JP2001092159A - Production of electrophotographic photoreceptor, coating fluid composition, electrophotographic photoreceptor, image forming method using same, image forming device and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To sufficiently carry out the crosslinking reaction of a siloxane resin in the production of an electrophotographic photoreceptor having a siloxane resin layer on the electrically conductive substrate, to produce an electrophotographic photoreceptor having the resin layer and excellent in strength characteristics and electrostatic characteristics, to obtain a coating fluid composition used in the production and to provide an electrophotographic image forming method using the photoreceptor, an electrophotographic image forming device and a process cartridge used in the device. SOLUTION: The coating fluid composition contains at least one of an organosilicon compound having a hydroxy group or a hydrolyzable group and its condensation product, an electric charge transferring compound having a reactive group and 0.01-20 wt.% metallic chelate on the basis of the amount of the electric charge transferring compound. A siloxane resin layer having a crosslinked structure is formed on an electrically conductive substrate by applying and drying the coating fluid composition and the objective electrophotographic photoreceptor having the siloxane resin layer on the electrically conductive substrate is produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrophotographic photosensitive member, a coating solution composition used in the method, an electrophotographic photosensitive member (hereinafter, also simply referred to as a photosensitive member), and an electrophotographic photosensitive member. The present invention relates to an electrophotographic image forming method, an electrophotographic image forming apparatus, and a process cartridge used in the apparatus.

[0002]

2. Description of the Related Art In recent years, an organic photoconductor containing an organic photoconductive substance has been most widely used as an electrophotographic photoconductor. Organic photoreceptors are advantageous over other photoreceptors in that materials that can be used for various exposure light sources from visible light to infrared light can be easily developed, materials that do not pollute the environment can be selected, and manufacturing costs are low. However, the only disadvantage is that the mechanical strength is weak,
This means that the surface of the photoconductor is deteriorated or scratched when copying or printing a large number of sheets.

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

[0004] For example, with respect to mechanical durability, it has been reported that the use of bisphenol Z-type polycarbonate as a binder (binder resin) on the surface of an organic photoreceptor improves the surface wear characteristics and toner filming characteristics. Have been. Japanese Patent Application Laid-Open No. 6-118681 reports that a curable silicone resin containing colloidal silica is used as a surface protective layer of a photoreceptor.

However, a photoreceptor using a bisphenol Z-type polycarbonate binder still lacks abrasion resistance and does not have sufficient durability. On the other hand, in the surface layer of the curable silicone resin containing colloidal silica, the wear resistance is improved, but the electrophotographic properties after repeated use are insufficient, and fog and image blur are liable to occur, which also has durability. Not enough.

As a method of improving the above-mentioned disadvantage, the present inventors disclosed in Japanese Patent Application No. 11-70308 a method in which a siloxane-based resin-containing layer having a structural unit having charge transport performance and having a cross-linked structure was exposed to light. Proposed as a body surface layer.
The photoreceptor having this surface layer has improved abrasion resistance and environmental resistance (changes in static charge generation characteristics with respect to temperature and humidity).

[0007]

A siloxane-based resin having a structural unit having charge transport performance and having a crosslinked structure has excellent strength characteristics and electric characteristics, and has strength characteristics which have been a drawback of organic photoconductors. This is a technology that can be greatly improved.

For example, Japanese Patent Application Laid-Open No. 9-190004 discloses that a hardening condition of a charge-transporting silicon hard coat is set at 140 ° C.
It is disclosed that a drying treatment is performed at 4 hours or 120 ° C. for 5 hours to form a surface layer having high film strength. Japanese Patent Application Laid-Open No. H10-83094 discloses that the drying treatment is similarly performed at 110 ° C. for 4 hours. Can be performed, and furthermore, JP-A-10-251277
Discloses performing a drying treatment at room temperature.
However, a siloxane having a structural unit having charge transport performance by reacting a compound containing a structural unit having charge transport performance (hereinafter also referred to as a charge transport compound having a reactive group) with an organosilicon compound and having a crosslinked structure It has been found that the reaction conditions for producing a system resin cannot provide sufficient resin layer strength characteristics and image characteristics in a high humidity environment under the above-mentioned conventional curing conditions.

The present inventors have conducted various studies to solve the above problems, and as a result, it has been found that it is important to carry out the reaction in an environment in which the organosilicon compound undergoes a sufficient condensation reaction.

The present invention has been made in view of the above circumstances, and has as its object the purpose of reacting a charge transporting compound having a reactive group with an organosilicon compound having a siloxane group to form a resin layer containing the siloxane-based resin. In producing, a method for producing an electrophotographic photoreceptor having excellent strength and electrostatic properties of a photoreceptor having the resin layer by sufficiently performing a crosslinking reaction of the siloxane-based resin, and a coating solution used in the production method An object of the present invention is to provide a composition, an electrophotographic photoreceptor (hereinafter, also simply referred to as a photoreceptor), an electrophotographic image forming method using the electrophotographic photoreceptor, an electrophotographic image forming apparatus, and a process cartridge used in the apparatus.

[0011]

The above object of the present invention is achieved by adopting one of the following constitutions.

1. In the method for producing an electrophotographic photoreceptor having a resin layer on a conductive support, when forming the resin layer on the conductive support, an organosilicon compound having a hydroxyl group or a hydrolyzable group or a condensate thereof At least one and a charge transporting compound having a reactive group, and 0.01 to the charge transporting compound having the reactive group.
A method for producing an electrophotographic photosensitive member, comprising applying a coating solution composition containing not less than 20% by weight and not more than 20% by weight of a metal chelate, followed by drying to form a siloxane-based resin layer having a crosslinked structure.

2. The coating liquid composition is 0.1% by weight or more and 10% by weight based on the charge transporting compound having a reactive group.
(1) The above-mentioned item (1), comprising the following metal chelate:
The method for producing the electrophotographic photosensitive member according to the above.

3. 3. The production of the electrophotographic photoreceptor according to the above 1 or 2, wherein the organosilicon compound having a hydroxyl group or a hydrolyzable group is a compound represented by the following general formula (1) or a hydrolysis product thereof. Method. Formula (1) _{R n Si (OR ') 4} -n ( wherein, R is an alkyl group having 1 to 10 carbon atoms, a phenyl group, an aryl group, a vinyl group, an amino group, .gamma.-glycidoxypropyl group, γ-methacryloxypropyl group, C _{m
F 2m + 1 C 2 H 4} - represents a. R ′ represents an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 0 to 3. m represents a positive integer. )

4. The organosilicon compound is a compound represented by the following general formulas (2) and (3) or a hydrolysis product thereof, and a molar ratio M1 / M1 / M2 of the compound represented by the general formula (2) and the compound represented by the general formula (3). 4. The method for producing an electrophotographic photosensitive member according to any one of the above items 1 to 3, wherein M2 is 0.1 or more and 10 or less. Formula (1) RaSi (OR ') 3 Formula (2) RaRbSi (OR') 2 (where Ra and Rb are an alkyl group having 1 to 10 carbon atoms, a phenyl group, an aryl group, a vinyl group, an amino group Γ-glycidoxypropyl group, γ-methacryloxypropyl group,
_{C m F 2m + 1 C 2} H 4 - represents a. R ′ represents an alkyl group having 1 to 3 carbon atoms. m represents a positive integer. )

5. The method for producing an electrophotographic photoreceptor according to any one of the above items 1 to 4, wherein at least a part of the organosilicon compound having a hydroxyl group or a hydrolyzable group has a γ-glycidoxypropyl group.

6. 6. The method for producing an electrophotographic photosensitive member according to any one of 1 to 5, wherein the metal chelate is an aluminum chelate.

[7] The method for producing an electrophotographic photosensitive member according to any one of the above items 1 to 5, wherein the metal chelate is a titanium chelate.

8. Wherein the reactive group of the charge transporting compound having a reactive group is a hydroxyl group.
8. The method for producing an electrophotographic photosensitive member according to any one of items 7 to 7.

9. The method for producing an electrophotographic photoreceptor according to any one of the above items 1 to 8, wherein the coating liquid composition contains colloidal silica.

10. The organic silicon compound having a hydroxyl group or a hydrolyzable group and at least one of the condensates thereof are dialkylsilanes having a hydroxyl group or a hydrolyzable group, or the condensates thereof.
10. The method for producing an electrophotographic photosensitive member according to any one of items 9 to 9.

11. The method for producing an electrophotographic photosensitive member according to any one of the above items 1 to 10, wherein the coating solution composition contains an antioxidant.

12. A coating liquid composition used for manufacturing an electrophotographic photoreceptor for forming a resin layer on a conductive support has an organic silicon compound having a hydroxyl group or a hydrolyzable group, or a charge having a reactive group with at least one of its condensate. A coating liquid composition comprising a transportable compound and a metal chelate in an amount of from 0.01% by weight to 20% by weight based on the charge transportable compound having the reactive group.

13. 12. An electrophotographic photosensitive member obtained by the production method according to any one of the above items 1 to 11.

14. 14. The electrophotographic photoconductor according to the above 13, wherein the resin layer of the electrophotographic photoconductor is a surface layer.

15. 15. An image forming method using the electrophotographic photoreceptor according to 13 or 14 above, comprising at least steps of charging, image exposure, development, and cleaning, and performing image formation by reversal development.

16. An image forming apparatus using the electrophotographic photosensitive member according to the above item 13 or 14, comprising at least steps of charging, image exposure, development, and cleaning, and forming an image through a step of performing development by a reversal development method. .

17. Using an electrophotographic photoreceptor, the process cartridge used in an electrophotographic image forming apparatus having at least charging, image exposure, development, and cleaning means is the electrophotographic photoreceptor and the charger according to the above 13 or 14, an image exposure device, A process cartridge having at least one of a developing unit and a cleaning unit in combination with each other and being designed to be freely inserted into and removed from the electrophotographic image forming apparatus.

In order to solve the above problems, the present invention relates to a coating liquid composition containing an organic silicon compound having a hydroxyl group or a hydrolyzable group or a charge transporting compound having a reactive group with at least one of its condensates. In the presence of a metal chelate, by performing a curing reaction of the coating film in the presence of the metal chelate, while suppressing the decomposition of the charge transport compound having a reactive group, the siloxane resin layer obtained from the coating solution composition It is based on the knowledge that sufficient crosslinking conditions can be ensured, and the presence of a metal chelate compound in a resin coating film formed from the coating solution composition allows the resin coating film to dry and harden. The present invention was found to promote the reaction and to obtain an electrophotographic photoreceptor having a siloxane-based resin layer having excellent strength properties and electrical properties. Than it is.

Hereinafter, the present invention will be described in detail.

[1] Method for Producing Electrophotographic Photoreceptor, Coating Composition, and Electrophotographic Photoreceptor The present invention relates to a method for producing an electrophotographic photoreceptor having a resin layer on a conductive support. The charge transporting compound having a reactive group with at least one of an organosilicon compound having a hydroxyl group or a hydrolyzable group or a condensate thereof, and 0.01% by weight based on the charge transporting compound having the reactive group This is achieved by forming a siloxane-based resin layer having a crosslinked structure by applying and drying a coating solution composition containing not less than 20% by weight of a metal chelate.

That is, the present invention is characterized in that a metal chelate is contained in the coating liquid composition when forming the siloxane-based resin layer. The metal chelate compound includes the following compounds. Representatively mentioned.

That is, the metal chelate in the present invention is 2
A complex in which a ligand having at least two coordinating atoms (polydentate ligand) forms a ring and binds to a central metal. Examples of the bidentate chelating ligand include ethylenediamine, glycinate ion, oxalate ion, acetylacetonate ion, ethylacetonate ion, and alkyleneglyconate ion. Examples of the tridentate or higher ligand include diethylenetriamine, iminodiacetic acid, methionine, and ethylenediaminetetraacetic acid, but are not particularly limited thereto.

The central metal is not particularly limited as long as it is a metal to which a bidentate or higher ligand can coordinate, but aluminum and titanium are particularly preferred. When an aluminum or titanium chelate compound is used, the film strength of the siloxane-based resin layer is high, and good electrophotographic image characteristics can be obtained even under high temperature and high humidity conditions.

Hereinafter, typical examples of metal chelate compounds used in the present invention will be described.

<Examples of Compounds> Aluminum chelate diisopropoxy (ethylacetoacetato) aluminum tris (ethylacetoacetato) aluminum tris (acetylacetonato) aluminum bis (ethylacetiacetato) (acetylacetonato)
Aluminum Tris (2-ethyl-1,3-hexanediolato) aluminum titanium chelate diisopropoxybis (acetylacetonato) titanium isopropoxy (2-ethyl-1,3-hexanediolato) titanium di (2-ethylhexoxy) Bis (2-ethyl-1,3
-Hexanediolato) titanium Tris (ethylacetoacetato) titanium Tris (acetylacetonato) titanium di-n-butoxybis (triethanolaminate) titanium Tetraacetylacetonatotitanium Hydroxybis (lactato) titanium Others Acetylacetone tributoxyzirconium dibutyltin Bis (2-ethylhexanoate) zinc acetylacetonate bis (2,4-pentadionato) nickel As the "organosilicon compound having a hydroxyl group or a hydrolyzable group and the condensate thereof" in the present invention, the following are typical. Examples thereof include an organosilicon compound having a hydroxyl group or a hydrolyzable group represented by the general formula (1) and a hydrolyzed condensate thereof.

Formula (1) (R) _n -Si- (X) _4-n R represents an organic group in which carbon is directly bonded to a silicon atom in the formula, and X represents a hydroxyl group or a hydrolyzable group. And n is 0 to
Represents an integer of 3.

In the organosilicon compound represented by the general formula (1), examples of the organic group in which carbon is directly bonded to silicon represented by R include alkyl groups such as methyl, ethyl, propyl and butyl, phenyl and tolyl. , Naphthyl, aryl groups such as biphenyl, γ-glycidoxypropyl, β-
Epoxy-containing groups such as (3,4-epoxycyclohexyl) ethyl, (meth) acryloyl groups such as γ-acryloxypropyl and γ-methacryloxypropyl, γ-hydroxypropyl and 2,3-dihydroxypropyloxypropyl Hydroxyl groups, vinyl, vinyl-containing groups such as propenyl, mercapto-containing groups such as γ-mercaptopropyl, γ-
Amino-containing groups such as aminopropyl and N-β (aminoethyl) -γ-aminopropyl; γ-chloropropyl;
Examples include a halogen-containing group such as 1,1-trifluorofluoropropyl, nonafluorohexyl, and perfluorooctylethyl, and other nitro and cyano-substituted alkyl groups. Particularly, an alkyl group such as methyl, ethyl, propyl, and butyl is preferable. Examples of the hydrolyzable group for X include an alkoxy group such as methoxy and ethoxy, a halogen group, and an acyloxy group. Particularly, an alkoxy group having 6 or less carbon atoms is preferable.

The organosilicon compound represented by the general formula (1) may be used alone or in combination of two or more kinds. However, in order to form a crosslinked structure, it is preferable to use an organosilicon compound in which at least n is 0 or 1.

When n is 2 or more in the specific compound of the organosilicon compound represented by the general formula (1), a plurality of Rs 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 (1) are used, R and X may be the same or different between the respective compounds.

As the organosilicon compound, a hydrolyzed condensate obtained by hydrolyzing the above organosilicon compound under acidic to basic conditions to form an oligomer may be used.

Colloidal silica may be added to the organosilicon compound or the hydrolytic condensate thereof. Colloidal silica may be added at the time of hydrolysis and condensation of the organosilicon compound, or may be added after that.

According to the present invention, "an organosilicon compound having a hydroxyl group or a hydrolyzable group and at least one condensate thereof,
A siloxane-based resin obtained by reacting a charge transporting compound having a reactive group '' is an organic silicon compound having a hydroxyl group or a hydrolyzable group and at least one of its condensates, and a reactive group described below. A siloxane-based resin having a charge-transporting compound that reacts to incorporate a structural unit having charge-transporting performance as a partial structure into a siloxane-based resin structure having a crosslinked structure.

The reaction between the charge transporting compound having a reactive group and at least one of an organosilicon compound having a hydroxyl group or a hydrolyzable group is carried out during the hydrolysis condensation of the organosilicon compound or after the hydrolysis condensation. By adding a charge transporting compound having the compound, the compound can be effectively produced.

When colloidal silica is added, a hydroxyl group on the surface of the colloidal silica reacts with an organosilicon compound or a charge-transporting compound having a reactive group to form a resin using the colloidal silica as a central point of crosslinking. There is also.

The charge transporting compound having a reactive group is typically a charge transporting substance having a chemical structure represented by the following general formula (2). The reactive group reacting with a hydroxyl group of an organosilicon compound or colloidal silica is exemplified. And a compound having a property of having electron or hole drift mobility is not limited to the following chemical structure.

Formula (2) A- (Z) _m A is a charge transporting compound group, Z is a hydroxyl group, a mercapto group,
It is a group selected from an amino group and an organic silicon-containing group, and m represents an integer of 1 to 4.

In the formula, as the charge transporting compound group of A, the hole transporting type is oxazole, oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidin, styryl, hydrazone, benzidine, pyrazoline, triaryl Amines, oxazolones, benzothiazoles, benzimidazoles,
Examples include a compound group containing a structural unit such as quinazoline, benzofuran, acridine, and phenazine, and a compound group derived from a derivative thereof. On the other hand, the electron transport type includes succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, melitic anhydride, tetratocyanoethylene, tetratocyanoquinodimethane, nitrobenzene, dinitrobenzene, trinitrobenzene, tetranitrobenzene, and nitrobenzene. Benzonitrile, picryl chloride, quinone chlorimide, chloranil, bromanyl, benzoquinone, naphthoquinone, diphenoquinone, tropoquinone,
Anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4, 4 '
-Dinitrobenzophenone, 4-nitrobenzalmalone dinitrile, α-cyano-β- (p-cyanophenyl)
-2- (p-chlorophenyl) ethylene, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 9-
Fluoronylidenedicyanomethylenemalonitrile, polynitro-9-fluoronylidenedicyanomethylenemalonitrile, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, perfluorobenzoic acid, 5- Examples include a compound group containing a structural unit such as nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and melitic acid, and a compound group derived from a derivative thereof, but are not limited to these structures.

The charge transporting compound having a hydroxyl group, a mercapto group, an amino group and an organic silicon-containing group will be described.

The charge transporting compound having a hydroxyl group is as follows:
It is a charge transport substance having a commonly used structure and a compound having a hydroxyl group. That is, typically, a charge transporting compound represented by the following general formula that can form a resin layer by bonding to the organosilicon compound can be exemplified, but is not limited to the following structure. Any compound having a charge transporting ability and having a hydroxyl group may be used.

X- (R ₇ -OH) _{m In the} formula, X represents a charge transporting group, R ₇ represents a single bond, a substituted or unsubstituted alkylene group or an arylene group, and m represents an integer.

Among them, the following are typical examples. For example, a triarylamine-based compound has a triarylamine structure such as triphenylamine as a charge transport performance-imparting group = X, and an alkylene extended through a carbon atom constituting X or extended from X;
A compound having a hydroxyl group via an arylene group is preferably used. m is preferably an integer of 1 to 5.

1. Triarylamine compounds

[0054]

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2. Hydrazine compounds

[0056]

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3. Stilbene compounds

[0058]

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4. Benzidine compound

[0060]

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5. Butadiene compound

[0062]

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6. Other compounds

[0064]

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Next, a synthesis example of a charge transporting compound having a hydroxyl group will be described.

Synthesis of Exemplified Compound T-1

[0067]

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

After the precipitated crystals were filtered and dried, they were purified by adsorption of impurities using silica gel or the like and recrystallization with acetonitrile to obtain Compound (2). Yield 30
g.

Step B 30 g of compound (2) and 100 ml of ethanol were charged into a kolben and stirred. After gradually adding 1.9 g of sodium borohydride, the solution was kept at 40 to 60 ° C. and stirred for about 2 hours. Next, the reaction solution was gradually poured into about 300 ml of water and stirred to precipitate crystals. After filtration, the resultant was sufficiently washed with water and dried to obtain a compound (3). The yield was 30 g.

Synthesis of Exemplified Compound S-1

[0072]

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Step A In a 300 ml Kolben equipped with a thermometer and a stirrer, add C
Then, 30 g of u, 60 g of K ₂ CO ₃ , 8 g of compound (1) and 100 g of compound (2) were added, and the mixture was heated to about 180 ° C. and stirred for 20 hours. After cooling, the mixture was filtered and purified by column to obtain 7 g of compound (3).

Step B A 100 ml kolben equipped with a thermometer, a dropping funnel, an argon gas introducing device and a stirrer was set to an argon gas atmosphere, and 7 g of the compound (3), 50 ml of toluene and 3 g of phosphoryl chloride were charged into the atmosphere. While stirring at room temperature, D
2 g of MF was slowly added dropwise, and then the temperature was raised to about 80 ° C., the mixture was stirred for 16 hours, poured into warm water of about 70 ° C., and cooled. This was extracted with toluene, and the extract was adjusted to pH 7 with water.
And washed with water. After drying over sodium sulfate, the mixture was concentrated and purified by column to obtain 5 g of compound (4).

Step C: 100 ml with an argon gas introducing device and a stirring device
1.0 g of t-BuOK and 60 ml of DMF were charged into the Kolben, and the atmosphere was changed to an argon gas atmosphere. Compound (4)
2.0 g and 2.2 g of the compound (5) were added, and the mixture was stirred at room temperature for 1 hour. This was poured into a large excess of water, extracted with toluene, the extract was washed with water, dried over sodium sulfate,
After concentration, column purification was performed, and 2.44 g of compound (6) was obtained.
I got

Step D Toluene was charged into a 100 ml colben equipped with a thermometer, a dropping funnel, an argon gas introducing device and a stirring device, and an argon gas atmosphere was established. 15 ml of a hexane solution of n-BuLi (1.72 M) was added thereto, and the mixture was heated to 50 ° C. To this, 2.44 g of compound (6) was added in 30 ml of toluene.
The dissolved liquid was added dropwise, and the mixture was stirred at 50 ° C. for 3 hours. After cooling to −40 ° C., 8 ml of ethylene oxide was added, the temperature was raised to −15 ° C., and the mixture was stirred for 1 hour.
Thereafter, the temperature was raised to room temperature, 5 ml of water was added, and ether 2 was added.
After extraction with 00 ml, the extract was washed with saturated saline.
After washing the washing solution to pH, it was dried over sodium sulfate, concentrated and purified by column to obtain 1.0 g of compound (7).

Next, specific examples of the charge transporting compound having a mercapto group are shown below.

The charge transporting compound having a mercapto group is a charge transporting substance having a commonly used structure and a compound having a mercapto group. That is, typically, a charge transporting compound represented by the following general formula that can form a resin layer by bonding to a curable organosilicon compound can be exemplified, but is not limited to the following structure. Any compound may be used as long as it has a charge transporting ability and a mercapto group.

X— (R ₈ —SH) _m X represents a charge-transporting group, R ₈ represents a single bond, a substituted or unsubstituted alkylene or arylene group, and m represents an integer. m is preferably an integer of 1 to 5.

The following are typical examples.

[0081]

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Next, the charge transporting compound having an amino group will be described.

The charge transporting compound having an amino group is a charge transporting substance having a commonly used structure and a compound having an amino group. That is, typically, a charge transporting compound represented by the following general formula that can form a resin layer by bonding to a curable organosilicon compound can be exemplified, but is not limited to the following structure. Any compound having a charge transporting ability and having an amino group may be used.

X— (R ₉ —NR ₁₀ H) _m X is a charge-transporting group, R ₉ is a single bond, substituted or unsubstituted alkylene, substituted or unsubstituted arylene group, R ₁₀ is a hydrogen atom, , An unsubstituted alkyl group, a substituted or unsubstituted aryl group, and m represents an integer. m is preferably an integer of 1 to 5.

The following are typical examples.

[0086]

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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.

Next, the charge transporting compound having an organic silicon-containing group will be described.

The charge transporting compound having an organic silicon-containing group is a charge transporting substance having the following structure. This compound is contained as a partial structure in the siloxane-based resin via a silicon atom in the compound.

[0090] X - in _{- (Y-Si (R 11} ) 3-a (R 12) a) n -type, X is a charge-transporting performance imparting group, R ₁₁ is a hydrogen atom, a substituted or unsubstituted alkyl group , An aryl group, R ₁₂ represents a hydrolyzable group or a hydroxyl group, and Y represents a substituted or unsubstituted alkylene group or an arylene group. a
Represents an integer of 1 to 3, and n represents an integer.

In the present invention, at least one of an organosilicon compound having a hydroxyl group or a hydrolyzable group and a condensate thereof is used.
And a siloxane-based resin obtained by reacting a charge-transporting compound having a reactive group with a monomer, oligomer, or polymer having a siloxane bond in a structural unit in advance to form a new chemical bond by adding a catalyst or a crosslinking agent. To form a three-dimensional network structure, and also promotes a siloxane bond by a hydrolysis reaction and subsequent dehydration condensation to form a monomer,
A three-dimensional network structure can also be formed from oligomers and polymers.

Generally, a three-dimensional network structure can be formed by a condensation reaction of a composition containing an alkoxysilane or a composition containing an alkoxysilane and colloidal silica.

Examples of the catalyst for forming a three-dimensional network structure include alkali metal salts of organic carboxylic acids, nitrous acid, sulfurous acid, aluminate, carbonic acid and thiocyanic acid, and organic amine salts (tetramethylammonium hydroxide, tetramethylammonium acetate). , Tin organic acid salts (stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin malate), aluminum, zinc octenoic acid, naphthenate, acetylacetone complex compounds And the like.

However, in order to cure the coating layer in which the charge transporting compound having a reactive group of the present invention is present to form a three-dimensional crosslinked structure, a metal chelate compound is specifically effective. A sufficient crosslinked structure cannot be obtained with the catalyst.

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

The above-mentioned antioxidant is a typical antioxidant which acts on the autoxidizing substance present in or on the electrophotographic photosensitive member under the conditions of light, heat, discharge and the like. It is a substance having the property of preventing or suppressing. Specifically, the following compounds may be mentioned.

(1) Radical chain inhibitor • Phenolic antioxidant (hindered phenol) • Amine antioxidant (hindered amine, diallyldiamine, diallylamine) • Hydroquinone antioxidant (2) Peroxidation Decomposers ・ Sulfur antioxidants (thioethers) ・ Phosphoric antioxidants (phosphites) Among the above antioxidants, the radical chain inhibitor of (1) is preferable, and particularly hindered phenol or Hindered amine antioxidants are preferred. Further, two or more kinds may be used in combination, for example, a combination of the hindered phenol antioxidant (1) and the thioether antioxidant (2) may be used. Further, a molecule containing the above structural unit, for example, a hindered phenol structural unit and a hindered amine structural unit in a molecule may be used.

Among the above-mentioned antioxidants, hindered phenol-based and hindered amine-based antioxidants are particularly effective in preventing fog and image blurring at high temperature and high humidity.

The content of the hindered phenol-based or hindered amine-based antioxidant in the coating solution composition is such that the content in the siloxane-based resin layer formed by coating and drying the coating solution composition is 0.01%. Preferred amounts are from 10 to 10% by weight. When the content in the resin layer is less than 0.01% by weight, there is no effect on fog and image blur at high temperature and high humidity, and when the content is more than 10% by weight, the charge transport ability in the resin layer is reduced, The residual potential tends to increase, and the film strength decreases.

The antioxidant may be contained in the lower charge generation layer, charge transport layer, intermediate layer, etc., if necessary. The amount of the antioxidant added to these layers is preferably 0.01 to 10% by weight based on each layer.

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).

A hindered amine compound is a compound having a bulky organic group near an N atom. As the bulky organic group, there is a branched alkyl group, and for example, a t-butyl group is preferable. For example, compounds having an organic group represented by the following structural formula are preferable.

The hindered amine is preferably, for example, a compound having an organic group represented by the following structural formula.

[0104]

Embedded image

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

As the organic phosphorus compound, for example, there are the following compounds represented by the general formula RO-P (OR) -OR. Here, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group or aryl group.

As the organic sulfur-based compound, for example, the following compounds are representative of the compounds represented by the general formula RSR. Here, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group or aryl group.

Examples of the 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 "and" Mark LA63 "or higher, and hindered amines, and thioethers such as" SUMILIZER-TP "
S "and" SUMILIZER TP-D ". Examples of the phosphite series include" Mark 2112 "and" Mark PEP-D ".
8 "," Mark PEP-24G "," Mark PEP-3 "
6 "," Mark 329K ", and" Mark HP-10 ". Among these, hindered phenol and hindered amine antioxidants are particularly preferred.

The layer structure of the electrophotographic photoreceptor of the present invention can employ a generally known layer structure of the photoreceptor, but a charge generation material and a charge transport material are dispersed in a binder resin as a photosensitive layer. It is preferable that a resin layer is provided on a single-layer structure or a layer structure in which a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport substance are stacked. However, the charge transport layer may be configured as the resin layer of the present invention, or a surface modification layer may be further provided on the resin layer. If necessary, an intermediate layer may be provided between the conductive support and the photosensitive layer.

In order to form a layer containing the siloxane resin of the present invention, the siloxane resin composition is usually dissolved in a solvent and applied. Methanol as a solvent,
Alcohols such as ethanol, propanol, butanol, methyl cellosolve and ethyl cellosolve and derivatives thereof; ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate and butyl acetate are used.

It is preferable that the resin layer of the present invention also serves as a curing treatment by applying and drying the resin layer coating solution on the photosensitive layer after applying and laminating the resin layer coating solution. Specifically, for example, a charge having a reactive group is formed by drying at a low temperature to form a condensate of a siloxane-based resin in advance, and then drying at a high temperature for a short time to promote high-density crosslinking. It is preferable to form a resin layer having strong film properties while suppressing the decomposition of the transportable compound.

The drying and curing temperature conditions are preferably such that the heat treatment is carried out while changing the conditions such as temperature and time, and the temperature in the first step is 40 to 100 ° C., preferably 50 to 80 ° C.
And the temperature during the subsequent heating process is 8
The temperature is 0 to 140 ° C, preferably 90 to 130 ° C.

The heating time in the first step is 1 to 60 minutes, preferably 5 to 30 minutes, and the time in the subsequent heating step is 10 to 360 minutes, preferably 20 to 120 minutes. It is preferred that

When the curing reaction is further promoted by heating, the temperature is 110 to 140 ° C., preferably 120 to 140 ° C.
To 140 ° C. for a time of 5 to 180 minutes, preferably 1 to
0-120 minutes.

As described above, after applying and laminating the resin layer coating solution, the curing process at the time of drying is provided a plurality of times,
In the first curing step, a condensate of the organosilicon compound is generated, and in the next step, a further cross-linking reaction of the condensate efficiently promotes a cross-linking reaction for forming a siloxane-based resin. Therefore, it is possible to suppress the decomposition reaction of the charge transporting compound having a reactive group and promote the crosslinking reaction, and to form a resin in which the charge transporting compound group is incorporated without being decomposed into the siloxane-based resin structure. Thus, a resin layer having high film strength is formed.

On the other hand, when the heating temperature is changed while fixing the location on the photosensitive member side, it is preferable that the time after the temperature reaches the set temperature after the temperature of the environment in which the hardening is changed is sufficient. .

Although the rate of change of the temperature is not particularly defined,
The range is preferably from 0.1 to 30 (° C./min). If the temperature change is lower than 0.1 ° C., the productivity is lowered, and if it is higher than 30 ° C., a rapid change in temperature tends to cause cracks and precipitation of components.

The temperature variation during curing is ± 10 ° C. or less, but is preferably controlled at ± 2 ° C. or less.

As the charge transporting material used in the photosensitive layer in the present invention, any known materials can be used.
For example, a triarylamine compound, a triarylamine styryl compound, a hydrazone compound, and a pyrazoline compound are mentioned. These charge transport materials are usually dissolved in a suitable binder resin to form a layer.

Solvents used for dispersing and dissolving the charge-generating substance and the charge-transporting substance include hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane; methyl ethyl ketone and cyclohexanone. Ketones; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, methyl cellosolve and ethyl cellosolve and derivatives thereof; tetrahydrofuran, 1,4-dioxane and 1,3
Ethers such as dioxolane; amines such as pyridine and diethylamine; amides such as N, N-dimethylformamide; other fatty acids and phenols; one or two of sulfur and phosphorus compounds such as carbon disulfide and triethyl phosphate; More than one species can be used.

The following resins can be used for the photosensitive layer other than the surface in the photosensitive layer in the present invention. For example, polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin,
Vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, and copolymers containing two or more of the repeating units of these resins resin. In addition to these insulating resins, polymer organic semiconductors such as poly-N-vinyl carbazole may be used.

In the present invention, the ratio of the binder resin to the charge generating substance in the photosensitive layer is determined by the ratio of the binder resin
50 to 600 parts by weight based on parts by weight is preferred. The ratio between the binder resin and the charge transport material is as follows.
10 to 100 parts by weight per 100 parts by weight is preferred.

In the present invention, the thickness of the photosensitive layer is 0.01 to 10 μm for the charge generation layer and 1 to 40 μm for the charge transport layer.
Is preferred. When the photosensitive layer has a single layer structure, 1 to 40 μm
Is preferred. The resin layer preferably has a thickness of 0.1 to 5 μm.

In the present invention, a conductive support for supporting the photosensitive layer may be a metal plate such as aluminum or nickel.
A metal drum, a plastic film on which aluminum, tin oxide, indium oxide, or the like is deposited, or a paper, plastic film, or drum coated with a conductive substance can be used.

Examples of the material used for the intermediate layer in the present invention include polyamide resins, vinyl chloride resins, vinyl acetate resins, and copolymer resins containing two or more of the repeating units of these resins. Further, a curable metal resin compound obtained by thermally curing an organic metal compound such as a silane coupling agent and a titanium coupling agent may be used. The thickness of the intermediate layer is preferably from 0.01 to 2 μm.

As a coating method for producing the electrophotographic photoreceptor of the present invention, dip coating, spray coating, circular amount control type coating and the like of a coating solution can be used. In particular, in the coating process on the surface layer side of the photosensitive layer, spray coating or circular amount control type coating (a typical example is a circular slide hopper) is used to dissolve the lower layer film as much as possible and to achieve uniform coating process. Is preferred. The spray coating is described in JP-A-3-90250 and JP-A-3-2692.
No. 38 describes the method, and the details of the circular amount control type coating are described in JP-A-58-189061.

[2] Image Forming Method, Image Forming Apparatus, and Process Cartridge The electrophotographic photosensitive member of the present invention is applicable to electrophotographic apparatuses such as copying machines, laser printers, LED printers, and liquid crystal shutter printers. Further, the present invention can be widely applied to devices such as display, recording, light printing, plate making, facsimile and the like to which electrophotographic technology is applied.

FIG. 1 is a sectional view showing an example of an image forming apparatus having the electrophotographic photosensitive member of the present invention.

In FIG. 1, reference numeral 10 denotes a photoreceptor (hereinafter, referred to as a photoreceptor drum, which is in the form of a drum, which is an image carrier), which is formed by coating a photosensitive layer on a conductive drum, and A siloxane-based resin is applied, grounded, and driven clockwise. Reference numeral 12 denotes a scorotron charger, which applies uniform charging to the peripheral surface of the photosensitive drum 10 by corona discharge. Prior to the charging by the charger 12, in order to remove the history in the previous image, the exposure of the peripheral surface of the photoconductor may be performed by performing exposure by the exposure unit 11 using a light emitting diode or the like.

After the photosensitive drum has been uniformly charged, the image exposure unit 13 performs image exposure based on the image signal. The image exposure device 13 in this figure uses a laser diode (not shown) as a light source. The light on the photosensitive drum is scanned by the light whose optical path is bent by the reflection mirror 132 through the rotating polygon mirror 131 and the fθ lens, and an electrostatic latent image is formed.

The electrostatic latent image is then developed by the developing device 14. At the periphery of the photoconductor drum 10, there is arranged a developing device 14 containing a developer composed of toner and carrier such as yellow, magenta, cyan, and black. First, one-color development has a built-in magnet and holds the developer. The rotation is performed by the developing sleeve 141 that rotates. The developer is composed of, for example, a carrier in which ferrite is used as a core and an insulating resin is coated around the core, and a toner in which a pigment, a charge control agent, silica, and titanium oxide are used as a main material with polyester as a main component. The agent is applied on the developing sleeve 141 by a layer forming means (not shown).
The toner is conveyed to the development zone while being regulated to a thickness of μm, and development is performed. At this time, normally, DC and AC biases are applied between the photosensitive drum 10 and the developing sleeve 141 to perform the development.

In the color image formation, after the visualization of the first color is completed, the image formation process of the second color is started, and uniform charging is performed again by the scorotron charger 12 to form the latent image of the second color. This is performed by the exposure unit 13. The image formation for the third and fourth colors is performed in the same manner as for the second color.
A visual image of four colors is formed on the zero circumference. On the other hand, in a monochrome electrophotographic apparatus, the developing device 14 is composed of one type of single color toner, and forms an image by one development.

After the image formation, the recording paper P is fed to the transfer area by the rotation of the paper feed roller 17 at the time when the transfer timing is adjusted. In the transfer area, a transfer roller (transfer device) is provided on the peripheral surface of the photosensitive drum 10 in synchronization with the transfer timing.
The recording paper 18 is pressed and pressed, and the fed recording paper P is narrowly attached to transfer the multicolor image at once.

Next, the recording paper P is neutralized by a separation brush (separator) 19 brought into pressure contact with the transfer roller, separated from the peripheral surface of the photosensitive drum 10 and conveyed to the fixing device 20, where the heat roller 201 and the pressure roller After the toner is fused by heating and pressurizing 202, the toner is discharged to the outside of the apparatus via the discharge roller 21. After the transfer roller 18 and the separation brush 19 have passed the recording paper P, they are retracted from the peripheral surface of the photosensitive drum 10 to prepare for the next toner image formation.

On the other hand, after the recording paper P is separated, the photosensitive drum 10 removes and cleans the residual toner by pressing the blade 221 of the cleaning device 22 and the action of the cleaning roller 222. 1
2 to prepare for the next image formation. When a color image is formed by superimposing a toner image on a photoconductor, the blade 221 is immediately retracted from the peripheral surface of the photoconductor drum 10 after cleaning.

Reference numeral 30 denotes a process cartridge which is provided with a photosensitive member, a charging device, a transfer device, a separator, and a cleaning device, and which is detachably set.

An electrophotographic image forming apparatus is constructed by integrally combining the above-described components such as the photoreceptor, the developing device, and the cleaning device as a process cartridge. May be. A process cartridge is formed by supporting at least one of a charging device, a developing device, an image exposing device, a transfer device, a separating device, and a cleaning device together with a photoreceptor. Alternatively, it may be configured to be detachable by a guide means such as a rail of the apparatus main body.

In image exposure, when used as a copier or printer, reflected light or transmitted light from a document is irradiated onto the photosensitive member, or the document is read by a sensor and converted into a signal.
Irradiation of a laser beam, driving of an LED array, and driving of a liquid crystal shutter array are performed according to this signal, and the photosensitive member is irradiated with light. In the case of a facsimile printer, the image exposure device performs exposure for printing received data.

Since the electrophotographic photoreceptor of the present invention can have a surface resin layer having high hardness as described above,
It is difficult to damage the photoreceptor surface. Such characteristics have a remarkable effect on the reversal development process, in which the surface of the photoreceptor is likely to be streaked or uneven on the image.

[0142]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 A photoreceptor was produced as follows.

The following undercoat layer coating solution was prepared on a drum-shaped aluminum conductive support (aluminum cylinder) having a diameter of 80 mm, and was applied to a dry film thickness of 1.0 μm.

<Undercoat Layer> Titanium chelate compound (TC-750 manufactured by Matsumoto Pharmaceutical) 30 g Silane coupling agent (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) 17 g 2-propanol 150 ml Was dispersed and prepared and applied.

<Charge Generation Layer> Titanyl phthalocyanine 60 g Silicon resin solution (KR5240, 15% xylene-butanol solution: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2000 ml was mixed, and dispersed using a sand mill for 10 hours to generate charge. A layer coating solution was prepared. This coating solution was applied on the intermediate layer by a dip coating method to form a 0.2 μm-thick charge generation layer.

<Charge Transporting Layer> Charge transporting substance (4-methoxy-4 '-(4-methyl-α-phenylstyryl) triphenylamine) 200 g Bisphenol Z-type polycarbonate (Iupilon Z300: manufactured by Mitsubishi Gas Chemical Company) 300 g 1 , 2-Dichloroethane (2,000 ml) was 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 thickness of 20 μm.

<Resin Layer> One part by weight of acetic acid was added dropwise to 100 parts by weight of methyltrimethoxysilane while stirring. To this solution, 26 parts by weight of pure water was added and stirred overnight. Next, 300 parts by weight of ethanol was added to this solution, and the mixture was further stirred at room temperature for 150 hours.

To this solution, 20 parts by weight of colloidal silica,
Dihydroxymethyltriphenylamine (T-1) 40
1 part by weight of hindered amine (Sanol LS2626: manufactured by Sankyo Co., Ltd.) and 0.4 part by weight of tris (acetylacetonato) aluminum were added and uniformly mixed, and then the solution was diluted with 30 parts by weight of 1-butanol.

Next, this solution was applied as a resin layer having a dry film thickness of 2 μm, and was heated and cured at 110 ° C. for 80 minutes to produce a photoreceptor 1.

Example 2 Photoconductor 2 was prepared in the same manner as in Example 1 except that 0.01 parts by weight was added instead of 0.4 parts by weight of tris (acetylacetonato) aluminum in the resin layer. Was prepared.

Example 3 Photoconductor 3 was prepared in the same manner as in Example 1 except that 12.5 parts by weight of tris (acetylacetonato) aluminum in the resin layer was added instead of 0.4 part by weight of aluminum. Was prepared.

Example 4 Example 1 was repeated except that no antioxidant was used.
In the same manner as in the above, a photoreceptor 4 was produced.

Example 5 A photoreceptor 5 was prepared in the same manner as in Example 1 except that colloidal silica was not used.

Example 6 A photoreceptor 6 was prepared in the same manner as in Example 1 except that titanium tetraacetylacetonate was used instead of tris (acetylacetonato) aluminum in the resin layer.

Example 7 A photoconductor 7 was prepared in the same manner as in Example 1 except that zinc acetylacetonate was used instead of tris (acetylacetonato) aluminum in the resin layer.

Example 8 A photoconductor 8 was prepared in the same manner as in Example 1 except that bis (2,4-pentadionato) nickel was used instead of tris (acetylacetonato) aluminum in the resin layer. Produced.

Example 9 A photoconductor 9 was prepared in the same manner as in Example 1 except that 70 parts by weight of methyltrimethoxysilane and 30 parts by weight of dimethoxydimethylsilane were used instead of 100 parts by weight of methyltrimethoxysilane. Produced.

Example 10 A photoconductor 10 was produced in the same manner as in Example 1, except that the resin layer was changed as follows. Preparation of Photoconductor 10 <Resin Layer> Methyltrimethoxysilane 80 parts by weight γ-glycidoxypropyltrimethoxysilane 20 parts by weight Compound (T-1) 40 parts by weight Antioxidant (Sanol LS2626: manufactured by Sankyo) 1 part by weight Part 2-propanol 300 parts by weight 3% acetic acid 20 parts by weight Trisacetylacetonatoaluminum 0.5 part by weight was mixed to prepare a coating solution for a resin layer. A 2 μm-thick resin layer was formed on the charge transport layer by a circular-amount-regulating coating device on the charge transport layer, and was heated and cured at 110 ° C. for 1 hour to form a siloxane-based resin layer having a crosslinked structure. The photoreceptor 10 was produced.

Comparative Example 1 A photoreceptor 11 was produced in the same manner as in Example 1 except that dihydroxymethyltriphenylamine (T-1) in the resin layer was not used.

Comparative Example 2 A photoreceptor 12 was produced in the same manner as in Comparative Example 1 except that tris (acetylacetonato) aluminum in the resin layer was not used.

Comparative Example 3 Photoconductor 13 was prepared in the same manner as in Example 1 except that 0.003 parts by weight was added instead of 0.4 parts by weight of tris (acetylacetonato) aluminum in the resin layer.
Was prepared.

Comparative Example 4 Photosensitive member 14 was produced in the same manner as in Example 1 except that 25 parts by weight was added instead of 0.4 parts by weight of tris (acetylacetonato) aluminum in the resin layer. did.

Comparative Example 5 A photoconductor 15 was produced in the same manner as in Example 1 except that tri-n-propoxyaluminum was used instead of tris (acetylacetonato) aluminum in the resin layer.

<Evaluation> Strength evaluation The strength evaluation was performed using the HEI for the photosensitive drum manufactured as described above.
The curvature of the tip is 0.15m on "Surface Tester" manufactured by DON
m diamond needle, scratching speed 1mm / s
The sample was moved at a speed of ec, and the minimum load at which damage started to be visually observed was measured.

2. Potential Evaluation / Evaluation of Actual Photographic Evaluation The photosensitive drum produced as described above was modified from a digital copying machine Konica 7060 (a copier having a laser exposure, reversal development process, and blade cleaning mechanism) manufactured by Konica Corporation, and the exposure amount was exposed. Mounted on an evaluator adjusted for body sensitivity, the initial charging potential was -650.
V was set, and the actual copying evaluation of 50,000 copies was performed in a high-temperature and high-humidity environment (30 ° C., 80% RH). The evaluation was carried out by measuring potential fluctuations in the exposed portion (ΔVL) and the unexposed portion (ΔVH) after 50,000 copies, and for a character image with a pixel rate of 7%, a human face photograph, a solid white image, and a solid black image, respectively. Using the original image in four equal parts, image evaluation of 50,000 continuous copies of A4 paper was performed. The sharpness, halftone, solid white image and solid black image of the character image were evaluated every 1000 sheets. Table 1 shows the results.

[0167]

[Table 1]

As is clear from Table 1, the electrophotographic photoreceptors 1 to 9 formed by coating and drying the coating composition of the present invention to form a siloxane-based resin layer have excellent strength characteristics, and have little potential fluctuation. It can be seen that the image is also improved without a decrease in density or occurrence of fog. However, the composition of the present invention does not contain a charge transporting compound having a reactive group and does not include a coating solution composition or a composition in which the amount of a metal chelate is deviated, or a coating solution composition using a metal compound other than a metal chelate. The electrophotographic photoreceptors 11, 12, 13, 14, and 15 having the siloxane-based resin layer formed thereon are not practically used because they do not have sufficient strength, have poor potential characteristics, and cause image density reduction and image deletion. It turns out that it can not stand.

[0169]

As is apparent from the present invention, the organic silicon compound, the charge transporting compound having a reactive group and the metal chelate of 0.01 to 20% by weight based on the charge transporting compound are contained. To produce an electrophotographic photoreceptor that has sufficient strength, has less potential fluctuation under high temperature and high humidity, and can obtain a good image by coating and drying the coating solution composition on a conductive support. Can be. Further, in the electrophotographic image forming method using the electrophotographic photoreceptor manufactured by the present invention, an apparatus for forming an image by incorporating the photoreceptor into an image forming apparatus, a very good image can be obtained. It is easy to see that it is suitable for practical use, such as improved durability.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of an image forming apparatus having an electrophotographic photosensitive member according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Photosensitive drum (or photoreceptor) 11 Exposure part using light emitting diode etc. 12 Charging device 13 Image exposing device 14 Developing device 17 Paper feed roller 18 Transfer roller (transfer device) 19 Separation brush (separator) 20 Fixing device 21 Discharge roller 22 Cleaning device 30 Process cartridge

Claims (17)

[Claims] 1. A method for producing an electrophotographic photoreceptor having a resin layer on a conductive support, wherein, when the resin layer is formed on the conductive support, an organosilicon compound having a hydroxyl group or a hydrolyzable group Alternatively, a coating containing at least one condensate thereof, a charge transporting compound having a reactive group, and a metal chelate in an amount of 0.01 to 20% by weight based on the charge transporting compound having the reactive group. A method for producing an electrophotographic photoreceptor, comprising applying a liquid composition and drying to form a siloxane-based resin layer having a crosslinked structure. 2. The composition according to claim 1, wherein the coating liquid composition contains 0.1 to 10% by weight of a metal chelate based on the charge transporting compound having a reactive group.
The method for producing the electrophotographic photosensitive member according to the above. 3. The method according to claim 1, wherein the organosilicon compound having a hydroxyl group or a hydrolyzable group is a compound represented by the following general formula (1) or a hydrolysis product thereof. A method for manufacturing an electrophotographic photosensitive member. Formula (1) _{R n Si (OR ') 4} -n ( wherein, R is an alkyl group having 1 to 10 carbon atoms, a phenyl group, an aryl group, a vinyl group, an amino group, .gamma.-glycidoxypropyl group, γ-methacryloxypropyl group, C _{m
F 2m + 1 C 2 H 4} - represents a. R ′ represents an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 0 to 3. m represents a positive integer. ) 4. The organic silicon compound is a compound represented by the following formulas (2) and (3) or a hydrolysis product thereof, and a compound represented by the formulas (2) and (3): The method according to any one of claims 1 to 3, wherein a molar ratio of M1 / M2 is 0.1 or more and 10 or less. Formula (1) RaSi (OR ') 3 Formula (2) RaRbSi (OR') 2 (where Ra and Rb are an alkyl group having 1 to 10 carbon atoms, a phenyl group, an aryl group, a vinyl group, an amino group Γ-glycidoxypropyl group, γ-methacryloxypropyl group,
_{C m F 2m + 1 C 2} H 4 - represents a. R ′ represents an alkyl group having 1 to 3 carbon atoms. m represents a positive integer. ) 5. The electrophotograph according to claim 1, wherein at least a part of the organosilicon compound having a hydroxyl group or a hydrolyzable group has a γ-glycidoxypropyl group. Manufacturing method of photoreceptor. 6. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the metal chelate is an aluminum chelate. 7. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the metal chelate is a titanium chelate. 8. The charge-transporting compound having a reactive group, wherein the reactive group is a hydroxyl group.
8. The method for producing an electrophotographic photosensitive member according to any one of items 7 to 7. 9. The method according to claim 1, wherein the coating liquid composition contains colloidal silica. 10. An organosilicon compound having a hydroxyl group or a hydrolyzable group and at least one of its condensates, a dialkylsilane having a hydroxyl group or a hydrolyzable group,
Alternatively, it is a condensate thereof.
The method for producing an electrophotographic photosensitive member according to any one of the above items. 11. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the coating liquid composition contains an antioxidant. 12. A coating solution composition used for producing an electrophotographic photoreceptor for forming a resin layer on a conductive support reacts with at least one of an organosilicon compound having a hydroxyl group or a hydrolyzable group or a condensate thereof. A coating liquid composition comprising: a charge transporting compound having a reactive group; and 0.01 to 20% by weight of a metal chelate based on the charge transporting compound having a reactive group. 13. An electrophotographic photosensitive member obtained by the production method according to claim 1. Description: 14. The electrophotographic photoconductor according to claim 13, wherein the resin layer of the electrophotographic photoconductor is a surface layer. 15. An image forming method using the electrophotographic photoreceptor according to claim 13 or 14, comprising at least steps of charging, image exposure, development and cleaning, and developing by a reversal developing method. Image forming method. 16. An image forming method using the electrophotographic photoreceptor according to claim 13 which comprises at least steps of charging, image exposure, development, and cleaning, and performing a step of developing by a reversal developing method. Characteristic image forming apparatus. 17. The process cartridge according to claim 13 or 14, wherein a process cartridge for use in an electrophotographic image forming apparatus using an electrophotographic photosensitive member and having at least means for charging, image exposure, development, and cleaning. A process cartridge having at least one of a device, an image exposing device, a developing device, and a cleaning device as a unit, and being designed to be freely inserted into and removed from the electrophotographic image forming apparatus.