd.) ) 700 g of 2-butanone (2000 ml) were mixed and dispersed for 10 hours using a sand mill to prepare a charge generation layer coating solution. This coating solution was applied onto the intermediate 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 substance [N- (4-methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine] 225 g Polycarbonate (viscosity average molecular weight 20,000) 300 g 6 g of an antioxidant (exemplary compound 1-3) and 2,000 ml of dichloromethane were mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a dry film thickness of 20 μm.

<Surface Layer A: Surface Layer of the Present Invention> Silyl group-containing vinyl resin (A) (solid content: 50% by mass) 100 g methyltrimethoxysilane 70 g 3-glycidoxypropyltrimethoxysilane 30 g 2-butyl 100 g of alcohol, 75 g of butyl cellosolve, 10 g of di-i-propoxyethyl acetoacetate aluminum were mixed and stirred well, and then 30 g of pure water was added dropwise with stirring, followed by reaction at 60 ° C. for 4 hours. Next, the mixture was cooled to room temperature, 10 g of a 2-propyl alcohol solution of dioctyltin dimaleate ester (solid content: 15% by mass) and 50 parts of a reactive charge transport agent (B-1) were added, followed by stirring to prepare a coating liquid. did. This coating solution was used to form a surface layer having a dry film thickness of 3 μm on the charge transporting layer by a circular quantity control type coating device, and was heated and cured at 120 ° C. for 1 hour. Photoconductor 1 having surface layer A having the components and the charge transporting structural component was prepared.

Preparation of Photoreceptors 2 to 9 The coating solution for the intermediate layer shown in Table 2 was used in place of the coating solution for the intermediate layer used for the photoreceptor 1, and the intermediate layer having the dry film thickness shown in Table 2 was provided. The photoreceptors 2 to 9 were produced in the same manner as in photoreceptor 1.

Production of Photoreceptor 10 In the same manner as for Photoreceptor 1, the components up to the charge transport layer were prepared.

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

Methyltrimethoxysilane oligomerization liquid 160 g Tetramethoxysilane 10 g Silyl group-containing vinyl resin (B) (solid content: 50% by mass) 60 g Reactive charge transporting compound (exemplified compound (B-1)) 40 g Oxidation An inhibitor (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 surface layer having a dry film thickness of 2 μm on the charge transporting layer by a circular amount control type coating device, and was cured by heating at 120 ° C. for 1 hour. A photoreceptor 10 having a surface layer B having a component and a charge transporting structural component was prepared.

Preparation of Photoreceptors 11 to 14 (Comparative Example) The intermediate layer coating solution shown in Table 2 was used in place of the intermediate layer coating solution used in Photoreceptor 1, and the intermediate layer having a dry film thickness shown in Table 2 was used. Photoconductors 11 to 14 were produced in the same manner as in Photoconductor 1, except that.

Preparation of Photoreceptor 15 (Comparative Example) <Surface Layer C: Surface Layer Outside the Present Invention> The preparation of photoreceptor 1 was carried out in the same manner except that Exemplified Compound (B-1) in the surface layer was omitted. Photoconductor 15 having surface layer C of a siloxane-based resin layer having no charge transporting structural unit was produced.

Evaluation Konica Digital Copier 7 manufactured by Konica Corporation was used as an evaluation machine.
075 (corona charging, laser exposure, reversal development, electrostatic transfer, nail separation, blade cleaning, cleaning auxiliary brush roller adoption process), and the photoconductors 1 to 15 were mounted on the copying machine and evaluated. The cleaning performance and the image evaluation were performed by copying an original image in which a character image having a pixel ratio of 7%, a portrait photograph, a solid white image, and a solid black image were each equal to 1/4 on A4 neutral paper. Copying conditions are considered to be the most severe in a high-temperature and high-humidity environment (30 ° C, 8
0% RH) to perform 200,000 copies continuously, halftone,
A solid white image and a solid black image were prepared and evaluated as follows.
The evaluation of the thickness loss of the photoreceptor was also performed as follows.

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 up to 200,000 copies at initial and every 10,000 copies. ◎: Black solid image is 1.2 or more ○: Black solid image is less than 1.2 to 1.0 ×: Black solid image is less than 1.0 Fog (solid up to 200,000 copies at initial and every 10,000 copies)白: No fogging occurs after copying 200,000 copies. ：: Fog occurs slightly after copying 150,000 copies. X: Fogging occurs after copying 100,000 copies. Resolution (determined by ease of character image discrimination) ：: There is no difference between the initial and the resolution after 200,000 copies. △: There is a slight decrease in the resolution after 200,000 copies in the halftone image. X: The remarkable decrease in the resolution after 200,000 copies. (Evaluated with a solid white image up to 200,000 copies at initial and every 10,000 copies.)
Judgment was made based on the number of black spots per A4 sheet.
Incidentally, the length of the black spot is measured by a microscope equipped with a video printer. The criterion for black spot evaluation is as follows.

A: Black spot frequency of 0.4 mm or more: all copied images are 3 pieces / A4 or less B: Black spot frequency of 0.4 mm or more: 4 pieces / A4 or more, 19 pieces / A4 or less C: Black spots of 0.4 mm or more: 20 / A4 or more of one or more sheets ΔEvaluation of ΔV ₁₂ After copying the above 200,000 sheets, a pause of one hour was performed, and ΔV ₁₂ was reached.
Was evaluated. A potential sensor was installed at the development position, and the first and second black solid portion potentials of the photoconductor were measured.
The absolute value of the difference was [Delta] V _12.

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

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

Developing conditions DC bias: -550 V The developer was a carrier coated with an insulating resin with ferrite as a core, a styrene acrylic resin as a main material, a colorant such as carbon black, a charge control agent, and the low molecular weight of the present invention. A toner developer in which silica, titanium oxide or the like is externally added to colored particles made of polyolefin is used. Transfer condition Transfer pole; corona charging method Cleaning condition 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 2.

[0232]

[Table 2]

As apparent from Table 2, the intermediate layer of the present invention,
Photoconductors 1 to 10 having a surface layer have image density, fog,
Image characteristics such as resolution are good, and potential fluctuation characteristics (ΔV
₁₂ ) and the occurrence of black spots is small, and the thickness loss is small, and all characteristics are improved in a balanced manner.

On the other hand, photosensitive member 1 having an intermediate layer outside the present invention
In No. 1, the occurrence of black spots was remarkable, and the evaluation of image density and fog was inferior. The photoconductors 12 to 14 are the photoconductors 1 to 5 of the present invention.
As compared with No. 10, the potential fluctuation characteristic (ΔV ₁₂ ) is large, and the effect of preventing occurrence of black spots is small. In addition, the photoreceptor 15 having a surface layer outside the present invention has larger fogging and lower resolution and a larger potential variation characteristic (ΔV ₁₂ ) than the photoreceptors 1 to 10 of the present invention.

[0235]

As is clear from the examples, the use of the photoreceptor having the surface layer and the intermediate layer according to the present invention produces good image characteristics, good charge characteristics, and image defects such as black spots. It is possible to provide an electrophotographic photoreceptor that does not need to be used.
Further, it is possible to provide an image forming method, an image forming apparatus, and a process cartridge capable of achieving a good electrophotographic image using the electrophotographic photosensitive member.

[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 Tetsu Uchino Konica Corporation, 2970 Ishikawa-cho, Hachioji-shi, Tokyo In-house (72) Inventor Shinichi Hamaguchi 1st Konica Corporation, Sakura-cho, Hino-shi, Tokyo In-house (72) Inventor Hirofumi Hayata 1st Sakuracho, Hino-shi, Tokyo Konica Corporation F-term (reference) 2H068 AA04 AA44 BA57 BA58 BB28 BB33 CA06 CA29 CA33 FA27

Claims (22)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support via an intermediate layer, wherein the intermediate layer is subjected to a plurality of surface treatments, and the final surface treatment is a reactive organosilicon. The composition contains N-type semiconductor fine particles and a binder resin, and the surface layer of the photosensitive layer contains a resin having an organic polymer component, a siloxane condensate component, and a charge transport structure component. An electrophotographic photosensitive member characterized by the following. 2. The electrophotographic photoconductor according to claim 1, wherein the siloxane condensate component is formed using an organosilicon compound having at least an epoxy group or a ring-opening group thereof. 3. The electrophotographic photoreceptor according to claim 1, wherein the reactive organosilicon compound is methyl hydrogen polysiloxane. 4. The electrophotographic photoreceptor according to claim 1, wherein the reactive organosilicon compound is an organosilicon compound represented by the following general formula (1). General formula (1) R-Si- (X) ₃ (wherein, R represents an alkyl group, an aryl group, and X represents a methoxy group, an ethoxy group, or a halogen group.) 5. The compound of the general formula (1) wherein R has 4 to 8 carbon atoms.
The electrophotographic photosensitive member according to claim 4, wherein the alkyl group is 6. An electrophotographic photoreceptor having a photosensitive layer on a conductive support via an intermediate layer, wherein the intermediate layer is subjected to a plurality of surface treatments, and the final surface treatment is a reactive organic titanium. The composition contains N-type semiconductor fine particles and a binder resin, and the surface layer of the photosensitive layer contains a resin having an organic polymer component, a siloxane condensate component, and a charge transport structure component. An electrophotographic photosensitive member characterized by the following. 7. An electrophotographic photoreceptor having a photosensitive layer on a conductive support via an intermediate layer, wherein the intermediate layer is subjected to a plurality of surface treatments, and the final surface treatment is a reactive organic zirconium. The composition contains N-type semiconductor fine particles and a binder resin, and the surface layer of the photosensitive layer contains a resin having an organic polymer component, a siloxane condensate component, and a charge transport structure component. An electrophotographic photosensitive member characterized by the following. 8. The electrophotographic photosensitive member according to claim 6, wherein the siloxane condensate component is formed using an organosilicon compound having at least an epoxy group or a ring-opening group thereof. 9. The method according to claim 1, wherein at least one of the plurality of surface treatments is a surface treatment of at least one of alumina, silica, and zirconia. Item 2. The electrophotographic photosensitive member according to Item 1. 10. The method according to claim 1, wherein the N-type semiconductor fine particles are subjected to a surface treatment with at least silica or alumina, and then subjected to a surface treatment with a reactive organosilicon compound. 13. The electrophotographic photoreceptor according to item 6. 11. The electrophotographic photosensitive member according to claim 6, wherein the N-type semiconductor fine particles are subjected to a surface treatment with at least silica or alumina, and then subjected to a surface treatment with a reactive organic titanium compound. body. 12. The electrophotographic photosensitive member according to claim 7, wherein the N-type semiconductor fine particles are subjected to a surface treatment with at least silica or alumina, and then subjected to a surface treatment with a reactive organic zirconium compound. body. 13. The electrophotographic photosensitive member according to claim 1, wherein the N-type semiconductor fine particles are titanium oxide particles. 14. The electrophotographic photoreceptor according to claim 1, wherein the N-type semiconductor fine particles have a rutile crystal type. 15. The electrophotographic photoreceptor according to claim 1, wherein the N-type semiconductor fine particles have a number average primary particle size of 10 nm or more and 200 nm or less. 16. An electrophotographic photosensitive member having a photosensitive layer on a conductive support via an intermediate layer, wherein the intermediate layer is surface-treated with a reactive organosilicon compound having a fluorine atom. An electrophotographic photosensitive member containing particles and a binder resin, wherein the surface layer of the photosensitive layer contains a resin having an organic polymer component, a siloxane condensate component, and a charge transport structure component. 17. The electrophotographic photoreceptor according to claim 16, wherein the siloxane condensate component is formed using an organosilicon compound having at least an epoxy group or a ring-opening group thereof. 18. The electrophotographic photosensitive member according to claim 16, wherein the number average primary particle diameter of the titanium oxide particles is 10 nm or more and 200 nm or less. 19. The electrophotographic photosensitive member according to claim 1, wherein the binder resin of the intermediate layer is a polyamide resin. 20. An image forming method for forming an image repeatedly, comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and a cleaning unit around the electrophotographic photosensitive member. Item 20. An image forming method comprising the electrophotographic photosensitive member according to any one of Items 1 to 19. 21. An image forming apparatus using the image forming method according to claim 20. 22. A process cartridge used in the image forming apparatus according to claim 21.
20. The electrophotographic photosensitive member and the charger according to any one of items 19 to 19,
A process cartridge having at least one of an image exposing unit, a developing unit, a transfer unit, and a cleaning unit, and configured to be able to be taken in and out of the image forming apparatus.