JP2001051576A - Method and device for forming electrophotographic image, process cartridge, and electrophotographic photoreceptor used in the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method and a device for forming an electrophotographic image by which a table copy image can be obtained even under the environment of high-temperature and high-humidity and to obtain a process cartridge and an electrophotographic photoreceptor used in the same. SOLUTION: As to this method for forming an electrophotographic image; after a toner image on the electrophotographic photoreceptor is transferred to a recording material, the toner remaining of the photoreceptor is removed by a brush roller and an elastic rubber blade. At this time, the photoreceptor has a structural unit having a function for transporting charges and a resin layer including a siloxane system resin having a cross-linking structure. The toner remaining on the photoreceptor is removed by using the brush roller in which the thickness of single fabric is 6 to 30 deniers, fabric density is 4.5×102 to 15.5×102 f/cm2 (filament number per 1 cm2) and the elastic rubber blade whose pressure force of the surface of the photoreceptor is set to 5 to 30 g/cm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic image forming method, an electrophotographic image forming apparatus, a process cartridge and an electrophotographic photosensitive member. More specifically, the present invention relates to a brush roller for removing toner remaining on a moving organic photosensitive member. The present invention relates to an electrophotographic image forming method, an electrophotographic image forming apparatus, a process cartridge used in the apparatus, and an electrophotographic photoreceptor having a step of performing cleaning with an elastic rubber blade.

[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,
The problem is that the photoreceptor surface is deteriorated or scratched when copying or printing a large number of sheets.

In general, in a Carlson method electrophotographic copying apparatus, after a photosensitive member is uniformly charged, an electric charge is erased imagewise by exposure to form an electrostatic latent image, and the electrostatic latent image is formed. The toner is developed and visualized with a toner, and then the toner is transferred and fixed on paper or the like.

However, not all of the toner on the photoreceptor is transferred, and some of the toner remains on the photoreceptor. When an image is repeatedly formed in this state, the formation of a latent image is disturbed by the influence of the residual toner. Therefore, it is not possible to obtain a high-quality copy without contamination. Therefore, it is necessary to remove the residual toner. The cleaning means is typically a fur brush roller, a magnetic brush roller, a blade, or the like, but a blade is mainly used in terms of performance, configuration, and the like. At this time, a plate-shaped rubber elastic body is generally used as the blade member.

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

In order to satisfy the various characteristics required as described above, various things have been studied so far.

[0007] Regarding 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. I have. Japanese Patent Application Laid-Open No. Hei 6-118681 reports that a curable silicone resin containing colloidal silica is used as a surface 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, the surface layer of the curable silicone resin containing colloidal silica has excellent strength properties, and has been widely studied as a means for improving abrasion resistance and scratch resistance, which were disadvantages of the conventional OPC. However, when a siloxane resin is used as the surface layer, there is a problem in the potential characteristics particularly in a low humidity environment. Attempts have been made to reduce the surface resistance by a method such as addition of conductive particles in order to improve this. However, this method has the problem of causing image deletion in a high-temperature and high-humidity environment. With respect to these problems, the present inventors have found that the incorporation of a structural unit having charge transport ability into a siloxane resin improves the potential characteristics under a low-temperature and low-humidity environment (Japanese Patent Application No. 11-70380).

However, with the improvement of the strength characteristics, it is difficult to remove the deposits due to the toner and paper powder on the surface of the photoreceptor which have been effectively removed by the conventional wear, and as a result, the deposited deposits deteriorate the image quality. You have a problem.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic image forming method, an electrophotographic image forming apparatus, a process cartridge used in the apparatus, and an electrophotographic apparatus capable of obtaining a stable and high quality electrophotographic image over a long period of time. In providing photoreceptors.

[0011]

Means for Solving the Problems The inventors of the present invention have made intensive efforts to solve the above problems, and as a result, have formed a resin layer containing a siloxane-based resin having a structural unit having a charge transporting property and having a crosslinked structure. It has been found that the object of the present invention can be attained by cleaning the electrophotographic photosensitive member having at least a cleaning step having both means of an elastic rubber blade and a brush roller. That is, it has been found that the object of the present invention is achieved by adopting any one of the following constitutions.

1. In the electrophotographic image forming method, after transferring the toner image on the electrophotographic photoreceptor to a recording material, the toner remaining on the photoreceptor is cleaned with a brush roller and an elastic rubber blade. And a resin layer containing a siloxane-based resin having a cross-linked structure. The toner remaining on the photoreceptor has a single fiber thickness of 6 to 30 denier and a fiber density of 4.5. × 10 ^{2 to} 15.5 × 10 ² f / cm
^2. An electrophotographic image forming apparatus, wherein cleaning is performed using a brush roller of ² (number of filaments per square centimeter) and an elastic rubber blade with a pressing force applied to the surface of the photoreceptor at 5 to 30 g / cm. Method.

2. In the electrophotographic image forming method, after transferring the toner image on the electrophotographic photoreceptor to a recording material, the toner remaining on the photoreceptor is cleaned with a brush roller and an elastic rubber blade. A resin layer containing a siloxane-based resin having a cross-linked structure and having a structural unit having a cross-linking structure, wherein the toner remaining on the photoconductor is brought into contact with the photoconductor under an effective driving torque of 0.1 kgf · cm to 2.0 kgf · cm and a pressing force against the surface of the photoreceptor is 5 to 30 g / cm.
An electrophotographic image forming method, wherein the cleaning is performed by using an elastic rubber blade set in (1).

Effective driving torque: T = T1−T2 T1: Driving torque of the brush roller when the brush roller contacts the photoconductor T2: Driving torque of the brush roller when the brush roller does not contact the photoconductor 3 . 3. The electrophotographic image forming method according to the above 1 or 2, wherein the structural unit having the charge transporting performance is represented by the following structural formula in the structure of the siloxane-based resin.

[0015]

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(Wherein, X is a structural unit having a charge transporting property, a group bonding to Y via a carbon atom or a silicon atom constituting the structural unit, and Y is an adjacent bonding atom (S
a divalent or higher atom or group excluding i and C). ) 4. 4. The electrophotographic image forming method according to the above item 3, wherein Y is an oxygen atom, a sulfur atom or NR.

(However, R is a hydrogen atom or a monovalent organic group.) The resin layer has a structural unit having charge transporting performance obtained by reacting an organic silicon compound having a hydroxyl group or a hydrolyzable group with a charge transporting compound having a hydroxyl group, and a siloxane-based resin having a crosslinked structure. Any one of the above items 1 to 4, which is a resin layer containing
The method for forming an electrophotographic image according to the above item.

6. The resin layer has an average particle size of 0.05 μm or more.
The electrophotographic image forming method according to any one of the above items 1 to 5, wherein the electrophotographic image forming method contains organic fine particles of 10 μm.

[7] 7. The electrophotographic image forming method according to the item 6, wherein the organic fine particles are fluorine atom-containing resin fine particles.

8. The electrophotographic image forming method according to any one of the above items 1 to 7, wherein the resin layer contains colloidal silica.

9. In an electrophotographic image forming apparatus having a cleaning unit for removing residual toner on an electrophotographic photoreceptor and repeatedly forming an image, the photoreceptor has a structural unit having charge transport performance, and a siloxane having a cross-linked structure. An electrophotographic photoreceptor having a resin layer containing a base resin, wherein the toner remaining on the photoreceptor has a single fiber thickness of 6
３０30 denier, fiber density 4.5 × 10 ² -15.
5 × 10 ² f / cm ² (the number of filaments per square centimeter) of the brush roller and the pressing force on the photoreceptor surface are 5 to 5.
An electrophotographic image forming apparatus, wherein the cleaning is performed by using an elastic rubber blade cleaning means set at 30 g / cm.

10. In an electrophotographic image forming apparatus having a cleaning unit for removing residual toner on an electrophotographic photoreceptor and repeatedly forming an image, the photoreceptor has a structural unit having charge transport performance, and a siloxane having a cross-linked structure. An electrophotographic photoreceptor having a resin layer containing a base resin, wherein the toner remaining on the photoreceptor is brought into contact with the photoreceptor under an effective driving torque of 0.1 kgf · cm or more.
An electrophotographic image forming apparatus, wherein cleaning is performed using a 2.0 kgf.cm brush roller and a cleaning means of an elastic rubber blade with a pressing force applied to the surface of the photoreceptor at 5 to 30 g / cm.

Effective driving torque: T = T1−T2 T1: Driving torque of the brush roller when the brush roller contacts the photoconductor T2: Driving torque of the brush roller when the brush roller does not contact the photoconductor 11 . A process cartridge used in an electrophotographic image forming apparatus having a cleaning means for removing residual toner on an electrophotographic photosensitive member has a structural unit having a charge transporting performance, and a resin layer containing a siloxane-based resin having a crosslinked structure Electrophotographic photoreceptor having a single fiber thickness of 6
３０30 denier, fiber density 4.5 × 10 ² -15.
5 × 10 ² f / cm ² (the number of filaments per square centimeter) of the brush roller and the pressing force on the photoreceptor surface are 5 to 5.
A process cartridge having at least an integrated cleaning means using an elastic rubber blade set to 30 g / cm, and designed to be able to be taken in and out of the image forming apparatus.

12. An electrophotographic photosensitive member comprising a siloxane-based resin having a structural unit having charge transport performance and having a crosslinked structure, a resin layer containing organic fine particles having an average particle diameter of 0.05 μm to 10 μm and an antioxidant. body.

The present invention will be described in more detail.

As the material for the brush of the brush roller used in the present invention, any material can be used, but it is preferable to use a fiber-forming polymer having hydrophobicity and a high dielectric constant. As such a high-molecular polymer,
For example, rayon, nylon, polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polypropylene, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer,
Vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol formaldehyde resin, styrene-alkyd resin, polyvinyl acetal (for example, polyvinyl butyral) and the like. . These binder resins can be used alone or as a mixture of two or more. Particularly preferred are rayon, nylon, polyester, acrylic resin and polypropylene.

The brush may be either conductive or insulative, and may be made of a constituent material containing a low-resistance substance such as carbon and adjusted to an arbitrary resistance.

The thickness of the single fiber of the brush used for the brush roller is not less than 6 denier and not more than 30 denier. 6
If it is less than denier, there is no sufficient rubbing force to remove surface deposits. On the other hand, if the denier is larger than 30 denier, the fiber becomes rigid, so that the surface of the photoconductor is damaged and the life of the photoconductor is shortened.

The term "denier" as used herein means the weight of the fibers constituting the brush, which is 9000 m in length, g (gram).
It is a numerical value measured in units.

The fiber density of the brush is 4.5 × 10 ²
f / cm ² or more and 15.5 × 10 ² f / cm ² or less.
If it is less than 4.5 × 10 ² f / cm ² , unevenness is caused in the rubbing, and the adhered substance cannot be removed uniformly. 15.5x
If it is larger than 10 ² f / cm ² , the toner and foreign matters that have entered between the brush fibers cannot be completely removed, so that packing occurs and the characteristics of the brush are lost.

The effective driving torque T of the brush roller used in the present invention is 0.1 kgf · cm or more and 2.0 kgf · cm or more.
f · cm or less, preferably 0.5 kgf · cm
Above, it is 1.5 kgf · cm or less. The effective drive torque T mentioned here is determined by rotating the photosensitive drum at the same rotational speed as in a normal copying operation in a state where the photosensitive drum and the brush roller are installed at predetermined positions and the photosensitive drum and the brush roller are in contact with each other. Then, the driving torque T1 when the brush roller was rotated at a predetermined rotation speed, the photosensitive drum was removed, and the brush roller was rotated at the same rotation speed as when measuring T1 with the brush roller not in contact with the photosensitive drum. Is defined as the difference (T1−T2) between the driving torques T2 at the time. This effective drive torque means a load on the brush generated by the relative movement between the photosensitive drum and the brush roller. This load corresponds to the rubbing force received from the brush when viewed from the photoconductor drum, and defining the range means that the photoconductor needs to be rubbed with an appropriate force. Effective driving torque T is 0.1 kgf · cm
If the particle size is smaller than the above, the rubbing force of the brush against the photoconductor drum is small, so that filming of the toner or paper powder on the photoconductor surface cannot be suppressed, and a defect such as unevenness occurs on an image. If it is larger than 2.0 kgf · cm, the abrasion force of the photoconductor drum by the brush is too large, so that the abrasion amount of the photoconductor increases, fog due to a decrease in sensitivity or scratches on the photoconductor surface occurs, This is a problem because a streak failure occurs on an image.

FIG. 2 is a schematic view of the apparatus used for measuring the torque of the brush roller according to the present invention.

As shown in FIG. 2, the measurement of the torque is performed by connecting the cylindrical brush support 2 of the brush roller 4 to the rotary shaft torque detector MD-204R via the micro coupling 7 (manufactured by Tokusei Seiko Co., Ltd.). (Manufactured by Ono Sokki Co., Ltd.), and the torque when the motor 9 is turned so as to reach the set rotation speed is indicated by a digital torque operation display TS-10.
It read with 600A (made by Ono Sokki Co., Ltd.).

As the support for the roller portion used in the brush roller of the present invention, metals such as stainless steel and aluminum, paper, plastic and the like are mainly used.
It is not limited by these.

If necessary, a member (flicker) for knocking off the toner and foreign matters adhering to the brush from the brush may be provided.

As shown in FIG. 1, the brush roller used in the present invention preferably has a configuration in which a brush is provided on the surface of a columnar support through an adhesive layer.

FIG. 1 is a schematic view showing the structure of an organic photoreceptor, a brush roller, and an elastic rubber blade according to the present invention.

In FIG. 1, the toner image formed on the organic photoreceptor 1 is transferred to the medium to be copied (not shown) while rotating in the direction of the arrow. The untransferred toner image remains on the organic photoreceptor and rotates in the direction of the arrow. Reference numeral 2 denotes a cylindrical brush support, reference numeral 3 denotes an adhesive layer, and reference numeral 4 denotes a brush roller. Most of the toner image described above is scraped off here. Then, a part of the remaining toner image is scraped off by the elastic rubber blade 5. The elastic rubber blade 5 is pressed by the support member 6 with a pressing force of 5 to 30 on the photoreceptor surface.
g / cm.

As shown in FIG. 1, the elastic rubber blade used in the present invention is preferably configured to have a free end on a support member.

In the present invention, if the pressing force of the elastic rubber blade against the surface of the photoreceptor is less than 5 g / cm, sufficient cleaning is not performed and toner slips through. On the other hand, if it is larger than 30 g / cm, the wear of the photoconductor is increased, the sensitivity of the photoconductor is reduced, and image defects such as fog occur.

The free end of the elastic rubber blade comes into pressure contact with the opposite side (counter) of the photosensitive member in the rotation direction.

The rubber hardness of the elastic rubber blade is JIS.
A 60 ° -70 °, rebound resilience 30-70%, Young's modulus 30-60 kgf / cm ² , thickness 1.5 m
m to 3.0 mm, and the free length is preferably 7 to 12 mm, but is not particularly limited.

Next, the electrophotographic photosensitive member used in the present invention will be described in detail.

In the present invention, the siloxane-based resin having a crosslinked structure is produced by a known method, that is, using an organosilicon compound having a hydroxyl group or a hydrolyzable group. The organosilicon compound has the following general formulas (A) to (D)
Is represented by the following chemical formula.

[0045]

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(Wherein, R _{1 to} R ₆ represent an organic group in which carbon is directly bonded to silicon in the formula, and Z represents a hydroxyl group or a hydrolyzable group.) In the case of a decomposable group, examples of the hydrolyzable group include a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, a butoxy group and a methoxyethoxy group. Examples of the organic group in which carbon is directly bonded to silicon represented by R _{1 to} R ₆ include alkyl groups such as methyl, ethyl, propyl and butyl, aryl groups such as phenyl, tolyl, naphthyl and biphenyl, and γ-glycidyl. Epoxy-containing groups such as xypropyl, β- (3,4-epoxycyclohexyl) ethyl, γ-acryloxypropyl, γ
-A (meth) acryloyl group containing methacryloxypropyl, a hydroxyl group such as γ-hydroxypropyl and 2,3-dihydroxypropyloxypropyl, a vinyl group such as vinyl and propenyl, a mercapto group such as γ-mercaptopropyl, Amino-containing groups such as γ-aminopropyl, N-β (aminoethyl) -γ-aminopropyl, and γ-chloropropyl, 1,1,1-trifluorofluoropropyl, nonafluorohexyl, perfluorooctylethyl, etc. Examples include a halogen group, other nitro and cyano-substituted alkyl groups, and the like. Further, R _{1 to} R ₆ may have the same or different organic groups.

In general, when the number n of hydrolyzable groups bonded to silicon atoms of the organosilicon compound used as a raw material of the siloxane-based resin is 1, the polymerization reaction of the organosilicon compound is suppressed. You. n is 2, 3 or 4
In the case of (3), the polymerization reaction is likely to occur.
It is possible to advance the crosslinking reaction to a high degree. Therefore, by controlling these, it is possible to control the preservability of the obtained coating layer liquid, the hardness of the coating layer, and the like.

As a raw material of the siloxane-based resin, a hydrolyzed condensate obtained by hydrolyzing the organosilicon compound under acidic or basic conditions to form an oligomer or a polymer can also be used.

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 with addition of a catalyst or a crosslinking agent, 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, and silica particles are incorporated in a part of the crosslinked structure.

The siloxane-based resin having a structural unit having a charge transporting property and having a crosslinked structure according to the present invention is a chemical structure having a characteristic of exhibiting electron or hole drift mobility (= a structure having a charge transporting property). Is incorporated as a partial structure into a siloxane-based resin having a crosslinked structure. Specifically, the siloxane-based resin having a structural unit having a charge transporting property of the present invention and having a crosslinked structure includes a compound generally used as a charge transporting substance (hereinafter, also referred to as a charge transporting compound or CTM). It has a partial structure in the siloxane-based resin.

The above-mentioned structural unit having charge transport performance is a structural unit exhibiting the property of having electron or hole drift mobility, or a charge transporting compound residue. It can also be expressed as a structural unit or a charge-transporting compound residue from which a detection current due to charge transport can be obtained by a known method capable of detecting charge-transporting performance such as the Of-Flight method.

The charge transporting compound capable of forming a structural unit having charge transporting ability in a siloxane-based resin by reaction with an organic silicon compound will be described below.

For example, hole transport type CTM: xazole, oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidin, styryl, hydrazone, benzidine, pyrazoline,
Stilbene compound, amine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine, aminostilbene, poly-N-vinylcarbazole, poly-1-vinylpyrene,
A chemical structure such as poly-9-vinylanthracene is contained as a partial structure of the siloxane-based resin.

On the other hand, electron transport type CTMs include succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, nitrobenzene, dinitrobenzene, trinitrobenzene, and the like. Tetranitrobenzene, nitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bromanyl, benzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4'-dinitrobenzophenone, 4-nitrobenzalmalonedinitrile, α-cyano-β- (p-cyanophenyl) -2-
(P-chlorophenyl) ethylene, 2,7-dinitrofluorene, 2,4,7-trinitrofluorenone, 2,
4,5,7-tetranitrofluorenone, 9-fluorenylidenedicyanomethylenemalononitrile, polynitro-9-fluoronylidenedicyanomethylenemalonodinitrile, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3, Chemical structures such as 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid and melitic acid are contained as partial structures of the siloxane-based resin.

In the present invention, the structural unit having a preferable charge transporting property is a residue of a commonly used charge transporting compound as described above, and has the following structure via a carbon atom or a silicon atom constituting the charge transporting compound. It is bonded to the linking atom or linking group represented by Y in the formula, and is contained in the siloxane-based resin via Y.

[0057]

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(Wherein, X is a structural unit having a charge transporting property, a group bonding to Y in the formula via a carbon atom or a silicon atom constituting the imparting group, and Y is an adjacent bonding atom ( It is a divalent or higher valent atom or group excluding Si and C).
However, when Y is a trivalent or higher atom, the bond of Y other than Si and C in the formula is bonded to any constituent atom in the curable resin capable of bonding or other atoms, It has a structure (group) linked to a 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 performance is shown as a monovalent group in the formula, but the charge transporting compound to be reacted with the siloxane-based resin is 2 When it has two or more reactive functional groups, it may be bonded as a divalent or higher valent crosslink group in the curable resin, or may be bonded 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 and an organic silicon compound having a hydroxyl group or a hydrolyzable group introduced into a compound having a charge transporting ability. 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.

Next, the charge transporting compound having a hydroxyl group, a mercapto group, an amine group, and an organic silicon-containing group in the present invention 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 a curable organosilicon compound can be exemplified, but is not limited to the following structure. Any compound having a charge transporting ability and a hydroxyl group may be used.

X- (R ₇ -OH) m m ≧ 1 wherein X: a structural unit having charge transporting ability, R ₇ : a single bond, a substituted or unsubstituted alkylene group, an arylene group, m: 1 to 5 Is an integer.

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

1. Triarylamine compounds

[0067]

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2. Hydrazine compounds

[0069]

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3. Stilbene compounds

[0071]

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4. Benzidine compound

[0073]

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5. Butadiene compound

[0075]

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6. Other compounds

[0077]

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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

[0080]

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

[0085]

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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. 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 kolben equipped with a thermometer, a dropping funnel, an argon gas introducing device and a stirrer to make an argon gas atmosphere. 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) mm ≧ 1 wherein X: a structural unit having charge transporting ability, R ₈ : a single bond, a substituted or unsubstituted alkylene, an arylene group, and m: 1 to 5 It is an integer.

[0093] Among them, the following are typical ones.

[0094]

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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 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) mm ≧ 1 wherein X: a structural unit having charge transporting ability; R ₉ : a single bond, a substituted or unsubstituted alkylene, a substituted or unsubstituted arylene group , R _10: a hydrogen atom, a substituted, unsubstituted alkyl groups, substituted, unsubstituted aryl group, m: an integer of 1 to 5.

Among them, the following are typical ones.

[0099]

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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 silicon atom-containing group will be described.

The charge transporting compound having a silicon atom-containing group is a charge transporting substance having the following structure. This compound can also combine with the curable organosilicon compound to form a resin layer.

X-(-Y-Si (R ₁₁ ) _3-a (R ₁₂ ) _a ) _n (wherein X is a group containing a structural unit having charge transport performance, R ₁₁ is a hydrogen atom, R ₁₂ represents a hydrolyzable group or a hydroxyl group, Y represents a substituted or unsubstituted alkylene group or an arylene group, a represents an integer of 1 to 3, and n represents Represents an integer.) Among them, there are the following as typical examples.

Raw material for forming the siloxane-based resin: The composition ratio of the above-mentioned general formulas (A) to (D) (hereinafter referred to as (A) to (D)) is as follows: organosilicon compound: (A) + (B) component 1
It is preferable to use 0.05 to 1 mol of the component (C) + (D) based on the mol.

When the colloidal silica (E) is added, 1 to 30 parts by weight of (E) is used based on 100 parts by weight of the total of the components (A) + (B) + (C) + (D). Is preferred.

The amount of the reactive charge transporting compound (F) capable of forming a resin layer by reacting with the above-mentioned organosilicon compound or colloidal silica is as follows: (A) + (B)
It is preferable to use 1 to 500 parts by weight of (F) based on 100 parts by total weight of + (C) + (D) components. (A)
When the + (B) component is used outside the above range,
When the amount of the components (A) and (B) is small, the siloxane resin layer has too low a crosslinking density and insufficient hardness. Also, (A) +
If the component (B) is too large, the crosslink density is too high and the hardness is sufficient, but a brittle resin layer is formed. Excess or deficiency of the colloidal silica component of the component (E) has the same tendency as that of the component (A) + (B). On the other hand, when the amount of the component (F) is small, the charge transporting ability of the siloxane resin layer is small, causing a decrease in sensitivity and an increase in residual charge. Be looked at.

The siloxane-based resin having a structural unit having charge transporting ability and having a crosslinked structure according to the present invention is prepared by adding a catalyst or a crosslinking agent to a monomer, oligomer or polymer having a siloxane bond in the structural unit in advance. A bond may be formed to form a three-dimensional network structure, or a siloxane bond may be promoted by a hydrolysis reaction and subsequent dehydration condensation to form a three-dimensional network structure from monomers, oligomers, and polymers.

In general, 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 the 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 hydroxide). Ammonium acetate), tin organic acid salts (stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin malate), aluminum, zinc octenoic acid, naphthenate, An acetylacetone complex compound is exemplified.

Further, an antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure is added to the resin layer in the present invention,
It is possible to effectively prevent the occurrence of fog and image blur at high temperature and high humidity. In particular, hindered phenol-based and hindered amine-based antioxidants are effective in preventing fogging and image blurring at high temperature and high humidity.

The content of the hindered phenol or hindered amine antioxidant in the resin layer is 0.01 to 1
0% by weight is preferred. When the content is less than 0.01% by weight, there is no effect on fogging 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, and the residual potential is easily increased, In addition, a decrease in film strength occurs.

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

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.

[0115]

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(In the formula, R ₂₁ represents a hydrogen atom or a monovalent organic group, R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ represent an alkyl group, and R ₂₆ 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 (P7 to P14).
The compounds described above are included, 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.

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 LS765"
"Sanol LS2626", "Sanol LS770",
“Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mark LA”
67 "," Mark LA62 "," Mark LA68 ",
"Mark LA63" or more is a hindered amine type.

<Organic Fine Particles> The organic fine particles have a volume average particle size of 0.05 μm to 10 μm, preferably 0.1 μm to 5 μm.
And 0.01 to 50% by weight is added to the outermost resin layer of the photoreceptor. Examples of the organic fine particles include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyfluoroethylene, polydichlorodifluoroethylene, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer. Coalescing,
Fine particles of resin such as tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinyl ether copolymer or silicone resin, polyethylene, polypropylene, melamine, etc. Is preferred. By including fluorine atom-containing resin fine particles in the resin layer, cleaning of residual toner becomes easy.

The layer constitution of the electrophotographic photoreceptor of the present invention is not particularly limited, but may be a charge generation layer, a charge transport layer, or a charge generation / charge transport layer (a single layer having both functions of charge generation and charge transport). It is preferable to adopt a structure in which a photosensitive layer such as a photosensitive layer) and a resin layer of the present invention are provided thereon. Further, each of the charge generation layer, the charge transport layer, or the charge generation / charge transport layer may be composed of a plurality of layers.

Examples of the charge generating substance (CGM) contained in the photosensitive layer of the present invention include phthalocyanine pigments, polycyclic quinone pigments, azo pigments, perylene pigments, indigo pigments, and the like.
Quinacridone pigments, azurenium pigments, squarylium dyes, cyanine dyes, pyrylium dyes, thiopyrylium dyes, xanthene dyes, triphenylmethane dyes, styryl dyes, and the like.
In M), a layer is formed alone or together with a suitable binder resin.

The charge transport material (C) contained in the photosensitive layer
TM) include, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazoline derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, benzidine compounds, pyrazoline derivatives, stilbenes Compound,
Amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, etc. These charge transport materials (CTM) are usually used to form a layer together with a binder.

As the binder resin contained in the charge generating layer (CGL) and the charge transport layer (CTL) in the case of the photosensitive layer having a single layer structure and the laminate structure, polycarbonate resin, polyester resin, polystyrene resin, methacrylic resin,
Acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl butyral resin, polyvinyl acetate resin, styrene-butadiene resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-maleic anhydride copolymer resin, urethane resin, silicon resin,
Epoxy resin, silicon-alkyd resin, phenol resin, polysilane resin, polyvinyl carbazole and the like can be mentioned.

In the present invention, the ratio between the charge generating substance and the binder resin in the charge generating layer is from 1:10 to 1 by weight.
0: 1 is preferred. The thickness of the charge generation layer is preferably 5 μm or less, and particularly preferably 0.05 to 2 μm.

The charge transport layer is formed by dissolving the charge transport material and the binder resin in a suitable solvent, and applying and drying the solution. The mixing ratio of the charge transport material and the binder resin is preferably from 10: 1 to 1:10 by weight.

The thickness of the charge transport layer is usually from 5 to 50 μm, preferably from 10 to 40 μm. When a plurality of charge transport layers are provided, the thickness of the upper layer of the charge transport layer is 10
μm or less, and preferably smaller than the total thickness of the charge transport layer provided below the charge transport layer.

The curable siloxane resin layer of the present invention may also serve as the charge transport layer, but is preferably formed on a photosensitive layer such as a charge transport layer or a charge generation layer or a single-layer charge generation / transport layer. In addition, it is preferable to provide a separate layer from these. In this case, it is more preferable to provide an adhesive layer between the photosensitive layer and the resin layer of the present invention.

Next, the electroconductive support of the electrophotographic photoreceptor of the present invention includes: 1) a metal plate such as an aluminum plate or a stainless steel plate;
A thin metal layer such as aluminum, palladium, or gold provided by lamination or vapor deposition. 3) On a support such as paper or plastic film,
Examples thereof include those in which a layer of a conductive compound such as a conductive polymer, indium oxide, or tin oxide is provided by coating or vapor deposition.

The material of the conductive support used in the present invention is mainly aluminum, copper, brass, steel,
A belt-shaped or drum-shaped metal material such as stainless steel or another plastic material is used. Among them, aluminum excellent in cost, workability and the like is preferably used, and a thin-walled cylindrical aluminum tube usually formed by extrusion or drawing is often used.

The conductive support may have a surface on which a sealed alumite film is formed.

Further, the shape of the support may be a drum shape, a sheet shape, or a belt shape, and is preferably a shape most suitable for an applied electrophotographic apparatus.

The solvent or dispersion medium used in the production of the photoreceptor of the present invention includes n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methylethylketone,
Methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethane, Tetrahydrofuran, dioxolan, dioxane,
Methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide,
Methyl cellosolve and the like. 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.

The coating method for producing the electrophotographic photoreceptor of the present invention includes dip coating, spray coating,
A coating method such as circular amount control type coating is used, but the coating process on the resin layer side of the photosensitive layer is performed by spray coating or circular amount control type in order to minimize dissolution of the lower layer film and to achieve uniform coating processing. (A typical example is the circular slide hopper type.)
It is preferable to use a coating method such as coating. The spray coating is described in detail in, for example, JP-A-3-90250 and JP-A-3-269238,
The circular amount control type coating is described in, for example, JP-A-58-1.
It is described in detail in JP-A-89061.

The photoreceptor of the present invention is preferably heated and dried at a temperature of 50 ° C. or more, preferably 60 to 200 ° C., after the resin layer is formed. By this heating and drying, the remaining coating solvent can be reduced, and the curable resin layer can be sufficiently cured.

In the present invention, it is preferable to provide an intermediate layer having a barrier function between the conductive support and the photosensitive layer.

Materials for the intermediate layer include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, and phenolic resin polyamides (nylon 6, nylon 66, nylon 610, copolymerized nylon, alkoxymethyl And an intermediate layer using polyurethane, gelatin, and aluminum oxide, or a curable intermediate layer using a metal alkoxide, an organic metal chelate, or a silane coupling agent as disclosed in JP-A-9-68870. The thickness of the intermediate layer is preferably from 0.1 to 10 μm, particularly preferably from 0.1 to 10 μm.
5 μm is preferred.

In the present invention, a coating for compensating for surface defects of the support is provided between the support and the intermediate layer. A conductive layer for the purpose of preventing generation and the like can be provided. This conductive layer is made of carbon black,
It can be formed by applying and drying a solution in which conductive powder such as metal particles or metal oxide particles is dispersed in a suitable binder resin. The thickness of the conductive layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

The electrophotographic photoreceptor of the present invention can be applied to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers. It can be widely applied to devices such as light printing, plate making, and facsimile.

FIG. 3 is a sectional view showing an example of an image forming apparatus having the electrophotographic photosensitive member of the present invention.

In FIG. 3, reference numeral 11 denotes a photosensitive drum (photosensitive member) serving as an image carrier, and an organic photosensitive layer is applied on the drum.
A photoreceptor coated with the resin layer of the present invention thereon is grounded and driven to rotate clockwise. Reference numeral 12 denotes a scorotron charger for uniformly charging the peripheral surface of the photosensitive drum 11 by corona discharge. Prior to the charging by the charger 12, in order to eliminate the history of the photoconductor in the previous image formation, exposure by the exposure unit 23 using a light emitting diode or the like may be performed to remove the charge on the peripheral surface of the photoconductor.

After the photosensitive member is uniformly charged, the image exposure device 13 performs image exposure based on the image signal. The image exposure device 13 in this figure uses a laser diode (not shown) as an exposure 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, the fθ lens, and the like, and an electrostatic latent image is formed.

The electrostatic latent image is then developed by the developing device 14. Around the periphery of the photosensitive drum 11, there are provided developing devices 14 each containing therein a developer having a toner and a carrier such as yellow (Y), magenta (M), cyan (C), black (K) and the like. The color development is performed by a developing sleeve 141 which rotates with a built-in magnet and holding a developer. The developer comprises, for example, a carrier in which an insulating resin is coated around a ferrite core, and a toner in which a pigment corresponding to a color and a charge control agent, silica, titanium oxide, etc. are added using polyester as a main material. The developer is regulated to a layer thickness of 100 to 600 μm on the developing sleeve 141 by a layer forming means (not shown), and is conveyed to a developing area to be developed. At this time, normally, a DC and / or AC bias voltage is applied between the photosensitive drum 11 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 forming process of the second color is started, and the uniform charging is performed again by the scorotron charger 12, and the latent image of the second color is formed. It is formed by the exposure device 13. For the third and fourth colors, the same image forming process as that for the second color is performed, and a visible image of four colors is formed on the peripheral surface of the photosensitive drum 11.

On the other hand, in a monochrome electrophotographic apparatus, the developing device 1
Reference numeral 4 is composed of one kind of black toner and can form an image by one development.

After the image is formed, the recording material P is fed to the transfer area by the rotation of the feed roller 17 at the time when the transfer timing is adjusted.

In the transfer area, a transfer roller (transfer device) 1 is mounted on the peripheral surface of the photosensitive drum 11 in synchronization with the transfer timing.
8 is pressed and fed, and the fed recording material (also referred to as recording paper) P
And a multi-color image is collectively transferred.

Next, the recording material P is neutralized by a separation brush (separator) 19 which is brought into pressure contact with the transfer roller almost at the same time, separated by the peripheral surface of the photosensitive drum 11 and conveyed to the fixing device 20, where the heat roller 201 and pressure roller 2
After the toner is welded by heating and pressurizing 02, the toner is discharged to the outside of the apparatus via the discharge roller 21. The transfer roller 18 and the separation brush 19 are retracted from the peripheral surface of the photosensitive drum 11 after passing through the recording material P to prepare for the formation of the next toner image.

On the other hand, the photosensitive drum 11 from which the recording material P has been separated removes and cleans the residual toner by pressing the blade 221 of the cleaning device 22 and rubbing the brush roller 222, and again removes electricity by the exposure unit 23 and recharges the charger. The next image forming process is started after receiving the charge by the charging unit 12. When a color image is formed on the photoconductor by superimposition, the blade 221 and the brush roller 222 move immediately after the cleaning of the photoconductor surface and retreat from the peripheral surface of the photoconductor drum 11.

As the recording material P, papers such as plain paper, neutral paper, acidic paper and the like, plastic supports such as polyester base and the like are generally used. However, any support capable of fixing a toner image is used in the present invention. It can be used as a recording material.

Reference numeral 30 denotes a detachable cartridge in which a photosensitive member, a charger, a transfer device / separator, and a cleaning device are integrated.

An electrophotographic image forming apparatus is configured by integrally combining the above-described photosensitive member, a developing device, a cleaning device, and other components as a process cartridge, and this unit is configured to be detachable from the apparatus main body. You may.
Also, a process cartridge is formed by integrally supporting at least one of a charger, an image exposing unit, a developing unit, a transfer or separating unit, and a cleaning unit together with a photoreceptor. It may be configured to be detachable using a guide means such as a rail of the apparatus body.

When the image forming apparatus is used as a copying machine or a printer, the image exposure is performed by irradiating the photosensitive member with light reflected or transmitted from the original, or by reading the original with a sensor and converting it into a signal. Scanning of a laser beam, driving of an LED array, or driving of a liquid crystal shutter array is performed by irradiating the photosensitive member with light.

When used as a facsimile printer, the image exposure unit 13 performs exposure for printing received data.

The electrophotographic photoreceptor of the present invention can be applied to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers. It can be widely applied to devices such as light printing, plate making, and facsimile.

[0155]

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

A photoreceptor was prepared as described below.

Preparation of Photoreceptor 1 <Intermediate Layer> A polyamide resin (Amilan CM-8000: manufactured by Toray Industries, Inc.) 60 g methanol 1600 ml 1-butanol 400 ml was mixed and dissolved to prepare an intermediate layer coating solution. This coating solution was applied by dip coating onto a cylindrical aluminum substrate having a diameter of 80 mm and a length of 360 mm to form an intermediate layer having a thickness of 0.3 μm.

<Charge Generating Layer> Titanyl phthalocyanine 60 g Silicone 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. A 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. As a result of measuring a Cu-Kα characteristic X-ray diffraction spectrum of titanyl phthalocyanine, a Bragg angle 2θ of 2
A maximum peak was observed at 7.2 °.

<Charge Transport Layer> 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 2000 ml Were mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a thickness of 25 μm.

<Resin Layer> Trimethoxymethylsilane 180 g 1-butanol 280 ml 1% acetic acid aqueous solution 106 ml was mixed and stirred at 60 ° C. for 2 hours, and then 370 m
1-butanol was added and stirring was continued for 48 hours.

To this were added 67.5 g of dihydroxymethyltriphenylamine (Exemplified Compound T-1), 1.7 g of an antioxidant (Sanol LS2626, manufactured by Sankyo) and 4.5 g of dibutyltin acetate, and mixed. Was applied as a resin layer having a dry film thickness of 1 μm, and was heated and cured at 120 ° C. for 1 hour to prepare a photoreceptor 1 for an example.

Preparation of Photoconductor 2 Photoconductor 2 was prepared in exactly the same manner as photoconductor 1 except that dihydroxymethyltriphenylamine in the resin layer was replaced with 4- [2- (triethoxysilyl) ethyl] triphenylamine. Produced.

Preparation of Photoconductor 3 Similarly to Photoconductor 1, a charge transport layer was prepared.

<Resin Layer> Trimethoxymethylsilane 120 g γ-glycidoxypropyltrimethoxysilane 60 g 1-butanol 280 ml 1% acetic acid aqueous solution 106 ml was mixed and stirred at 60 ° C. for 2 hours, and then 370 m
1-butanol was added and stirring was continued for 48 hours.

To this were added 60 g of Exemplified Compound S-2, 10 g of PTFE fine particles having an average particle size of 0.2 μm (Rublon L2: manufactured by Daikin Industries, Ltd.) and 4.5 g of dibutyltin acetate, and the mixture was mixed. It was applied as a resin layer having a thickness of 1 μm, and was heated and cured at 120 ° C. for 1 hour to produce a photoreceptor 3.

Preparation of Photoconductor 4 Similarly to Photoconductor 1, a charge transport layer was prepared.

<Resin Layer> Trimethoxymethylsilane 120 g γ-glycidoxypropyltrimethoxysilane 60 g 1-butanol 280 ml 1% acetic acid aqueous solution 106 ml was mixed and stirred at 60 ° C. for 2 hours, and then 370 m
1-butanol was added and stirring was continued for 48 hours.

60 g of Exemplified Compound H-1, 10 g of PTFE fine particles having an average particle size of 0.2 μm (Rubron L2: manufactured by Daikin Industries, Ltd.), colloidal silica (solid content: 30%)
(Methanol solution) 100 g was added and mixed, and this solution was applied as a resin layer having a dry film thickness of 1 μm.
Heat curing was performed for a long time to produce a photoreceptor 4.

Preparation of Photoreceptor 5 Photoreceptor 5 was prepared in the same manner as in Photoreceptor 1 except that dihydroxymethyltriphenylamine (Exemplified Compound T-1) in the resin layer was removed.

Preparation of Photoreceptor 6 Photoreceptor 6 was prepared in the same manner as for photoreceptor 1 except that the resin layer was omitted.

Preparation of Photoreceptor 7 Photoreceptor 7 for the example was prepared in the same manner as for photoreceptor 1 except that the antioxidant in the resin layer was removed.

Examples (20 examples in total) The photosensitive member manufactured as described above was used in a digital copier K
onica 7050 (manufactured by Konica Corporation: the cleaning member was set as follows in the laser exposure and reversal development process).

As the cleaning blade, rubber hardness J
An elastic rubber blade having an IS A of 70 °, a rebound resilience of 30%, a thickness of 2 mm and a free length of 9 mm was contacted at a contact angle of 20 ° in a counter direction against the rotation of the photoreceptor with a pressing force of 20 g / cm.

Further, an acrylic conductive brush having a single fiber thickness of 15 denier and a fiber density of 9.3 × 10 ² f / cm ² was formed on a SUS core having a diameter of 6 mm so as to have an outer diameter of 15 mm. A roller was installed below the blade so as to have a bite amount of 1 mm, and was set to operate in synchronization with the photoconductor at a rotation speed of 500 rpm with respect to the photoconductor. At this time, the amount of bite into the brush is 1m
m, a flicker for removing toner from the brush was provided.

A real image test of 50,000 copies was performed under the conditions of 30 ° C. and 80 RH, and the quality of the copied image was evaluated. Table 1 shows the results.

[0176]

[Table 1]

The evaluation was carried out in such a manner that a character image having a pixel rate of 7%, a portrait image of a person, a solid white image and a solid black image each having an equal size of １ ／ were 50,000 sheets in A4. Copies were made and a solid black image, solid white image, and poor cleaning were evaluated every 1000 sheets. Poor cleaning is due to the presence or absence of white spots on the solid black image (diameter 0.3 mmφ).
Were evaluated, and the number of white spots where 5 or more occurred was evaluated. The image density was determined by measuring the absolute reflection density of a solid black image using RD-918 manufactured by Macbeth Co., Ltd., and comparing the initial image and the image after 50,000 sheets. Further, for the fog, a solid white image was used, and the fog was visually confirmed at the initial stage and after 50,000 sheets.

The blade turn-up was evaluated by the number of turn-ups during the 50,000-sheet copy actual test.

Image density ：: 1.2 or more: good ○: less than 1.2 to 0.8: no problem in practical use ×: less than 0.8: level in which there is no practical problem Fog ：: no fog occurs ○: Slight fog is generated, but there is no practical problem. △: Occasional fog is generated. X: Continuous fog is generated. Cleaning failure is not generated. ：: No white spot is generated. : 6 to 20 out of 50,000 sheets with white spots ×: 21 or more out of 50,000 sheets with white spots

The following can be said from Table 1. As described in the background of the invention, in Comparative Example 10 using the conventional photoconductor (photoconductor of polycarbonate on the surface: No. 6), cleaning was performed with a blade and a brush roller. Fog and cleaning properties) were good, but the amount of wear on the surface of the photoreceptor was much greater than in the present invention. This indicates that the photosensitive layer is further abraded as it is further used, resulting in an adverse effect on the image quality, and that it is difficult to control the image quality by simply using the blade and the brush roller.

In Comparative Examples 4, 5, 6, 7, 8, and 9, the same photosensitive member 1 as in Example 1 was used. However, when the conditions of the brush roller and the blade are out of the range of the present invention, the image quality is adversely affected. Note that in Comparative Example 1, a photoreceptor 5 having no structural unit having charge transport performance in the surface layer was used for the photoreceptor 1 of Example 1. When such a photoconductor is used, as described in the related art, the photoconductor has a problem in image quality.

In order to obtain good image quality, it is very difficult to control not only the photosensitive member but also the cleaning means. However, in Examples 1 to 11, good image quality was able to be achieved in all of the 50,000-sheet actual test under high temperature and high humidity conditions. It can be seen that excellent image quality can be stably obtained by properly combining the type of the photoconductor, the condition of the brush roller, and the condition of the cleaning blade within the scope of the present invention.

[0183]

An electrophotographic image forming method capable of obtaining a highly durable and high-quality copy image even in a high-temperature and high-humidity environment by employing a configuration in which the photoreceptor of the present invention is combined with a cleaning means. A photographic image forming apparatus, a process cartridge and an electrophotographic photosensitive member used in the apparatus can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a configuration of an organic photoreceptor, a brush roller, and an elastic rubber blade according to the present invention.

FIG. 2 is a schematic diagram of an apparatus used for torque measurement.

FIG. 3 is a cross-sectional view illustrating an example of an image forming apparatus having the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Organic photoreceptor 2 Columnar brush support 3 Adhesive layer 4 Brush roller 5 Elastic rubber blade 6 Support member 11 Photoreceptor drum (or photoreceptor) 12 Charger 13 Image exposure device 14 Developing device 17 Feed roller 18 Transfer roller (Transfer device) 19 Separation brush (separator) 20 Fixing device 21 Discharge roller 22 Cleaning device 23 Exposure unit using light emitting diode 30 Photoconductor, charger, transfer device / separator and cleaning device are integrated Removable process cartridge

Continuing on the front page (72) Inventor Yoko Kitahara 2970, Ishikawacho, Hachioji-shi, Tokyo Konica Corporation (72) Inventor Masahiko Kurachi 2970, Ishikawacho, Hachioji-shi, Tokyo Konica Corporation (72) Inventor Kazuhisa Shida Tokyo Konica Corporation, 2970 Ishikawa-cho, Hachioji-shi, Tokyo

Claims (12)

[Claims] 2. An electrophotographic image forming method comprising the steps of: transferring a toner image on an electrophotographic photosensitive member to a recording material; and cleaning a toner remaining on the photosensitive member with a brush roller and an elastic rubber blade. Has a resin layer containing a siloxane-based resin having a cross-linking structure and having a structural unit having charge transport performance, and the toner remaining on the photoreceptor has a single fiber thickness of 6 to 30 denier, The density is 4.5 × 10 ^{2 to} 15.5 × 10 ² f / cm ² (1
An electrophotographic image forming method, wherein cleaning is performed using a brush roller of (number of filaments per square centimeter) and an elastic rubber blade having a pressing force applied to the surface of the photoreceptor at 5 to 30 g / cm. 2. An electrophotographic image forming method, comprising: transferring a toner image on an electrophotographic photoreceptor to a recording material; and cleaning the toner remaining on the photoreceptor with a brush roller and an elastic rubber blade. Has a resin layer containing a siloxane-based resin having a cross-linking structure and having a structural unit having charge transport performance, and a condition in which toner remaining on the photoconductor is brought into contact with the photoconductor by an effective driving torque Wherein the cleaning is performed using a brush roller of 0.1 kgf · cm to 2.0 kgf · cm and an elastic rubber blade with a pressing force applied to the surface of the photoreceptor at 5 to 30 g / cm. Image forming method. Effective driving torque: T = T1−T2 T1: Driving torque of the brush roller when the brush roller contacts the photoconductor T2: Driving torque of the brush roller when the brush roller does not contact the photoconductor 3. The electrophotographic image forming method according to claim 1, wherein the structural unit having the charge transporting performance is in the structure of the siloxane-based resin by the following structural formula. Embedded image (Wherein, X is a structural unit having charge transport performance,
Y via a carbon atom or a silicon atom constituting the structural unit
And Y is a divalent or higher valent atom or group excluding adjacent bonding atoms (Si and C). ) 4. The method according to claim 3, wherein Y is an oxygen atom, a sulfur atom or NR. (However, R is a hydrogen atom or a monovalent organic group.) 5. The resin layer has a structural unit having a charge transporting property obtained by reacting an organic silicon compound having a hydroxyl group or a hydrolyzable group with a charge transporting compound having a hydroxyl group, and having a crosslinked structure. 5. A resin layer containing a siloxane-based resin.
The method for forming an electrophotographic image according to any one of the above items. 6. The resin layer has an average particle size of 0.05 μm to 1 μm.
The electrophotographic image forming method according to any one of claims 1 to 5, further comprising 0 µm of organic fine particles. 7. The electrophotographic image forming method according to claim 6, wherein the organic fine particles are fluorine atom-containing resin fine particles. 8. The method according to claim 1, wherein the resin layer contains colloidal silica. 9. An electrophotographic image forming apparatus having a cleaning unit for removing residual toner on an electrophotographic photoreceptor and repeatedly forming an image, wherein the photoreceptor has a structural unit having charge transport performance, and An electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a crosslinked structure, wherein the toner remaining on the photoreceptor has a single fiber thickness of 6 to
30 denier, fiber density 4.5 × 10 ^{2 to} 15.5
The pressing force on the brush roller of × 10 ² f / cm ² (the number of filaments per square centimeter) and the photosensitive member surface is 5 to 3
An electrophotographic image forming apparatus, wherein the cleaning is performed by using an elastic rubber blade cleaning means set to 0 g / cm. 10. An electrophotographic image forming apparatus which has a cleaning unit for removing residual toner on an electrophotographic photoreceptor and repeatedly forms an image, wherein the photoreceptor has a structural unit having charge transporting performance, and An electrophotographic photoreceptor having a resin layer containing a siloxane-based resin having a crosslinked structure, wherein the toner remaining on the photoreceptor is brought into contact with the photoreceptor under an effective driving torque of 0.1 kgf · cm to 2 kg. .
An electrophotographic image forming apparatus, wherein the cleaning is performed using a brush roller of 0 kgf · cm and an elastic rubber blade cleaning means with a pressing force applied to the surface of the photoreceptor at 5 to 30 g / cm. Effective driving torque: T = T1−T2 T1: Driving torque of the brush roller when the brush roller contacts the photoconductor T2: Driving torque of the brush roller when the brush roller does not contact the photoconductor 11. A siloxane-based resin having a structural unit having charge transport performance and a cross-linked structure, wherein a process cartridge used in an electrophotographic image forming apparatus having cleaning means for removing residual toner on an electrophotographic photosensitive member is provided. An electrophotographic photoreceptor having a resin layer containing: a single fiber having a thickness of 6 to 30 denier and a fiber density of 4.5 × 10
Cleaning means using a brush roller of ^{2 to} 15.5 × 10 ² f / cm ² (the number of filaments per 1 cm ² ) and an elastic rubber blade with a pressing force applied to the surface of the photoreceptor at 5 to 30 g / cm. Characterized in that the process cartridge is at least integrally formed, and is designed to be able to be taken in and out of the image forming apparatus. 12. A resin layer comprising a siloxane-based resin having a structural unit having charge transport performance and having a crosslinked structure, organic fine particles having an average particle diameter of 0.05 μm to 10 μm, and an antioxidant. Electrophotographic photoreceptor.