JP2002123031A - Method for producing electrophotographic photoreceptor, electrophotographic photoreceptor, image forming method, image forming device and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor with a protective layer having superior toner cleaning performance and superior stability to the curling of a cleaning blade and to provide a method for producing the photoreceptor, an image forming method using the photoreceptor, an image forming device and a process cartridge. SOLUTION: In the method for producing the electrophotographic photoreceptor, a coating liquid containing a reactive electric charge transferring compound, an organosilicon compound having a β-(3,4-epoxycyclohexyl) group or its hydrolyzate and a solvent is applied and cured to form a resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In recent years, an organic photoconductor containing an organic photoconductive material has been most widely used as an electrophotographic photoconductor (hereinafter, also simply referred to as a photoconductor). 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 deteriorated or scratched when copying or printing a large number of sheets.

Generally, in the electrophotographic photosensitive member image forming method of the Carlson method, after the photosensitive member is uniformly charged, the charge is erased imagewise by exposure to form an electrostatic latent image. Next, the electrostatic latent image on the photoconductor is developed with toner,
After the toner is visualized and the toner is transferred to paper or the like, the toner remaining on the photoreceptor is removed by a cleaning blade or the like, and if necessary, is subjected to erasure exposure of residual charges, and then proceeds to image formation.

As described above, since the surface of the electrophotographic photosensitive member is directly applied with an electric or mechanical external force by a charger, a developing device, a transfer means, a cleaning device, etc., the durability thereof is required. In particular, with respect to the durability against the occurrence of abrasion and scratches on the surface of the photoreceptor due to rubbing, the incorporation of foreign matter, and the peeling of the film due to the impact during paper jam processing, the strength as high as that of the inorganic photoreceptor is strongly required.

[0005] In order to satisfy the various characteristics required as described above, various studies have been made so far. For example, techniques such as providing a high-strength protective layer on the surface of a photoreceptor have been studied. For example, Japanese Patent Laid-Open No. 9-1900
No. 04 and JP-A-10-251277 disclose photoreceptors using a siloxane resin having excellent strength for the surface layer. However, the protective layer using a siloxane resin has a large torque applied to the cleaning blade,
There was a problem that blade turning easily occurred.

In order to prevent blade turning, it is effective to reduce the surface energy of the protective layer and reduce the frictional force with the cleaning blade. For example, JP
Japanese Patent Application Publication No. 0-83094 describes a method of using a protective layer having a small surface energy having a contact angle with water of 90 ° or more. However, it is clear that blade turning has not only a chemical affinity but also an element due to the viscoelastic properties of the protective layer, and cannot be solved only by introducing the F atom-containing substituent into the silane compound described in the above patent. Was.

[0007] In order to solve these problems, a siloxane crosslinked film containing a bifunctional silane compound as a main component and a structural unit having a charge transporting ability are used instead of the silane compound used in the conventional silicon-based hard coat. It has been clarified that the blade torque can be reduced by using a resin layer having both of them on the surface of the photoreceptor, but the strength has been reduced by using a bifunctional silane compound as a main component. That is, it has become apparent that it is necessary to find a silane compound that can achieve both strength and blade torque reduction.

[0008]

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

[0009]

The present inventors have made intensive efforts to solve the above problems, and as a result, when forming a siloxane-based resin layer having a charge transporting group, a β- (3,4-epoxycyclohexyl) group was formed. It has been found that by using an organosilicon compound having the following characteristics, the blade torque can be effectively reduced and very good characteristics can be obtained in terms of strength.

That is, the object of the present invention is achieved by the following constitutions. 1. A reactive charge transporting compound and the general formula (1);
An electron produced by applying a coating solution containing at least one of the organosilicon compounds of (2) and (3) or a hydrolysis product thereof and a solvent, followed by curing to form a resin layer. Manufacturing method of photoreceptor.

2. 2. The method for producing an electrophotographic photosensitive member according to the above item 1, wherein the coating liquid contains the organosilicon compound represented by the general formula (4) or a hydrolysis product thereof.

3. 3. The method for producing an electrophotographic photosensitive member according to the above item 1 or 2, wherein the resin layer forms a siloxane-based resin layer having a structure represented by the general formula (5).

4. 4. The method for producing an electrophotographic photosensitive member according to any one of the above items 1 to 3, wherein the coating liquid contains an antioxidant.

5. An electrophotographic photosensitive member manufactured by using the manufacturing method according to any one of the above items 1 to 4.

6. 6. The electrophotographic photoreceptor according to the above item 5, which has the resin layer as a protective layer. 7. An image forming method including an electrophotographic photosensitive member, a charging unit, an image exposing unit, a developing unit, and a cleaning unit, wherein the electrophotographic photosensitive member described in the above item 5 or 6 is used as the electrophotographic photosensitive member. Method.

8. An image forming apparatus having an electrophotographic photosensitive member, a charging unit, an image exposing unit, a developing unit, and a cleaning unit, wherein the electrophotographic photosensitive member described in 5 or 6 above is used as the electrophotographic photosensitive member. apparatus.

9. 7. The electrophotographic photosensitive member according to claim 5 or 6, wherein the process cartridge used in the image forming apparatus having an electrophotographic photosensitive member, a charging unit, an image exposing unit, a developing unit, and a cleaning unit, A process cartridge having at least one of cleaning means integrally combined and being designed to be freely inserted into and removed from the image forming apparatus.

Hereinafter, the present invention will be described in detail. A resin layer formed by applying a coating solution containing the reactive charge transporting compound and the organosilicon compound of the present invention, or a hydrolysis product thereof, and a solvent and then curing the resin is a siloxane-based resin containing a charge transporting group. Form a layer. Here, the siloxane-based resin layer means a resin layer having a three-dimensional structure having a siloxane bond.

According to the present invention, the use of an organosilicon compound having a β- (3,4-epoxycyclohexyl) group as an organosilicon compound as a raw material for forming the siloxane-based resin layer is effective in reducing blade torque and is effective. With respect to the strength of the resin layer, very good characteristics were obtained, and the electrophotographic characteristics were also found to be good.

That is, the coating solution used for forming the resin layer of the photoreceptor of the present invention comprises at least one organosilicon compound of the above general formulas (1), (2) and (3), or a hydrolysis product thereof. It is characterized by containing.

In the general formulas (1), (2) and (3),
Z is preferably a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, a butoxy group, or a methoxyethoxy group.

As a specific example of the general formula (1), β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

As a specific example of the general formula (2), β- (3,
4-epoxycyclohexyl) ethylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, diβ-
(3,4-epoxycyclohexyl) ethyldiethoxysilane and the like.

As a specific example of the general formula (3), β- (3,
4-epoxycyclohexyl) ethyldimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyldiethylethoxysilane, and the like.

Further, the coating liquid of the present invention preferably contains the organosilicon compound represented by the general formula (4) or a hydrolysis product thereof.

Specific examples of the organosilicon compound represented by the general formula (4) include the following compounds.

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

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

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

By using the compounds of the general formulas (1) to (3) and the compound of the general formula (4) together, the blade torque can be reduced, the strength of the resin layer and the electrophotographic properties can be controlled more freely. be able to. The proportion of the compounds of the general formulas (1) to (3) in the total organosilicon compound in the coating solution is 1 to 5
0% by mass is preferred. More preferably, the content is 5 to 35% by mass. If the compounding ratio of the compounds of the general formulas (1) to (3) is small, the cleaning performance of the toner and the stability against the turning of the cleaning blade become insufficient, and the general formulas (1) to (3)
If the compounding ratio of the compound (3) is too large, image blur tends to occur in a high humidity environment or a low humidity environment.

The organosilicon compound of the general formula (4) is generally a polymer of an organosilicon compound when n of the number of hydrolyzable groups (4-n) bonded to a silicon atom is 3. The formation reaction is suppressed. When n is 0, 1 or 2, a polymerization reaction easily occurs. In particular, when n is 1 or 0, the crosslinking reaction can be advanced to a high degree. Therefore, by controlling these, it is possible to control the storability of the obtained coating layer liquid and the hardness of the coating film.

In order to form a resin layer having a three-dimensional structure by forming a crosslinked structure in the resin layer of the present invention, the components of general formulas (1) and (2) and n in general formula (4) are 1 or It is necessary that the component 0 be contained in the coating solution. In the present invention, the component of the general formula (1) or the general formula (2) is preferably contained in an amount of 1 to 50% by mass, particularly 5 to 30% by mass based on the total mass of the organosilicon compound in the coating solution.

The condensate of the organosilicon compound of the present invention means a siloxane condensate obtained by hydrolyzing the above organosilicon compound under acidic or basic conditions to oligomerize or polymerize.

As described above, the siloxane-based resin of the present invention is obtained by reacting a monomer, oligomer, or polymer having a siloxane bond in a chemical structural unit in advance (hydrolysis reaction, reaction in which a catalyst or a crosslinking agent is added, etc.). (Included) means a resin that has formed and cured a three-dimensional network structure. That is, it means a siloxane-based resin having a cross-linked structure formed by promoting a siloxane bond by a hydrolysis reaction and subsequent dehydration condensation of an organosilicon compound having a siloxane bond to form a three-dimensional network structure.

The siloxane-based resin may be a resin in which colloidal silica having a hydroxyl group or a hydrolyzable group is contained in the resin, and silica particles are incorporated in a part of a crosslinked structure.

The reactive charge transporting compound of the present invention means a charge transporting compound having a reactive group capable of chemically bonding to the above-mentioned organosilicon compound or a condensate of the organosilicon compound. As a result of this reaction, the reactive charge transporting compound is contained in the siloxane-based resin layer as a partial structure in the resin.

The resin layer of the present invention is preferably a siloxane resin layer having a structure represented by the following general formula (5).

[0038]

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In the formula, X represents a structural unit having charge transport performance, and Y represents an arbitrary divalent or higher valent linking group.

Preferably, Y in the general formula (5) is 2 except for an adjacent bonding atom (silicon atom Si and carbon atom C constituting a part of the structural unit having the charge transporting ability).
It is an atom or group of valence or higher.

However, when Y is an atom having three or more valences, S in the formula
The bond of Y other than i and C is bonded to any constituent atom in the curable resin capable of bonding or has a structure (group) connected to another atom or molecular group.

In the above formula, an oxygen atom (O), a sulfur atom (S), and a nitrogen atom (N) are particularly preferable as the Y atom.

Here, when Y is a nitrogen atom (N), the linking group is represented by -NR- (R is a hydrogen atom or a monovalent organic group).

The structural unit X having charge transporting ability is a residue of the above-mentioned reactive charge transporting compound, and is represented by Y in the following formula via a carbon atom or a silicon atom constituting the charge transporting compound. And is contained in the siloxane-based resin via Y. The structural unit X having charge transporting performance is shown as a monovalent group in the formula. However, when the charge transporting compound to be reacted with the siloxane resin has two or more reactive functional groups, curing is performed. It may be joined as a divalent or higher valent crosslink group in the conductive resin, or may be joined simply as a pendant group.

The above-mentioned atoms, ie, the atoms of O, S, and N, are formed by the reaction of a hydroxyl group, a mercapto group, or an amine group introduced into a compound having a charge transporting ability with an organic silicon compound having a hydroxyl group or a hydrolyzable group. It is a linking group that is formed and incorporates a structural unit having charge transport performance into the siloxane-based resin as a partial structure.

Hereinafter, the reactive charge transporting compound will be described. Note that a charge transporting compound is a compound having a property of having electron or hole drift mobility. Another definition is a charge transporting compound known in the art, such as a Time-Of-Flight method, which can detect charge transporting performance. It can also be expressed as a compound from which a detection current resulting from transport can be obtained.

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
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 an organosilicon compound can be given, but is not limited to the following structure, Any compound having transport ability and having a hydroxyl group may be used.

X- (R ₇ -OH) _m wherein X: Structural unit having charge transport performance R ₇ : Single bond, substituted or unsubstituted alkylene group, arylene group m: Integer of 1 to 5.

Among them, the following are typical ones.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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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

[0058]

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

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

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

Synthesis of Exemplified Compound S-1

[0063]

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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 added thereto. While stirring at room temperature, D
2 g of MF was slowly added dropwise, and then the temperature was raised to about 80 ° C. and the mixture was stirred for 16 hours. The mixture was poured into warm water of about 70 ° C. and cooled. This was extracted with toluene, and the extract was washed with water until the pH of the water reached 7. 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 stirrer to make an argon gas atmosphere. To this, 15 ml of a hexane solution of n-BuLi (1.72 M) was added, 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 an organosilicon compound can be given, but is not limited to the following structure, Any compound having a transport ability and having a mercapto group may be used.

X- (R ₈ -SH) _m wherein X: Structural unit having charge transporting ability R ₈ : Single bond, substituted or unsubstituted alkylene, arylene group m: Integer of 1-5.

[0070] Among them, the following are typical ones.

[0071]

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Further, 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 an organosilicon compound can be given, but is not limited to the following structure, Any compound having a transporting ability and having an amino group may be used.

X- (R ₉ -NR ₁₀ H) _m wherein X: Structural unit having charge transport performance R ₉ : Single bond, substituted or unsubstituted alkylene, substituted or unsubstituted arylene group R ₁₀ : hydrogen Atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group m: an integer of 1 to 5.

Among them, the following are typical ones.

[0075]

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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.

Further, the charge transporting compound having a silyl group will be described. The charge transporting compound having a silyl group is a charge transporting substance having the following structure. This compound can also combine with the organosilicon compound to form a resin layer.

[0078] X - in _{- (Z-Si (R 11} ) 3-a (R 12) a) n -type, X is a group containing a structural unit having charge transportability, R ₁₁ is a hydrogen atom, a substituted or R ₁₂ represents a hydrolyzable group or a hydroxyl group; Z represents a substituted or unsubstituted alkylene group, an arylene group; and Si represents a silicon atom. a represents an integer of 1 to 3, and n represents an integer.

The composition in the coating solution of the present invention is represented by the general formula (1)
The compounding ratio of the reactive charge transporting compound to the total mass of the organosilicon compound of (4) is preferably 1: 0.1 to 10.

When metal oxide particles such as colloidal silica are added, it is preferable to use 1 to 30 parts by mass of metal oxide particles based on 100 parts by mass of the resin layer.

When the compounding ratio of the reactive charge transporting compound is small, the charge transporting ability of the resin layer is small, the sensitivity is reduced, the residual charge is increased, and the image blur is easily generated. When the amount is too large, the resin layer has too low a crosslink density, and the film strength of the resin layer is reduced, and poor cleaning and film peeling are likely to occur.

In the present invention, an organic solvent can be used in order to adjust the total solid content of the resin layer coating solution and also adjust the viscosity. As such an organic solvent, it is preferable to use an organic solvent such as alcohols, aromatic hydrocarbons, ethers, ketones and esters. As the alcohols, for example, monovalent or divalent
Alcohols, specifically methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, Ethylene glycol, diethylene glycol, triethylene glycol,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n
-Propyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like. Among them, monovalent saturated aliphatic alcohols having 1 to 8 carbon atoms are preferred. Specific examples of the aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of the ethers include tetrahydrofuran and dioxane, and specific examples of the esters. Examples include ethyl acetate, n-propyl acetate, n-butyl acetate, propylene carbonate and the like. These organic solvents can be used alone or in combination of two or more. The method for adding the organic solvent is not particularly limited, and the organic solvent can be added at the time of preparing the resin layer coating solution of the present invention and / or at an appropriate stage after the preparation.

It is preferable to use the solvent in such an amount that the solid content in the coating solution (the component remaining after drying the coating solution) is adjusted to 5 to 40% by mass.

The resin layer of the present invention is cured after the application liquid is applied to form a resin layer having a crosslinked structure.

In order to accelerate these curing reactions, it is preferable that a metal chelate compound (III) is present in the coating solution.

Examples of such a metal chelate compound (III) include compounds represented by the general formulas (7), (8) and (9), or partial hydrolysates of these compounds.

Formula (7) Zr (OR_Five)_p(R₆COCHCOR₇)_4-p General formula (8) Ti (OR_Five)_q(R₆COCHCOR₇)_4-q General formula (9) Al (OR_Five)_r(R₆COCHCOR₇)_3-r R in the general formulas (7), (8) and (9)_FiveAnd R
₆Is independently a monovalent hydrocarbon having 1 to 6 carbon atoms
Groups, specifically, ethyl group, n-propyl group, i-pro
Pill group, n-butyl group, sec-butyl group, t-butyl
Group, n-pentyl group, n-hexyl group, cyclohexyl
Group, phenyl group, etc.,₇Is R_FiveAnd R ₆the same as
In addition to the monovalent hydrocarbon group having 1 to 6 carbon atoms,
16 alkoxy groups, specifically, methoxy group, ethoxy group
Si group, n-propoxy group, i-propoxy group, n-buto
Xy group, sec-butoxy group, t-butoxy group, lauri
A ruoxy group, a stearyloxy group and the like. Also, p
And q are integers of 0 to 3, and r is an integer of 0 to 2.

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

The amount of the metal chelate compound (III) added is
The amount of the solid content of the coating solution such as the organic silicon compound, the condensate of the organic silicon compound, and the reactive charge transporting compound (the solid content of the coating solution is a component remaining after drying the coating solution) is 0 with respect to the total mass. 0.01 to 20% by mass, preferably 0.5
The amount is such that it becomes 〜20% by mass. If the amount of the metal chelate compound (III) is too small, the protective layer resin may not be made three-dimensional, while if it is too large, the pot life of the coating liquid is deteriorated.

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

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

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

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

[0094]

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

The following are examples of typical antioxidant compounds.

[0099]

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[0100]

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[0101]

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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. It is preferable to use 0.1 to 10 parts by mass of the antioxidant based on 100 parts by mass of the resin layer composition.

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

The layer constitution of the organic photoreceptor is not particularly limited, but may be a charge generation layer, a charge transport layer, or a charge generation / charge transport layer (a layer having the functions of charge generation and charge transport in the same layer).
It is preferable to adopt a constitution in which a photosensitive layer such as that described above and a protective layer are coated thereon.

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

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

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

The conductive support used in the present invention may have a surface on which a sealed alumite film is formed. The alumite treatment is usually performed in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid, and sulfamic acid, but anodizing treatment in sulfuric acid gives the most preferable result. In the case of 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, an intermediate layer having a barrier function may be provided between the conductive support and the photosensitive layer.

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

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

Photosensitive Layer The photosensitive layer of the photoreceptor of the present invention may have a single-layered structure in which a charge generation function and a charge transport function are provided in one layer on the intermediate layer. It is preferable to adopt a configuration in which the functions of the layers are separated into a charge generation layer (CGL) and a charge transport layer (CTL). By adopting a configuration in which functions are separated, an increase in residual potential due to repeated use can be controlled to be small, and other electrophotographic characteristics can be easily controlled according to the purpose. In the photoreceptor for negative charging, 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 Charge generation layer: The charge generation layer contains a charge generation material (CGM). As other substances, a binder resin and other additives may be contained as necessary.

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

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

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

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

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

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

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

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

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

Next, as a coating method for producing the organic electrophotographic photoreceptor of the present invention, a coating method such as dip coating, spray coating, and circular amount control type coating is used.
The coating process on the upper layer side of the photosensitive layer is performed by a spray coating or a coating method of a circular amount control type (a typical example is a circular slide hopper type) coating so as not to dissolve the lower layer film as much as possible and to achieve a uniform coating process. It is preferable to use It is most preferable that the protective layer of the present invention uses the above-mentioned circular amount control type coating method. The circular amount control type coating is described in detail in, for example, JP-A-58-189061.

FIG. 1 is a schematic configuration diagram showing the overall configuration of the image forming apparatus of the present invention. The image forming apparatus shown in FIG.
The image forming apparatus is a digital image forming apparatus, and includes an image reading unit A, an image processing unit B (not shown), an image forming unit C, and a transfer paper transport unit D as a transfer paper transport unit.

An automatic document feeder for automatically feeding a document is provided above the image reading section A.
The document placed on the document 11 is separated and conveyed one by one by a document conveying roller 112, and an image is read at a reading position 113a. The document for which reading of the document has been completed is discharged onto the document discharge tray 114 by the document conveying roller 112.

On the other hand, the image of the original placed on the platen glass 113 is read in the form of a V-shape by a reading operation at a speed v of a first mirror unit 115 comprising an illumination lamp and a first mirror constituting a scanning optical system. Reading is performed by moving the second mirror unit 116 including the second and third mirrors located in the same direction at the speed v / 2.

The read image is formed on the light receiving surface of the image sensor CCD, which is a line sensor, through the projection lens 117. The linear optical image formed on the image sensor CCD is sequentially subjected to A / D conversion after being photoelectrically converted into an electric signal (luminance signal), and subjected to processing such as density conversion and filter processing in an image processing unit B. After that, the image data is temporarily stored in the memory.

In the image forming section C, a drum-shaped photosensitive member 121 as an image carrier, a charger 122 as a charging unit, a developing unit 123 as a developing unit, and a transfer unit as an image forming unit. A transfer unit 124, a separator 125 as a separating unit, a cleaning device 126 as a cleaning unit, and a PCL (precharge lamp) 127
Are arranged in the order of operation. The photoconductor 121 is formed by coating a photoconductive compound on a drum substrate, and for example, an organic photoconductor (OPC) is preferably used, and is driven to rotate clockwise in the drawing.

After the rotating photosensitive member 121 is uniformly charged by the charger 122, the exposure optical system 130 performs image exposure based on the image signal called from the memory of the image processing section B. Exposure optical system 13 as image exposure means
Numeral 0 designates a laser diode (not shown) as a light-emitting light source, and an optical path is bent by a reflection mirror 132 through a rotating polygon mirror 131, an fθ lens (no sign), and a cylindrical lens (no sign) to perform main scanning. Image exposure is performed on the photoconductor 121 at the position Ao, and a latent image is formed by rotation (sub-scan) of the photoconductor 121. In one example of the present embodiment, a character portion is exposed to form a latent image.

The latent image on the photosensitive member 121 is subjected to reversal development by the developing device 123, and a visible toner image is formed on the surface of the photosensitive member 121. In the transfer paper transport section D, a paper feed unit 141 (A) as transfer paper storage means in which transfer papers P of different sizes are stored below the image forming unit, 1
41 (B) and 141 (C) are provided, and a manual paper feed unit 142 for performing manual paper feed is provided on the side. Transfer paper P selected from any of them is guided by guide rollers 143. The transfer sheet P is fed along the conveyance path 140, and the transfer sheet P is temporarily stopped by a pair of registration rollers 144 for correcting the inclination and deviation of the transfer sheet to be fed. The toner image on the photosensitive member 121 is transferred to the transfer paper P by the transfer device 124 at the transfer position Bo, guided by the pre-transfer roller 143a and the transfer entry guide plate 146, and then the charge is removed by the separator 125, so that the transfer paper P is exposed to light. The sheet is separated from the surface of the body 121 and transported to the fixing device 150 by the transport device 145.

The fixing device 150 has a fixing roller 151 and a pressure roller 152, and transfers the transfer paper P to the fixing roller 15.
1 and the pressure roller 152,
The toner is fused by heating and pressing. The transfer paper P on which the toner image has been fixed is discharged onto the discharge tray 164.

[0132]

EXAMPLES The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto. Example Preparation of Photoconductor 1 <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 It was applied on a cylindrical conductive support so as to have a thickness of 0.5 μm.

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

<Charge Transport Material> Charge transport material (N- (4-methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine) 225 g Polycarbonate (viscosity average molecular weight 30,000) 300 g 6 g of antioxidant (exemplary compound 1-3) and 2,000 ml of dichloromethane were mixed and dissolved to prepare a coating solution for the charge transport layer. 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 as shown in Table 1. <Resin Layer> β- (3,4-epoxycyclohexyl) trimethoxysilane 15 g Dimethoxydimethylsilane 145 g Reactive charge-transporting compound (Exemplary Compound T-1) 52 g Antioxidant (Exemplary Compound 2-1) 2.6 g Ethanol 280 g 4% acetic acid 31 g Trisacetylacetonatoaluminum 2 g was mixed to prepare a coating solution for a resin layer. This coating solution was applied on the charge transport layer by a circular amount-regulating type coating device at 3 μm.
m, and then heat-cured at 110 ° C. for 1 hour to form a siloxane-based resin layer having a cross-linked structure.

Preparation of Photoconductor 2 Photoconductor 1 was prepared in the same manner as photoconductor 1, except that β- (3,4-epoxycyclohexyl) trimethoxysilane was replaced with β- (3,4-epoxycyclohexyl) triacetoxysilane. In the same manner as in the above, a photoreceptor 2 was produced.

Preparation of Photoconductor 3 Photoconductor 1 was prepared in the same manner as photoconductor 1 except that 15 g of β- (3,4-epoxycyclohexyl) trimethoxysilane was replaced by 80 g and 145 g of dimethoxydimethylsilane was replaced by 80 g. Photoconductor 3 was prepared.

Preparation of Photoconductor 4 Photoconductor 1 was prepared in the same manner as photoconductor 1 except that 15 g of β- (3,4-epoxycyclohexyl) trimethoxysilane was replaced by 145 g and 145 g of dimethoxydimethylsilane was replaced by 15 g. Photoconductor 4 was prepared.

Preparation of Photoconductor 5 Photoconductor 1 was prepared in the same manner as photoconductor 1, except that β- (3,4-epoxycyclohexyl) trimethoxysilane was replaced with β- (3,4-epoxycyclohexyl) methyldimethoxysilane. In the same manner as in the above, a photoreceptor 5 was produced.

Preparation of Photoreceptor 6 Photoreceptor 1 was prepared except that β- (3,4-epoxycyclohexyl) trimethoxysilane was replaced with β- (3,4-epoxycyclohexyl) methyldiethoxysilane. Photoconductor 6 was produced in the same manner as in Example 1.

Preparation of Photoconductor 7 Photoconductor 7 was prepared in the same manner as photoconductor 1, except that dimethoxydimethylsilane was replaced with γ-methacryloxypropylmethyldiethoxysilane.

Preparation of Photoconductor 8 Photoconductor 8 was prepared in the same manner as photoconductor 1, except that β- (3,4-epoxycyclohexyl) trimethoxysilane was replaced with methyltrimethoxysilane. did.

Preparation of Photoconductor 9 In the preparation of Photoconductor 1, the amount of dimethoxydimethylsilane used was changed to 15 g, and β- (3,4-epoxycyclohexyl) trimethoxysilane was changed to methyltrimethoxysilane. Photoconductor 9 was prepared in the same manner as Photoconductor 1, except that 145 g was used.

Preparation of Photoconductor 10 Photoconductor 1 was prepared in the same manner as photoconductor 1 except that β- (3,4-epoxycyclohexyl) trimethoxysilane was replaced with γ-chloropropyltrimethoxysilane. The body 10 was produced.

Evaluation The evaluation was performed using a digital copier Konic manufactured by Konica Corporation.
a7060 (having laser exposure, reversal development, nail separation, blade cleaning process) was remodeled, mounted on an evaluator with an appropriate exposure amount, set to a surface potential of -750 V, and placed in a high temperature and high humidity environment (HH: 38 ° C). , 80%), after 50,000 consecutive copies, pause for 1 hour, and then in a low temperature and low humidity environment (L
(L: 10 ° C., 20%).

As a copy image, an original image in which a character image having a pixel ratio of 7%, a portrait of a person, a solid white image, and a solid black image are each 等 equally divided is copied in A4.
The halftone, solid white image and solid black image were evaluated for each sheet. The image density was determined by comparing the density of a solid black image with RD- manufactured by Macbeth.
918 was used to measure the absolute reflection density. Fog was visually evaluated using a solid white image. The presence or absence of image blur was also evaluated visually.

Evaluation criteria Image density 濃度: 1.2 or more: good ○: less than 1.2 to 0.8: no problem in practical use ×: less than 0.8: level in which no practical problem occurs Fog ○: no fog occurs ×: Occasionally fog occurred Image blur ◎: Occurrence of 5 or less out of 100,000 sheets ○: Occurrence of 6 to less than 20 out of 100,000 sheets ×: Occurrence of 20 or more out of 100,000 sheets In the test, the copied image and the cleaning blade were visually observed and checked for the presence of toner slippage and blade turning during the copying.

：: No toner slippage or blade turn-up occurred on 100,000 sheets ×: toner slip-off or blade turn-up occurred on 100,000 sheets Photoreceptor depletion amount The above 100,000 continuous copies were made. For the photoreceptor, an eddy current type film thickness measuring device EDDY560C (HELMUT F
ISHER GMBTE CO.) And evaluated by the absolute value of the difference from the film thickness before copying. Table 1 shows the results.

[0148]

[Table 1]

As is clear from Table 1, the β-
A photoreceptor having a resin layer manufactured using an organosilicon compound having a (3,4-epoxycyclohexyl) group includes:
In the actual shooting evaluation, the image quality such as density, fogging, and image blurring is good, the toner slip-through and blade turn-up are improved, and the photoreceptor wear is also reduced. On the other hand, the photoreceptor outside the range of the present invention is inferior to the photoreceptor within the range of the present invention in any of the image quality, the cleaning property, and the wear amount of the photoreceptor. It is clear that it is excellent.

[0150]

As is clear from the examples, the photoreceptor produced by the production method of the present invention has good image quality, good cleaning properties, and strong abrasion resistance under both high-temperature, high-humidity and low-temperature, low-humidity conditions. It shows that the properties are maintained, and the effect can be maintained for long-term use even under severe environmental conditions.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an overall configuration of an image forming apparatus of the present invention.

[Explanation of symbols]

 121 Photoconductor 122 Charger 123 Developing Device 124 Transfer Device 125 Separator 126 Cleaning Device 127 PCL (Precharge Lamp) 130 Exposure Optical System

Claims (9)

[Claims] 1. A coating solution containing a reactive charge transporting compound, at least one organosilicon compound of the following general formulas (1), (2) and (3), or a hydrolysis product thereof, and a solvent: And then curing to form a resin layer. General formula (1) R ₁ Si (Z) ₃ General formula (2) R ₁ R ₂ Si (Z) ₂ General formula (3) R ₁ R ₂ R ₃ Si (Z) (R ₁ in the formula is β- A (3,4-epoxycyclohexyl) group, wherein R ₂ and R ₃ are an alkyl group having 1 to 10 carbon atoms, an aryl group, a vinyl group, an amino group, a γ-glycidoxypropyl group, and a γ-methacryloxypropyl group. , Β-
(3,4-epoxycyclohexyl) group, C _n F _{2n + 1} C ₂
H ₄ — (n is an integer of 1 to 10), which may be the same or different. In the formula, Z is a hydrolyzable alkoxy group or a halogen atom, and a plurality of Z bonded to the same silicon atom may be the same alkoxy group or halogen atom, or may be different alkoxy groups or halogen atoms. ) 2. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the coating solution contains an organosilicon compound represented by the following general formula (4) or a hydrolysis product thereof. Formula _{(4) R n Si (Z} ) 4-n ( wherein R is an alkyl group having 1 to 10 carbon atoms, an aryl group,
Vinyl group, amino group, γ-glycidoxypropyl group, γ
- methacryloxypropyl _{group, C n F 2n + 1 C} 2 H 4 - (n
Is an integer of 1 to 10), and when R is plural, plural Rs may be the same group or different groups. In the formula, Z is a hydrolyzable alkoxy group or a halogen atom, and a plurality of Zs bonded to the same silicon atom may be the same alkoxy group or halogen atom, or may be different alkoxy groups or halogen atoms. n is an integer of 0-3. ) 3. The method according to claim 1, wherein the resin layer comprises a siloxane-based resin layer having a structure represented by the following general formula (5). Method. Embedded image (In the formula, X represents a structural unit having charge transport performance, and Y represents an arbitrary divalent or higher valent linking group.) 4. The method according to claim 1, wherein the coating solution contains an antioxidant. 5. An electrophotographic photoreceptor produced by using the production method according to claim 1. Description: 6. The electrophotographic photoreceptor according to claim 5, having the resin layer as a protective layer. 7. An image forming method comprising an electrophotographic photosensitive member, a charging unit, an image exposing unit, a developing unit, and a cleaning unit, wherein the electrophotographic photosensitive member according to claim 5 is used as the electrophotographic photosensitive member. An image forming method comprising: 8. An image forming apparatus having an electrophotographic photosensitive member, a charging unit, an image exposing unit, a developing unit, and a cleaning unit, wherein the electrophotographic photosensitive member according to claim 5 is used as the electrophotographic photosensitive member. An image forming apparatus comprising: 9. The process cartridge used in an image forming apparatus having an electrophotographic photoreceptor, a charging unit, an image exposing unit, a developing unit, and a cleaning unit. A process cartridge having at least one of an exposure unit, a development unit, and a cleaning unit in combination with one another, and is designed to be freely inserted into and removed from the image forming apparatus.