JPH0437858A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance electrophotographic characteristics and printing resistance by successively laminating on a conductive substrate an electric charge generating layer and a charge transfer layer containing an improved binder to form a photosensitive layer. CONSTITUTION:The charge transfer layer contains as the binder resin the polymer having repeating units each represented by formula I and the compound represented by formula II, and in formulae I and II, Z is a nonmetallic atomic group necessary to form an optionally substituted carbon ring or hetero ring; each of R1 - R8 is H, Cl, Br, or methyl; each of Ar1 and Ar2 is an aliphatic or aromatic group and each may combine with each other to form a ring; Ar3 is phenylene; and each of R11 and R12 is H, an aliphatic or aromatic group; and R13 is an aliphatic or aromatic group, thus permitting the binder resin to exhibit the superior characteristics of the polycarbonate; electric charging characteristics, repetition characteristics, printing resistance, and the like for the photosensitive body.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrophotographic photoreceptor, and more particularly to an organic photoconductive electrophotographic photoreceptor, and further to the film properties of the constituent layers of the electrophotographic photoreceptor.

[Conventional technology]

In an electrophotographic copying machine using the Carlson method, the surface of the photoreceptor is uniformly charged, the charge is erased imagewise by exposure to form an electrostatic latent image, and the electrostatic latent image is developed with toner. Then, the toner image is transferred and fixed onto paper or the like.

On the other hand, the photoreceptor is subjected to removal of adhered toner, neutralization of static electricity, and surface cleaning, and is used repeatedly over a long period of time.

Therefore, as an electrophotographic photoreceptor, it not only has good charging characteristics and sensitivity, but also has electrophotographic characteristics such as low dark decay.
In addition, it has good physical properties such as printing durability, abrasion resistance, and moisture resistance after repeated use, as well as resistance to ozone generated during corona discharge and ultraviolet rays during exposure (environmental resistance). required.

Conventionally, as electrophotographic photoreceptors, inorganic photoreceptors whose photosensitive layer is mainly composed of inorganic photoconductive substances such as selenium, zinc oxide, and cadmium sulfide have been widely used.

In recent years, carrier generation and carrier transport functions have been assigned to different materials for the photosensitive layer of electrophotographic photoreceptors, and materials that exhibit each function are selected from a wide range according to the desired characteristics, resulting in high sensitivity and durability. There is a trend toward practical use of organic photoreceptors with large sizes.

Conventionally, such functionally divided organic photoreceptors have been mainly used for negative charging, and as described in JP-A-60-247647, a thin carrier generation layer is provided on a support.
A relatively thick carrier transport layer is provided on top of this.

As a binder used for such photoreceptors, it is well known that bisphenol A type polycarbonate shown by the following structural formula exhibits good characteristics in terms of charging characteristics, sensitivity, residual potential, repeatability, etc. It is being

However, as a result of studies conducted by the present inventors, the above-mentioned bisphenol A type polycarbonate has the disadvantage that its solution tends to gel due to the high crystallinity of the polymer, and becomes unusable in about 1 to 2 days. have. In addition, when forming a film by coating, crystalline polycarbonate tends to precipitate on the surface of the film during coating formation, resulting in convex portions, which may cause tailing of the coating and reduce yield, or may cause problems as a photoreceptor. During use, toner adheres to the convex portions and remains without being cleaned, which tends to cause image defects due to so-called poor cleaning.

Furthermore, when an electrophotographic photoreceptor using the above-mentioned bisphenol A type polycarbonate as a binder resin is used as a photoreceptor in an electrophotographic copying machine, it may be scratched by a magnetic brush or cleaning blade and the surface of the photosensitive layer may be scratched or the photosensitive layer may be damaged. It has the disadvantage that it gradually wears out.

On the other hand, high image quality and smooth copying workability also depend on the quality of the smooth, homogeneous surface of the photoreceptor with uniform thickness. , Yuzuki skin caused by dryness, pinholes, application streaks,
Film surface failures such as cracks (solvent cracks) are a major problem in terms of copying characteristics and production technology.

In addition, surfactants are also useful for improving surface properties or slipperiness, and are effective for dispersing suspended solids and improving dispersion stability in suspension-based paints, and are effective for improving dispersion stability in solution-based paints. It also has value in terms of production technology, such as promoting dissolution and improving coating properties. However, if the type is incorrectly selected, poor adhesion between layers, breakdowns due to deterioration, or problems with moisture resistance often occur.

To deal with the above-mentioned problems, introduction of a substituent having fluorine on the carbon between the phenylene rings (Japanese Patent Application Laid-Open No. 63-65444), substitution of an alkyl group, a hall: 1983-148263), or a conjugate of monomers in which both phenylene rings are substituted with phenyl groups or nclohexyl groups (JP-A-1-269942 and JP-A-1-269943), but these methods have not yet been proposed. It lacks sufficient surface strength and smoothness, is susceptible to abrasion, scratches, and ozone, and suffers from deterioration in image quality with repeated use, as well as deterioration in sensitivity due to reduction in film thickness due to abrasion.

[Purpose of the invention]

An object of the present invention is to provide a photoreceptor in which the photosensitive layer of an electrophotographic photoreceptor has high mechanical durability, good surface smoothness, good ozone resistance, and less deterioration of image quality and sensitivity. Another object is to provide a photoreceptor with a good pot life (storability) of the photosensitive layer coating.

[Structure of the invention]

The object of the present invention is to provide an electrophotographic photoreceptor having a photosensitive layer in which a charge generation layer and a charge transport layer are sequentially laminated on a conductive substrate, in which the charge transport layer contains the following binder resin:
This is achieved by an electrophotographic photoreceptor characterized in that it contains a polymer containing as a main structural composition the repeating sites shown by the pattern hole CB), and further contains a compound shown by the pattern hole (T) below.

-Momona CB] In the formula, 2 is the following two substituted or unsubstituted groups; a nonmetallic atomic group necessary to form a carbocyclic group or a heterocyclic group, R +
, Rs, Rs, R4 and Rs, Rs, Ry, Ra
represents a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group.

However, not all of them are hydrogen atoms.

General formula [T] In the formula, Ar, Arc is an aliphatic group or an aromatic group, Ar3
represents a phenylene group, and may form a ring with A ri I A rz ++ Rll+Rl! represents a hydrogen atom, an aliphatic group, or an aromatic group, and Rls represents an aliphatic group or an aromatic group.

These carbonate resins are made by modifying the drawbacks of the conventionally used bisphenol A type carbonate, and since a ring is formed by Z at the central carbon atom of these polycarbonates, the polycarbonate molecule The strands are effectively prevented from aligning in a particular direction. This prevents the polycarbonate from crystallizing, causing the solution to gel, or precipitating on the film surface during the formation of the photosensitive layer, thereby preventing property deterioration such as a decrease in yield due to abnormal convexities and image defects due to poor cleaning. be able to. The ring formed by the above-mentioned hole CB) directly contributes to this remarkable effect.

Furthermore, in the present invention, by using the polycarbonate shown in the above-mentioned pattern hole CB) as the binder resin, the film has excellent physical properties, excellent electrophotographic properties such as charge retention and sensitivity residual potential, and is suitable for repeated use. It is possible to create an electrophotographic photoreceptor that exhibits stable characteristics with little fatigue deterioration even when used.

In addition, when used as a photoreceptor, the surface of the photosensitive layer is less likely to be scratched even when rubbed with a magnetic brush or cleaning blade, and there is less wear on the photosensitive layer. An electrophotographic photoreceptor can be created.

The polybonate resin of the present invention can be easily synthesized according to a conventional method using, for example, the phenolic compounds shown in the following section.

In the formula, Z is a substituted or unsubstituted group of the following two groups: a nonmetallic atomic group necessary to form a carbocyclic group, a heterocyclic group, RIR
! ,R! +R4 and Rs, Rs, Ry, and Ra represent a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group.

However, not all of them are hydrogen atoms.

To illustrate the method for producing the polybonate resin of the present invention, specifically, in the presence of an inert solvent such as methylene chloride or 1,2-dichloroethane, the phenolic compound is added with an aqueous alkaline solution or pyridine as an acid acceptor. An example is a method in which the reaction is carried out while introducing phosgene.

When using an alkaline aqueous solution as an acid acceptor, the reaction rate can be increased by using a tertiary amine such as trimethylamine or triethylamine, or a quaternary ammonium compound such as tetrabutylammonium chloride or benzyltributylammonium bromide as a catalyst. .

In addition, as a molecular weight regulator, phenol, p-t
- Monohydric phenol such as butylphenol may be present. The catalyst may be added from the beginning, or any method may be used, such as adding it after the oligomer is produced to increase the molecular weight.

In addition, the polycarbonate resin according to the present invention may optionally contain a co-condensation type polycarbonate containing other repeating units in addition to the repeating unit of -mona CB), such as 4,
Physical, chemical or electrical properties may be adjusted using a polycarbonate prepared by co-condensing 4'-dihydroxy-3-methylphenyl-II-cyclohexane with a small amount of bisphenol A. Furthermore, if necessary, other polymers may be mixed and used within a range that does not interfere with the intended effects. The mixing ratio at this time is preferably 50 wt/% or less.

Since the binder used in the present invention is polycarbonate-based, it can provide the photoreceptor with the excellent charging performance, repeatability, printing durability, etc. that polycarbonate inherently exhibits.

Next, the groups R1 to R in the general formula [B] may be a hydrogen atom, a halogen atom, or an alkyl group such as a methyl group.

In addition, in the polycarbonate of the general formula [B],
Z may form a 5- or 6-membered carbocyclic ring or a heterocyclic ring, such as a cyclohexyl ring, a cyclopentyl ring, etc., and a part of the ring may include an acetyl group or an acetylamino group. Substituents such as the following may be introduced.

Specifically, the repeating units of the polycarbonate used in the present invention include the following.

Example B Repeating Unit B-10 B-13 Among these B-3. B-6. B-10i: A polycarbonate with a repeating structure shown as L has particularly excellent mechanical durability.

Examples of binders that may be used in combination with the polycarbonate used as the binder described above include the following.

(1) Polyester (2) Methacrylic resin (3) Acrylic resin (4) Polyvinyl chloride (5) Polyvinylidene chloride (6) Polystyrene (7) Polyvinyl acetate (8) Styrene copolymer resin (e.g. styrene-butadiene copolymer) styrene-methyl methacrylate copolymer, etc.) (9) Acrylonitrile copolymer resin (e.g., vinylidene chloride-acrytronitrile copolymer, etc.) (1O) Vinyl chloride-vinyl acetate copolymer (11) ) Vinyl chloride-vinyl acetate-maleic anhydride copolymer (12) Silicone resin (13) Silicone-alkyd resin (14)
Phenol m1fWI (e.g. phenol-formaldehyde resin, cresol formaldehyde resin, etc.) (15) Styrene-alkyd resin (16) Poly-N-vinylcarbazole (17) Polyvinyl butyral (18) Polyvinyl formal (19) Polyhydroxystyrene These The binder can be used alone or in combination in the carbonate of the present invention as a mixture of two or more.

Next, the compound represented by the general formula [T] will be explained.

General formula (T) may be used. R+++Rrt represents a hydrogen atom, an aliphatic group, or an aromatic group, and R and s represent an aliphatic group or an aromatic group.

The aromatic group represents a phenyl group, a naphthyl group, or a condensed polycyclic ring, and includes A r, , A r, , A r3. R+++Rll
The aliphatic group and aromatic group mentioned in +R include an alkyl group,
It may contain substituents such as an alkoxy group, a halogen atom, and an amine group.

Ar, Arl may form a ring such as a carbazole ring or an indoline ring, and the ring formed by R+z and R13 is 5 to 7.
is a membered carbocyclic or heterocyclic ring.

The above compound has a high carrier transport ability and contributes to high sensitivity.

Examples of compounds represented by Monana [T] will be described below, but the compounds are not limited thereto.

In the following margin formulas, Ar2 is an aliphatic group or an aromatic group, Ars
represents a phenylene group, and a specific example of a knee-shaped (T) compound in which a ring is formed with Ar, , Ar; 37 T-38 T-57 T-58 T-77 Carrier transport substances that can be used in combination in the present invention (
CTM) is not particularly limited, but includes, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidasilone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds,
hydrazone compounds, pyrazoline derivatives, amine derivatives,
Oxacilone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, heptanazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, etc. It is.

The CTM used in the present invention is preferably one that not only has an excellent ability to transport holes generated during light irradiation to the support side, but also is suitable for combination with the organic pigment used in the present invention.

In the photoreceptor of the present invention, a carrier generating substance (CGM)
), organic pigments such as those shown in the following representative examples are used.

(1) Azo pigments such as monoazo pigments, bisazo pigments, triazo pigments, and metal complex azo pigments (2) Perylene pigments such as perylene acid anhydride and perylene acid imide 1: (3) Anthraquinone derivatives, anthanthrone derivatives, dibenzpyrene quinone derivatives, pyracitron derivatives,
Polycyclic quinone pigments such as violanthrone derivatives and inviolanthrone derivatives (4) Indigoid pigments such as indigo derivatives and thioindigo derivatives Particularly in the electrophotographic photoreceptor of the present invention, fluorenone-based disazo pigments, 7-fluorenylidene-based disazo pigments, polycyclic It is preferable to use organic pigments such as quinone pigments. In particular, when the following fluorenone-based disazo pigments, fluorenylidene-based disazo pigments, and polycyclic quinone pigments are used in the present invention, remarkable improvements in sensitivity, durability, image quality, etc. are exhibited.

The fluorenone disazo pigment used in the present invention is represented by the following general formula [F1].

General formula [F1] Xl and X each represent a halogen atom, an alkyl group, an alkokino group, a nitro group, a cyan group, a hydroquino group, or a substituted or unsubstituted amino group.

p and q each represent an integer of 0.1 or 2, and when p and q are 2, Xl and X2 may be the same or different groups, respectively.

A represents a group represented by the following general formula CF, -1).

Ichimonana CF, -1) In the formula, A represents a fluorinated hydrocarbon group or an aromatic carbocyclic group or an aromatic heterocyclic group having a substituent.

2 represents a group of nonmetallic atoms necessary to form a substituted or unsubstituted aromatic carbocycle or a substituted or unsubstituted aromatic heterocycle. m and n each represent an integer of 01 or 2. However, m and n cannot be 0 at the same time b. Specific examples of the fluorenone disazo pigment used in the present invention are listed below, but the invention is not limited thereto.

Sample No.

A The fluorenone disazo pigment represented by the general formula (Fl) used in the present invention can be easily synthesized by the known method I, for example, by the method disclosed in Japanese Patent Application No. 62-304862.

The fluorenylidene disazo pigment used in the present invention has the following general formula [F,] where R7 Z is a substituted or unsubstituted group; constitutes an aromatic carbocycle or an aromatic heterocycle. Atom group Y necessary for: hydrogen atom, hydroxy group, carboxy group, or ester group thereof, sulfo group, substituted or unsubstituted two groups; carbamoyl group, sulfamoyl group R3: hydrogen atom, substituted or unsubstituted Synopsis of four groups: alkyl group, amino group, carbamoyl group, carboxyne group or its ester group or diano group Ar: substituted or unsubstituted aryl group R3 Substituted or unsubstituted continuation Three groups: alkyl group, Represents an aralkyl group or an aryl group.

Specific examples of the disazo pigments effective in the present invention represented by the above-mentioned -mona [F,] include those represented by the following structures F, -2 F, -3; The disazo pigment to be used in the present invention is not limited.

F, -5 The polycyclic quinone pigment used in the present invention is as follows- It is represented by the pattern holes [Q1] to [Q,].

- Monkey (Q,): F, -6 General formula General formula CQ, "J: In each formula, X represents a halogen atom, a nitro group, a cyano group, an acyl group, or a carboxy group, and n is θ~4 an integer of
m represents an integer of 0 to 6.

Specific examples of the polycyclic quinone pigments used in the present invention represented by the above-mentioned -Momonana (Ql) to [Q,] are shown below, but the invention is not limited thereto.

- Specific examples of compounds of the anthoanthrone pigments indicated by the symbol (Q,) are as follows.

Ql I Ql-2Q, -6 Specific compound examples of the dibenzpyrenequinone pigment represented by the general formula [Q2] are as follows.

Q, -1 Q, -4 Q, -5 Specific examples of compounds of vilantrone a represented by the general formula [Q,] are as follows.

The polycyclic quinone pigments represented by the above-mentioned -Momonana [Q1] to [Q,] used in the present invention can be easily synthesized by a known method.

Dispersion media for organic pigments used in the present invention include, for example, hexane, benzene, toluene, hydrogen chlorides such as xylene, methylene chloride, methylene bromide,
．． 2-dichloroethane, 5yn-tetrachloroethane,
cis-1,2-dichloroethylene, 1゜1.2-trichloroethane, 1.1.1-trichloroethane, 1.2
-; Chlorpropane, chloroform, bromoform,
Halogenated hydrocarbons such as chlorobenzene, ketones such as acetone, methyl ethyl ketone, cyclohexanone, esters such as ethyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, cyclohexanol, heptatool, ethylene glycol, methyl cellosolve, ethyl Alcohols and their derivatives such as cellosolve and cellosolve acetate, ethers such as tetrahydro-7rane, 1,4-dioxane, furan, and furfural, acetals, amines such as pyridine, butylamine, diethylamine, ethylenediamine, and inpropaturamine, N, Examples include nitrogen compounds such as amides such as N-dimethylformamide, fatty acids and phenols, and sulfur and phosphorus compounds such as carbon disulfide and triethyl phosphate.

In the present invention, the photosensitive layer may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential and fatigue during repeated use, and the like.

Examples of electron-accepting substances that can be used here include succinic anhydride, maleic anhydride, dibromaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride,
4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetraanoethylene, tetracyanoquinodimethane, O-dinitrobenzene, m-dinitrobenzene, 1.3.5-trinitrobenzene, varanitrobenzonitrile, Picryl chloride, quinone chlorimide,
Chloranil, Brumanil, Dichlorzine Anovabenzoquinone, Anthraquinone, Dinitroanthraquinone, 2
．． 7-cyclohexanone, 2,4.7-h-nitrofluorenone, 2,4.5.7-titranitrofluorenone, 9-fluorenylidene [dicyanomethylenemalonodinitrile 1, polynitro-9-fluorenylidene-[di-nano] methylene malono dinitrile], picric acid,
0-nitrobenzoic acid, p-nitrobenzoic acid, 35-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3.5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds with high electron affinity (・Further, the addition ratio of the electron-accepting substance is as follows: organic pigment used in the present invention = electron-accepting substance -100:0.01 to 200, preferably 100:0
．． It is 1-100.

The proportion of electron-accepting substances added to such a layer is based on the weight ratio of total C.
TM=receptor-100: 0.01-100,
Preferably it is 100:0.1-50.

Further, organic amines can be added to the photosensitive layer of the present invention for the purpose of improving the charge generation function of CGM, and in particular, 2
Preferably, a grade amine is added.

These compounds are described in JP-A-59-218447 and JP-A-62.
-8160.

In addition, the photoreceptor of the present invention may also contain an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, if necessary, and may also contain a dye for color sensitivity correction.

In addition, the protective layer according to the present invention includes improvements in processability and physical properties (
If necessary, a thermoplastic resin can be contained in an amount of less than 50 wt% for the purpose of preventing cracks, imparting flexibility, etc.

The intermediate layer functions as an adhesive layer or a blocking layer, and in addition to the binder resin, it may contain, for example, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-anhydride. Maleic acid copolymers, casein, N-alkoxymethylated nylon, starch, etc. are used.

As the conductive support used in the construction of the electrophotographic photoreceptor of the present invention, the following are mainly used, but the support is not limited thereto.

1) Metal plates such as aluminum plates and stainless steel plates.

2) A thin layer of metal such as aluminum, palladium, or gold is provided on a support such as paper or plastic film by lamination or vapor deposition.

3) A layer of a conductive compound such as a conductive polymer, indium oxide, or tin oxide is provided on a support such as paper or a plastic film by coating or vapor deposition.

As shown in FIGS. 1 and 2, the photoreceptor of the present invention comprises a conductive support L containing C containing CGM as a main component, L 2 and CTL 3 containing CTM according to the present invention as a main component. A photosensitive layer 4 made of a laminate is provided. As shown in FIGS. 3 and 4, the photosensitive layer 4 may be provided on the conductive support 1 via an intermediate layer 5.

When the photosensitive layer 4 has a two-layer structure in this manner, an electrophotographic photoreceptor having the most excellent electrophotographic properties can be obtained.

Further, in the present invention, as shown in FIGS. 5 and 6, fine particulate CGM is included in the layer 6 mainly composed of CTM.
A photosensitive layer 4 having 7 dispersed therein may be provided directly on the conductive support l or via an intermediate layer 5. Furthermore, a protective layer 8 may be provided on the photosensitive layer 4 if necessary.

Here, when the photosensitive layer 4 has a two-layer structure, CGL 2 and C
Which of TL 3 is to be used as the upper layer is determined depending on whether the charging polarity is positive or negative. That is, when forming a negatively charged photosensitive layer, it is advantageous to use CTL 3 as an upper layer, because CTM in CTL 3 is a substance that has a high transport ability for holes.

Further, the CGL 2 constituting the photosensitive layer 4 having a two-layer structure can be formed directly on the conductive support 1 or the CTL 3 or after providing an intermediate layer such as an adhesive layer or a blocking layer as necessary, by the following method. can be formed by

(1) Vacuum deposition method (2) Method of applying a solution of CGM dissolved in a suitable solvent (3) Forming CGM into fine particles in a dispersion medium using a ball mill, sand grinder, etc. If necessary, mixing and dispersing with a binder A method of applying the resulting dispersion.

That is, specifically, a vapor deposition method such as vacuum evaporation, sputtering, or CVD, or a coating method such as dipping, spray, blade, or roll method may be arbitrarily used.

The thickness of CGL 2 formed in this way is 0.0
It is preferably 1 μwl to 5 μl, more preferably 0
．． 05μ+n to 3μm.

Further, the thickness of the CTL 3 can be changed as necessary, but it is usually preferably 57,711 to 30 μm. This C
The composition ratio in TL 3 is preferably 0.1 to 5 parts by weight of the binder to 1 part by weight of the CTIj of the present invention, but when forming the photosensitive layer 4 in which fine particulate CGM is dispersed, CGM 5 parts by weight of binder
It is preferable to use it within a range of parts by weight or less.

Further, when CGL is configured as a dispersed type in a binder, it is preferable to use the binder in an amount of 5 parts by weight or less based on the amount of CGMlffi.

The photoreceptor of the present invention has the above-mentioned structure, and has excellent charging characteristics, sensitivity characteristics, and image forming characteristics, as is clear from the examples described below. In particular, it exhibits excellent durability with little fatigue deterioration even when subjected to repeated transfer electrophotography.

〔Example〕

Examples of the present invention will be specifically described below, but the embodiments of the present invention are not limited thereby.

Example 1 30 g of polyamide copolymerized with a monomer composition of ε-amino-caproic acid, adipic acid and N-(β-aminoethyl)piperazine in a ratio of 1:1:1 was heated to 50° C. to produce 800+a12 methanol EL. Pour into the standard (manufactured by Kanto Kagaku Co., Ltd.) while stirring and let it dissolve. After cooling to room temperature, 200 mQ of 1-butanol special grade (manufactured by Kanto Kagaku Co., Ltd.) was added. Thereafter, it was applied by dip coating onto an aluminum drum having a diameter of 80 mm to form an intermediate layer having a thickness of 05 μm.

Next, 20 g of fluorenone-based disazo pigment (exemplified compound F + 23) and 10 g of polyvinyl butyral resin S-LEC BX-1 (manufactured by Tanezu Kagaku Co., Ltd.) as a binder were dissolved in methyl ethyl ketone (EL standard, manufactured by Kanto Kagaku Co., Ltd.) 1000v2. , at the sand mill 2
After 4 hours of milling, CGL ii! A working solution was obtained. This was applied by dip coating on the above intermediate layer to form a CGL with a thickness of 0.3μ.
was formed.

Thereafter, 120 g of the above (exemplified CTM, T-2) and 3165 g of polymer B were dissolved in 1,2-dichloroethane special grade (manufactured by Kanto Kagaku Co., Ltd.) 1000+12, and CTL
A coating liquid was obtained.

This was coated on the CGL by dip coating and dried at 100°C for 1 hour to form a CTL with a thickness of 20 μl. In this way, a photoreceptor was produced in which the intermediate layer - GL-CTL were sequentially laminated.

Example 2 A photoreceptor was produced in the same manner as in Example 1 except that CTM was used as an example; T-3.

Example 3 The intermediate layer was formed in the same manner as in Example 1.

As CGM, polycyclic bovine non-based pigment: (Exemplary compound; Q
, -3) 20g and 10g of polycarbonate resin L-1250 (manufactured by Kijin Kasei Co., Ltd.) as a binder at 1.2
．． It was dissolved in special grade dichloroethane (manufactured by Kanto Kagaku Co., Ltd.) and milled in a ball mill for 24 hours to obtain a ccLih working solution. This was applied by dip coating on the intermediate layer to form a CGL with a thickness of 0.3 μm.

Next, CTM is exemplified, T-4 is used, and the binder is copolymer B-
A photoreceptor was produced by laminating CTLs in the same manner as in Example 1, except that the number was 4.

Example 4 After dissolving 12 g of polyvinyl butyral resin (S-LEC BX-1° manufactured by Seishui Kagaku Co., Ltd.) in methyl ethyl ketone 10100O, Exemplified Compound Q13;5.
7 g of Exemplified Compound F+ 23; 0.3 g were mixed and dispersed with a sand grinder for 10 hours.

This was applied by dip coating onto the intermediate layer described in Example 1, and CGL
was formed, and then a CTL was formed in the same manner as in Example 2 to produce a photoreceptor.

Comparative Example 1 A photoreceptor was prepared in the same manner as in Example 1 except that bisphenol A polycarbonate (Kijin Kasei Panlite K-1300) was used as the CTL binder.

However, the stability of the coating liquid was poor, and the viscosity increased significantly when left unused, and it became completely gel-like after one month, and did not return to its original state even after redispersion treatment such as ultrasonic treatment.
Only unstable liquid was obtained.

Comparative Example 2 A photoreceptor was produced in the same manner as in Example 1 except that bisphenol A polycarbonate (Mitsubishi Gas Chemical Z-200) was used as the CTL binder.

Comparative Example 3 A photoreceptor was produced in the same manner as in Example 1 except that the following hydrazone compound was used as the CTM.

Comparative example 4 A photoreceptor was produced in the same manner except that the following was used.

Measurement of cyclic characteristics The photoreceptors of Examples 1 to 4 and Comparative Examples 1 to 4 were each
-Equipped with Bix 2025J (manufactured by Konica), 10
Copies were made 10,000 times, and the surface potential before and after the actual copying was measured.

Black paper potential: Surface potential for an original with a reflection density of 1.3 White paper potential Two Surface potential for an original with a reflection density of 0.0 Residual potential: Surface potential after static elimination Regarding film wear due to surface friction, after 100,000 copies are completed, The photoreceptor film thickness was measured and compared with the initial thickness.

Regarding the image quality, image samples were checked successively and the number of copies with streaks due to scratches in the circumferential direction of the drum and cleaning defects were compared.

In the following margin Example 1, the following pyrazoline compound was used as the CTM. [Effects of the Invention] The photoreceptor of the present invention has excellent electrophotographic performance, shows little change in properties even with repeated use, and has excellent wear resistance. , has extremely high printing durability.

[Brief explanation of drawings]

1 to 6 are sectional views showing examples of the mechanical structure of the photoreceptor of the present invention, respectively. 1... Conductive support 2... Carrier generation layer 3... Carrier transport layer 4... Photosensitive layer 5... Intermediate layer 6... Layer containing carrier transport material 7... Carrier Generated materials 8...protective layer

Claims (1)

[Claims] (1) In an electrophotographic photoreceptor having a photosensitive layer in which a charge generation layer and a charge transport layer are sequentially laminated on a conductive substrate, the charge transport layer contains a repeating unit represented by the following general formula [B] as a binder resin. An electrophotographic photoreceptor comprising a polymer as a main structural composition and further comprising a compound represented by the following general formula [T]. General formula [B] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Z is the following two groups, substituted or unsubstituted; nonmetallic atomic groups necessary to form a carbocyclic group, a heterocyclic group, R_
1, R_2, R_3, R_4 and R_5, R_6, R_
7, R_8 represents a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group. However, not all of them are hydrogen atoms. ] General formula [T] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Ar_1 and Ar_2 are aliphatic groups or aromatic groups,
Ar_3 represents a phenylene group, and Ar_1 and Ar_2 may form a ring. R_1_1 and R_1_2 represent a hydrogen atom, an aliphatic group, or an aromatic group, and R_1_3 represents an aliphatic group or an aromatic group. ]