JPH07325414A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic photoreceptor having high sensitivity and capable of imparting high-speed function to an image forming device such as a copying machine. CONSTITUTION:An org. photosensitive layer formed on an electrically conductive substrate contains an electric charge generating agent, a trinitrofluorenoneimine deriv. represented by the formula (where each of R<1>-R<5> is H, alkyl, aryl, alkoxy, aralkyl or halogen) as an electron transferring agent and one kind of compd. selected from among a butadiene deriv., a pyrene-hydrazone deriv., etc., as a positive hole transferring agent.

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 in an image forming apparatus such as a copying machine.

[0002]

2. Description of the Related Art In an image forming apparatus such as a copying machine, an organic photoconductor (OPC) having sensitivity in a wavelength region of a light source of the apparatus is often used. As the organic photoreceptor, a single layer type photoreceptor having a single layer type photosensitive layer in which a charge generating agent and a charge transporting agent are dispersed in a film made of a suitable binder resin, and the above charge transporting agent are contained. There is known a laminated-type photoreceptor in which a charge transport layer for controlling the charge generation layer and a charge generation layer containing a charge generation agent are laminated.

Charge transport agents used in these photoreceptors are required to have high carrier mobility, but most charge transport agents having high carrier mobility have hole transporting properties. Therefore, what has been put to practical use is limited to a negative charging type laminated organic photoreceptor having a charge transport layer as the outermost layer from the viewpoint of mechanical strength. However, since a negatively charged organic photoreceptor uses negative corona discharge, it produces a large amount of ozone, which causes problems such as environmental pollution and deterioration of the photoreceptor.

Therefore, in order to eliminate such drawbacks, the use of an electron transfer agent as a charge transfer agent has been studied, and in JP-A-1-206349, a compound having a diphenoquinone structure is electrophotographic. It has been proposed to use it as an electron transfer material for photoreceptors. However, in general, electron transfer agents such as diphenoquinones are
Since it was difficult to match with the charge generating agent, the electron injection from the charge generating agent to the electron transporting agent was insufficient, and therefore the photosensitivity was insufficient. Further, in the single-layer type organic photosensitive layer, there is a problem that the electron transport is hindered by the interaction between the diphenoquinone and the hole transport material.

Regarding the charging polarity of the photosensitive member, if one photosensitive member can be used for both positive charging and negative charging, the application range of the photosensitive member can be expanded. Further, if the organic photoconductor can be used in a single-layer dispersion type, the photoconductor can be easily manufactured, there are many advantages in preventing the occurrence of coating defects and improving the optical characteristics. A main object of the present invention is to solve the above-mentioned technical problems and to provide an electrophotographic photoreceptor in which injection and transportation of electrons from a charge generating agent are smoothly performed and sensitivity is improved as compared with the conventional case.

[0006]

Means and Actions for Solving the Problems The inventors have
As a result of earnest research to achieve the above problems, the general formula
(1):

[0007]

[Chemical 15]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ is the same or different and represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a halogen atom. ) Was found to have a higher electron-transporting ability than the conventional diphenoquinone-based compound, and as a result of further studies on the hole-transporting agent and the like to be combined therewith, the present invention was completed. I arrived.

That is, in the electrophotographic photosensitive member of the present invention, the organic photosensitive layer provided on the conductive substrate is represented by the above general formula (1) as a binder resin, a charge generating agent, and an electron transporting agent. A trinitrofluorenone imine derivative and the following general formula (2) as a hole transfer agent:

[0010]

[Chemical 16]

(In the formula, R ¹⁰¹ and R ¹⁰² are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ and R ^{10 6} are the same or different. Represents a hydrogen atom, an alkyl group or an aryl group), a general formula (3):

[0012]

[Chemical 17]

(Wherein R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are
The same or different, a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom is shown. ) Pyrene
Hydrazone derivative, general formula (4):

[0014]

[Chemical 18]

(Wherein R ¹¹⁰ , R ¹¹¹ , R ¹¹² and R
¹¹³ is the same or different and is a hydrogen atom, an alkyl group,
An alkoxy group or a halogen atom is shown. ) An acrolein derivative represented by the general formula (5):

[0016]

[Chemical 19]

(Wherein R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷
And R ¹¹⁸ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. ) A phenanthrene diamine derivative represented by the general formula (6):

[0018]

[Chemical 20]

[0019] (wherein, R ¹¹⁹ represents a hydrogen atom or an alkyl group, R ^120, R ¹²¹ and R ^{12 2} are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.) In Carbazole-hydrazone derivative represented by the general formula (7):

[0020]

[Chemical 21]

(Wherein R ¹²³ , R ¹²⁴ and R ¹²⁵ are
The same or different, a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom is shown. ) A quinoline-hydrazone derivative represented by the general formula (8):

[0022]

[Chemical formula 22]

(In the formula, R ¹²⁶ and R ¹²⁷ are the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ¹²⁸ and R ¹²⁹ are the same or different and are a hydrogen atom or an alkyl group. Or a stilbene derivative represented by the general formula (9):

[0024]

[Chemical formula 23]

(In the formula, R¹³⁰, R¹³¹, R¹³²，
R¹³³, R¹³⁴And R¹³⁵Are the same or different,
Hydrogen atom, alkyl group, alkoxy group or halogen source
Indicates a child, R ¹³⁶And R¹³⁷Are the same or different
Represents a hydrogen atom, an alkyl group or an aryl group. )
And an enamine derivative represented by the general formula (10):

[0026]

[Chemical formula 24]

(Wherein R ¹³⁸ , R ¹³⁹ , R ¹⁴⁰ and R
¹⁴¹ is the same or different and is a hydrogen atom, an alkyl group,
Represents an alkoxy group or a halogen atom, and Ar represents the following formulas (Ar1) (Ar2) and (Ar3):

[0028]

[Chemical 25]

A divalent group represented by any of the following is shown. )
And at least one of the stilbene-hydrazone derivatives represented by
The trinitrofluorenone imine derivative represented by the general formula (1) as an electron transfer agent has good solubility in a solvent and compatibility with a binder resin, and is excellent in matching with a charge generating agent. Electrons are smoothly injected, and the electron transport property is excellent especially in a low electric field. In addition, since the bulky substituent is introduced into the molecule of the above-mentioned trinitrofluorenone imine derivative, a steric hindrance may form a charge transfer complex with the hole transfer agent, which causes a decrease in sensitivity. Is suppressed.

Therefore, the electrophotographic photosensitive member of the present invention has high sensitivity in an arbitrary wavelength region and can be suitably used for an image forming apparatus of a digital optical system or an analog optical system. In the trinitrofluorenone imine derivative represented by the general formula (1), examples of the alkyl group corresponding to the groups R ^{1 to} R ⁵ include methyl, ethyl,
n-propyl, isopropyl, t-butyl, pentyl,
Examples thereof include an alkyl group having 1 to 6 carbon atoms such as a hexyl group.

Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, t-butoxy, pentyloxy and hexyloxy groups. Examples of the aryl group include phenyl, o-terphenyl, naphthyl, anthryl and phenanthryl groups. The aryl group may have a substituent such as an alkyl group, an alkoxy group or a halogen atom at any position thereof.

Examples of the aralkyl group include benzyl, α-phenethyl, β-phenethyl, 3-phenylpropyl, benzhydryl and trityl groups. The aralkyl group has an alkyl group at any position thereof,
It may have a substituent such as an alkoxy group or a halogen atom. Examples of the halogen atom include chlorine, bromine, fluorine and iodine.

This derivative can be synthesized, for example, by condensing 2,4,7-trinitrofluorenone and aniline or a derivative thereof in a solvent as shown in the following reaction process formula. Examples of the solvent include acetic acid, propionic acid, butanoic acid, chloroform, tetrahydrofuran, dimethylformamide, dimethylsulfoxide and the like. If necessary, the reaction may be carried out in the presence of a suitable catalyst such as zinc chloride. The reaction may be performed usually at a temperature of 30 to 170 ° C. for about 20 minutes to 4 hours.

[0034]

[Chemical formula 26]

(In the formula, R ^{1 to} R ⁵ are the same as above.) Suitable examples of the trinitrofluorenone imine derivative include compounds represented by any of the general formulas (11) to (13). can give.

[0036]

[Chemical 27]

(Wherein R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R
⁴³ is the same or different and represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. )

[0038]

[Chemical 28]

(In the formula, R ⁴⁴ and R ⁴⁵ are the same or different and each represents an alkyl group, an alkoxy group or a halogen atom. Α and β are integers whose sum is 0 to 4.)

[0040]

[Chemical 29]

(In the formula, R ⁴⁶ and R ⁴⁷ are the same or different and represent an alkyl group, an alkoxy group or a halogen atom. Γ and δ are integers such that their sum total is 0 to 4.) The specific compound of the nitrofluorenone imine derivative is not particularly limited, for example, as a specific example of the trinitrofluorenone imine derivative represented by the general formula (11), compounds represented by the following formulas (11a) to (11d) Can be given.

[0042]

[Chemical 30]

Specific examples of the trinitrofluorenone imine derivative represented by the general formula (12) include the following formula (12a)
The compounds represented by (12d) are mentioned.

[0044]

[Chemical 31]

Further, specific examples of the trinitrofluorenone imine derivative represented by the general formula (13) include the following formula (13
Examples thereof include compounds represented by a) to (13d).

[0046]

[Chemical 32]

In the butadiene derivative represented by the general formula (2), which is contained in the organic photosensitive layer as a hole transporting material together with the trinitrofluorenone imine derivative, an alkyl group corresponding to the groups R ¹⁰¹ and R ^102. , Alkoxy groups, halogen atoms, and groups R ¹⁰³ , R ¹⁰⁴ , R
Examples of the alkyl group and aryl group corresponding to ¹⁰⁵ and R ¹⁰⁶ include the same groups as described above.

Specific examples of the butadiene derivative represented by the general formula (2) include compounds represented by the following formula (2a).

[0049]

[Chemical 33]

In the pyrene-hydrazone derivative represented by the general formula (3), examples of the alkyl group, alkoxy group and halogen atom corresponding to the groups R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ include the same groups as described above. . Specific examples of the pyrene-hydrazone derivative represented by the general formula (3) include compounds represented by the following formula (3a).

[0051]

[Chemical 34]

[0052] In the acrolein derivative represented by the general formula (4), the alkyl group corresponding to group ^{R 110, R 111, R 11} 2, R 113, an alkoxy group, as the halogen atom,
Examples are the same groups as described above. Specific examples of the acrolein derivative represented by the general formula (4) include compounds represented by the following formula (4a).

[0053]

[Chemical 35]

Fenance ranger represented by the general formula (5)
In the min derivative, the group R¹¹⁴, R ¹¹⁵, R¹¹⁶, R
¹¹⁷, R¹¹⁸Corresponding to alkyl group, alkoxy group,
The same group as the above is illustrated also as a logen atom. one
Component of phenanthrene diamine derivative represented by general formula (5)
Examples of the body include compounds represented by the following formulas (5a) and (5b).
To be

[0055]

[Chemical 36]

In the carbazole-hydrazone derivative represented by the general formula (6), as an alkyl group corresponding to the group R ¹¹⁹ and an alkyl group, an alkoxy group or a halogen atom corresponding to the groups R ¹²⁰ , R ¹²¹ and R ¹²² , Also, the same groups as described above are exemplified. Specific examples of the carbazole-hydrazone derivative represented by the general formula (6) include the following formula (6a)
Examples thereof include compounds represented by (6b).

[0057]

[Chemical 37]

In the quinoline-hydrazone derivative represented by the general formula (7), the alkyl group, alkoxy group and halogen atom corresponding to the groups R ¹²³ , R ^{12 4} and R ¹²⁵ may also be
Examples are the same groups as described above. Specific examples of the quinoline-hydrazone derivative represented by the general formula (7) include the following formula (7
a) The compound represented by (7b) may be mentioned.

[0059]

[Chemical 38]

In the stilbene derivative represented by the general formula (8), an alkyl group, an alkoxy group, a halogen atom corresponding to the groups R ¹²⁶ and R ¹²⁷ , and an alkyl group and an aryl group corresponding to the groups R ¹²⁸ and R ^129. Also, the same groups as above are exemplified. Specific examples of the stilbene derivative represented by the general formula (8) include compounds represented by the following formulas (8a) and (8b).

[0061]

[Chemical Formula 39]

In the enamine derivative represented by the general formula (9), the groups R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ and R
An alkyl group corresponding to ¹³⁵ , an alkoxy group, a halogen atom, and an alkyl group corresponding to the groups R ¹³⁶ and R ¹³⁷ ,
Examples of the aryl group also include the same groups as described above. Specific examples of the enamine derivative represented by the general formula (9) include:
Examples thereof include compounds represented by the following formulas (9a) and (9b).

[0063]

[Chemical 40]

Further, the stilbene represented by the general formula (10)
-In the hydrazone derivative, the group R ¹³⁸, R¹³⁹, R
¹⁴⁰, R¹⁴¹Corresponding to alkyl group, alkoxy group,
The same group as the above is illustrated also as a logen atom. one
Component of stilbene-hydrazone derivative represented by general formula (10)
A body example is a compound represented by the following formulas (10a) (10b) (10c).
I can give you something.

[0065]

[Chemical 41]

The organic photosensitive layer is of a single layer type containing the above-mentioned electron transporting agent and hole transporting agent in the same layer together with a charge generating agent, and a laminated type comprising a charge transporting layer and a charge generating layer. Sometimes it is. The photoconductor of the present invention may be either a positive charging type or a negative charging type, but it is particularly preferable to use the positive charging type. In the positive charge type photoreceptor, the electrons released from the charge generating agent in the exposure step are smoothly injected into the trinitrofluorenone imine derivative (electron transfer agent) represented by the general formula (1), and then the electron transfer agent Due to the transfer of electrons between them, the electrons move to the surface of the photosensitive layer and cancel the positive charge (+) charged on the surface of the photosensitive layer in advance. On the other hand, holes (+) are represented by the general formula (2)
Injected into the hole transfer material represented by ~ (6), it moves to the surface of the conductive substrate without being trapped in the middle, and is negatively charged (-) on the surface of the conductive substrate in advance. Canceled. In this way, the sensitivity of the positive charging type photoconductor is considered to be improved.

Examples of the charge generating agent used in the present invention include selenium, selenium-tellurium, amorphous silicon, pyrylium salts, azo pigments, disazo pigments, ansanthrone pigments, phthalocyanine pigments, naphthalocyanine pigments, Examples thereof include indigo pigments, triphenylmethane pigments, slene pigments, toluidine pigments, pyrazoline pigments, quinacridone pigments and dithioketopyrrolopyrrole pigments. These charge generating agents may be used alone or in combination of two or more so as to have an absorption wavelength in a desired region.

Further, in particular, it is used in a digital optical system image forming apparatus using a light source such as a semiconductor laser.
Examples of the charge generating agent suitable for the organic photoreceptor having a sensitivity in the wavelength region of 00 nm or more include phthalocyanine-based pigments such as metal-free phthalocyanine and oxotitanyl phthalocyanine. These phthalocyanine-based pigments are excellent in matching with the trinitrofluorenone imine derivative represented by the general formula (1), and therefore the electrophotographic photoreceptor using both of them is highly sensitive in the above wavelength region,
It can be suitably used for an image forming apparatus of a digital optical system. As the binder resin for dispersing the above components, various resins conventionally used in organic photosensitive layers can be used, and examples thereof include a styrene-based polymer, a styrene-butadiene copolymer, and a styrene- Acrylonitrile copolymer, styrene-maleic acid copolymer,
Acrylic copolymer, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer, chlorinated polyethylene, polyvinyl chloride, polypropylene, ionomer, vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide , Thermoplastic resins such as polyurethane, polycarbonate, polyarylate, polysulfone, diallylphthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, polyester resin, silicone resin, epoxy resin, phenol resin, urea resin, melamine resin, etc. Examples thereof include crosslinkable thermosetting resins, and photocurable resins such as epoxy acrylate and urethane-acrylate. These binder resins can be used alone or in combination of two or more. Suitable resins are styrene polymers, acrylic polymers, styrene-acrylic copolymers, polyesters, alkyd resins, polycarbonates, polyarylates and the like.

In the photosensitive layer, various additives known per se, such as antioxidants, radical scavengers, singlet quenchers, and ultraviolet absorbers, are deteriorated to the extent that they do not adversely affect electrophotographic properties. Inhibitors, softeners, plasticizers, surface modifiers, extenders, thickeners, dispersion stabilizers, waxes, acceptors, donors and the like can be added. The amounts of these additives to be added may be the same as conventional amounts. For example, the sterically hindered phenolic antioxidant is preferably added in an amount of about 0.1 to 50 parts by weight with respect to 100 parts by weight of the binder resin.

In order to improve the sensitivity of the photosensitive layer,
For example, known sensitizers such as terphenyl, halonaphthoquinones and acenaphthylene may be used in combination with the charge generating agent. In addition to the trinitrofluorenone imine derivative represented by the general formula (1), another conventionally known electron transfer agent may be contained in the photosensitive layer. Examples of such electron transfer agents include benzoquinone-based, diphenoquinone-based, malononitrile, thiopyran-based compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone,
Fluorenone compounds such as 3,4,5,7-tetranitro-9-fluorenone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, dibromomaleic anhydride and the like. .

These electron transfer agents may be used alone or in combination of two or more. Further, in addition to the hole transfer agents represented by the general formulas (2) to (10), other conventionally known hole transfer agents may be contained in the photosensitive layer. Examples of such hole transporting agents include oxadiazole compounds such as 2,5-di (4-methylaminophenyl) and 1,3,4-oxadiazole, 9- (4-diethylaminostyryl) anthracene. And other styryl compounds, polyvinylcarbazole and other carbazole compounds, organic polysilane compounds, 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline and other pyrazoline compounds, hydrazone compounds other than the above, triphenylamine compounds , Indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds,
Examples thereof include nitrogen-containing cyclic compounds such as triazole compounds and condensed polycyclic compounds.

These hole transfer agents are used alone or in combination of two or more. Further, when using a hole transporting agent having film-forming properties such as polyvinylcarbazole, the binder resin is not always necessary. As the conductive substrate used in the photoreceptor of the present invention, various materials having conductivity can be used, and examples thereof include aluminum, copper, tin,
Simple metals such as platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass, and plastic materials in which the above metals are vapor-deposited or laminated, aluminum iodide, tin oxide, indium oxide. Examples include glass coated with the like.

The conductive substrate may be in the form of a sheet, a drum or the like, as long as the substrate itself has conductivity or the surface of the substrate has conductivity. Further, it is preferable that the conductive substrate has sufficient mechanical strength when used. The photosensitive layer according to the present invention is manufactured by coating a coating solution prepared by dissolving or dispersing a resin composition containing each of the above components in a solvent on a conductive substrate and drying the coating solution.

The effect of the use of the electron transfer agent, hole transfer agent and electron accepting compound in the present invention is remarkably exhibited in the single layer type photoreceptor. The single-layer type photoreceptor of the present invention can be applied to both positive charging and negative charging, but it is particularly preferable to use the positive charging type. In the single-layer type photoreceptor, the charge generating agent is preferably added to the photosensitive layer in an amount of 0.5 to 20 parts by weight, particularly 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin.

The hole-transporting agent is preferably added to the photosensitive layer in an amount of 5 to 200 parts by weight, particularly 30 to 150 parts by weight, based on 100 parts by weight of the binder resin. The electron transfer agent is 5 to 100 parts by weight, especially 10 to 100 parts by weight of the binder resin.
It is preferable to add 80 parts by weight to the photosensitive layer. When the electron-accepting compound is added, the compounding ratio of the electron-accepting compound is 0.01 to 1 with respect to 100 parts by weight of the binder resin.
00 parts by weight, especially 0.1 to 30 parts by weight is preferred.

In the single-layer type photoreceptor, the thickness of the photosensitive layer is 5
The thickness is preferably about 50 to 50 μm, particularly about 10 to 40 μm. In order to obtain a laminated type photoreceptor, a charge generating agent is vapor-deposited alone on a conductive substrate to form a charge generating layer (evaporation type charge generating layer), or charge generating is performed by means such as coating. Forming a charge generation layer (resin-dispersed charge generation layer) containing an agent and a binder resin and, if necessary, a hole transfer agent, and containing an electron transfer agent and a binder resin on the charge generation layer. The charge transport layer may be formed. Alternatively, conversely to the above, the charge transport layer may be formed on the conductive substrate, and then the charge generation layer may be formed.

In the laminated photoreceptor, the charge generating agent and the binder resin which constitute the resin-dispersed charge generating layer can be used in various ratios, but the charge can be changed with respect to 100 parts by weight of the binder resin. Generating agent 5 to 1000 parts by weight, especially 30 to 5
It is preferably used in a proportion of 00 parts by weight. When the electron-accepting compound is added to the resin-dispersed charge generation layer, the compounding ratio is 0.1 to 100 parts by weight of the binder resin.
100 parts by weight, especially 1 to 30 parts by weight is preferred.

The electron-transporting agent and the binder resin constituting the charge-transporting layer can be used in various proportions within a range that does not hinder the transport of electrons and a range that does not crystallize. In order to easily transport the electrons generated in step 1, the electron transfer agent 10 is added to 100 parts by weight of the binder resin.
It is preferably used in an amount of ˜500 parts by weight, particularly 25 to 200 parts by weight. When the electron-accepting compound is added to the charge transport layer, the compounding ratio thereof is 0.01 to 100 parts by weight, particularly 0.1 to 3 parts by weight with respect to 100 parts by weight of the binder resin.
0 parts by weight is preferred.

The thickness of the laminated photosensitive layer is preferably 0.01 to 5 μm, particularly 0.1 to 3 μm for the charge generation layer, and 2 to 100 μm for the charge transport layer.
It is preferable that it is formed to a thickness of m, especially about 5 to 50 μm. In the single-layer type photoreceptor, between the conductive substrate and the photosensitive layer, in the laminated type photoreceptor, between the conductive substrate and the charge generation layer, or between the conductive substrate and the charge transport layer. In between, a barrier layer may be formed in a range that does not impair the characteristics of the photoreceptor. A protective layer may be formed on the surface of the photosensitive layer.

When the above-mentioned photosensitive layer is formed by a coating method, the charge-generating agent, charge-transporting agent, electron-accepting compound, binder resin and the like exemplified above may be used together with a suitable solvent by a known method, for example, A dispersion may be prepared by dispersing and mixing using a roll mill, a ball mill, an attritor, a paint shaker, an ultrasonic disperser, or the like, and the dispersion may be applied and dried by a known means.

As the solvent for forming the dispersion liquid, various organic solvents can be used. For example, alcohols such as methanol, ethanol, isopropanol and butanol, and aliphatic hydrocarbons such as n-hexane, octane and cyclohexane. , Benzene, toluene, xylene, etc., aromatic hydrocarbons, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, etc., halogenated hydrocarbons, dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. ethers, acetone, methyl ethyl ketone , Ketones such as cyclohexanone, esters such as ethyl acetate and methyl acetate, dimethylformaldehyde, dimethylformamide, dimethylsulfoxide and the like. That. These solvents are 1 type or 2 types.
A mixture of two or more species can be used.

Further, in order to improve the dispersibility of the charge transport agent or the charge generating agent and the smoothness of the surface of the photosensitive layer, a surfactant,
A leveling agent or the like may be used.

[0083]

EXAMPLES The present invention will be described below based on Examples and Comparative Examples. Examples 1 to 53 5 parts by weight of a phthalocyanine pigment as a charge generating agent, 50 parts by weight of a compound belonging to the derivative represented by any one of the general formulas (2) to (10) as a hole transferring agent, and an electron transferring agent. Of the compound of the general formula (11), which belongs to the trinitrofluorenone imine derivative, together with 100 parts by weight of the polycarbonate as the binder resin, 800 parts by weight of tetrahydrofuran as the solvent, and 50 minutes in a ball mill. , And mixed and dispersed to prepare a coating liquid for a single-layer type photosensitive layer. Then, this coating solution is applied on an aluminum base tube as a conductive base material by a dip coating method and dried with hot air at 100 ° C. for 60 minutes to give a film thickness of 15 to 15
A single-layer type photoreceptor for a digital light source having a single-layer type photosensitive layer of 20 μm was manufactured.

Comparative Examples 1 to 9 As the electron transfer agent, the compound represented by the formula (Q):

[0085]

[Chemical 42]

The procedure of Examples 1 to 53 was repeated, except that 30 parts by weight of the diphenoquinone derivative represented by
A single-layer type photoreceptor for a digital light source having a single-layer type photosensitive layer having a film thickness of 15 to 20 μm was manufactured. In addition, each of the above embodiments,
The specific compounds of the hole transfer material and the electron transfer material used in the comparative examples are shown in Tables 1 to 3 by using the compound numbers of the above specific examples. Further, as the phthalocyanine pigment, two types of X-type metal-free phthalocyanine and oxotitanyl phthalocyanine were used. Which of the phthalocyanine pigments was used in each Example and Comparative Example is shown in Tables 1 to 3 below. Showed.

X: X-Type Metal-Free Phthalocyanine Ti: Oxotitanyl Phthalocyanine The following tests were conducted on the single-layer type photoreceptors of the above Examples and Comparative Examples to evaluate the characteristics. Photosensitivity test Using a drum sensitivity tester manufactured by GENTEC, an applied voltage was applied to the surface of each of the photoconductors of Examples and Comparative Examples to charge the surface to + 700V. Then, the surface of the photoconductor is irradiated with monochromatic light having a wavelength of 780 nm (half-value width of 20 nm) and a light intensity of 16 μW / cm ² extracted from white light of a halogen lamp which is an exposure light source using a bandpass filter (irradiation time 80 msec. ), And 330 msec. From the start of exposure. The surface potential at the time when it passed was measured as the post-exposure potential V _L (V).

The results are shown in Tables 1 to 3.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

From the results of Tables 1 to 3 above, in each of Examples 1 to 53 having the constitution of the present invention, the post-exposure potential V _L (V) is higher than that of Comparative Examples 1 to 9 using the conventional electron transfer material. It was found that the sensitivity characteristic was excellent because of low (). Examples 54 to 106 A film thickness of 1 was obtained in the same manner as in Examples 1 to 53 except that 30 parts by weight of a compound belonging to the trinitrofluorenone imine derivative represented by the general formula (11) was used as the electron transfer agent.
A single-layer type photoreceptor for a digital light source having a single-layer type photosensitive layer of 5 to 20 μm was manufactured.

The post-exposure potential V _L (V) of the single-layer type photoconductor of each of the above examples was determined in the same manner as described above, and the characteristics thereof were evaluated. The results are shown in Table 4 together with the results of Comparative Examples 1 to 9 above.
~ 6. The specific compounds of the charge generating agent, hole transporting agent, and electron transporting agent used in each example are shown in Tables 4 to 6 by using the compound number of each specific example.

[0094]

[Table 4]

[0095]

[Table 5]

[0096]

[Table 6]

From the results of Tables 4 to 6 above, in each of Examples 54 to 106 having the constitution of the present invention, the post-exposure potential V _L (V) is higher than that of Comparative Examples 1 to 9 using the conventional electron transfer agent. It was found that the sensitivity characteristic was excellent because of low (). Examples 107 to 159 A film thickness of 1 was obtained in the same manner as in Examples 1 to 53 except that 30 parts by weight of a compound belonging to the trinitrofluorenone imine derivative represented by the general formula (12) was used as the electron transfer agent.
A single-layer type photoreceptor for a digital light source having a single-layer type photosensitive layer of 5 to 20 μm was manufactured.

The post-exposure potential V _L (V) of the single-layer type photoconductor of each of the above examples was determined in the same manner as described above, and the characteristics thereof were evaluated. The results are shown in Table 7 together with the results of Comparative Examples 1 to 9 above.
~ 9. The specific compounds of the charge generating agent, hole transporting agent, and electron transporting agent used in each example are shown in Tables 7 to 9 by using the compound numbers of each specific example as described above.

[0099]

[Table 7]

[0100]

[Table 8]

[0101]

[Table 9]

From the results of Tables 7 to 9 above, in each of Examples 107 to 159 having the constitution of the present invention, the post-exposure potential V _L (V) is higher than that of Comparative Examples 1 to 9 using the conventional electron transfer agent. )
It was found that the sensitivity characteristic was excellent because of low.

[0103]

As described above in detail, the electrophotographic photosensitive member of the present invention has high sensitivity and has a unique effect that the speed of an image forming apparatus such as a copying machine can be increased.

Front page continuation (72) Inventor Shunichi Matsumoto 1-2-2 Tamatsukuri, Chuo-ku, Osaka-shi, Osaka Mita Industry Co., Ltd.

Claims (28)

[Claims] 1. An electrophotographic method in which an organic photosensitive layer is provided on a conductive substrate.
A true photoconductor, wherein the organic photosensitive layer comprises a binder resin and
The following general formula (1) as a charge generation agent and an electron transfer agent:(In the formula, R¹, R², R³, R^FourAnd R^FiveAre the same
Or a hydrogen atom, an alkyl group, an aryl group,
Indicates a lucoxy group, aralkyl group or halogen atom.
You ) Trinitrofluorenone imine derivative represented by
And the following general formula (2) as a hole-transporting agent:(In the formula, R¹⁰¹And R¹⁰² Are the same or different
Hydrogen atom, alkyl group, alkoxy group or halogen
R atom¹⁰³, R¹⁰⁴, R¹⁰⁵And R
^{Ten 6}Are the same or different and represent a hydrogen atom, an alkyl group or
Or an aryl group. ) Derived from butadiene
Body, general formula (3):(In the formula, R¹⁰⁷, R¹⁰⁸And R¹⁰⁹Are the same or different
Becomes a hydrogen atom, alkyl group, alkoxy group or
Indicates a logen atom. ) Pyrene-hydrazone invitation
Conductor, general formula (4):(In the formula, R¹¹⁰, R¹¹¹, R¹¹²And R¹¹³Are the same
Or differently, a hydrogen atom, an alkyl group, an alkoxy group
Alternatively, it represents a halogen atom. ) Acrolein
Derivative, general formula (5):(In the formula, R¹¹⁴, R¹¹⁵, R¹¹⁶, R¹¹⁷And R¹¹⁸
Are the same or different and each represents a hydrogen atom, an alkyl group,
Indicates a coxy group or a halogen atom. )
Nonslenediamine derivative, general formula (6):(In the formula, R¹¹⁹Represents a hydrogen atom or an alkyl group, R
¹²⁰, R¹²¹And R^{12 2}Are the same or different, water
Elemental atom, alkyl group, alkoxy group or halogen atom
Indicates. ) Carbazole-hydrazone induction represented by
Body, general formula (7):(In the formula, R^{one two Three}, R¹²⁴And R¹²⁵Are the same or different
Becomes a hydrogen atom, alkyl group, alkoxy group or
Indicates a logen atom. ) Quinoline-hydrazone
Derivative, general formula (8):(In the formula, R¹²⁶And R¹²⁷Are the same or different,
Hydrogen atom, alkyl group, alkoxy group or halogen source
Indicates a child, R¹²⁸And R¹²⁹Are the same or different
Represents a hydrogen atom, an alkyl group or an aryl group. )
A stilbene derivative represented by the general formula (9):(In the formula, R¹³⁰, R¹³¹, R¹³², R¹³³, R¹³⁴And
And R¹³⁵Are the same or different, and are hydrogen atom, alkyl
A group, an alkoxy group or a halogen atom, R ¹³⁶Oh
And R¹³⁷Are the same or different and are hydrogen atom,
Represents a group or aryl group. ) Enamine invitation
Conductor and general formula (10):(In the formula, R¹³⁸, R¹³⁹, R¹⁴⁰And R¹⁴¹Are the same
Or differently, a hydrogen atom, an alkyl group, an alkoxy group
Or a halogen atom, and Ar is represented by the following formulas (Ar1) (Ar2)
And (Ar3):Represents a divalent group represented by any of the above. )
At least one of the tilbene-hydrazone derivatives and
An electrophotographic photosensitive member comprising: 2. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin, a charge generating agent, and an electron transporting agent represented by the following general formula (11). ): (In the formula, R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.) And a trinitrofluorenone imine derivative An electrophotographic photosensitive member containing a butadiene derivative represented by the general formula (2) according to claim 1 as a hole transfer material. 3. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer serves as a binder resin, a charge generating agent, and an electron transporting agent. The trinitrofluorenone imine derivative represented by the general formula (11), and the general formula according to claim 1 as a hole transfer agent.
An electrophotographic photoreceptor containing the pyrene-hydrazone derivative represented by (3). 4. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer serves as a binder resin, a charge generating agent, and an electron transporting agent. The trinitrofluorenone imine derivative represented by the general formula (11), and the general formula according to claim 1 as a hole transfer agent.
An electrophotographic photoreceptor containing the acrolein derivative represented by (4). 5. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer serves as a binder resin, a charge generating agent, and an electron transporting agent. The trinitrofluorenone imine derivative represented by the general formula (11), and the general formula according to claim 1 as a hole transfer agent.
An electrophotographic photoreceptor containing a phenanthrene diamine derivative represented by (5). 6. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer serves as a binder resin, a charge generating agent and an electron transporting agent. The trinitrofluorenone imine derivative represented by the general formula (11), and the general formula according to claim 1 as a hole transfer agent.
An electrophotographic photoreceptor containing a carbazole-hydrazone derivative represented by (6). 7. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer serves as a binder resin, a charge generating agent and an electron transporting agent. The trinitrofluorenone imine derivative represented by the general formula (11), and the general formula according to claim 1 as a hole transfer agent.
An electrophotographic photoreceptor containing a quinoline-hydrazone derivative represented by (7). 8. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer serves as a binder resin, a charge generating agent and an electron transporting agent. The trinitrofluorenone imine derivative represented by the general formula (11), and the general formula according to claim 1 as a hole transfer agent.
An electrophotographic photoreceptor containing the stilbene derivative represented by (8). 9. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer serves as a binder resin, a charge generating agent, and an electron transporting agent. The trinitrofluorenone imine derivative represented by the general formula (11), and the general formula according to claim 1 as a hole transfer agent.
An electrophotographic photoreceptor containing the enamine derivative represented by (9). 10. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (11) according to claim 2 as an electron transfer agent, and a general formula according to claim 1 as a hole transfer agent.
An electrophotographic photoreceptor containing the stilbene-hydrazone derivative represented by (10). 11. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent and the following general formula (12) as an electron transfer agent: (In the formula, R ⁴⁴ and R ⁴⁵ are the same or different and each represents an alkyl group, an alkoxy group or a halogen atom. Α and β are integers whose sum is 0 to 4.)
An electrophotographic photosensitive member comprising a trinitrofluorenone imine derivative represented by: and a butadiene derivative represented by the general formula (2) according to claim 1 as a hole transporting agent. 12. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (12) according to claim 11 as an electron transfer agent, and a general formula (3) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing the pyrene-hydrazone derivative represented. 13. An electrophotographic photoreceptor having an organic photosensitive layer on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (12) according to claim 11 as an electron transfer agent, and a general formula (4) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing an acrolein derivative represented by the formula. 14. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (12) according to claim 11 as an electron transfer agent, and a general formula (5) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing a phenanthrene diamine derivative represented by the formula. 15. An electrophotographic photoreceptor having an organic photosensitive layer on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (12) according to claim 11 as an electron transfer agent, and a general formula (6) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing the carbazole-hydrazone derivative represented. 16. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (12) according to claim 11 as an electron transfer agent, and a general formula (7) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing a quinoline-hydrazone derivative represented by the formula. 17. An electrophotographic photoreceptor having an organic photosensitive layer on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (12) according to claim 11 as an electron transfer agent, and a general formula (8) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing a stilbene derivative represented by the formula. 18. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (12) according to claim 11 as an electron transfer agent, and a general formula (9) according to claim 1 as a hole transfer agent. An electrophotographic photosensitive member containing the represented enamine derivative. 19. An electrophotographic photoreceptor having an organic photosensitive layer on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (12) according to claim 11 as an electron transfer agent, and a general formula (10) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing the stilbene-hydrazone derivative represented. 20. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent and the following general formula (13) as an electron transfer agent: (In the formula, R ⁴⁶ and R ⁴⁷ are the same or different and each represents an alkyl group, an alkoxy group or a halogen atom. Γ and δ are integers whose sum is 0 to 4.)
An electrophotographic photosensitive member comprising a trinitrofluorenone imine derivative represented by: and a butadiene derivative represented by the general formula (2) according to claim 1 as a hole transporting agent. 21. An electrophotographic photosensitive member comprising an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (13) according to claim 20 as an electron transfer agent, and a general formula (3) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing the pyrene-hydrazone derivative represented. 22. An electrophotographic photosensitive member having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (13) according to claim 20 as an electron transfer agent, and a general formula (4) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing an acrolein derivative represented by the formula. 23. An electrophotographic photoreceptor having an organic photosensitive layer on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (13) of claim 20 as an electron transfer agent, and a general formula (5) of claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing a phenanthrene diamine derivative represented by the formula. 24. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (13) according to claim 20 as an electron transfer agent, and a general formula (6) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing the carbazole-hydrazone derivative represented. 25. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (13) of claim 20 as an electron transfer agent, and a general formula (7) of claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing a quinoline-hydrazone derivative represented by the formula. 26. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (13) according to claim 20 as an electron transfer agent, and a general formula (8) according to claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing a stilbene derivative represented by the formula. 27. An electrophotographic photoreceptor having an organic photosensitive layer provided on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
A charge generating agent, a trinitrofluorenone imine derivative represented by the general formula (13) of claim 20 as an electron transfer agent, and a general formula (9) of claim 1 as a hole transfer agent. An electrophotographic photosensitive member containing the represented enamine derivative. 28. An electrophotographic photoreceptor having an organic photosensitive layer on a conductive substrate, wherein the organic photosensitive layer comprises a binder resin.
The charge generating agent, the trinitrofluorenone imine derivative represented by the general formula (13) of claim 20 as an electron transfer agent, and the general formula (10) of claim 1 as a hole transfer agent. An electrophotographic photoreceptor containing the stilbene-hydrazone derivative represented.