JP2001249480A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high durability electrophotographic photoreceptor free of the rise of residual potential in repetitive use and having high transfer efficiency and improved cleanability and an image forming device using the photoreceptor and to provide a photoreceptor having the same dispersibility enhancing effect as that of a titanate coupling gent by adding an adequate amount of a metallic salt of a fatty acid (metallic soap) having a relatively simple structure and less liable to the deterioration of electrostatic characteristics even in long-term storage and an image forming device using the photoreceptor. SOLUTION: In the electrophotographic photoreceptor obtained by disposing a photosensitive layer on an electrically conductive substrate, the outermost layer of the photoreceptor contains fine metallic soap particles surface-treated with a fatty acid ester compound.

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 used for a copying machine, a printer, and the like, and an image forming apparatus using the same, and more particularly, to a highly durable electrophotographic photosensitive member having excellent environmental stability. More specifically, a highly durable electrophotographic photoreceptor having excellent toner transfer efficiency and cleanability as well as excellent environmental stability because the outermost layer contains metal soap fine particles, and metal The present invention relates to an electrophotographic photoreceptor having a soap containing intermediate layer on a conductive support and having excellent long-term storage stability, and an image forming apparatus using the same.

[0002]

2. Description of the Related Art Conventionally, inorganic photoconductive materials such as selenium, a-silicon, zinc oxide and the like have been mainly used as photoconductive materials for electrophotographic photosensitive members in terms of sensitivity and durability. The inorganic materials are disadvantageous in that they are harmful substances and have high productivity due to poor productivity. For this reason, organic photoreceptors that are non-polluting, can be mass-produced by coating, and can be easily reduced in cost have been actively developed in recent years.

[0003] Although these organic photoreceptors have advantages such as no pollution and low cost, they still have problems in sensitivity, environmental stability and durability, and especially excellent in environmental stability and durability. The development of electrophotographic photoreceptors is eagerly desired. Further, in recent years, the demand for higher image quality in addition to colorization is in the direction of reducing the particle size of the toner, and an electrophotographic photoreceptor having a high transfer efficiency and a high cleaning property corresponding to this is required.

As a method for solving these disadvantages, a method has been proposed in which a charge transport layer provided on the surface of a photoreceptor contains a silicone resin or a silicone-containing polymer (Japanese Patent Application Laid-Open No. 57-64243, Japanese Patent Application Laid-Open No. 57-64243). Kaisho 60-2
JP-A-56146, JP-A-61-95358, JP-A-61-132954, JP-A-61-2190
No. 47, etc.). However, the method of adding a silicone resin or a silicone-containing polymer has drawbacks in that the abrasion resistance is poor and the residual potential increases. On the other hand, a method of containing metal stearate as a reinforcing aid (Japanese Patent Application Laid-Open No. 62-279342).
However, there is a disadvantage that the residual potential increases. As described above, the conventional organic photoreceptors have various durability problems, and improvements thereof are eagerly desired. Also, Japanese Patent Application No. 10-269044 (JP-A-2000-89)
No. 495), surface treatment of metal soap fine particles with an organic solvent (alcohol / halogen-based solvent)
It describes that an electrophotographic photoreceptor in which accumulation of residual charges is suppressed is obtained, and the compatibility (affinity) between fine metal soap particles and a binder resin is improved by the surface treatment, whereby fine particles-resin are obtained. A technique for reducing the interfacial condenser effect is described. As described above, in reality, sufficient characteristics have not been obtained in spite of the need for high transfer efficiency and cleanability, as well as various durability problems.

On the other hand, conventionally, it has been attempted to improve the physical properties of an electrophotographic photosensitive member by providing an intermediate layer between the support and the photosensitive layer.
No. 3398 discloses that by including a titanate-based coupling agent in an intermediate layer, an electrophotographic photoreceptor which is not affected by temperature and humidity due to improvement in dispersibility and thickening can be obtained. . In addition, Japanese Patent Application Laid-Open No. 6-236062
JP, JP-A-7-271078, JP-A-8-1
JP-A-66679, JP-A-9-80787, JP-A-9-80788, JP-A-9-80789, and the like, by including a silane coupling agent and an organometallic compound in the intermediate layer, It is disclosed that an electrophotographic photosensitive member having a similar effect is obtained.

However, when the titanate-based coupling agent described in JP-A-5-313398 is used,
If the photoreceptor is stored for a long period of time in a high-temperature and high-humidity environment, the chargeability decreases and the residual potential increases. This is not mentioned in other patent publications containing a silane coupling agent and an organometallic compound.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to solve the above-mentioned problems by preventing the residual potential from increasing during repeated use, and further improving the transfer efficiency and cleaning performance. An object of the present invention is to provide a durable electrophotographic photosensitive member and an image forming apparatus using the same. Further, a second object of the present invention is to provide, in view of the above-mentioned problems of the prior art, the addition of an appropriate amount of a fatty acid metal salt (metal soap) having a relatively simple structure to the intermediate layer, thereby obtaining the same effect as the titanate-based coupling agent. It is an object of the present invention to provide a photoreceptor which has an effect of improving dispersibility and has a small deterioration of the electrostatic characteristics even during long-term storage, and an image forming apparatus using the same.

[0008]

The metal soap fine particles are considered to have a high transfer efficiency in repeated use, a long lasting cleaning property, and an effect of lowering the surface energy. And the disadvantage that the residual potential increases. In the prior art, it has been shown that the above-mentioned drawbacks can be significantly improved by adding a fatty acid ester to the surface treatment of the metal soap fine particles with a specific organic solvent, but it has been found that it is still insufficient. . Therefore, in the present invention, it has been found that the surface treatment of the metal soap fine particles with a fatty acid ester compound more positively improves the charge storage property of the electric charge during repeated use. Although the reason has not been clarified yet, a selective masking effect on active species and the like that may be generated on the outermost surface of the metal soap fine particles, and further a binder resin accompanying the outermost surface modifying effect. It is considered that the further improvement of the compatibility with has some effect.

That is, as a result of repeated studies to achieve the above object, the metal soap fine particles described in the specification of Japanese Patent Application No. 10-269044 (Japanese Patent Application Laid-Open No. 2000-89495) were dissolved in an organic solvent (alcohol). / Halogen solvent)
Electrophotographic photoreceptor in which the accumulation of residual charges has been suppressed by surface treatment with a resin, and the surface treatment improves the compatibility (affinity) between the fine metal soap particles and the binder resin, thereby providing a capacitor at the fine particle-resin interface. In addition to reducing the effect, in the first group of the present invention, the fatty acid ester compound is contained, so that the synergistic effect of further improving the effect and lowering the surface energy by the low molecular component (fatty acid ester compound) is obtained. And completed the first group of the present invention. Also,
We have surprisingly improved the dispersibility similar to titanate-based coupling agents by adding an appropriate amount of a fatty acid metal salt (metal soap) having a relatively simple structure to the intermediate layer in the course of studying the above problem. It has been found that a photoreceptor having the above-mentioned effect and having a small deterioration in the above-mentioned electrostatic characteristics even after long-term storage can be obtained. As a result of intensive studies, the present inventors have reached the second group of the present invention.

[First Group of the Invention] That is, the first group
The object of (1) of the present invention is to provide an electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the outermost layer of the electrophotographic photosensitive member is made of metal soap fine particles surface-treated with a fatty acid ester compound. (2) “The electrophotographic photoreceptor according to the above (1), wherein the metal soap fine particles are zinc-containing metal soap fine particles”, (2) 3) The metal soap fine particles for an electrophotographic photosensitive member according to the above item (1), wherein the metal soap fine particles are surface-treated with an organic solvent containing a fatty acid ester compound. The metal soap for an electrophotographic photoreceptor according to the above (1), wherein the metal soap fine particles have been subjected to a surface treatment by a mechanical pulverization step together with an organic solvent containing a fatty acid ester compound. Fine particles ”, ( (3) The metal soap fine particles for an electrophotographic photoreceptor according to the above (3) or (4), wherein the organic solvent for surface treatment is an alcoholic solvent containing a fatty acid ester compound. (6)
(The metal soap fine particles for an electrophotographic photoreceptor according to the above (3) or (4), wherein the organic solvent for surface treatment is a halogen-based solvent containing a fatty acid ester compound), ( 7) The above item (1) to item (6), wherein the outermost binder resin is a polycarbonate having a structural unit represented by the following general formula (1) as a main repeating unit. Electrophotographic photoreceptor,

Embedded image (In the formula, Z represents a group of nonmetallic atoms necessary to form a carbocyclic or heterocyclic ring which may have a substituent, and R _{1 to} R ₈ represent a hydrogen atom, a halogen atom, or each of a substituent. An aliphatic group or a carbocyclic group which may be present.) "

[Second Group of the Invention] The second object of the present invention is to provide (8) an intermediate comprising a pigment and a binder resin as main components between a conductive support and a photosensitive layer. In the electrophotographic photoreceptor provided with a layer, the ratio P / R of the pigment (P) to the binder resin (R) in the intermediate layer is in the range of 1/1 to 3/1 by volume ratio, and (9) The electrophotographic photosensitive member according to (8), wherein the intermediate layer contains a metal soap, and (9) the metal soap is an octylate. (10) or (9), wherein the metal soap accounts for 0.1% to 5% by weight of the pigment (P) in the intermediate layer. (11) The electrophotographic photoreceptor according to (8), wherein the pigment (P) is titanium oxide. Photoconductor ", (12)" The electrophotographic photosensitive member according to claim (8) section, wherein the pigment (P) is characterized in that it is a tin oxide and titanium oxide "(13)
The electrophotographic photosensitive member according to the above item (8), wherein the pigment (P) comprises titanium oxide and tin oxide, and tin oxide is 1% by weight to 25% by weight with respect to titanium oxide. (14) "The purity of the titanium oxide is 99
% Or more.
The electrophotographic photosensitive member according to any one of the above item 1), item (12) and item (13) ".

The above object is also achieved by the present invention, wherein (15)
"The electrophotographic photoreceptor according to the above (1) is used,
An image forming apparatus having at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and a cleaning unit, wherein the electrophotographic photosensitive member according to the above item (1) or (8) is used. Characteristic image forming apparatus ".

Hereinafter, the present invention will be described in detail with reference to the drawings. First, the first group of the present invention will be described.
FIG. 2 is a cross-sectional view showing a first group of single-layer photosensitive members used in the present invention, and a single-layer photosensitive layer mainly composed of a charge generation material and a charge transport material (11) on a conductive support (11). 15) is provided. FIG. 2 and FIG. 3 are cross-sectional views showing a configuration example of a first group of laminated photoconductors used in the present invention, wherein a charge generation layer (17) mainly composed of a charge generation material and a charge transport material And a charge transport layer (19) whose main component is laminated. FIG. 4 shows an intermediate layer (13) on a conductive support (11) by applying the second group of the present invention. Is a layer configuration interposed.

In the first group of the present invention, the outermost layer is a layer containing metal soap fine particles subjected to the surface treatment described in the above items (1) to (6). Refers to a layer provided on the surface. Therefore, in the case of a single-layer photoreceptor, the photosensitive layer is the outermost layer, and in the case of a laminated photoreceptor, the layer provided on either the charge generation layer or the charge transport layer is the outermost layer. In the first group of the present invention, an insulating layer or a protective layer can be further provided on the photosensitive layer. In this case, the insulating layer or the protective layer is the outermost layer. In the first group of the present invention, the surface-treated metal soap fine particles shown in the above items (1) to (6) are dispersed in a coating liquid corresponding to the outermost layer. When the added amount is increased in order to enhance the effect, a predetermined material is dissolved or dissolved in a coating liquid solvent containing the surface-treated metal soap fine particles described in the above (1) to (6). It is preferable to disperse them. The dispersing method can be carried out by a paint shaker, a sand mill, a bead mill, a ball mill or the like, if necessary.

The first group of metal soap fine particles used in the present invention is considered to have high transfer efficiency, sustainability of cleaning property and effect of lowering surface energy when used repeatedly. Has the disadvantage that the charge accumulation property is high and the residual potential rises. However, the use of the surface-treated metal soap fine particles described in the above items (1) to (6) enables the The charge storage of the electric charge is greatly improved. Although the reason has not been clarified yet, as described above, the effect of masking active species and the like that may be generated on the outermost surface of the metal soap fine particles, and the effect of modifying the outermost surface are also described. It is considered that the accompanying improvement in the compatibility with the binder resin has some effect.

The first group of metal soap fine particles used in the present invention is a non-alkali metal salt of an organic acid such as a fatty acid, and is generally commercially available, for example, aluminum stearate, calcium stearate, olein. Calcium acid, zinc stearate, zinc laurate, zinc oleate, magnesium stearate, nickel stearate, cobalt stearate, barium stearate and the like can be used. Among them, metal soap fine particles containing zinc as a metal have a particularly low charge accumulation property when used repeatedly, and are thus preferable.

The above-mentioned (1) used in the first group of the present invention.
The addition amount of the metal soap fine particles shown in (6) to (6) is preferably 1 to 30% (weight ratio) with respect to the binder resin. There is no sustainability of cleaning,
If the addition amount is larger than this, the film-forming property is deteriorated, and image defects such as initial background stain are likely to occur.

The above-mentioned (1) used in the first group of the present invention.
The surface treatment of the metal soap fine particles described in the items (6) to (6) can be easily performed by bringing the metal soap fine particles to be used into contact with various organic solvents which are surface treating agents. At this time, if necessary, grinding treatment such as mechanical stirring,
Heat treatment at room temperature to about 50 ° C. can be combined.

Various organic solvents can be used as the organic solvent used as a surface treatment agent for metal soap fine particles in the first group of the present invention, such as methanol, ethanol, and the like.
Alcohols such as isopropanol and butanol, n-
Aliphatic hydrocarbons such as hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene, dimethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol Ethers such as dimethyl ether; ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and methyl acetate; dimethylformamide, dimethylformaldehyde, dimethyl sulfoxide and the like. Among them, alcohols and halogenated hydrocarbons have a high effect of modifying metal soap fine particles by surface treatment, and a further improvement in properties can be expected by using these in combination.

Without the solvent treatment, the residual charge increases after repeated use of the photoreceptor, the post-exposure potential (VL) increases in an actual machine, and the resulting image is liable to have background stains. In the present invention, the increase in the residual charge after repeated use of the photoreceptor is prevented, the post-exposure potential (VL) is prevented from increasing in an actual machine, and the occurrence of background stain on the resulting image is avoided. be able to. The reason for this is unclear at present and therefore is not intended to be limited by the mechanism, but avoiding the capacitor effect due to, for example, the effect of a partial compatibility balance between binder resin and / or charge transport material (CTM) and metal soap particles. It can be considered as a cause, for example, or avoidance of dielectric polarization.

The metal soap may have various particle sizes depending on the kind, the manufacturer, etc., but it is not necessarily essential in the present invention.
It is used in the form of a relatively small particle size, preferably of the order of 1 to 30 μm. Unlike titanium oxide and silica fine particles, these metal soap particles are not merely finely divided by a dispersing operation but are pulverized into flakes (scales), which are once melted in a drying step at the time of forming a charge transport layer (CTL). Etc., and in some cases in the coating operation, the final filling form in the formation layer depends on these series of dispersion, coating, drying conditions and the like.

The surface treatment of the metal soap fine particles can be carried out by bringing the metal soap fine particles into contact with a solution obtained by dispersing and dissolving a fatty acid ester compound in the above-mentioned organic solvent. Alternatively, by combining the milling treatment, the dispersion stability is further improved, and the electric charge storage property at the time of repeated use is further improved.

The content of the fatty acid ester compound at the time of the surface treatment depends on the solubility in the organic solvent to be dispersed and dissolved, but is preferably 1% or more (weight ratio) with respect to the metal soap fine particles. Insufficient effect.

As the fatty acid ester compound of the first group of the present invention, a compound represented by the following general formula (A) can be preferably used.

[0025]

Embedded image R ₁ —COO—R ₂ or R ₃ —OCO— (CH ₂ ) n—COO—R ₄ (A) wherein R _{1 to} R ₄ represent a hydrocarbon group and n represents 0 When the number of carbon chains and n are increased, the initial transfer efficiency, which is also a function of the fatty acid ester compound alone, and the cleaning property are improved, but the compatibility with the resin is reduced, and The effect of the invention (reduction of charge accumulation) cannot be obtained. Preferably, those having about 8 to 30 carbon atoms are used, and various commercially available fatty acid esters can be used. The amount of the fatty acid ester compound to be added in the present invention is 0.1 to 100% (preferably by weight) based on the metal soap fine particles. When the amount is small, the effect of reducing the charge accumulation is insufficient. And the like) are preferred.

As shown in FIGS. 1 to 3, the conductive support (11) in the first group of the present invention has a volume resistivity of 10 ¹⁰ Ωcm or less, for example, aluminum, nickel or the like. , Chrome, nichrome, copper, silver, gold,
Metals such as platinum, metal oxides such as tin oxide and indium oxide, coated on film or cylindrical plastic or paper by vapor deposition or sputtering, or plates made of aluminum, aluminum alloy, nickel, stainless steel, etc. A tube or the like that has been surface-treated by cutting, superfinishing, polishing, or the like after it has been formed into a tube can be used.

Next, the first group of the photosensitive layer (15) in the present invention will be described. The photosensitive layer may be a single layer or a laminate, but for convenience of explanation, the case where the photosensitive layer is composed of the charge generation layer (17) and the charge transport layer (19) will be described first. The charge generation layer (17) is a layer containing a charge generation material as a main component.
As the charge generation material, inorganic and organic materials are used, and as typical examples, monoazo pigments, disazo pigments, trisazo pigments, perylene pigments, perinone pigments, quinacridone pigments, quinone condensed polycyclic compounds, squaric acid dyes, Phthalocyanine pigments, naphthalocyanine pigments,
Azulhenium salt dyes, selenium, selenium-tellurium, selenium-arsenic alloys, amorphous silicon and the like are used. The charge generation materials are used alone or in combination of two or more.

The charge generating layer (17) is prepared by dispersing a charge generating material together with a binder resin as appropriate and using a suitable solvent such as tetrahydrofuran, cyclohexanone, dioxane, 2-butanone or dichloroethane by a ball mill, an attritor, a sand mill or the like. It can be formed by applying a dispersion. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like. As the binder resin used as appropriate, polyamide, polyurethane, polyester, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal,
Polyvinyl ketone, polystyrene, polyacrylamide and the like are used. When the charge generation layer (17) corresponds to the outermost layer as shown in FIG. 3, a structural unit represented by the following general formula is used as a main repeating unit. The polycarbonate has excellent affinity with the metal soap fine particles shown in the above items (1) to (6), and is more preferable in terms of productivity.

[0029]

Embedded image (In the formula, Z represents a group of nonmetallic atoms necessary to form a carbocyclic or heterocyclic ring which may have a substituent, and R _{1 to} R ₈ represent a hydrogen atom, a halogen atom, or each of a substituent. Represents an aliphatic group or a carbocyclic group which may be present.)

As the amount of the binder resin as described above,
0 to 2 parts by weight is appropriate for 1 part by weight of the charge generating material. When the charge generation layer (17) does not correspond to the outermost layer, the charge generation layer (17) can be provided by a known vacuum thin film manufacturing method.
The thickness of the charge generation layer (17) is suitably about 0.01 to 5 μm, and preferably 0.1 to 2 μm.

The charge transporting layer (19) can be formed by dissolving or dispersing a charge transporting material and a binder resin in a suitable solvent, and applying and drying the same. Further, a plasticizer or the like can be added as necessary. Examples of the charge transport material include materials represented by the following general formulas. These charge generation materials may be used alone or in combination.

The charge transporting materials used in the first group of the electrophotographic photoreceptors of the present invention include oxazole derivatives, imidazole derivatives, triphenylamine derivatives, and general formulas (2) to (20) described below. Can be used.

[0033]

Embedded image (Wherein, R ₁ represents a methyl group, an ethyl group, a 2-hydroxyethyl group, or a 2-chloroethyl group, R ₂ represents a methyl group, an ethyl group, a benzyl group, or a phenyl group, and R ₃ represents a hydrogen atom. , A bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group or a nitro group.) The compound represented by the general formula (2) includes, for example, 9-ethyl. Carbazole-3-aldehyde-1-methyl-1-
Phenylhydrazone, 9-ethylcarbazole-3-aldehyde-1-benzyl-1-phenylhydrazone, 9
-Ethylcarbazole-3-aldehyde-1,1-diphenylhydrazone.

[0034]

Embedded image (In the formula, Ar represents a naphthalene ring, an anthracene ring, a styryl ring, or a substituted product thereof, or a pyridine ring, a furan ring, or a thiophene ring, and R represents an alkyl group or a benzyl group.) Formula (3) Examples of the compound include 4-diethylaminoacrylyl-β-aldehyde-1-methyl-
1-phenylhydrazone, 4-methoxynaphthalene-1
-Aldehyde-1-benzyl-1-phenylhydrazone.

[0035]

Embedded image (Wherein, R ₁ is an alkyl group, a benzyl group, a phenyl group,
Or a naphthyl group, wherein R ₂ is a hydrogen atom,
3 represents an alkyl group, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, a diaralkylamino group, or a diarylamino group; n represents an integer of 1 to 4;
In the above case, R ₂ may be the same or different. R ₃ represents a hydrogen atom or a methoxy group. Examples of the compound represented by the general formula (4) include 4-methoxybenzaldehyde-1-methyl-1-phenylhydrazone and 2,4-dimethoxybenzaldehyde-1-
Benzyl-1-phenylhydrazone, 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone,
4-methoxybenzaldehyde-1-benzyl-1-
(4-methoxy) phenylhydrazone, 4-diphenylaminobenzaldehyde-1-benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde-
1,1-diphenylhydrazone and the like.

[0036]

Embedded image (Wherein, R ₁ represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group, or a heterocyclic group;
R _2, R ₃ may be the same as or different from each other, a hydrogen atom, an alkyl group, a hydroxyalkyl group, chloroalkyl group, or a substituted or unsubstituted aralkyl group having 1 to 4 carbon atoms, also, R ₂ , R ₃ may combine with each other to form a heterocyclic ring containing a nitrogen atom. R ₄ may be the same and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen atom. The compounds represented by the general formula (5) include, for example, 1,1
-Bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, 1,1-
Bis (4-dibenzylaminophenyl) propane, 2,
2'-dimethyl-4,4'-bis (diethylamino)-
And triphenylmethane.

[0037]

Embedded image (In the formula, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group and a phenyl group, and R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, or a halogen atom.) Examples of the compound represented by 6) include N-ethyl-3,6-tetrabenzylaminocarbazole.

[0038]

Embedded image (Wherein, R represents a hydrogen atom or a halogen atom;
r represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, or carbazolyl group. The compounds represented by the general formula (7) include, for example, 9-
(4-Diethylaminostyryl) anthracene, 9-bromo-10- (4-diethylaminostyryl) anthracene and the like.

[0039]

Embedded image Compounds represented by the general formula (8) include, for example, 9-
(4-dimethylaminobenzylidene) fluorene, 3-
(9-Fluorenylidene) -9-ethylcarbazole and the like.

[0040]

Embedded image (Wherein, R is a carbazolyl group, a pyridyl group, a thienyl group, an indolyl group, a furyl group, or a substituted or unsubstituted phenyl group, a styryl group, a naphthyl group, or an anthryl group, and these substituents are dialkyl Amino group, alkyl group, alkoxy group, carboxy group,
Or a group selected from the group consisting of an ester thereof, a halogen atom cyano group, an aralkylamino group, an N-alkyl-N-aralkylamino group, an amino group, a nitro group, and an acetylamino group. The compounds represented by the general formula (9) include, for example, 1,2
-Bis (4-diethylaminostyryl) benzene, 1,
2-bis (2,4-dimethoxystyryl) benzene and the like.

[0041]

Embedded image (Wherein, R ₁ represents a lower alkyl group, a substituted or unsubstituted phenyl group, or a benzyl group, and R ₂ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, an amino group, or a lower group. Represents an amino group substituted with an alkyl group or a benzyl group, and n is 1 or 2
Represents an integer. The compound represented by the general formula (10) includes, for example, 3-
Examples include styryl-9-ethylcarbazole and 3- (4-methoxystyryl) -9-ethylcarbazole.

[0042]

Embedded image (Wherein R ₁ is a hydrogen atom, an alkyl group, an alkoxy group,
Or a halogen atom, and R ₂ and R ₃ are an alkyl group,
Represents a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, R ₄ represents a hydrogen atom, a lower alkyl group or a substituted or unsubstituted phenyl group, and Ar represents a substituted or unsubstituted phenyl group. Or a naphthyl group. The compound represented by the general formula (11) includes, for example, 4-
Diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-
Diphenylaminostyryl) naphthalene, 1- (4-diethylaminostyryl) naphthalene and the like.

[0043]

Embedded image (In the formula, n is an integer of 0 or 1, R ₁ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted phenyl group;
r ₁ represents a substituted or unsubstituted aryl group; R ₅ represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group;

[0044]

Embedded image Represents a 9-anthryl group or a substituted or unsubstituted carbazolyl group, wherein R ₂ represents a hydrogen atom, an alkyl group,
An alkoxy group, a halogen atom, or

[0045]

Embedded image <However, R ₃ and R ₄ are an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, even R ₃ and R ₄ are the same or different, R ₄ May form a ring. And m is an integer of 0, 1, 2, or 3. When m is 2 or more, R ₂ may be the same or different. When n is 0, A and R ₁ may form a ring together. The compound represented by the general formula (12) includes, for example, 4 ′
-Diphenylamino-α-phenylstilbene, 4′-
Bis (4-methylphenyl) amino-α-phenylstilbene and the like.

[0046]

Embedded image (In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a dialkylamino group, or a halogen atom, and n represents 0 or 1.) Formula (13) Examples of the compound include, for example, 1-
Phenyl-3- (4-diethylaminostyryl) -5
(4-diethylaminophenyl) pyrazolin, 1-phenyl-3- (4-dimethylaminostyryl) -5- (4
-Dimethylaminophenyl) pyrazolin and the like.

[0047]

Embedded image (Wherein R ₁ and R ₂ represent an alkyl group including a substituted alkyl group, or a substituted or unsubstituted aryl group;
Represents a substituted amino group, a substituted or unsubstituted aryl group or an allyl group. The compound represented by the general formula (14) includes, for example, 2,
5-bis (4-diethylaminophenyl) -1,3,4
-Oxadiazole, 2-N, N-diphenylamino-
5- (4-diethylaminophenyl) 1,3,4-oxadiazole, 2- (4-dimethylaminophenyl)-
5- (4-diethylaminophenyl) -1,3,4-oxadiazole and the like.

[0048]

Embedded image (Wherein, X represents a hydrogen atom, a lower alkyl group, or a halogen atom, R represents an alkyl group including a substituted alkyl group,
Or A represents a substituted or unsubstituted aryl group, and A represents a substituted amino group or a substituted or unsubstituted aryl group. The compound represented by the general formula (15) includes, for example, 2-
N, N-diphenylamino-5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole, 2
-(4-diethylaminophenyl) -5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole and the like.

[0049]

Embedded image (Wherein, R ₁ represents a lower alkyl group, a lower alkoxy group or a halogen atom, n represents an integer of 0 to 4,
₂ and R ₃ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. The benzidine compound represented by the general formula (16) includes, for example, N, N′-diphenyl N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-
Diamine, 3,3′-dimethyl-N, N, N′N′-tetrakis (4-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine and the like.

[0050]

Embedded image (Wherein R ₁ , R ₃ and R ₄ are a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom, or a substituted or unsubstituted Is an aryl group of R
₂ represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group, or a halogen atom. Where R ₁ , R ₂ , R
Except when all ₃ and R ₄ are hydrogen atoms. Also,
k, l, m and n are integers of ₁ , ₂ , 3 or 4, and when each is an integer of 2, 3 or 4, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. Is also good. The biphenylamine compound represented by the general formula (17) includes, for example, 4′-methoxy N, N-diphenyl-
[1,1′-biphenyl] -4-amine, 4′-methyl-N, N′-bis (4-methylphenyl)-[1,1 ′
-Biphenyl] -4-amine, 4'-methoxy-N,
N'-bis (4-methylphenyl)-[1,1'-biphenyl] -4-amine and the like.

[0051]

Embedded image (Wherein, Ar represents a condensed polycyclic hydrocarbon group having 18 or less carbon atoms, and R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group,
Represents a substituted or unsubstituted phenyl group, which may be the same or different. Examples of the triarylamine compound represented by the general formula (18) include 1-phenylaminopyrene, 1-di (p
-Tolylamino) pyrene;

[0052]

Embedded image Examples of the diolefin aromatic compound represented by the general formula (19) include 1,4-bis (4-diphenylaminostyryl) benzene and 1,4-bis [4-di (p-tolyl) aminostyryl] benzene Etc.

[0053]

Embedded image (In the formula, Ar represents an aromatic hydrocarbon group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group. N is 0 or 1, m is 1 or 2, and n is
When = 0 and m = 1, Ar and R may form a ring together. Examples of the styrylpyrene compound represented by the general formula (20) include 1- (4-diphenylaminostyryl) pyrene, 1- [4-di (p-tolyl) aminostyryl] pyrene, and the like.

The charge transport layer (19) together with the charge transport material
Polystyrene, as the binder resin used for
Styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer,
Polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, acrylic resin, Thermoplastic or thermosetting resins such as silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin can be used. Among these, polycarbonate is preferable because it has excellent environmental properties, abrasion resistance and mechanical properties when used as an electrophotographic photoreceptor, and the structural unit represented by the following general formula (1) is particularly preferred as a main repeating unit. The polycarbonate has excellent affinity with the metal soap fine particles in the present invention, and is more preferable in terms of productivity.

[0055]

Embedded image (In the formula, Z represents a group of nonmetallic atoms necessary to form a carbocyclic or heterocyclic ring which may have a substituent, and R _{1 to} R ₈ represent a hydrogen atom, a halogen atom, or each of a substituent. Represents an aliphatic group or a carbocyclic group which may be present.)

As the solvent, tetrahydrofuran, dioxane, toluene, 2-butanone, monochlorobenzene, dichloroethane, methylene chloride and the like are used. The thickness of the charge transport layer (19) is suitably from 5 to 100 μm. In the present invention, a plasticizer may be added to the charge transport layer (19). As a plasticizer, dibutyl phthalate,
What is used as a plasticizer of a general resin such as dioctyl phthalate can be used as it is, and its use amount is suitably about 0 to 30% by weight based on the binder resin.

Next, the case where the photosensitive layer (15) has a single-layer structure will be described. In many of these cases, a function-separated type comprising a charge generating substance and a charge transporting substance is exemplified. That is,
It can be formed by dissolving or dispersing at least the charge generating material and the charge transporting material in a suitable solvent together with a binder resin, and applying and drying this. Further, a plasticizer or the like can be added as necessary. As the binder resin, the binder resin described in the charge transport layer (19) may be used as it is, or the binder resin described in the charge generation layer (17) may be mixed. The thickness of the single-layer photosensitive layer is suitably from 5 to 100 μm.

The first group of electrophotographic photoreceptors of the present invention includes:
An undercoat layer can be provided between the conductive support (11) and the photosensitive layer. The undercoat layer generally contains a resin as a main component. However, considering that the photosensitive layer is coated thereon with a solvent, these resins are resins having high solubility resistance to general organic solvents. desirable. Such resins include polyvinyl alcohol, casein, water-soluble resins such as sodium polyacrylate, copolymerized nylon, alcohol-soluble resins such as methoxymethylated nylon, polyurethane, melamine resin, alkyd-melamine resin, epoxy resin, and the like. Curable resins that form a three-dimensional network structure are exemplified.

In order to prevent moiré and reduce residual potential, fine powder of a metal oxide exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide or the like may be added to the undercoat layer. Good. These undercoat layers can be formed by a suitable solvent and coating method as in the above-mentioned photosensitive layer. Further, as an undercoat layer of the first group of the present invention, an intermediate layer of a second group of the present invention described later can be suitably applied. A metal oxide layer formed by a sol-gel method or the like using a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like as the undercoat layer of the first group of the present invention is also useful. is there.
In addition, the undercoat layer of the first group of the present invention is provided with Al ₂ O ₃ by anodic oxidation, an organic substance such as polyparaxylylene (parylene), SiO, SnO ₂ , TiO _2. , IT
Those provided with an inorganic substance such as O and CeO ₂ by a vacuum thin film manufacturing method can also be used favorably. The thickness of the undercoat layer is suitably from 0 to 5 μm.

An example of an image forming apparatus equipped with the electrophotographic photosensitive member according to the first group of the present invention will be described with reference to FIG. In the example of the image forming apparatus shown in FIG. 5, an elastic roller (2) as a contact member is provided around the photoconductor (22).
1), static elimination lamp (23), charging charger (24),
Eraser (25), image exposure section (26), developing unit (27), pre-transfer charger (28), registration roller (29), transfer paper (30), transfer charger (31),
It includes a separation charger (32), a separation claw (33), a pre-cleaning charger (34), a fur brush (35), a cleaning blade (36), and the like. In the figure, the temperature sensor is not shown because it is not necessary to arrange it in contact with the photoconductor (22). However, when the surface potential measuring means of the photoconductor (22) is used, the temperature sensor of the image exposure unit (26) is used. It can be located before or before the eraser (25). And, needless to say, the first group of the present invention is not limited to only the image forming apparatus as illustrated,
What is necessary is just to have an image exposure unit, a development unit, a transfer unit, and a cleaning unit.

Such an image forming apparatus can be used as an image forming apparatus in which a second group of electrophotographic photosensitive members according to the present invention described in detail below is mounted.

Next, the second group of the present invention will be described in detail. As shown in FIG. 4, in the second group of the present invention, a photosensitive layer is provided on a conductive support (11) via an intermediate layer (13) containing metal soap. Second
Examples of the metal soaps used in the present invention include Zn, Co, Mn, Ni, Fe, Pb, Cu, and S of fatty acids such as octylic acid, stearic acid, lauric acid, and naphthenic acid.
Examples thereof include salts of n, Al, Mg, Ca, Ba, and Li. Among them, a chain fatty acid having better dispersibility of the pigment is preferable. The metal soap used in the second group of the present invention is preferably in the range of 0.1% by weight to 5% by weight with respect to the pigment, and if it is less than this, the dispersibility of the pigment is slightly lowered. If so, the residual potential after electrostatic fatigue slightly increases.

The pigments dispersed in the intermediate layer according to the second group of the present invention include those which hardly absorb visible light and near infrared light.
White or near white is desirable from the viewpoint of increasing the sensitivity of the photoreceptor. Examples of such pigments include white pigments such as inorganic titanium oxide, zinc white, zinc sulfide, lead white, and lithopone, and extenders such as alumina, calcium carbonate, and barium sulfate. In particular, when writing is performed on the photoreceptor using coherent light such as laser light, a white pigment having a large diffuse reflectance is preferably used to prevent the occurrence of moire, and titanium oxide is optimal.

Further, it has been found that even when titanium oxide and tin oxide are used in combination as a pigment dispersed in the resin of the intermediate layer, the coating liquid containing the metal soap is stable for a long time. The amount of tin oxide used in the second group of the present invention is preferably in the range of 5 to 20% by weight based on titanium oxide. If it is less than 5%, the effect of lowering the electrical resistance of the intermediate layer cannot be exerted by adding tin oxide, and if it exceeds 20%, dark decay when the photoreceptor is charged becomes large, and the image quality deteriorates.

Further, it is desirable that the titanium oxide has no hygroscopicity and has little environmental fluctuation. That is, among the titanium oxide pigments, there are hygroscopic substances such as Na ₂ O and K ₂ O as impurities, which absorb moisture at high humidity and cause deterioration of the photoreceptor characteristics. Therefore, the purity of this type of titanium oxide pigment is desirably 99.0% by weight or more.

As the resin of the intermediate layer in the second group of the present invention, any resin can be used, but considering that the photosensitive layer is coated thereon with a solvent, A resin having high solvent resistance is desirable. Such a resin forms a three-dimensional network structure such as a water-soluble resin such as polyvinyl alcohol, casein and sodium polyacrylate, an alcohol-soluble resin such as copolymerized nylon and methoxymethylated nylon, a polyurethane, a melamine resin, and an epoxy resin. Curable resin.

The photosensitive layer of the electrophotographic photoreceptor of the second group of the present invention can be of a single layer type or a function separation type comprising two or more layers by combining a charge generation layer and a charge transport layer. . When the layer structure is a single layer type, a photosensitive layer in which a charge generating substance and a charge transporting substance are dispersed in a resin is provided on a conductive support or an intermediate layer as described above.

In the case of the function separation type, a charge generation layer containing a charge generation substance and a resin is formed on a support similar to the single layer type, and a charge transport layer containing a charge transport substance and a resin is formed thereon. However, when a positive charge type is used, the charge generation layer and the charge transport layer may be stacked in reverse. Further, in the case of a function separation type, a charge transport material may be contained in the charge generation layer,
Particularly, in the case of a positive charge type in which a charge transport layer and a charge generation layer are sequentially laminated, the sensitivity is improved.

In the case where a function-separated type photoreceptor having the above-mentioned layer structure is prepared, there are preferable ranges for the film thickness and the ratio of the substance. In the case of the negative charge type (lamination of the support / charge generation layer / charge transport layer), the ratio of the resin to the charge generation substance in the charge generation layer is 0 to 400% by weight, and the film thickness is 0.1 to 5%.
μm is preferred. In the charge transport layer, the ratio of the charge transport material to the resin is 20 to 200% by weight, and the film thickness is 5%.
It is desirable to set it to 50 μm. In the case of the positive charge type (support / lamination of charge transport layer / charge generation layer), the charge transport layer in the charge transport layer has a ratio of the charge transport material to the resin of 20 to 20.
The thickness is preferably 200% by weight and the film thickness is preferably 5 to 50 μm. In the charge generation layer, the charge generation substance is preferably 10 to 500% by weight based on the resin, and the film thickness is preferably 0.1 to 10 μm. Further, it is preferable that the charge generation layer contains a charge transporting substance, which is effective for suppressing the residual potential and improving the sensitivity. In this case, the charge transporting material is 20 to 200% by weight based on the resin.
It is preferable to include them.

In the case of the single layer type, the ratio of the charge transporting substance and the charge generating substance to the resin is 50 to 150, respectively.
% By weight, 10 to 50% by weight, and the film thickness is preferably 5 to 50 μm.

As the charge generation material that can be used in the electrophotographic photoreceptor of the second group of the present invention, any of inorganic and organic substances can be used as long as they absorb light to generate charge carriers. it can. Examples of the inorganic substance include amorphous selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy, cadmium sulfide, zinc oxide, amorphous silicon, and the like. As the organic substance, for example, CI Pigment Blue 25 [Color Index (C
I) 21180], CI Pigment Red 41 (CI 2
1200), CIA Acid Red 52 (CI 4510)
0), CI Basic Red 3 (CI 45210), phthalocyanine-based pigments having a porphyrin skeleton, azulenium salt pigments, squaric salt pigments, and azo pigments having a carbazole skeleton (JP-A-53-95033)
JP-A-53-123), azo pigments having a styrylstilbene skeleton (described in JP-A-53-138229), and azo pigments having a triphenylamine skeleton (described in JP-A-53-123)
No. 547), an azo pigment having a dibenzothiophene skeleton (described in JP-A-54-21728), and an azo pigment having an oxathiazole skeleton (described in JP-A-54-12)
742), an azo pigment having a fluorenone skeleton (described in JP-A-54-22834), an azo pigment having a bisstilbene skeleton (described in JP-A-54-17733), and a distyryloxadiazole skeleton. Pigments (described in JP-A-54-2129) and azo pigments having a distyrylcarbazole skeleton (JP-A-54-129).
17734), trisazo pigments having a carbazole skeleton (described in JP-A-57-195767 and JP-A-57-195768), and phthalocyanine-based pigments such as CI Pigment Blue 16 (CI 74100). Sea Ibat Brown 5 (CI 7341
0), indigo-based pigments such as sea butt die (CI 73030), perylene-based pigments such as Argo Scarlet B (manufactured by Violet), and Indus Scarlet R (manufactured by Bayer); Examples include quinone imine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, and bisbenzimidazole pigments.

The charge transport material includes a hole transport material and an electron transport material. Examples of the hole transport material include poly-N-vinylcarbazole and its derivatives, poly-γ-carbazolylethylglutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives,
Oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (P-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazolin, phenylhydrazones, An electron donating substance such as an α-phenylstilbene derivative may be used.

Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone. 2,4,5,7-tetranitroxanthone,
2,4,8-trinitrothioxanthone, 2,6,8-
Electron accepting substances such as trinitro-4H-indeno [1,2-b] thiophen-4-one and 1,3,7-trinitrodibenzothiophene-5,5-dioxide are exemplified. These charge transport materials are used alone or in combination of two or more.

The binder resin used in the second group of the present invention includes polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, and polychlorinated resin. Vinyl, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal,
Polyvinyl toluene, poly-N-vinyl carbazole,
Thermoplastic or thermosetting resins such as acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin are exemplified.

In the second group of the present invention, a plasticizer or a leveling agent may be added to the charge transport layer. As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount of the plasticizer is 0 to 3 with respect to the binder resin.
About 0% by weight is appropriate. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil are used, and the amount of the silicone oil is suitably about 0 to 1% by weight based on the binder resin.

In the second group of the present invention, it is possible to further provide an insulating layer or a protective layer on the photosensitive layer. In this case, the outermost layer in the first group of the present invention is suitably applied as an insulating layer or a protective layer.

As a method for forming the above-mentioned auxiliary layer such as the photosensitive layer and the intermediate layer and the protective layer, a dip coating method, a spray coating method, a bead coating method and the like can be used.

The conductive support used in the electrophotographic photoreceptor of the second group of the present invention includes metal drums and sheets of aluminum, brass, stainless steel, nickel and the like, materials such as polyethylene terephthalate, polypropylene, nylon and paper. Aluminum, nickel or other metal deposited, laminated, or coated with conductive paint,
Examples include plastic drums and sheets in which conductive pigments such as carbon are dispersed.

[0079]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but these examples explain the present invention in detail, and the present invention is not limited by the examples. All raw materials used in the examples are parts by weight unless otherwise specified.

[Regarding the First Group of the Invention] Example 1 Zinc stearate fine particles (manufactured by Kanto Chemical Co., Ltd.) were added to 180 parts of a methanol solution prepared by dispersing and dissolving 20 parts of butyl myristate.
After adding 10 parts and stirring at room temperature for 60 minutes, a filtration treatment was performed. The obtained fine particles were dried under reduced pressure with a vacuum dryer (50 ° C.) to obtain the desired metal soap fine particles A for electrophotography.

Example 2 The same procedure as in Example 1 was carried out except that methanol, which was a processing organic solvent, was changed to methylene chloride, thereby obtaining target metal soap fine particles B for electrophotography.

Example 3 The same procedure as in Example 1 was carried out except that methanol, which was a processing organic solvent, was changed to n-butanol, to thereby obtain metal soap fine particles C for electrophotography.

Example 4 The same procedure as in Example 1 was carried out except that methanol, which was an organic solvent for processing, was changed to chloroform, to obtain metal soap fine particles D for electrophotography.

Example 5 The same procedure as in Example 1 was carried out, except that methanol, which was a processing organic solvent, was changed to methyl ethyl ketone, whereby metal soap fine particles E for electrophotography were obtained.

Example 6 The same procedure as in Example 1 was carried out except that methanol, which was an organic solvent for processing, was changed to cyclohexane, to thereby obtain metal soap fine particles F for electrophotography.

Example 7 The same procedure as in Example 1 was carried out except that methanol, which is an organic solvent for processing, was changed to toluene, thereby obtaining metal soap fine particles G for electrophotography.

Example 8 The same procedure as in Example 1 was carried out except that the zinc stearate fine particles were changed to zinc oleate (manufactured by Kanto Chemical Co., Ltd.) to obtain the desired metal soap fine particles H for electrophotography.

Example 9 The intended metal soap fine particles I for electrophotography were obtained in the same manner as in Example 1 except that the zinc stearate fine particles were changed to calcium stearate (manufactured by Kanto Chemical Co., Ltd.).

Example 10 The intended metal soap fine particles J for electrophotography were obtained in the same manner as in Example 1 except that the zinc stearate fine particles were changed to magnesium stearate (manufactured by Kanto Kagaku).

Example 11 The intended metal soap fine particles K for electrophotography were obtained in the same manner as in Example 1 except that the zinc stearate fine particles were changed to nickel stearate (manufactured by Kanto Chemical Co., Ltd.).

Example 12 The same procedure as in Example 1 was carried out except that butyl myristate was changed to myristyl myristate, to thereby obtain metal soap fine particles L for electrophotography.

Example 13 The intended metal soap fine particles M for electrophotography were obtained in the same manner as in Example 1, except that butyl myristate was changed to n-dodecyl stearate.

Example 14 The same procedure as in Example 1 was carried out except that butyl myristate was changed to diethyl sebacate, to obtain metal soap fine particles N for electrophotography.

Example 15 Zinc stearate fine particles (manufactured by Kanto Chemical Co., Ltd.) were added to 180 parts of a methanol solution in which 20 parts of butyl myristate were dispersed and dissolved.
10 parts were charged, and vibration dispersion was performed using zirconia balls having a diameter of 2 mm as a medium for 60 minutes to perform a filtration treatment. The obtained fine particles were dried under reduced pressure with a vacuum dryer (50 ° C.) to obtain the desired metal soap fine particles O for electrophotography.

Example 16 10 parts of zinc stearate fine particles (manufactured by Kanto Kagaku) were added to 180 parts of a methylene chloride solution in which 20 parts of butyl myristate were dispersed and dissolved, and vibration dispersion was performed for 60 minutes using zirconia balls having a diameter of 2 mm as a medium. No filtration was performed. The obtained fine particles were dried under reduced pressure with a vacuum drier (50 ° C.) to obtain target metal soap fine particles P for electrophotography.

Comparative Example 1 The same procedure as in Example 1 was carried out except that butyl myristate was not added, to obtain fine metal soap particles Q.

Comparative Example 2 The same procedure as in Example 15 was carried out except that butyl myristate was not used, to obtain the desired metal soap fine particles R.

Examples 17 to 32 An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following compositions were sequentially coated and dried on an aluminum cylinder having an outer diameter of 100 mm, each having a thickness of 3 μm. Sublayer, 0.2
An electrophotographic photoreceptor of Examples 17 to 32 was prepared by forming a charge generation layer of μm and a charge transport layer of 28 μm.

[Undercoat layer coating solution] Oil-free alkyd resin 15 parts (Dainippon Ink Chemical: Beckolite M6401) Melamine resin 10 parts (Dainippon Ink Chemical: Super Beckamine G-821) Titanium dioxide (Ishihara) Sangyo Co., Ltd .: Taipaque R-670) 50 parts 2-butanone 40 parts

[Coating Solution for Charge Generating Layer] Y-part titanyl phthalocyanine 5 parts Polyvinyl butyral resin 5 parts (Eslec BM-S, manufactured by Sekisui Chemical) 350 parts of cyclohexanone

[Solvent for Coating Liquid] 1 part of each of the metal soap fine particles A to P for electrophotography was charged into 75 parts of a methylene chloride solution.
Vibration dispersion was performed for 3 hours using zirconia balls having a diameter of 2 mm as a medium to obtain a solvent for a coating liquid in which metal soap fine particles were uniformly dispersed.

[Charge Transport Layer Coating Solution] 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Company) 10 parts Coating solution solvent 76 parts

Comparative Example 3 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that a coating solution for a charge transport layer having the following composition was used.

[Charge Transport Layer Coating Solution] 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Inc. Iupilon Z-200) 10 parts Methylene chloride 76 parts

Comparative Example 4 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that a coating solution for a charge transport layer having the following composition was used.

[Solvent for Coating Liquid] 1 part of zinc stearate fine particles (manufactured by Kanto Chemical Co., Ltd.) was charged into 75 parts of a methylene chloride solution, and vibration dispersion was carried out for 3 hours using zirconia balls having a diameter of 2 mm as a medium. Was uniformly dispersed to obtain a coating solution solvent.

[Coating Solution for Charge Transport Layer] 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Iupilon Z-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) 10 parts Solvent for coating solution 76 parts

Comparative Example 5 An electrophotographic photosensitive member was prepared in the same manner as in Comparative Example 4, except that the zinc stearate fine particles were changed to zinc oleate fine particles (manufactured by Kanto Chemical Co., Ltd.).

Comparative Example 6 An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 4, except that the zinc stearate fine particles were changed to calcium stearate fine particles (manufactured by Kanto Kagaku).

Comparative Example 7 An electrophotographic photoreceptor was prepared in the same manner as in Comparative Example 4, except that the zinc stearate fine particles were changed to magnesium stearate fine particles (manufactured by Kanto Chemical Co., Ltd.).

Comparative Example 8 An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 4, except that the zinc stearate fine particles were changed to nickel stearate fine particles (manufactured by Kanto Chemical Co., Ltd.).

Comparative Example 9 An electrophotographic photosensitive member was prepared in the same manner as in Example 17, except that a coating solution for a charge transport layer having the following composition was used.

[Solvent for Coating Liquid] 1 part of zinc stearate fine particles (manufactured by Kanto Chemical Co., Ltd.) was put into 75 parts of a methylene chloride solution, and vibration dispersion was performed for 3 hours using zirconia balls having a diameter of 2 mm as a medium. Was uniformly dispersed to obtain a coating solution solvent.

[Charge Transport Layer Coating Solution] Butyl myristate 0.1 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Ltd. Iupilon Z-200) 10 parts Coating solution 76 parts of solvent

Comparative Examples 10 to 11 Electrophotographic photosensitive members were prepared in the same manner as in Example 17 except that a coating solution for a charge transport layer having the following composition was used.

[Solvent for Coating Liquid] 1 part of each of the metal soap fine particles Q and R was put into 75 parts of a methylene chloride solution, and the diameter was 2 mm.
Using zirconia balls as a medium, vibration dispersion was performed for 3 hours to obtain a coating liquid solvent in which metal soap fine particles were uniformly dispersed.

[Charge Transport Layer Coating Solution] Butyl myristate 0.1 part 4-Diethylaminobenzaldehyde-1-benzyl-1-phenylhydrazone 7 parts Polycarbonate (Mitsubishi Gas Chemical Co., Ltd. Iupilon Z-200) 10 parts Coating solution 76 parts of solvent

Each of the above photoreceptors is described in JP-A-60-10016.
The following measurement was performed with the evaluation device disclosed in Japanese Patent Publication No. A potential Vm (V) after charging for 20 seconds at a corona discharge voltage of -6.0 kV, a potential Vo (V) after 20 seconds for dark decay,
Monochromatic light with an intensity of 1 μW / cm ² (780 nm, half width 20)
nm), the exposure potential E1 / necessary to attenuate the residual potential VR (V) after 20 seconds of exposure and the potential Vo to 1/2.
2 [μJ / cm ² ] was measured. The potential holding ratio is defined as follows. Potential holding ratio = Vo / Vm Each photoconductor of the example and the comparative example was used as a copying machine DA manufactured by Ricoh Co., Ltd.
A copy of 50,000 sheets was continuously made in a -355 modified machine (regular development), and the presence or absence of an abnormal image was visually determined. After completion of the copying test, the characteristics of the photoconductors were measured by the same method as described above. Table 1 shows the test results.

[0119]

[Table 1]

[Regarding the Second Group of the Invention]
Examples of the present invention of the group (1) will be specifically described. Example 33 18% by weight of an alkyd resin [Beccosol TD-50-30 (manufactured by Dainippon Ink and Chemicals)] and 4% by weight of a melamine resin [Beckamine P-138 (manufactured by Dainippon Ink and Chemicals)] and a metal soap ( Zinc naphthenate) [Naphtex Zn (manufactured by Nippon Chemical Industry Co., Ltd.)] 0.6% by weight is dissolved in 30% by weight of methyl ethyl ketone (MEK), and fine powder of titanium oxide having a purity of 99.7% [TM-1 (Fuji) (Manufactured by Titanium Industry Co., Ltd.)] and dispersed in a ball mill for 24 hours to prepare a coating liquid for an intermediate layer. This has a diameter of 30
It was dip-coated on an aluminum drum having a length of 340 mm and a length of 340 mm, and dried at 150 ° C. for 20 minutes to form an intermediate layer having a thickness of 10 μm.

Next, 4% by weight of a polyvinyl butyral resin [ESLEK BL-S (manufactured by Sekisui Chemical Co., Ltd.)] is dissolved in 150% by weight of cyclohexanone, and 10% by weight of a trisazo pigment of the following structural formula (21) is added thereto. After dispersing for 48 hours in a ball mill, 210% by weight of cyclohexanone was further added and dispersed for 3 hours. This was taken out into a container and diluted with cyclohexanone so that the solid content was 1.5% by weight. The thus-obtained coating solution for a charge generation layer was dip-coated on the intermediate layer, and dried at 150 ° C. for 10 minutes.
A charge generation layer having a thickness of 0.2 μm was formed.

[0122]

Embedded image

Next, as a charge transport material, the following structural formula (2)
2) 8% by weight of α-phenylstilbene compound, 10% by weight of polycarbonate resin [Panlite L-1250 (manufactured by Teijin Chemicals)], 0.001% by weight of silicone oil [KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.)] Was dissolved in 90% by weight of methylene chloride. The coating solution for the charge transport layer thus obtained was applied onto the charge generation layer by dip coating.
After drying for 25 minutes, a charge transport layer having a thickness of 25 μm was formed.

[0124]

Embedded image

Example 34 The electrophotograph of Example 34 was carried out in the same manner as in Example 33, except that zinc octylate [Octix Zn (manufactured by Nippon Chemical Industry Co., Ltd.)] was used instead of zinc naphthenate. A photoreceptor was made.

Example 35 An electrophotographic photosensitive member of Example 35 was prepared in the same manner as in Example 33, except that the amount of the metal soap added to the intermediate layer was changed to 0.12% by weight. .

Example 36 An electrophotographic photosensitive member of Example 36 was prepared in the same manner as in Example 33, except that the addition amount of the metal soap to the intermediate layer was changed to 3% by weight.

Example 37 An electrophotographic photosensitive member of Example 37 was prepared in the same manner as in Example 33, except that the addition amount of the metal soap to the intermediate layer was changed to 0.03% by weight. .

Example 38 An electrophotographic photosensitive member of Example 38 was prepared in the same manner as in Example 33, except that the amount of the metal soap added to the intermediate layer was changed to 4.8% by weight. .

Example 39 In order to observe the influence from the surface of the support, 5% by weight of a polyamide resin [CM8000 (manufactured by Toray Industries, Ltd.)] was added to 45% of methanol.
2% by weight of conductive carbon black, dispersed in a ball mill for 72 hours, and sprayed a coating liquid diluted with 50% by weight of butanol onto an aluminum drum having a diameter of 30 mm and a length of 340 mm. By coating, a black conductive layer having a thickness of 2 μm was formed. An intermediate layer and a photosensitive layer similar to those in Example 33 were formed on the support thus produced, whereby an electrophotographic photosensitive member of Example 39 was produced.

Example 40 The procedure of Example 33 was repeated except that the titanium oxide fine powder was changed to 81% by weight of zinc oxide fine powder [SX-9 (manufactured by Sakai Chemical)] and 0.81% by weight of zinc naphthenate. 33, an electrophotographic photosensitive member of Example 40 was prepared.

Example 41 An electrophotographic photosensitive member of Example 41 was prepared in the same manner as in Example 40, except that the support was changed to the black support used in Example 39.

Comparative Example 12 An electrophotographic photosensitive member of Comparative Example 12 was prepared in the same manner as in Example 33 except that no metal soap was added to the intermediate layer. The evaluation was stopped because air bubbles were generated sometimes.

Comparative Example 13 Comparative Example 13 was carried out in the same manner as in Example 33 except that a titanate coupling agent [PR-581 (manufactured by Nippon Soda)] was added to the intermediate layer instead of the metal soap. Thirteen electrophotographic photosensitive members were prepared.

Comparative Example 14 In Example 33, the titanium oxide fine powder in the intermediate layer was replaced with 1
An electrophotographic photoreceptor of Comparative Example 14 was prepared in the same manner as in Example 33 except that the amount of the metal soap was changed to 20% by weight and the amount of the metal soap was changed to 1.2% by weight.

Comparative Example 15 In Example 33, the fine titanium oxide powder in the intermediate layer was replaced with 2 powders.
An electrophotographic photoreceptor of Comparative Example 15 was prepared in the same manner as in Example 33, except that 0% by weight and 0.2% by weight of metal soap were used.

The electrophotographic photoreceptor produced as described above is stored in a dark place at 30 ° C. and 80% RH for 12 months, and then exposed in a real machine at 20 ° C. and 50% RH. Plain paper copier modified to enable measurement of body surface potential [imagio MF250 (manufactured by Ricoh)]
Then, a white paper image was output, and the background stain and the dark portion potential VD (V) in the actual machine in the initial stage were evaluated. The solid black image was output to evaluate the bright portion potential VL (V).

Then, while rotating the electrophotographic photosensitive drum at 1000 rpm in a dark box in the same environment,
Corona charging and exposure (LED array λ = 660nm)
To adjust the surface potential to −850 V and the passing current to −50 μA. Then, the background stain of the white image immediately after the forced fatigue for 60 minutes, the dark portion potential VD ′ (V) in the actual device, and the light portion in the actual device The potential VL '(V) was evaluated as in the initial stage.

The evaluation of the background stain was made by observing the copied image with a magnifying glass and determining the number of black spots of 0.05 mm or more per 1 cm ² . Images with the number of black spots of less than 1 are marked with 、, 1 to
Five images were evaluated as Δ, and six or more images were evaluated as ×. If the evaluation result is ○ or Δ, it is practical, but if it is ×, it may not be practical. Table 2 shows the results.

[0140]

[Table 2] *) Titanate coupling agent addition amount (wt%)

As described above, by setting the addition amount of the metal soap and the volume ratio of the pigment and the resin within the ranges of the examples, good chargeability, residual potential, and images can be obtained even after fatigue.

Example 42 In the same manner as in Example 33, except that the fine titanium oxide powder in the intermediate layer was changed to fine titanium oxide powder having a purity of 97.0% [JR (manufactured by Teikoku Chemicals)]. Example 4
2 was prepared.

Example 43 Example 34 was carried out in the same manner as in Example 34, except that the fine titanium oxide powder in the intermediate layer was changed to fine titanium oxide powder having a purity of 97.0% [JR (manufactured by Teikoku Chemicals)]. Example 4
An electrophotographic photosensitive member of No. 3 was prepared.

Examples 42 and 43 thus obtained
At 30 ° C. together with the photoconductors of Examples 33 and 34.
Store in a dark place under the condition of 80% RH for 12 months, and then, in the environment of 30 ° C. and 80% RH, at 20 ° C. and 50% RH.
The same evaluation as in the case of was performed. Table 3 shows the results.

[0145]

[Table 3]

As described above, by setting the purity of the pigment, titanium oxide, within the range of the examples, good chargeability, residual potential, and images can be obtained even after fatigue under high temperature and high humidity conditions.

Example 44 Except that in Example 33, 60% by weight of titanium oxide fine powder [KA-20 (manufactured by Titanium Industry)] and 3.3% by weight of tin oxide (manufactured by Mitsubishi Metals) were used as pigments for the intermediate layer. In the same manner as in Example 33, an electrophotographic photosensitive member of Example 44 was prepared.

Example 45 An electrophotographic photosensitive member of Example 45 was prepared in the same manner as in Example 44, except that the content was changed to 6.6% by weight of tin oxide (manufactured by Mitsubishi Metals).

Example 46 Example 4 was repeated in the same manner as in Example 44, except that tin oxide (manufactured by Mitsubishi Metal) was changed to 13% by weight.
6 was prepared.

Example 47 Example 4 was repeated in the same manner as in Example 44, except that tin oxide (manufactured by Mitsubishi Metal Corporation) was changed to 20% by weight.
7 was prepared.

Examples 44 to 47 thus obtained
Of the photosensitive member together with the photosensitive members of Examples 33 and 34
Stored in a dark place for 12 months under the conditions of 80 ° C. and 80% RH, and then stored at 20 ° C. and 50% in an environment of 10 ° C. and 20% RH.
The same evaluation as in the case of RH was performed. Table 4 shows the results.

[0152]

[Table 4]

As described above, in the second group of the present invention, by setting the ratio of the titanium oxide to the tin oxide of the pigment in the intermediate layer in the range of the embodiment, even after fatigue under low-temperature and low-humidity conditions,
Good chargeability, residual potential, and image are obtained.

[0154]

As described above, as is apparent from the detailed and concrete description, in the first group of the present invention, specific metal soap fine particles and fatty acid ester compounds are used.
It is possible to provide an electrophotographic photosensitive member that exhibits excellent stability even when repeatedly used without losing high sensitivity. In the second group of the present invention, by adding the metal soap of the above item (8), deterioration of chargeability and residual potential due to repeated fatigue is reduced even after storage for 12 months under high temperature and high humidity. , Can form an electrophotographic photoreceptor with excellent stability,
By adding octylate (linear metal salt) having a very simple structure as described in the above item (9), a higher effect can be obtained. As described in the above item (10), By setting the addition amount of the metal soap to 0.1% by weight to 5% by weight with respect to the pigment, a higher effect can be obtained. As described in the above item (11), by using titanium oxide as the pigment, A higher effect is obtained, and as described in the above item (12), by using a mixed system of titanium oxide and tin oxide as the pigment, deterioration of chargeability and residual potential due to repeated fatigue under low temperature and low humidity is reduced. ,
An electrophotographic photosensitive member having excellent stability can be formed, and the (1)
As described in item 3), the pigment is titanium oxide and tin oxide, and tin oxide is contained in an amount of 1% by weight to 25% by weight based on titanium oxide.
By doing so, a higher effect can be obtained, and the (14)
As described in the section, by setting the purity of the pigment titanium oxide to 99% or more, the deterioration of chargeability and residual potential due to repeated fatigue under high temperature and high humidity is small, and an electrophotographic photosensitive member excellent in stability is formed. it can. In addition, as in the above item (15), the image forming apparatus using the electrophotographic photosensitive member according to the above items (8) to (14) is stable under various environments. Electrophotographic images can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view of a single-layer photoreceptor used in the present invention.

FIG. 2 is a configuration example of a laminated photoreceptor used in the present invention.

FIG. 3 is another configuration example of the laminated photoconductor used in the present invention.

FIG. 4 is a diagram illustrating still another example of the configuration of the laminated photoconductor used in the present invention.

FIG. 5 is an explanatory diagram of an example of the device of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 11 conductive support 13 intermediate layer 15 single-layer photosensitive layer 17 charge generation layer 19 charge transport layer 21 elastic roller 22 photosensitive member 23 static elimination lamp 24 charging charger 25 eraser 26 image exposure unit 27 developing unit 28 pre-transfer charger 29 resist roller 30 Transfer paper 31 Transfer charger 32 Separation charger 33 Separation claw 34 Charger before cleaning 35 Fur brush 36 Cleaning blade

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03G 5/14 101 G03G 5/14 101E

Claims (15)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the outermost layer of the electrophotographic photosensitive member contains metal soap fine particles surface-treated with a fatty acid ester compound. Electrophotographic photoreceptor. 2. The electrophotographic photoreceptor according to claim 1, wherein said metal soap fine particles are zinc-containing metal soap fine particles. 3. The metal soap fine particles for an electrophotographic photosensitive member according to claim 1, wherein the metal soap fine particles are surface-treated with an organic solvent containing a fatty acid ester compound. 4. The metal soap for an electrophotographic photoreceptor according to claim 1, wherein said metal soap fine particles have been subjected to a surface treatment by a mechanical pulverization step together with an organic solvent containing a fatty acid ester compound. Fine particles. 5. The metal soap fine particles for an electrophotographic photosensitive member according to claim 3, wherein the organic solvent for surface treatment is an alcoholic solvent containing a fatty acid ester compound. 6. The metal soap fine particles for an electrophotographic photosensitive member according to claim 3, wherein the organic solvent for surface treatment is a halogen-based solvent containing a fatty acid ester compound. 7. The electrophotograph according to claim 1, wherein the binder resin of the outermost layer is a polycarbonate having a structural unit represented by the following general formula (1) as a main repeating unit. Photoconductor. Embedded image (In the formula, Z represents a group of nonmetallic atoms necessary to form a carbocyclic or heterocyclic ring which may have a substituent, and R _{1 to} R ₈ represent a hydrogen atom, a halogen atom, or each of a substituent. Represents an aliphatic group or a carbocyclic group which may be present.) 8. An electrophotographic photoreceptor comprising an intermediate layer containing a pigment and a binder resin as main components between a conductive support and a photosensitive layer, wherein the intermediate layer is bound to the pigment (P). Resin (R)
An electrophotographic photoreceptor, wherein the ratio P / R to the intermediate layer is in the range of 1/1 to 3/1 by volume, and the intermediate layer contains metal soap. 9. The electrophotographic photoreceptor according to claim 8, wherein the metal soap is an octylate. 10. The electrophotographic photoreceptor according to claim 8, wherein the metal soap accounts for 0.1% to 5% by weight based on the pigment (P) in the intermediate layer. 11. The electrophotographic photoconductor according to claim 8, wherein the pigment (P) is titanium oxide. 12. The electrophotographic photoreceptor according to claim 8, wherein said pigment (P) is titanium oxide and tin oxide. 13. The electrophotograph according to claim 8, wherein the pigment (P) comprises titanium oxide and tin oxide, and tin oxide is 1% by weight to 25% by weight with respect to titanium oxide. Photoconductor. 14. The method according to claim 8, wherein the titanium oxide has a purity of 99% or more.
The electrophotographic photosensitive member according to any one of the above. 15. At least charging means, image exposure means,
An electrophotographic method using an electrophotographic photosensitive member including a developing unit, a transfer unit, a cleaning unit, a charge removing unit, and an electrophotographic photosensitive member, and attaching a colored member charged to the same polarity as the charged polarity to the exposed portion. 15. An image forming apparatus in a photographic system, wherein the electrophotographic photosensitive member according to claim 8 is used as the electrophotographic photosensitive member.