JP2001142243A - Method for producing electrophotographic photoreceptor, electrophotographic photoreceptor using the method, image forming method and device using the photoreceptor, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an electrophotographic photoreceptor having high surface hardness, high wear and scuffing resistances and stable electrophotographic characteristics in repetitive use and capable of reducing cleaning torque with good suitability to coating. SOLUTION: In the production of the electrophotographic photoreceptor with at least a photosensitive layer and a resin layer on the electrically conductive substrate, the resin layer is formed by adding colloidal silica previously dispersed in a dispersion medium selected form water, alcoholic solvents or ketone solvents to a coating solution containing a compound having electric charge transferring performance and a siloxane resin or its monomer and carrying out coating and heat curing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrophotographic photoreceptor, and an electrophotographic photoreceptor using the method.
Photoreceptor), an image forming method using the same, 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 substance has been most widely used as an electrophotographic photoconductor. Organic photoreceptors have advantages over other photoreceptors, such as easy development of materials corresponding to various exposure light sources from visible light to infrared light, selection of materials that do not cause environmental pollution, and low manufacturing costs. It is. However, the only drawback is that the mechanical strength is weak, and the photoreceptor surface is deteriorated or scratched when copying or printing many sheets.

In general, in the electrophotographic image forming method of the Carlson method, a photoreceptor is uniformly charged, and then charge is erased imagewise by exposure to form an electrostatic latent image.
Next, after being transferred to paper or the like, the photoreceptor is removed of toner remaining on the photoreceptor by blade cleaning or the like. The surface of the electrophotographic photosensitive member is electrically and electrically controlled by a charger, a developing device, a transfer device, a cleaning device, and the like.
Since a mechanical external force is directly applied, durability against them is required. In particular, with respect to the durability against scratches and film peeling due to the abrasion and damage of the photoreceptor surface due to rubbing, the inclusion of foreign matter and the impact during paper jam processing, the same strength as the inorganic photoreceptor is strongly required. Various studies have been made so far to satisfy various required characteristics.

[0004] For example, with respect to mechanical durability, it has been reported that the use of bisphenol Z-type polycarbonate as a binder (binder resin) on the surface of an organic photoreceptor improves the surface wear characteristics and toner filming characteristics. Have been. Japanese Patent Application Laid-Open No. 6-118681 reports that a curable siloxane resin 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 abrasion resistance is improved in the surface layer of the curable siloxane-based resin, but the siloxane-based resin is inferior in coatability and has a high friction coefficient between the blade used in blade cleaning and the photoreceptor. And there is a problem that blade turning occurs. Further, an electrophotographic photosensitive member having a siloxane-based resin in a surface layer tends to easily cause image blur and fog in a high-temperature and high-humidity environment.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems by providing high surface hardness, high wear resistance, high scratch resistance, stable electrophotographic properties when used repeatedly, And the cleaning blade torque can be reduced,
An object of the present invention is to provide a method for manufacturing an electrophotographic photoreceptor and an electrophotographic photoreceptor having good coatability during the production of a photoreceptor. Another object of the present invention is to provide an image forming method, an image forming apparatus, and a process cartridge using the photosensitive member.

[0007]

The present inventors have made intensive efforts to solve the above-mentioned problems, and as a result, introduced a structural unit having a charge transporting property into a siloxane-based resin layer having a cross-linked structure and dispersed in a photosensitive layer. By heating and drying the coating solution prepared by containing the appropriate colloidal silica in the medium to produce a photoreceptor, good coating properties can be obtained, without impairing electrostatic performance, cleaning blade torque,
The present inventors have found that the photoreceptor surface strength can be compatible, and have reached the present invention.

That is, the object of the present invention is achieved by adopting one of the following constitutions. [1] In a method for producing an electrophotographic photoreceptor having at least a photosensitive layer and a resin layer on a conductive support, the resin layer contains a compound having charge transporting performance, and comprises a siloxane-based resin or a siloxane-based resin monomer. A method for producing an electrophotographic photoreceptor, comprising: adding a colloidal silica previously dispersed in a dispersion medium selected from water or an alcohol-based solvent or a ketone-based solvent to a contained coating solution; .

[2] The method for producing an electrophotographic photosensitive member according to [1], wherein the hydrogen ion concentration (pH) of the coating solution for the resin layer is adjusted to 3 to 7.

[3] The colloidal silica has a hydrogen ion concentration in a range of 2 to 6. [1]
Or the method for producing an electrophotographic photosensitive member according to [2].

[4] The colloidal silica dispersion medium contains at least one straight-chain or branched alcohol having 4 or less carbon atoms [1],
The method for producing an electrophotographic photosensitive member according to [2] or [3].

[5] The method for producing an electrophotographic photosensitive member according to any one of [1] to [4], wherein the coating liquid satisfies the formula (1).

Formula (1) 0% <t ≦ 50% where t = B / A × 100 A: mass after curing of siloxane-based resin monomer B: mass of silicon dioxide in the coating solution.

[6] Any one of [1] to [5], wherein the average particle diameter r (nm) of silicon dioxide contained in the colloidal silica is in the range of 5 ≦ r ≦ 40. The method for producing an electrophotographic photoreceptor according to the above item.

[7] The method for producing an electrophotographic photosensitive member according to any one of [1] to [6], wherein the coating solution for the resin layer further contains an antioxidant.

[8] An electrophotographic photosensitive member manufactured by the method for producing an electrophotographic photosensitive member according to any one of [1] to [7].

[0017]

[9] The electrophotographic photosensitive member according to [8], wherein the resin layer is a surface layer of the photosensitive member.

[10] In the image forming method having at least steps of charging, image exposure, development, and cleaning on the electrophotographic photosensitive member, the electrophotographic photosensitive member may be subjected to [8] or

[9] An image forming method using the electrophotographic photosensitive member according to [9].

[11] In an image forming apparatus having an electrophotographic photosensitive member and at least a charger, an image exposing device, a developing device, and a cleaning device, the electrophotographic photosensitive member may be replaced by [8] or

[9] An image forming apparatus using the electrophotographic photosensitive member according to [9].

[12] A process cartridge used in an image forming apparatus having an electrophotographic photosensitive member and at least a charger, an image exposing unit, a developing unit, and a cleaning unit includes:
[8] or

[9] The electrophotographic photosensitive member described in [9] and any one of a charger, an image exposing unit, a developing unit, and a cleaning unit are integrally combined, and are designed to be freely inserted into and removed from the image forming apparatus. A process cartridge.

The colloidal silica in the present invention is defined as a dispersion of silicon dioxide previously dispersed in a dispersion medium.

Colloidal silica is formed by dispersing amorphous silica particles in a dispersion medium to form a colloid, thereby improving affinity with a siloxane resin and lowering a surface friction coefficient. As a result, it has become possible to realize a photoreceptor capable of simultaneously satisfying electrostatic characteristics, cleaning blade torque, and photoreceptor surface strength.

When the siloxane-based resin layer contains a charge-transporting substance, the solvent used for the resin layer is an important factor in determining the compatibility between the siloxane-based resin layer and the charge-transporting substance. By optimizing the type and amount of the dispersion medium used, good compatibility can be maintained without causing microphase separation between the photoconductor coating solution and the charge transport material.

Further, the present inventors have maintained the hydrogen ion concentration of the colloidal silica dispersion medium (the hydrogen ion concentration in this specification refers to pH) in an appropriate range of 2 to 6,
By maintaining the pH of the coating solution in an appropriate range of 3 to 7, and more preferably 3 to 5, in the siloxane-based resin solution containing the charge transporting substance, deterioration of the charge transporting substance is prevented and curing of the silane compound is prevented. A new concept of control was created, and an unexpected effect was obtained in which the coating solution of the photoreceptor did not change with time and had excellent storage stability.

Generally, colloidal silica is used in a state where silicon dioxide is dispersed in a dispersion medium. Water or an organic solvent is used as the dispersion medium. Water as a preferred dispersion medium,
Examples include monohydric alcohols, polyhydric alcohols, and ketones.

As a specific example, methanol silica sol M
A-ST-M, isopropanol silica sol IPA-S
T, ethylene glycol silica sol EG-ST, methyl ethyl ketone silica sol MEK-ST, methyl isobutyl ketone silica sol MIBK-ST, xylene / n-butanol silica sol XBA-ST (all trade names, manufactured by Nissan Chemical Industries, Ltd.).

In the present invention, the siloxane-based resin monomer means a monomer for constituting the siloxane-based resin. Further, the term “siloxane-based resin or siloxane-based resin monomer” refers to a case including one of them, a case including both of them, and a case including a polymerized siloxane-based resin monomer to some extent.

The post-coating heating for forming the resin layer of the present invention may be carried out to the extent necessary for curing, and is carried out at a temperature within a range that does not impair the characteristics of the photosensitive layer. There is no particular limitation,
Usually, it is 80 to 150 ° C. for about 30 to 120 minutes.

In order to achieve the object of the present invention, the resin layer of the present invention is usually preferably provided on the uppermost layer of a photoreceptor. However, from the viewpoint of the other performance of the photoreceptor, an overcoat layer may be further provided thereon as long as the effects of the present invention are not impaired.

The resin layer of the present invention must contain a siloxane-based resin in an amount necessary to achieve the object of the present invention, but at the same time contains a substance for imparting another function. Is also good.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic photosensitive member used in the present invention will be described in detail.

In the present invention, the resin layer has a siloxane-based resin having a structural unit having charge transporting performance and a crosslinked structure as a main component.

The siloxane-based resin is produced by a known method, that is, using an organosilicon compound having a hydroxyl group or a hydrolyzable group. The siloxane-based resin monomer (sometimes referred to as an organosilicon compound) is represented by the following general formulas (A) to (D).

[0034]

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In the formula, R _{1 to} R ₆ represent an organic group in which carbon is directly bonded to silicon in the formula, and Y _{1 to} Y ₄ represent a hydroxyl group or a hydrolyzable group.

When Y ₁ to Y ₄ in the above formula are a hydrolyzable group, the hydrolyzable group is a methoxy group, an ethoxy group,
Examples include 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 and β- (3,4-epoxycyclohexyl) ethyl;
(Meth) acryloyl groups such as acryloxypropyl and γ-methacryloxypropyl, hydrous groups such as γ-hydroxypropyl and 2,3-dihydroxypropyloxypropyl, vinyl groups such as vinyl and propenyl, and γ-mercaptopropyl An amino-containing group such as mercapto group, γ-aminopropyl, N-β (aminoethyl) -γ-aminopropyl, γ-chloropropyl, 1,1,1-trifluoropropyl, nonafluorohexyl, perfluorooctyl Examples include a halogen-containing group such as ethyl, and other nitro and cyano-substituted alkyl groups. Also, R ₁
-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 in which a catalyst or a cross-linking 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.

In the present invention, the compound having a charge transporting property (sometimes referred to as a charge transporting compound) is incorporated into a siloxane-based resin to form a structural unit when a resin layer is finally formed. Therefore, this siloxane-based resin is a siloxane-based resin in which a chemical structure (= structural unit having charge transport performance) having a characteristic of drift mobility of electrons or holes is incorporated as a partial structure in the siloxane-based resin.

Specifically, the compound having a charge transporting property of the present invention generally means a charge transporting substance (also referred to as CTM).
Is a compound having a structure used as a compound having a functional group to be incorporated as a partial structure in a 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.

Hereinafter, a charge transporting compound capable of forming a structural unit having a charge transporting property by reacting with an organosilicon compound in a siloxane-based resin will be described.

For example, examples of the hole transport type CTM include oxazole, oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidin, styryl, hydrazone, benzidine and the like.
Pyrazoline, stilbene compound, amine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine, aminostilbene, poly-N-vinylcarbazole, poly-1-
There are vinylpyrene, poly-9-vinylanthracene, and the like, which are compounds that can contain these chemical structures as a partial structure of the siloxane-based resin.

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

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

In the general formula (1)-(Si-YX) _n, preferably, Y in the general formula (1) is a group in which an adjacent bonding atom (a silicon atom Si and a part of the structural unit having the charge transporting performance) A divalent or higher valent atom or group excluding the constituent carbon atom C).

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 resin capable of bonding or has a structure (group) connected to another atom or molecular group.

In the above general formula, Y is an atom,
In particular, oxygen atom (O), sulfur atom (S), nitrogen atom (N)
Is preferred.

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 resin has two or more reactive functional groups. In this case, the resin may be joined as a divalent or higher crosslink group in the curable resin, or may be joined simply as a pendant group.

The above-mentioned general formula (1)-(Si-Y-
X) _n means that atoms and atomic groups are arranged as described above, and the Si, Y, and X bonds are not exactly represented by "-". Actually, each of them may have more bonds and may be bonded to an atomic group such as an atom or a functional group which is not described, but the characteristic portion is shown.

The O, S, and N atoms are formed by the reaction of a hydroxyl group, a mercapto group, an amine group, and an organosilicon compound having a hydroxyl group or a hydrolyzable group, each of which is introduced into a compound having charge transport performance. Is a linking group that incorporates, as a partial structure, a structural unit having charge transport performance into a siloxane-based resin.

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
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 may be used as long as it has charge transport performance and has a hydroxyl group.

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

Among them, the following are typical ones. For example, the triarylamine-based compound has a triarylamine structure such as triphenylamine as a structural unit (X) having a charge transporting property, and has an alkylene extended through a carbon atom constituting X or extended from X. And a compound having a hydroxyl group via an arylene group is preferably used. 1. Triarylamine compounds

[0058]

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[0059]

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[0060]

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[0061]

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[0062] 2. Hydrazine compounds

[0063]

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[0064]

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[0065]

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3. Stilbene compounds

[0067]

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[0068]

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4. Benzidine compound

[0070]

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5. Butadiene compound

[0072]

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6. Other compounds

[0074]

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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 combined with a curable organosilicon compound,
Examples of the charge transporting compound represented by the following general formula that can form a resin layer include, but are not limited to, the following structure, having charge transporting performance, and having a mercapto group. Any compound may be used.

X- (R ₈ -SH) _m wherein X is a structural unit having charge transport performance, R _{8 is a} single bond, a substituted or unsubstituted alkylene or arylene group, and m is an integer of 1 to 5 .

Among them, the following are typical ones.

[0078]

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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 charge transporting performance and having an amino group may be used.

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

Among them, the following are typical ones.

[0082]

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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 remaining as a branch, a group causing a crosslinking reaction, or a compound residue containing a charge transport substance.

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.

[0085] 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 or an arylene group; a represents an integer of 1 to 3, and n represents an integer.

In order to incorporate the structural unit having the charge transporting property into a siloxane-based resin, the most preferable is
It is a charge transporting compound having up to three hydroxyl groups.

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

When 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 mass of (F) based on 100 parts by mass of the total of + (C) + (D) components. (A) +
When the amount of the component (B) is small, the siloxane-based resin layer has too low a crosslinking density and insufficient hardness. On the other hand, if the amount of the component (A) + (B) is too large, the crosslinking density is too high and the hardness is sufficient, but the resin layer becomes brittle. Excess or deficiency of the colloidal silica 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 transport performance of the siloxane-based resin layer is small, resulting in a decrease in sensitivity and an increase in residual charge.
When the amount of the component (F) is large, the film strength of the siloxane-based resin layer tends to be weak.

The siloxane-based resin of the present invention having a structural unit having charge transporting ability and having a crosslinked structure 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, which is one of the preferred embodiments of the present invention.

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). 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.

Next, an antioxidant is preferably added to the resin layer of the present invention. Antioxidants are typically used to prevent or suppress the action of oxygen under the conditions of light, heat, discharge, etc., on auto-oxidizing substances present in or on the electrophotographic photoreceptor. It is a substance having the property of Specifically, the following compounds may be mentioned.

(1) Radical chain inhibitor • Phenol antioxidant Hindered phenol • Amine antioxidant Hindered amine diallyldiamine diallylamine • Hydroquinone antioxidant (2) Peroxide decomposer • Sulfur Antioxidants Thioethers Phosphoric acid antioxidants Phosphite esters Hindered phenols are compounds having a bulky organic group at the ortho position of the phenolic OH group or the alkoxylated group of the phenolic OH, A hindered amine is a compound having a bulky organic group near an N atom. As the bulky organic group, there is a branched alkyl group, and for example, a t-butyl group is preferable.

Among the above antioxidants, the radical chain inhibitor (1) is preferable, and a hindered phenol or hindered amine antioxidant is particularly preferable.

Further, two or more kinds may be used in combination. For example, a combination of the hindered phenol antioxidant (1) and the thioether antioxidant (2) may be used.

In the present invention, those having the above hindered amine structure in the molecule are more preferable for improving image quality such as prevention of image blurring and black spots. In another embodiment, the hindered phenol structural unit and the hindered amine structure Those containing units in the molecule are likewise preferred.

The hindered phenol-based and hindered amine-based antioxidants preferably used in the present invention include compounds having the following general formulas [A] and [B] as structural units.

[0099]

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Where R₁, R_Two, R_ThreeAnd R_FourAre hydrogen sources
And Z represents a nitrogen-containing alicyclic group.
Represents an atomic group necessary for constituting Also R₁, R_TwoOrganization
And R _Three, R_FourIn each of the sets, one of them is in Z
It may be incorporated to provide a double bond.

Further, R ₅ is a branched alkyl group, R ₆ and R ₇
And R ₈ each represent a hydrogen atom, a hydroxy group, an alkyl group or an aryl group, and R ₆ , R ₇ and R ₈ may be mutually connected to form a ring.

R ₉ represents a hydrogen atom, an alkyl group or an alkylidene group. R ₁ , R ₂ , R ₃ and R ₄ are preferably an alkyl group having 1 to 40 carbon atoms, and the alkyl group may have a substituent. As the substituent, for example, an aryl group, Arbitrary ones such as an alkoxy group, a carboxylic acid group, an amide group, and a halogen atom are exemplified.

Z is an atomic group necessary for constituting a nitrogen-containing alicyclic ring, and is preferably an atomic group constituting a 5- or 6-membered ring.

Preferred ring structures include piperidine, piperazine, morpholine, pyrrolidine, imidazolidine,
Oxazolidine, thiazolidine, selenazolidine, pyrroline, imidazoline, isoindoline, tetrahydroisoquinoline, tetrahydropyridine, dihydropyridine, dihydroisoquinoline, oxazoline, thiazoline, selenazoline, pyrrole and the like, and particularly preferably piperidine, piperazine, morpholine and pyrrolidine. Each ring.

R ₅ and R ₆ are tert-carbon having 3 to 40 carbon atoms.
-Or a sec-alkyl group is preferred.

R ₇ and R ₈ are preferably alkyl groups having 1 to 40 carbon atoms, and aryl groups include phenyl, naphthyl and pyridyl groups. Also R
_{When 6} and R ₇ are rings, a chroman ring is preferred.

The alkyl group and the alkylidene group represented by R ₉ preferably have 1 to 40 carbon atoms, and particularly preferably have 1 to 18 carbon atoms.

The content of the hindered phenol or hindered amine antioxidant in the resin is 0.01 to 25.
% By mass is preferred. When the content is more than 25% by mass, the charge transporting performance in the resin layer is reduced, the residual potential is likely to be increased, and the film strength may be reduced.
More preferably, the content is 0.1 to 10% by mass.

The antioxidant may be contained 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 25% by mass with respect to each layer.

Examples of the commercially available antioxidants include the following compounds, for example, “Irganox 107
6, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076, 3,5-di-t-butyl- 4
-Hydroxybiphenyl ", hindered phenols," Sanol LS2626 "," Sanol LS76 "
5, "Sanol LS770", "Sanol LS74"
4, "Tinuvin 144", "Tinuvin 622LD",
"Mark LA57", "Mark LA67", "Mark L
A62 "," Mark LA68 "," Mark LA63 ",
The hindered amine type is mentioned above.

Further, the configuration of the present invention will be described. The layer constitution of the electrophotographic photoreceptor of the present invention is not particularly limited, and a photosensitive layer such as a charge generation layer, a charge transport layer, or a charge generation / charge transport layer and a resin layer of the present invention provided thereon. It has already been mentioned that a configuration is preferred.

The charge generation substance (CGM) contained in the photosensitive layer of the present invention is used alone or together with a suitable binder resin to form a layer. Examples of typical charge generating substances include pyrylium dyes, thiopyrylium dyes, phthalocyanine pigments, anthantrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments, trisazo pigments, and disazo pigments. Pigments, indigo pigments, quinacridone pigments, cyanine pigments and the like.

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 photosensitive layer having a single-layer structure and the charge generation layer (CGL) and the charge transport layer (CTL) in the case of a multilayer 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 resins, urethane resins, silicone resins, epoxy resins, silicon-alkyd resins, phenol resins, polysilane resins, polyvinyl carbazole, and the like can be used.

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

The charge transport layer is formed by dissolving the charge transport material and the binder resin in an appropriate solvent, and applying and drying the solution. The mixing ratio of the charge transport material and the binder resin is preferably from 3: 1 to 1: 3 by mass ratio.

The thickness of the charge transport layer is preferably 5 to 50 μm, particularly preferably 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.
m or less, and preferably smaller than the total thickness of the charge transport layer provided below the charge transport layer.

The solvent or dispersion medium used in the present invention includes n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methylethylketone, methylisopropylketone, cyclohexanone, Benzene, toluene,
Xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2
-Trichloroethane, 1,1,1-trichloroethane,
Examples include 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.

Next, the conductive support of the electrophotographic photoreceptor of the present invention includes: 1) a metal plate such as an aluminum plate or a stainless steel plate; 2) a support such as paper or a plastic film;
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 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.

Next, the coating method for producing the electrophotographic photosensitive member of the present invention includes dip coating, spray coating,
A coating method such as a circular amount control type coating is used, but the coating process on the upper layer side of the photosensitive layer is performed by spray coating or a circular amount control type in order to minimize dissolution of the lower layer film and to achieve a uniform coating process. A typical example is a circular slide hopper type. It is preferable to use a coating method such as coating. The spray coating is described in detail in, for example, JP-A-3-90250 and JP-A-3-269238, and the circular amount control type coating is described in, for example, JP-A-58-18.
No. 9061 discloses this in detail.

In the present invention, an intermediate layer having a barrier function may be provided 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 hardening intermediate layer using a metal alkoxide, an organic metal chelate, or a silane coupling agent as described 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.

The shape of the support may be a drum shape, a sheet shape, or a belt shape, and may be any shape suitable for the electrophotographic apparatus to be applied.

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. 1 is a sectional view of an image forming apparatus according to one embodiment of the present invention. In the present invention, reference numeral 4 denotes a photosensitive drum, which is formed by forming an organic photosensitive layer on the outer peripheral surface of a drum base made of aluminum and a resin layer of the present invention on the surface thereof, and rotating at a predetermined speed in the direction of the arrow. In the embodiment, the photosensitive drum 4 has an outer diameter of 60 mm.

In FIG. 1, exposure light is emitted from the semiconductor laser light source 1 based on information read by a document reading device (not shown). This is irradiated onto the surface of the photoreceptor via the polygon mirror 2 and the fθ lens 3 for correcting image distortion to form an electrostatic latent image. The photoreceptor is uniformly charged in advance by the charger 5 and starts rotating clockwise in synchronization with the timing of image exposure.

The electrostatic latent image on the surface of the photoreceptor is developed by the developing device 6 and the formed toner image is transferred to the image support (recording material) 8 which has been conveyed at the proper timing by the operation of the transfer device 7. Is done. Further, the photosensitive drum 4 and the recording material 8
Are separated by a separator (separation pole) 9, and the toner image is transferred and carried on the recording material 8, guided to a fixing device 10 and fixed.

The untransferred toner remaining on the photoreceptor surface is
It is cleaned by a cleaning device 11 of a cleaning blade type, and the remaining charge is removed by a pre-charging exposure (PCL) 12, and is uniformly charged again by the charger 5 for the next image formation.

The recording material is typically plain paper.
There is no particular limitation as long as an unfixed image after development can be transferred, and a PET base for OHP and the like are of course included.

The cleaning blade 13 has a thickness of 1 mm.
A rubber-like elastic body of about 30 mm is used, and urethane rubber is most often used as a material. Since this is used while being pressed against the photoconductor, heat is easily transmitted, and it is desirable to keep the photoconductor away from the photoconductor when the image forming operation is not performed.

In recent years, in the field of electrophotography and the like in which an electrostatic latent image is formed on a photoreceptor and this latent image is developed to obtain a visible image, it is easy to improve image quality, convert, edit, etc., and obtain a high quality image. Research and development of an image forming method employing a digital method capable of forming are being actively conducted.

As a scanning optical system which modulates light by a digital image signal from a computer or a copy original employed in the image forming method and apparatus, an acousto-optic modulator is interposed in a laser optical system, and the light is modulated by the acousto-optic modulator. There is a device that modulates and a device that directly modulates laser intensity using a semiconductor laser. A spot image is formed on a uniformly charged photoconductor from these scanning optical systems to form a dot-shaped image.

The beam emitted from the above-described scanning optical system has a round or elliptical luminance distribution approximating a normal distribution with a skirt spreading left and right. One or both of the scanning direction and the sub-scanning direction has a very small circular or elliptical shape of 20 to 100 μm.

The image forming apparatus includes the photosensitive drum 4
And a process cartridge including at least one of the charger 5, the developing device 6, the cleaning device 11, the transfer device 7, and the like.

FIG. 2 is a sectional view (a) and a perspective view (b) of an example of a process cartridge to be mounted on the image forming apparatus of the present invention. This process cartridge 15
Is loaded into the apparatus by a guide rail or the like from the side of the image forming apparatus, that is, a direction perpendicular to the direction in which the recording material is conveyed.

Although the above-described electrophotographic image forming apparatus is an apparatus for forming a monochrome image, it is needless to say that the present invention can be similarly applied to a color image forming apparatus.

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, image exposure is performed for printing received data.

[0140]

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

Example 1 A photoreceptor was prepared as follows. <Undercoat layer> Titanium chelate compound (TC-750: manufactured by Matsumoto Pharmaceutical Co., Ltd.) 30 g Silane coupling agent (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) 17 g 2-propanol 150 ml On this undercoat layer, apply the following photosensitive layer coating solution. A dispersion was prepared and applied so as to have a film thickness of 0.5 μm. <Charge Generating Layer> Y-type titanyl phthalocyanine 60 g Silicon-modified butyral resin (X-40-1211: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2000 ml was mixed and dispersed using a sand mill for 10 hours, and the charge generating layer coating solution was dispersed. Prepared. 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 Layer> Charge transport material (D1) 200 g Polycarbonate (TS2050: manufactured by Teijin Chemicals Ltd.) 300 g Dichloromethane 2000 ml was mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a thickness of 20 μm.

[0142]

Embedded image

<Resin Layer> Methyltrimethoxysilane (solid content after curing is 49%) 182 g Compound (T-1) 40 g Antioxidant (Sanol LS2626: manufactured by Sankyo) 1 g 2-propanol 255 g 2% acetic acid 106 g dibutyltin acetate 1 g of the mixture, colloidal silica (15% methanol solution, silicon dioxide average particle diameter 70 nm, pH =
2.5: Nissan Chemical Co., Ltd.) to add 315 g to the siloxane-based resin so that the mass content of silicon dioxide in the colloidal silica becomes 53% and the pH of the coating solution becomes 4.5. It was prepared to prepare a coating solution for the resin layer. A 2.5 μm-thick resin layer is formed on the charge transport layer by a circular-amount-control type coating apparatus, and the coating liquid is cured by heating at 110 ° C. for 1 hour to form a siloxane-based resin layer having a crosslinked structure. did. This is the photoconductor of the first embodiment.

Example 2 A photoconductor was prepared by the same way as that of Example 1 except that the dispersion medium of colloidal silica in the resin layer was changed to methyl ethyl ketone.

Example 3 A photoconductor was prepared by the same way as that of Example 1 except that the dispersion medium of colloidal silica in the resin layer was changed to isopropanol.

Example 4 A photoconductor was prepared by the same way as that of Example 1 except that the pH was adjusted to 1.8 by adding an appropriate amount of hydrochloric acid to the dispersion medium of colloidal silica.

Example 5 A photoconductor was prepared by the same way as that of Example 1 except that the pH was adjusted to 8.5 by adding an appropriate amount of sodium hydroxide to the dispersion medium of colloidal silica.

Example 6 A photoconductor was prepared by the same way as that of Example 1 except that the pH was adjusted to 8 except for acetic acid.

Example 7 In the same manner as in Example 1, a structure up to the charge transport layer was produced. <Resin Layer> Methyltrimethoxysilane (solid content after curing is 49%) 150 g Phenyltrimethoxysilane (solid content is 65% after curing) 30 g Compound (T-1) 75 g Antioxidant (Irganox1010: manufactured by Ciba Geigy) 1 g 2- 225 g of propanol, 106 g of 2% acetic acid, and 4 g of trisacetylacetonatoaluminum were mixed. Colloidal silica (30% methanol solution, silicon dioxide average particle diameter of 10 nm, pH =
2.5: manufactured by Nissan Chemical Industries, Ltd.), and the mass content of colloidal silica was 30
% And the pH of the coating solution was adjusted to 4.5 to prepare a coating solution for the resin layer.

A siloxane-based resin having a crosslinked structure was formed by forming a resin layer having a thickness of 2.5 μm on the above-mentioned charge transporting layer by a circular amount-regulating type coating device and heating and curing at 110 ° C. for 1 hour. A layer was formed, and a photoreceptor of Example 7 was produced.

Example 8 A photoconductor was prepared by the same way as that of Example 1 except that the antioxidant in the resin layer was omitted.

Example 9 In Example 1, 4- [2- (triethoxysilyl) ethyl] triphenylamine was used instead of the compound (T-1) in the resin layer (the silicon compound of Synthesis Example 1 in JP-A-10-251277). A photoreceptor was prepared in exactly the same manner except that the photoreceptor was replaced with (atom-containing compound).

Example 10 The procedure up to the formation of the charge transport layer was carried out in the same manner as in Example 1. <Resin Layer> Methyltrimethoxysilane (solid content 49% after curing) 100 g Dimethyldimethoxysilane (solid content 62% after curing) 53 g Compound (T-1) 45 g Antioxidant (Sanol LS2626: manufactured by Sankyo) 1 g 2- A mixture of 225 g of propanol, 30 g of 3% acetic acid, and 3 g of trisacetylacetonatoaluminum was mixed with colloidal silica (30% methanol solution, silicon dioxide average particle diameter of 10 nm, pH =
2.5: Nissan Chemical Co., Ltd.) 81 g was added, and the mass content of colloidal silica was 30% based on the siloxane-based resin.
And the pH of the coating solution is adjusted to 4.5.
A coating solution for a resin layer was prepared. This coating solution was coated on the charge transport layer by a circular amount-regulating coating device to a thickness of 2.5 μm.
Was formed, followed by heat curing at 110 ° C. for 1 hour to form a siloxane-based resin layer having a crosslinked structure. Thus, a photoreceptor of Example 10 was produced.

Example 11 The procedure up to the formation of the charge transport layer was carried out in the same manner as in Example 1. <Resin Layer> Methyltrimethoxysilane (solid content after curing is 49%) 100 g γ-glycidoxypropyltrimethoxysilane (69% solid content after curing) 30 g Compound (T-1) 75 g Antioxidant (Sanol LS2626: Sankyo) 1 g methyl ethyl ketone 225 g 3% acetic acid 30 g trisacetylacetonatoaluminum 3 g was mixed, and colloidal silica (30% methanol solution, silicon dioxide average particle diameter 10 nm, pH =
2.5: manufactured by Nissan Chemical Co., Ltd.) 79 g was added, and the mass content of colloidal silica was 30% based on the siloxane resin.
The coating solution for the resin layer was prepared by adjusting the pH of the coating solution to 4.5. A 2.5 μm-thick resin layer is formed on the charge transport layer by using a circular amount-regulating coating device on the charge transporting layer. Example 1
In this manner, No. 1 photoconductor was produced.

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1, except that colloidal silica was omitted.

Comparative Example 2 A photoconductor was prepared by the same way as that of Example 1 except that the dispersion medium of colloidal silica was changed to dimethylacetamide.

Comparative Example 3 A photoconductor was prepared in the same manner as in Comparative Example 1, except that 20 g of silicone resin fine particles (Tospearl 105 manufactured by Toshiba Silicone Co., Ltd.) were dispersed in the coating solution for the resin layer.

<Evaluation> Evaluation of Coatability When the prepared coating liquid was applied onto the charge transport layer using a circular amount-regulating coating device, the haze of the photoreceptor was visually evaluated.

After the coating solution was left at room temperature for one week, it was again coated using the same coating apparatus, and the fogging of the photoreceptor was visually evaluated.

[0160]

[0161] 2. Actual photo evaluation The above photoreceptor was evaluated using Konica's digital copier koni.
ca7050 (having laser exposure, reversal development, nail separation, blade cleaning process) was modified and mounted on an evaluator that optimized the exposure amount, and the initial charging potential was -750.
V in a high temperature and high humidity environment (38 ° C., 80% RH)
After continuous copying of 10,000 sheets, a low temperature and low humidity environment (10 ° C, 20%
(RH), 30,000 continuous copy actual copying evaluation was performed.

In the image evaluation, a character image having a blackening ratio of 7%
And a halftone, solid white image and solid black image were evaluated every 1000 sheets.

The image density was measured as the absolute reflection density of a solid black image using RD-918 manufactured by Macbeth. Fog was visually confirmed using a solid white image. In addition, the presence or absence of image blur and turning of the cleaning blade was visually evaluated.

Image density ◎: Good at 1.2 or higher, ：: 0.8 to less than 1.2, no practical problem, ×: Less than 0.8, practical problem.

[0165]

Image blur ◎: Good without blurred image, レ ベ ル: Practically no problem, ×: Character flow and bleeding occurred, and practically problematic.

Blade turning: No blade turning out of 60,000 sheets, ○: No blade turning out of 60,000 sheets, but abnormal noise when photoconductor is installed (no problem in practical use), ×: 60,000 sheets One or more turning of the middle blade occurred.

[0168]

[Table 1]

As is clear from Table 1, the resin layer of the present invention prepared by using an alcohol-based solvent and a ketone-based solvent as a dispersion medium of colloidal silica and maintaining the hydrogen ion concentration of the colloidal silica and the coating solution in an appropriate range. The electrophotographic photoreceptor has good coatability, no turning of the cleaning blade, and good image quality after continuous copying.

On the other hand, those outside the scope of the present invention (comparative example) suffer from fogging and precipitation at the time of coating, resulting in poor cleaning due to blade turning and image blur due to continuous copying.

From the above results, the effect of the present invention is remarkably shown.

[0172]

According to the present invention, the surface hardness is high, the abrasion resistance and the scratch resistance are high, the electrophotographic characteristics during repeated use are stable, the cleaning blade torque can be reduced, and the applicability during photoreceptor production is good. In addition, it is possible to provide an electrophotographic photosensitive member manufacturing method and an electrophotographic photosensitive member. Further, an image forming method, an image forming apparatus, and a process cartridge using the photosensitive member can be provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an image forming apparatus according to one embodiment of the present invention.

FIG. 2 is a sectional view and a perspective view of a process cartridge to which the present invention is applied.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 semiconductor laser light source 2 polygon mirror 3 fθ lens 4 photoreceptor drum 5 charger 6 developing device 7 transfer device 8 image support (recording material) 9 separator (separation pole) 10 fixing device 11 cleaning device 12 pre-charge exposure (PCL) ) 13 Cleaning blade 15 Process cartridge

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/04 C08L 83/04 F-term (Reference) 2H068 AA03 AA04 AA08 BB32 BB33 BB49 BB57 CA06 EA12 EA14 EA43 FA27 FC01 FC05 FC08 FC15 4J002 BC012 BJ002 CP031 CP051 CP081 CP091 CP101 CP141 CP161 DJ017 EA046 EE056 EF116 EL076 EL136 EN006 EN066 ER006 ER016 ES006 ET006 EU036 EU106 EU116 EU136 EU166 EU216 EU226 EV326 FD017 CA12HACA112 GP03 BA0201 HA02 HA03 HA06 HB02 LA03 LB01 LB20

Claims (12)

[Claims] 1. A method for producing an electrophotographic photoreceptor having at least a photosensitive layer and a resin layer on a conductive support, wherein the resin layer contains a compound having a charge transporting property and is a siloxane-based resin or a siloxane-based resin. An electrophotographic photoreceptor, characterized in that colloidal silica previously dispersed in a dispersion medium selected from water or an alcohol-based solvent or a ketone-based solvent is added to a coating solution containing a monomer, and formed by heating after application. Production method. 2. The method according to claim 1, wherein a hydrogen ion concentration (pH) of the coating solution for the resin layer is 3 to 7. 3. The method according to claim 1, wherein a hydrogen ion concentration of the colloidal silica is in a range of 2 to 6. 4. The method according to claim 1, wherein the colloidal silica dispersion medium contains at least one linear or branched alcohol having 4 or less carbon atoms. Method. 5. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the coating liquid satisfies the formula (1). Formula (1) 0% <t ≦ 50% where t = B / A × 100 A: Mass after curing of siloxane-based resin monomer B: Mass of silicon dioxide in coating liquid 6. The method according to claim 1, wherein the average particle diameter r (nm) of the silicon dioxide contained in the colloidal silica is in the range of 5 ≦ r ≦ 40. A method for producing an electrophotographic photoreceptor. 7. The method according to claim 1, wherein the coating solution for the resin layer further contains an antioxidant. 8. An electrophotographic photosensitive member manufactured by the method of manufacturing an electrophotographic photosensitive member according to claim 1. 9. The electrophotographic photoconductor according to claim 8, wherein the resin layer is a surface layer of the photoconductor. 10. An image forming method having at least steps of charging, image exposure, development, and cleaning on an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member according to claim 8 or 9 is used as the electrophotographic photosensitive member. An image forming method comprising: 11. An image forming apparatus having an electrophotographic photosensitive member and at least a charger, an image exposing device, a developing device, and a cleaning device, wherein the electrophotographic photosensitive member according to claim 8 or 9 is used as the electrophotographic photosensitive member. An image forming apparatus comprising: 12. A process cartridge used in an image forming apparatus having an electrophotographic photosensitive member and at least a charger, an image exposing unit, a developing unit, and a cleaning unit.
Or the electrophotographic photoreceptor according to 9 and any one of a charger, an image exposure device, a developing device, and a cleaning device are integrally combined, and are designed to be freely inserted into and removed from the image forming apparatus. Characteristic process cartridge.