JP2001100441A - Electrophotographic photoreceptor and method and device for forming electrophotographic image and process cartridge using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor high in surface hardness, wear resistance and flawlessness, stable in electrophotographic characteristic even under the conditions of high temperature and high humidity in the case of being repeatedly used and giving good images repeatedly and to provide a method and a device for forming an electrophotographic image and a process cartridge using the photoreceptor. SOLUTION: This electrophotographic photoreceptor has at least a photosensitive layer and a resin layer on an electrically conductive support. The resin layer comprises a siloxane-based resin containing a structural unit having charge transferring ability and containing a cross-linked structure and the photosensitive layer comprises polycarbonate having a Si atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member (hereinafter, also simply referred to as a photosensitive member), an electrophotographic image forming method using the photosensitive member, an electrophotographic image forming apparatus, and a process cartridge. is there.

[0002]

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

In 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, the electrostatic latent image on the photoreceptor is developed and visualized with toner, and then the toner is transferred to paper or the like. Then, the toner remaining on the photoreceptor is removed by a cleaning blade or the like. After receiving the charge erasing exposure, the process proceeds to next image formation.

As described above, since the surface of the electrophotographic photosensitive member is directly applied with an electrical or mechanical external force by a charger, a developing device, a transfer means, a cleaning device, etc., it is required to have durability against them. 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.

[0005] In order to satisfy the various characteristics required as described above, various items have been studied so far.

For example, with regard 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-based resin is used as a surface layer of a photoreceptor.

However, a photoreceptor using a bisphenol Z type polycarbonate binder still lacks abrasion resistance properties 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 has poor adhesion to the binder resin used in the photosensitive layer of the organic electrophotographic photoreceptor and is used as the surface layer. However, there is a problem that peeling from the photosensitive layer occurs due to stress caused by an external force caused by long-term repeated use. In particular, when the photoconductor is used in an environment where a separation claw is used to ensure separation from paper, external force is applied to the abutment position of the claw more than the normal part, and film peeling occurs in particular. This causes black streak failure at the contact position.

[0008] To solve this problem, many attempts have been made to improve the adhesiveness of a siloxane-based resin to an organic resin, particularly to a polycarbonate used for a photosensitive layer of an electrophotographic photosensitive member. For example, measures have been taken to improve adhesion by providing an adhesive layer between the photosensitive layer and the siloxane-based resin layer. However, there is a problem in the charge injection property at the interface between the adhesive layer and the photosensitive layer and between the adhesive layer and the siloxane-based resin layer, and there has been a problem that sufficient electrical characteristics cannot be obtained even if the adhesive property is ensured.

An electrophotographic photoreceptor having a siloxane-based resin in its surface layer has a high temperature and high humidity condition (hereinafter also referred to as HH condition).
Below, fogging and image blur tend to occur easily.

[0010]

An object of the present invention is to solve the above-mentioned problems.

That is, the present invention provides an electrophotographic photoreceptor having high surface hardness, high abrasion resistance and high scratch resistance, and stable electrophotographic characteristics even under high temperature and high humidity when repeatedly used, and therefore, a good image can be repeatedly obtained. Is to do. Another object of the present invention is to provide an electrophotographic image forming method, an electrophotographic image forming apparatus, and a process cartridge using the photoconductor.

[0012]

The inventors of the present invention have made intensive efforts to solve the above problems, and as a result, introduced a structural unit having a charge transporting property into a siloxane-based resin layer having a crosslinked structure, and introduced Si into a photosensitive layer. It has been found that by including a polycarbonate containing atoms, the adhesion between the two layers can be improved without impairing the electrical properties.

That is, the Si atom-containing polycarbonate is S
By introducing the i-atom-containing group, the affinity with the siloxane-based resin is improved, and good adhesiveness can be obtained without using an adhesive layer. As a result, they have found that it is possible to realize a high-strength organic photoreceptor (also referred to as OPC) that can simultaneously satisfy the electrical characteristics and the adhesiveness, and has reached the present invention.

[1] In an electrophotographic photosensitive member having at least a photosensitive layer and a resin layer on a conductive support, the resin layer contains a structural unit having charge transporting performance and contains a siloxane-based resin having a crosslinked structure. An electrophotographic photosensitive member, wherein the photosensitive layer contains a polycarbonate having Si atoms.

[2] The electrophotographic photoreceptor according to [1], wherein the siloxane resin having a crosslinked structure is a siloxane resin having a structure represented by the following general formula (1).

General formula (1) (Si · Y) _n · X (where X is a structural unit having charge transport performance, and Y is Si
Represents a divalent or higher valent atom or group bonding X and X. n represents an integer of 1 or more. [3] The electrophotographic photoreceptor according to [1] or [2], wherein the resin layer contains colloidal silica.

[4] The electrophotographic photosensitive member according to [1], [2] or [3], wherein the polycarbonate is a copolymer having a structural unit represented by the following general formula (2).

[0018]

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(Wherein, Y ₁ each independently represents an alkylene group or an alkylidene group having 1 to 6 carbon atoms, R _{1 to} R ₈ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms) , A substituted or unsubstituted aryl group, n represents an integer of 1 to 4 for each substituent, and p and q represent a total of 1 to 200.) [5] The polycarbonate is represented by the following general formula: It is a copolymer having the structural unit of (3) [1].
The electrophotographic photoreceptor according to any one of the above-mentioned [4].

[0020]

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(Wherein X is a linear, branched or cyclic alkylidene group having 1 to 15 carbon atoms, an aryl-substituted alkylidene group, an arylenedialkylidene group, -O-, -S
—, —CO—, —SO—, —SO ₂ —, and Z _{1 to} Z ₄
At least one of Si represented by the following general formula (3 ′)
Others represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group. )

[0022]

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(Wherein, Y ₂ each independently represents 1 to 6 carbon atoms)
Represents an alkylene group or an alkylidene group of R _{9 to} R ₁₅
Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group each having 1 to 10 carbon atoms. r and s represent an integer of 1 to 200 in total. [6] The polycarbonate is a copolymer having a structural unit represented by the following general formula (4): [1]
The electrophotographic photosensitive member according to any one of claims 1 to 5, wherein

[0024]

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Wherein R is independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group, A is a substituted or unsubstituted alkylene group,
Represents a substituted or unsubstituted arylene group;
Represents an integer of 00. [7] The electrophotographic photosensitive member according to any one of [1] to [6], wherein the resin layer further contains an antioxidant.

[8] The electrophotographic photosensitive member according to any one of [1] to [7], wherein the resin layer is a surface layer of the photosensitive member.

[0027]

[9] The electrophotographic image forming method, which comprises at least a step of performing charging, image exposure, development, and cleaning on the electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is described in any one of [1] to [8]. An electrophotographic image forming method, comprising using the electrophotographic photosensitive member of (1).

[10] In an electrophotographic image forming apparatus having an electrophotographic photoreceptor and at least means for charging, image exposure, development and cleaning, the electrophotographic photoreceptor may be provided with [1]
An electrophotographic image forming apparatus using the electrophotographic photoreceptor according to any one of the above items [8] to [8].

[11] The process cartridge according to any one of [1] to [8], wherein the process cartridge used in an electrophotographic image forming apparatus having an electrophotographic photosensitive member and at least means for charging, image exposure, development and cleaning. An electrophotographic photoreceptor,
A process cartridge having at least one of a charging device, an image exposure device, a developing device, and a cleaning device in an integrated manner, and is designed to be freely inserted into and removed from the electrophotographic image forming apparatus.

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 standpoint of the other performance of the photoreceptor, an overcoat layer may be further provided thereon, and this layer contains a siloxane-based resin having a structural unit having charge transport performance and having a crosslinked structure. You can also.

Therefore, the resin layer of the present invention must contain the 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. May be.

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 cross-linked structure and having a structural unit having a charge transporting property can be prepared by a known method, that is, an organosilicon compound having a hydroxyl group or a hydrolyzable group. It is manufactured using The 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 are a hydrolyzable group, the hydrolyzable group includes a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, a butoxy group, a methoxyethoxy group and the like. No. 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-containing γ-acryloxypropyl and γ-methacryloxypropyl, γ-hydroxypropyl, 2,3-dihydroxy A hydroxyl group such as propyloxypropyl, a vinyl group such as vinyl and propenyl, a mercapto group such as γ-mercaptopropyl, an amino group such as γ-aminopropyl and N-β (aminoethyl) -γ-aminopropyl; γ-chloropropyl, 1,1,1-trifluoropropyl, nonafluorohexyl, perfluorooctylethyl And nitro and cyano-substituted alkyl groups. 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 polymer can 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 crosslinking agent is added, etc.). (Included) means a resin that has formed and cured a three-dimensional network structure. That is, it means a siloxane-based resin having a cross-linked structure formed by promoting a siloxane bond by a hydrolysis reaction and subsequent dehydration condensation of an organosilicon compound having a siloxane bond to form a three-dimensional network structure.

The siloxane-based resin may be a resin in which colloidal silica having a hydroxyl group or a hydrolyzable group is contained, 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). (Unit) in a siloxane-based resin as a partial 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 having the property of having electron or hole drift mobility, or a charge transporting compound residue. Another definition is Time- 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 resin in which a charge transporting compound capable of forming a structural unit having a charge transporting property by reaction with an organosilicon compound in a siloxane-based resin is introduced will be described.

For example, examples of the hole transport type CTM include oxazole, oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidine, 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 is a resin containing their chemical structure 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. , 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, There are 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, melitic acid and the like, and a resin containing these chemical structures as a partial structure 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.

[0046]

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(In the formula, X represents a structural unit having charge transporting ability, Y represents an arbitrary divalent or higher linking group, and n is an integer of 1 or more.) Preferably, Y in the aforementioned general formula (1) is used. Is a divalent or higher valent atom or group excluding adjacent bonding atoms (silicon atom Si and carbon atom C constituting a part of the structural unit having the charge transporting performance).

However, when Y is an atom having three or more valences, S in the formula
The bond of Z 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 atoms, ie, the atoms of O, S and N are hydroxyl groups introduced into the compound having the charge transporting performance, respectively.
A linking group formed by the reaction of a mercapto group or an amine group with an organic silicon compound having a hydroxyl group or a hydrolyzable group, and incorporating a structural unit having a charge transporting property into a 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
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 transport compound having a mercapto group is a charge transport 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 having charge transport performance and a mercapto group may be used.

X- (R ₈ -SH) _m wherein X is a structural unit having charge transporting ability, 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.

[0079]

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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 examples.

[0084]

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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.

X-(-Z-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, Z 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.) The raw material for forming the siloxane-based resin: From the general formulas (A) to (D) (hereinafter referred to as (A) to (D)), the composition ratio is an organosilicon compound: (A) + (B) It is preferable to use 0.05 to 1 mol of the component (C) + (D) per 1 mol of the component).

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 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 transport performance of the siloxane resin layer is low, and the sensitivity and the residual charge increase. When the amount of the component (F) is large, the film strength of the siloxane resin layer tends to be weak. 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 obtained 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 hydrolysis reaction and subsequent dehydration condensation may promote a siloxane bond to form a three-dimensional network structure from monomers, ologomers and polymers.

In general, a three-dimensional network structure can be formed by a condensation reaction of a composition having an alkoxysilane or a composition having 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 hydroxide). Ammonium acetate), tin organic acid salts (stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin malate, etc.), octenoic acid, naphthenate of aluminum and zinc, An acetylacetone complex compound is exemplified.

Next, the Si atom-containing polycarbonate in the present invention is a polymer containing a Si atom-containing group in the main chain and / or side chain of the polycarbonate. The Si atom-containing polycarbonate may be a polymer or a copolymer having a structural unit containing a Si atom in a repeating unit or at a terminal.

The present invention also includes a polycarbonate having a substituent capable of forming a chemical bond with a siloxane resin, such as an alkoxysilyl group or a hydrolysis product thereof. Specific examples include a polycarbonate having a trialkoxysilyl group or a hydrolysis product thereof in a repeating unit of bisphenol.

The structural units (structural units containing Si atoms) of the above general formulas (2) and (3) will be specifically described below.

[0097] In the general formula (2), Y ₁ represents an alkylene group or alkylidene group having 1 to 6 carbon atoms, R ₁
To R ₈ represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group such as a substituted or unsubstituted phenyl group or a naphthyl group; n represents an integer of 1 to 4; The sum of q represents an integer of 1 to 200.

Preferred examples of the compound represented by the general formula (2) include the following.

[0099]

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[0100]

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In the general formula (3), X is a single bond,
A linear, branched or cyclic alkylidene group having 1 to 15 carbon atoms, an alkylidene group substituted with an aryl group such as a phenyl group or a naphthyl group, an arylenedialkylene group substituted with an arylene group such as a phenylene group or a naphthylene group. , —O—, —S—, —CO—, —SO—, or —SO ₂ —, wherein at least one of Z _{1 to} Z ₄ is a Si atom-containing group represented by the general formula (3 ′). And the others represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group such as a phenyl group or a naphthyl group.

In the general formula (3 '), Y ₂ represents an alkylene group or an alkylidene group having 1 to 6 carbon atoms;
_{9 to} R ₁₅ represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group such as a substituted or unsubstituted phenyl group or a naphthyl group, wherein the total of r and s is 1 to 200;
Represents an integer.

Preferred examples of the compound represented by formula (3) include the following.

[0104]

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[0105]

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[0106]

Next, an antioxidant is preferably added to the resin layer of the present invention. What is an antioxidant?
A typical example is a substance having a property of preventing or suppressing the action of oxygen under conditions of light, heat, discharge, etc. with respect to an autoxidizable substance present in or on an electrophotographic photoreceptor. is there. 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 ThioethersPhosphoric acid antioxidants Phosphite estersHindered phenols are compounds having a bulky organic group at the ortho position of a phenolic OH group or an alkoxylated group of 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 blur and black spots. In another embodiment, the hindered phenol structural unit and the hindered amine structure are preferred. Those containing units in the molecule are likewise preferred.

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

[0112]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or an alkyl group or an aryl group, and Z represents an atomic group necessary for constituting a nitrogen-containing alicyclic ring. Also, in each set of R ₁ and R ₂ and each set of R ₃ and R ₄ , one of them may be incorporated into Z 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. Aryl groups, alkoxy groups, carboxylic acid groups, amide groups, halogen atoms and the like are optional.

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.

R ₉ represents an alkyl group or an alkylidene group, preferably having 1 to 40 carbon atoms, and particularly preferably having 1 to 18 carbon atoms.

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

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 weight based on each layer.

Examples of the antioxidants that have been commercialized 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.

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, but 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 formed thereon. It has already been mentioned that a painted configuration is preferred.

The charge generation material (CGM) contained in the photosensitive layer of the present invention is used alone or together with a suitable binder resin to form a layer. Typical examples of the charge generating substance include pyrylium dyes, thiopyrylium dyes, phthalocyanine pigments, anthrone-based pigments, dibenzpyrenequinone-based pigments, pyranthrone-based pigments, azo-based pigments, trisazo-based pigments, and disazo-based 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.

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 include 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 1: 5 to 5: 1 by weight.
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 a suitable 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 weight.

The thickness of the charge transport layer is preferably 5 to 50 μm, and more 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 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; 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.

The coating method for producing the electrophotographic photoreceptor 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.

Examples of the material for the intermediate layer include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, and phenol resin polyamides (nylon 6, nylon 66, nylon 610, copolymer 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, as long as it is a shape suitable for the applied electrophotographic apparatus.

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 a color image forming apparatus as an example of an image forming apparatus equipped with the electrophotographic photosensitive member of the present invention. However, the present invention is not limited to color image formation, but can also be applied to monochrome image formation.

In FIG. 1, reference numeral 10 denotes a photosensitive drum (photoreceptor) 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, which applies uniform charging to the peripheral surface of the photosensitive drum 10 by corona discharge. Prior to the charging by the charger 12, in order to eliminate the history of the photoconductor in the previous image formation, exposure by the exposure unit 11 using a light emitting diode or the like may be performed to remove electricity from the peripheral surface of the photoconductor.

After the photosensitive member is uniformly charged, the image exposure unit 13 performs image exposure based on the image signal. The image exposure device 13 in this figure uses a laser diode (not shown) as 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.

Next, the electrostatic latent image is developed by the developing device 14. Developing devices 14 each having a built-in developer composed of toner and carrier such as yellow (Y), magenta (M), cyan (C), black (K), etc., at the periphery of the photosensitive drum 10.
First, development of the first color 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 10 and the developing sleeve 141 to perform the development.

In the color image formation, after the visualization of the first color is completed, the image 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. An image forming process similar to that for the second color is performed for the third color and the fourth color, and a visible image of four colors is formed on the peripheral surface of the photosensitive drum 10.

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.

The recording paper P is fed to the transfer area by the rotation of the paper feed roller 17 at the time when the transfer timing is adjusted.

In the transfer area, a transfer roller (transfer device) 1 is mounted on the peripheral surface of the photosensitive drum 10 in synchronization with the transfer timing.
8, the multicolor image is transferred collectively by sandwiching the fed recording paper P.

Next, the recording paper P is neutralized by a separation brush (separator) 19 which is brought into pressure contact with the transfer roller almost at the same time, is separated by the peripheral surface of the photosensitive drum 10 and is 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 and separated from the peripheral surface of the photosensitive drum 10 after the recording paper P has passed to prepare for the formation of the next toner image.

On the other hand, the photosensitive drum 10 from which the recording paper P has been separated removes and cleans the residual toner by pressing the blade 221 of the cleaning unit 22 and receives the charge removal by the exposure unit 11 and the charge by the charger 12 again. The next image forming process is started. When a color image is formed on the photoconductor by superimposition, the blade 221 moves immediately after the cleaning of the photoconductor surface and retreats from the peripheral surface of the photoconductor drum 10.

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

An electrophotographic image forming apparatus is configured by integrally combining the above-described photoreceptor, a developing unit, a cleaning unit, 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.

The process cartridge generally includes an integral type cartridge and a separate type cartridge described below. The integral type cartridge is configured such that at least one of a charger, an image exposing unit, a developing unit, a transfer or separating unit, and a cleaning unit is integrally formed with a photoconductor, and is detachable from an apparatus main body. Are a charging device, an image exposure device, a developing device, a transfer or separation device, and a cleaning device which are configured separately from the photoreceptor, but have a configuration detachable from the apparatus main body and are incorporated in the apparatus main body. When integrated, it is integrated with the photoconductor. The process cartridge in the present invention includes both types of cartridges.

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 reflected light or transmitted light 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.

[0157]

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

Example 1 A photoreceptor was produced as follows.

The following undercoat layer coating solution was applied onto a conductive support drum made of aluminum.

<Coating solution for 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 The solution was dispersed and prepared to a film thickness of 0.
It was applied to a thickness of 5 μm.

<Charge Generating Layer Coating Solution> 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. A generating layer coating solution was prepared.

This coating solution was applied on the undercoat layer by a dip coating method to form a charge generation layer.

<Coating Solution for Charge Transport Layer> 200 g of the charge transport material (D1), 300 g of polycarbonate (B-1), and 2,000 ml of dichloromethane were mixed and dissolved to prepare a coating solution for the charge transport layer.

[0164]

Embedded image

[0165]

Embedded image

[0166]

Embedded image

This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a thickness of 20 μm.

<Resin Layer Coating Solution> Methyltrimethoxysilane 182 g Compound (T-1) 40 g Antioxidant (Sanol LS2626: manufactured by Sankyo Pharmaceutical Co., Ltd.) 1.0 g 2-propanol 225 g 2% acetic acid 106 g Colloidal silica (30% methanol Solution) 106 g of dibutyltin acetate 1.0 g were mixed to prepare a coating solution for a resin layer.

Using this coating solution, a resin layer having a thickness of 2.5 μm was formed on the above-mentioned charge transporting layer by a circular amount controlling type coating device, and was heated and cured at 110 ° C. for 1 hour to obtain a siloxane having a crosslinked structure. A photosensitive resin of Example 1 was manufactured by forming a base resin layer.

Example 2 In Example 1, the polycarbonate (B-
A photoconductor was prepared in the same manner as in Example 1, except that 1) was replaced with polycarbonate (B-2).

Example 3 In Example 1, the polycarbonate (B-
A photoconductor was prepared by the same way as that of Example 1 except that 1) was replaced by polycarbonate (B-3).

Example 4 A photoconductor was prepared by the same way as that of Example 1 except that colloidal silica in the resin layer was omitted.

Example 5 A photoconductor was prepared by the same way as that of Example 1 except that the antioxidant in the resin layer was omitted.

Example 6 The procedure up to the formation of the charge transport layer was carried out in the same manner as in Example 1.

<Resin Layer Coating Solution> Methyltrimethoxysilane 150 g Phenyltrimethoxysilane 30 g Compound (T-1) 75 g Antioxidant (Irganox 1010: manufactured by Ciba-Geigy) 1.0 g 2-propanol 225 g 2% acetic acid 106 g colloidal silica ( (30% methanol solution) 106 g Trisacetylacetonatoaluminum 4.0 g was mixed to prepare a coating solution for a resin layer.

With this coating solution, a resin layer having a thickness of 2.5 μm was formed on the charge transporting layer by a circular amount control type coating apparatus. Heat curing was performed at 110 ° C. for 1 hour to form a siloxane-based resin layer having a crosslinked structure, whereby a photoconductor of Example 6 was produced.

Example 7 A photoconductor was prepared by the same way as that of Example 1 except that the compound (S-1) was used instead of the compound (T-1) of the resin layer.

Example 8 In Example 1, 4- [2- (triethoxysilyl) ethyl] triphenylamine was used in place of compound (T-1) in the resin layer (Japanese Patent Application Laid-Open No. 10-251277, Synthesis Example 1). A photoreceptor was prepared in exactly the same manner except that the photoreceptor was replaced with (atom-containing compound).

Example 9 The procedure up to the formation of the charge transport layer was performed in the same manner as in Example 1.

<Resin Layer Coating Solution> Methyltrimethoxysilane 100 g Dimethoxydimethylsilane 53 g Compound (T-1) 45 g Antioxidant (Sanol LS2626: manufactured by Sankyo Pharmaceutical Co., Ltd.) 1.0 g 2-propanol 225 g 3% acetic acid 30 g colloidal silica (30% methanol solution) 80 g 3.0 g of trisacetylacetonatoaluminum was mixed to prepare a coating solution for a resin layer.

Using this coating solution, a resin layer having a thickness of 2.5 μm was formed on the charge transporting layer by a circular amount-regulating coating apparatus. Heat curing was performed at 110 ° C. for 1 hour to form a siloxane-based resin layer having a crosslinked structure, whereby a photoreceptor of Example 9 was produced.

Example 10 The procedure up to Example 1 was repeated to fabricate a charge transport layer.

<Resin Layer Coating Solution> Methyltrimethoxysilane 100 g γ-glycidoxypropyltrimethoxysilane 30 g γ-methacryloxypropyltrimethoxysilane 20 g Compound (T-1) 65 g Antioxidant (Sanol LS2626: Sankyo Pharmaceutical Co., Ltd.) 1.5 g Methyl ethyl ketone 225 g 3% acetic acid 30 g Colloidal silica (30% methanol solution) 80 g Trisacetylacetonatoaluminum 3 g was mixed to prepare a coating solution for a resin layer.

Using this coating solution, a resin layer having a thickness of 5 μm was formed on the charge transporting layer by a circular amount control type coating apparatus. Heat curing was performed at 120 ° C. for 1 hour to form a siloxane-based resin layer having a crosslinked structure, whereby a photoconductor of Example 10 was produced.

Comparative Example 1 In Example 1, the polycarbonate (B-
A photoconductor was prepared in the same manner as in Example 1, except that 1) was replaced with bisphenol Z-type polycarbonate (Iupilon Z300: manufactured by Mitsubishi Gas Chemical Company).

Comparative Example 2 In Comparative Example 1, silicone resin fine particles (Tospearl 105: manufactured by Toshiba Silicone Co., Ltd.) were used as the coating solution for the charge transport layer.
A photoconductor was prepared by the same way as that of Comparative Example 1 except that g was dispersed.

Comparative Example 3 Comparative Example 1 was the same as Comparative Example 1 except that a primer layer (PC-7A: manufactured by Shin-Etsu Chemical Co., Ltd.) was provided between the charge transport layer and the resin layer.
A photoreceptor was produced in the same manner as described above.

[Characteristics Evaluation] Potential evaluation / Evaluation of actual photo prints
The ica 7050 (having a laser exposure, reversal development, nail separation, blade cleaning process) was modified and mounted on an evaluator having an appropriate exposure amount. The initial charging potential was set to -750 V, and the temperature and humidity were high (HH: 38 ° C, 8
0% RH), pause for 1 hour after continuous copying of 30,000 sheets, and then in a low temperature and low humidity environment (LL: 10 ° C., 20% RH).
An evaluation of 10,000 continuous copies was made.

The evaluation was carried out using A4 using an original image having a character image having a pixel ratio of 7%, a portrait of a person, a solid white image, and a solid black image each having a quarter size.
A halftone, solid white image, and solid black image were evaluated for every 0 sheets. The image density is the density of a solid black image, RD manufactured by Macbeth.
The absolute reflection density was measured using -918.

The fog was visually checked using a solid white image.

The presence or absence of image blur was also evaluated by visual judgment.

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 practical use

Fog ：: No fog occurred X: Fog sometimes occurred 々: Continuous fog occurred.

Occurrence of image blur A: Occurrence of 5 or less out of 60,000 images O: Occurrence of 6 to 20 images out of 60,000 images X: Occurrence of 20 or more images out of 60,000 images

Film peeling and scratching (black streaks in copied images,
(Evaluation was made in accordance with the occurrence of white streaks and the observation of scratches on the surface of the photoreceptor) ◎: No black streaks or white streaks occurred even in 60,000 sheets ○: 1 to 10 black streaks or white out of 60,000 sheets Streaks ×: 10 or more black streaks or white streaks out of 60,000 sheets.

2. Adhesion evaluation Evaluation was performed by forming a 1 mm square grid on the photoreceptor and counting the number of grids removed by peeling the adhesive tape out of 100 grids, and used as an index of adhesiveness.

[0197]

[Table 1]

As apparent from Table 1, the electrophotographic photosensitive member having the resin layer containing the siloxane-based resin having the crosslinked structure of the present invention and the photosensitive layer containing the polycarbonate having Si atoms has an image defect due to film peeling. And the image quality of the continuous copy image is good, whereas the image quality outside the range of the present invention (comparative example) causes black streak and white streak image defects due to film peeling and surface scratches. Image blur is also generated, and the effect of the present invention is remarkably shown.

[0199]

According to the present invention, an electrophotograph having a high surface hardness, a high abrasion resistance and a high scratch resistance, and stable electrophotographic characteristics even under high temperature and high humidity when used repeatedly, so that a good image can be repeatedly obtained. A photoreceptor can be provided. Further, an electrophotographic image forming method, an electrophotographic image forming apparatus, and a process cartridge using the photoreceptor can be provided.

[Brief description of the drawings]

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

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 Photosensitive drum (or photoreceptor) 11 Exposure part using light emitting diode etc. 12 Charging device 13 Image exposing device 14 Developing device 17 Paper feed roller 18 Transfer roller (transfer device) 19 Separation brush (separator) 20 Fixing device 21 Discharge roller 22 Cleaning device 30 Removable process cartridge in which photoconductor, charging device, transfer device / separator and cleaning device are integrated.

Claims (11)

[Claims] 1. An electrophotographic photoreceptor having at least a photosensitive layer and a resin layer on a conductive support, wherein the resin layer contains a structural unit having charge transport performance and contains a siloxane-based resin having a crosslinked structure. An electrophotographic photosensitive member, wherein the photosensitive layer contains a polycarbonate having Si atoms. 2. The electrophotographic photoreceptor according to claim 1, wherein the siloxane-based resin having a crosslinked structure is a siloxane-based resin having a structure represented by the following general formula (1). General formula (1) (Si · Y) _n · X (where X is a structural unit having charge transport performance, and Y is Si
And a divalent or higher atom or group connecting X and X. n represents an integer of 1 or more. ) 3. The electrophotographic photoconductor according to claim 1, wherein the resin layer contains colloidal silica. 4. The electrophotographic photosensitive member according to claim 1, wherein the polycarbonate is a copolymer having a structural unit represented by the following general formula (2). Embedded image (Wherein, Y ₁ each independently represents an alkylene group or an alkylidene group having 1 to 6 carbon atoms, R _{1 to} R ₈ each represent a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group, and n represents an integer of 1 to 4 for each substituent. P and q are 1 to 20 in total
Represents an integer of 0. ) 5. The electrophotographic photosensitive member according to claim 1, wherein the polycarbonate is a copolymer having a structural unit represented by the following general formula (3). Embedded image (In the formula, X is a linear, branched or cyclic alkylidene group having 1 to 15 carbon atoms, an aryl-substituted alkylidene group, an arylenedialkylidene group, -O-, -S-, -CO-,
-SO -, - SO ₂ - represents at least one of Z ₁ to Z ₄ is a Si atom-containing group represented by the following general formula (3 '), the other is hydrogen atom and a Represents an alkyl group or an aryl group. ) (Wherein, Y ₂ each independently represents an alkylene group or an alkylidene group having 1 to 6 carbon atoms, and R _{9 to} R ₁₅ each represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted Wherein r and s are 1 to 1 in total
Represents an integer of 200. ) 6. The electrophotographic photosensitive member according to claim 1, wherein the polycarbonate is a copolymer having a structural unit represented by the following general formula (4). Embedded image (Wherein, R is each independently a substituted or unsubstituted carbon atom of 1
To 6 alkyl groups, substituted or unsubstituted aryl groups,
A represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and n represents an integer of 0 to 200. ) 7. The electrophotographic photosensitive member according to claim 1, wherein said resin layer further contains an antioxidant. 8. The electrophotographic photoconductor according to claim 1, wherein the resin layer is a surface layer of the photoconductor. 9. An electrophotographic photosensitive member having at least a charge,
2. An electrophotographic image forming method comprising the steps of performing image exposure, development, and cleaning, wherein the electrophotographic photoreceptor is provided on the electrophotographic photosensitive member.
An electrophotographic image forming method, comprising using the electrophotographic photoreceptor according to any one of claims 1 to 8. 10. An electrophotographic photoreceptor, at least charged,
9. An electrophotographic image forming apparatus having image exposure, development, and cleaning means, wherein the electrophotographic photosensitive member is provided on the electrophotographic photosensitive member.
An electrophotographic image forming apparatus using the electrophotographic photosensitive member according to any one of the above. 11. An electrophotographic photoreceptor, at least charged,
A process cartridge used in an electrophotographic image forming apparatus having means for image exposure, development, and cleaning, wherein the electrophotographic photosensitive member according to claim 1, a charger,
A process cartridge having at least one of an image exposing device, a developing device, and a cleaning device in combination, and is designed to be freely inserted into and removed from the electrophotographic image forming apparatus.