JPH0437860A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity and mechanical durability of a photosensitive layer, to improve surface smoothness, and to reduce deteriorations of image quality and sensitivity by incorporating a specified polymer and a specified compound as a binder resin in an electric charge transfer layer. CONSTITUTION:The polycarbonate resin used as the binder resin has carbon rings or hetero rings other than the main chain rings of the polycarbonate and it is hindered from arranging its polymer chain in the specified direction, freed of gelation of a solution and precipitation on the surface of a film, and deterioration of yield due to protuberances, and free from image defects, and so, excellent photographic characteristics and high printing resistance are obtained. Sensitivity, durability, image quality, and the like are enhanced by using a combination of, for example,an oxazole derivative superior in transfer ability of holes generated by light illumination toward a substrate, with an organic pigment for the charge transfer layer 3, and an organic pigment, such as fluorenylidene type disazo pigment.

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 is important not only to have electrophotographic properties such as good charging characteristics and sensitivity, and low dark decay, but also physical properties such as printing durability, abrasion resistance, and moisture resistance after repeated use. It is also required to have good resistance to ozone generated during corona discharge, ultraviolet rays during exposure, etc. (environmental resistance).

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.

Such a functionally divided organic photoreceptor has conventionally been used for negative charging, and as described in JP-A No. 60-247647, a thin carrier generation layer is provided on the 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 drawback 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, the surface of the photosensitive layer may be scratched due to abrasion by a magnetic bra/cleaning blade, or the surface of 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/collection depend on the quality of the smooth, homogeneous surface of the photoreceptor with uniform thickness. Film surface failures such as citrus skin, pinholes, coating streaks, and cracks (solvent cranks) caused by coating and drying 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 surface active agents 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 address the above-mentioned problems, introduction of a substituent having fluorine on the carbon of the phenylene ring (Japanese Patent Application Laid-Open No. 63-65441)
, substitution of an alkyl group or halogen atom on the phenylene ring (Japanese Patent Application Laid-open No. 148263/1983), or a conjugate of seven mercury in which both phenylene rings are substituted with a phenyl group or a cyclohexyl group (Japanese Patent Application Laid-open No. 1-269942) No. 1-269
No. 943), or the combined use of distyryl and bisphenol z as a carrier transport substance in polycarbonate (
JP-A No. 64-32265), etc., have been proposed, but they still lack sufficient surface strength and surface smoothness, are susceptible to abrasion and scratches, deteriorate image quality with repeated use, and reduce film thickness due to abrasion. Problems such as decreased sensitivity remain.

[Purpose of the invention]

An object of the present invention is to provide a photoreceptor with high sensitivity, high mechanical durability of the photosensitive layer of an electrophotographic photoreceptor, good surface smoothness, and less deterioration of image quality and decrease in sensitivity. The purpose of this invention 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 a repeating unit represented by Monna [B] as a main structural composition, and further contains a compound represented by Monna (T) below.

General formula [B] In the formula, Z is the following two substituted or unsubstituted groups; a nonmetallic atomic group necessary to form a carbocyclic group or a heterocyclic group, R,
R, , R, , R4 and R, , R, , R, , R represent a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group.

However, not all of them are hydrogen atoms.

The degree of polymerization is 10 to 5,000, preferably 50 to 1,000.

These carbonate resins have improved the drawbacks of the conventionally used bisphenol Am carbonate, and the central carbon atom of these polycarbonates contains
Since a ring is formed by Z, the molecular chains of polycarbonate are effectively prevented from arranging in a specific direction. This prevents polycarbonate from crystallizing, causing the solution to gel, or depositing on the film surface during the formation of the photosensitive layer.
Deterioration of characteristics such as a decrease in yield due to abnormal convex portions and image defects due to poor cleaning can be prevented.

The ring formed by the above-mentioned hole CB) directly contributes to this remarkable effect.

That is, in the present invention, by using the polycarbonate shown in the above-mentioned pattern hole CB) as a binder resin, it has excellent film properties, excellent electrophotographic properties such as charge retention power and sensitivity residual potential, and can be used repeatedly. It is possible to create an electrophotographic photoreceptor that exhibits stable characteristics with little fatigue deterioration even when exposed to various conditions.

Furthermore, when used as a photoreceptor, the surface of the photosensitive layer is less likely to be scratched even when rubbed by a magnetic brush or cleaning blade, and the photosensitive layer has less abrasion, and it has a high printing durability without defective properties such as poor cleaning. A photoreceptor can be created.

The polypropylene lipometry 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 the following two substituted or unsubstituted groups; a group of nonmetallic atoms necessary to form a carbocyclic group or a heterocyclic group, Rl+
R*, R3, R4 and Rs, Rs, Ry, 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 bocarbonate resin of the present invention, specifically, in the presence of an inert solvent such as methylene chloride or l,2-dichloroethane, an aqueous alkali solution or pyridine or the like is added to the phenolic compound 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. .

Phenol, p-
Monohydric phenol such as t-butylphenol may also 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.

The polycarbonate resin according to the present invention may optionally contain other repeating units in addition to the repeating units of general formula CB), such as co-knitted polycarbonate, for example 4
．． 4'-dihydroxy・3-methyl7enyl-1.1-
Physical, chemical, or electrical properties may be adjusted using a polycarbonate prepared by cocondensing a mixture of 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 R6 in the general formula CB) 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, and examples of such a ring include a /clohequinyl ring, a ncrobentyl ring, etc., and a part of the ring includes an acetyl group, A substituent such as an acetylamino group may be introduced.

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

Exemplary B Repeating Units B-8 B-12 Among these, the polycarbonates having the repeating structures shown in B-3, B-6, and B-10 have 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) (10) Vinyl chloride-vinyl acetate copolymer (11) )
Vinyl chloride-vinyl acetate-ruic anhydride copolymer (12) Silicone resin (13) Silicone-alkyd resin (14)
Phenolic resin (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 binders can be used alone or in combination in the carbonate of the present invention as a mixture of two or more.

Next, a carrier transport material (CTM) represented by the general formula (T)
) will be explained.

Three groups: fused polycyclic hydrocarbon group, heterocyclic group,
Represents a fused polycyclic heterocyclic group.

Represents three substituent groups: a fused polycyclic hydrocarbon group, a heterocyclic group, and a fused polycyclic heterocyclic group.

Represents three substituent groups: a fused polycyclic hydrocarbon group, a heterocyclic group, and a fused polycyclic heterocyclic group.

Represents three substituent groups: a fused polycyclic hydrocarbon group, a heterocyclic group, and a fused polycyclic heterocyclic group, and may also form a ring in collaboration with Ar and Art.

R1 is a substituted or unsubstituted alkyl group, a phenyl group, an alkoxy group, a phenoxy group, a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amine group, and six substituted or unsubstituted gun groups. ; Represents an alkylamino group, an arylamino group, an aralkylamino group, a cyclic hydrocarbon group, a fused polycyclic hydrocarbon group, and a heterocyclic group.

R4, RI and R are substituted or unsubstituted four groups; alkyl group, phenyl group, alkoxy group, phenoxy group and cyano group, halogen atom, carboxyl group,
Acyl group, hydroxyl group, nitro group, amino group, and six substituted or unsubstituted groups; alkylamino group, arylamino group, aralkylamino group, cyclic hydrocarbon group, fused polycyclic hydrogen group, heterocycle represents a group.

In i, l represents an integer of 0 to 5, and j represents an integer of 0 to 4.

The above compound has high performance as a CTM and contributes to high sensitivity.

Next, specific examples of CTMs represented by the general formula [T] are listed. Thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidacilone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, amine derivatives, oxacylone derivatives,
benzothiazole derivatives, benzimidazole derivatives,
These include quinazoline derivatives, benzofuran derivatives, acridine derivatives, heptanazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, and the like.

The CTl11 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 (C is 1
As 4), organic pigments as 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 (3) Anthraquinone derivatives, anthanthrone derivatives, and dibenzpyrenequinone derivatives , vilantrone derivative,
Polycyclic quinone pigments such as violanthrone derivatives and isoviolanthrone conductors (4) Indigoid pigments such as indigo derivatives and thioindigo derivatives Particularly in the electrophotographic photoreceptor of the present invention, fluorenone-based disazo pigments, fluorenylidene-based disazo pigments, polycyclic quinone pigments, etc. It is preferable to use organic pigments such as ring 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 [F,].

General formula [F1] xl and X each represent a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a hydroxy group, or a substituted or unsubstituted amine group; p and q each represent O, l or represents an integer of 2, and when p and q are 2, X and X may be the same group or two different groups, respectively.

A represents a group represented by the following general formula CF, ~l].

General formula (Fl-1) 2 In the formula, Ar represents a fluorinated hydrogen group or an aromatic carbocyclic group or an aromatic heterocyclic group having a substituent.

Z 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 Ol or an integer of 2. However, m and n never become 0 at the same time.

Specific examples of the fluorenone disazo pigment used in the present invention are listed below, but the present invention is not limited thereto.

Sample N.

The fluorenone-based disazo pigment represented by -Momona [F1] used in the present invention can be easily synthesized by a known method, for example, by the method described in Japanese Patent Application No. 62-304862.

The fluorenylidene-based disazo pigment used in the present invention is shown below - Monana [F! ].

- Monana [F,] In the formula, A is Z: Substituted or unsubstituted two groups as shown below; Atom group necessary to constitute an aromatic carbocycle or an aromatic heterocycle Y: Hydrogen atom, hydroxy group, Carboxine group or its ester group, sulfo group, substituted or unsubstituted two groups; carbamoyl group, sulfamoyl group R1: hydrogen atom, substituted or unsubstituted four groups; alkyl group, amino group, carbamoyl group, a carboxy group or its ester group, or an ano group Ar: Substituted or unsubstituted aryl group R3: Substituted or unsubstituted three groups: an alkyl group, an aralkyl group, and an aryl group.

Specific examples of the disazo pigments indicated by the above-mentioned pattern [F,] that are effective in the present invention include those shown by the following structural formula; is not limited.

F, -] pt-5 F, -3 F, -7 F, -4 The polycyclic quinone pigment used in the present invention has the formula [Q,] ~
It is represented by [Q,].

- Numerical formula (Q, )2 General formula (Qx)' Below - In each formula, X represents a halogen atom, nitro group, cyano group, acyl group, or carboxy group, and n represents an integer from θ to 4,
m represents an integer of 0 to 6.

Specific examples of the polycyclic quinone pigments used in the present invention represented by formulas [Q,] to [Q3] are shown below, but the invention is not limited thereto.

- Specific examples of compounds of the anthanthrone pigment represented by the formula [Q1] are as follows.

Ql-I Q+ 2-Formula Ql-5 Q, -6 Q, -3 Specific compound examples of the dibenzpyrenequinone pigment represented by the general formula [Q,] are as follows.

Q, -2 Q, -5 Specific examples of compounds of the pyracitron pigment represented by the general formula [Q,] are as follows.

The polycyclic quinone pigments represented by formulas [Q1] to [Q,] used in the present invention can be easily synthesized by known methods.

Examples of the dispersion medium for the organic pigment used in the present invention include hydrocarbons such as hexane, benzene, toluene, and quinolene, methylene chloride, methylene bromide,
．． 2-dichloroethane, 5yn-tetrachloroethane,
CI S -1+ 2-dichloroethylene, l.

1.21 Lichloroethane, 1,1. i Trichloroethane, 1.2-; halogenated hydrocarbons such as chloropropane, chloroform, bromoform, and chlorobenzene, ketones such as acetone, methyl ethyl ketone, and nclohexanone, esters such as ethyl acetate and butyl acetate, methanol, and ethanol. , furopanol, butanol, cyclohexanol, heptatool, ethylene glycol,
Alcohols and their derivatives such as methyl cellosolve, ethyl cellosolve, acetic cellosolve, tetrahydrofuran,
1. Nitrogen compounds such as ethers and acetals such as 4-nooxane, furan, and furfural; amines such as pyridine, butylamine, diethylamine, ethylenediamine, and isomalonolamine; and amides such as N,N-dimethylformamide; fatty acids and Examples include phenols, 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,
-Nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetraanoquinodimethane, 0-dinitrobenzene, π-dinitrobenzene,
1,3.5-trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, brumanil, dichlordicyanono (labenzoquinone, anthraquinone, dinitroanthraquinone, 2
．． 7-cynitrofluorenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, 9-fluorenylidene [dicyanomethylenemalonodinitrile], polynitro-9-fluorenylidene-[dicyanomethylene malonodinitrile], picric acid, 0-nitrobenzoic acid, p-nitrobenzoic acid, 3, S
-,; Nitrobenzoic acid, Pentafluorobenzoic acid, 5-
Examples include nitrosalicylic acid, 3.5-dinitrosalicylic acid, phthalic acid, Merit a, and other compounds with high electron affinity. The addition ratio of the electron-accepting substance is as follows: the organic pigment used in the present invention = the electron-accepting substance - 100: 0.01 to 200, preferably 1
00.0.1 to 100.

The proportion of electron-accepting substances added to such a layer is based on the weight ratio of total C.
TM: Electron accepting substance-100: 0.01-100
, preferably 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
It is preferable to add a grade amine.

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 vt% 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, hapholyvinyl alcohol, ethyl cellulose, carboxyl methyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acetic acid. Vinyl-maleic anhydride copolymer, 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.

■) 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 glass 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 is a laminate of CCL 2 containing CCM as a main component and CTL 3 containing CTM according to the present invention as a main component on a conductive support l. A photosensitive layer 4 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 best 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 member-charged photosensitive layer, it is advantageous to use CTL 3 as the upper layer, since CTM in CTL 3 is a substance that has a high transport ability for holes. .

Further, the CGL 2 constituting the two-layered photosensitive layer 4 can be applied directly onto the conductive support 1 or CTL S, 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. and mixing and dispersing with a binder as necessary 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 o, (
It is preferably 11 μml to 5 μm, more preferably 0. 5 μl to 3 μl infusion.

Further, the thickness of the CTL 3 can be changed as necessary, but it is usually preferably from 5 μm to 30 II m. This CT
The composition ratio in L3 is preferably 0.1 to 5 parts by weight of the binder to 1 part by weight of the CTM of the present invention, but when forming the photosensitive layer 4 in which fine particulate cGM is dispersed, CGM1 ! 5 fU of binder for i amount of parts
It is preferable to use it in a range of 1 part or less.

Further, when CGL is configured as a dispersed type in a binder, it is preferable to use pine da in a range of 5 parts by weight or less per 1 part by weight of CGM.

The photoreceptor of the present invention has the above-described 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 Methanol EL specification of 800 m12 in which 30 g of polyamide copolymerized with a monomer composition of ε~ruamino-caprone, adipic acid and N-(β-aminoethyl)piperazine in a ratio of 1:1:1 was heated to 50°C. (Manufactured by Kanto Kagaku Co., Ltd.)
was added to the solution while stirring, and dissolved.

After cooling to room temperature, add 1-butanol special grade (manufactured by Kanto Kagaku Co., Ltd.) 2
00-g was added. Thereafter, it was applied by dip coating onto an aluminum drum with a diameter of 80 mm to form an intermediate layer with a thickness of 0.5 μm.

Next, 20 g of a fluorenone disazo pigment (exemplified compound F + -23) as CGM and 10 g of polyvinyl butyral resin S-LEC BX-1 (manufactured by Okisui Kagaku Co., Ltd.) as a binder were mixed with methyl ethyl ketone (EL, manufactured by Kanto Kagaku Co., Ltd.).
Standard) Dissolved in 1000+IQ and milled in a sand mill for 24 hours.
Time milling was performed to obtain a CGL coating solution. This was applied by dip coating onto the above intermediate layer to form a CGL having a thickness of 0.3 μm.

Thereafter, 120 g of the above (exemplified CTM, T-2) and 3165 g of Polymer B-2 were dissolved in 1,2-dichloroethane special grade (manufactured by Kanto Kagaku Co., Ltd.) 1ooo+CI2, and CT
L 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 about 20 μm.

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 CT and 11 were used as examples; T-1.

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

As CGM, polycyclic bovine non-based pigment (exemplary compound: Ql-
3) 20g and polycarbonate resin L as a binder
-1250 (manufactured by Ondai Kasei Co., Ltd.) 10g was dissolved in 1,2-dichloroethane special grade (manufactured by Kanto Kagaku Co., Ltd.) and milled in a ball mill for 24 hours to obtain CGL I! A working solution was obtained. This was applied by dip coating on the above intermediate layer to form a CGL with a thickness of 0.3 μm.
was formed.

Next, CTM is illustrated; T-:L 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 CTM is exemplified by T-13, CTL binder is copolymer B
A photoreceptor was produced in the same manner as in Example 1 except that the sample was changed to -4.

Example 5 12 g of polyvinyl butyral [tf (S-LEC Bχ-11 manufactured by Sekisui Chemical Co., Ltd.) was mixed with methyl ethyl ketone 10100O
Exemplary compound Q, -3 as CGM;
5.7 g and 0.3 g of Exemplified Compound F +-23 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 produced in the same manner as in Example 1 except that bisphenol A polycarbonate (Kijin Kasei Panlite 1300) was used as the CTL binder.

However, the stability of the coating solution 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 an unstable liquid was obtained.

Comparative Example 2 '14 'fR1teCTL /< Bisphenol 2 polycarbonate (Mitsubishi Gas Chemical Z-200
) A photoreceptor was prepared in the same manner except that the photoreceptor was used.

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.

Measurement of cyclic characteristics The photoreceptors of Examples 1 to 5 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, surface potential for an original with a reflection density of 0.0.Residual potential: Surface potential after static electricity removal.Regarding film wear due to friction on the surface, 10,000 copies are completed before exposure. Body membrane thickness was measured and compared with the initial value.

Regarding the image quality, image samples were checked one after another, and there were no streaks or creases due to scratches in the circumferential direction of the drum.[Effects of the Invention] The photoreceptor of the present invention has excellent electrophotographic performance, and its characteristics do not change even with repeated use. It has extremely high printing durability as it has low friction and excellent abrasion resistance.

[Brief explanation of the drawing]

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)

[Scope of Claims] 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, a binder resin represented by the following general formula [B] is added to the charge transport layer. Contains a polymer containing repeating units as a main structural composition,
An electrophotographic photoreceptor 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 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Substituted or unsubstituted continuation Three groups; Condensed polycyclic carbonized Represents a hydrogen group, a heterocyclic group, or a fused polycyclic heterocyclic group. Ar_2 and Ar_3 represent ▲a numerical formula, a chemical formula, a table, etc.▼, three substituted or unsubstituted groups; a fused polycyclic hydrocarbon group, a heterocyclic group, and a fused polycyclic heterocyclic group. Ar_4 and Ar_5 represent ▲a numerical formula, a chemical formula, a table, etc.▼, three substituted or unsubstituted groups; a fused polycyclic hydrocarbon group, a heterocyclic group, and a fused polycyclic heterocyclic group. R_1 and R_2 represent ▲a numerical formula, a chemical formula, a table, etc.▼, substituted or unsubstituted continuation three groups; a fused polycyclic hydrocarbon group, a heterocyclic group, a fused polycyclic heterocyclic group, A
It may form a ring together with r_4 and Ar_5. R_3 is a substituted or unsubstituted alkyl group, phenyl group,
Alkoxy group, phenoxy group, cyano group, halogen atom, carboxyl group, acyl group, hydroxyl group, nitro group, amino group, and further substituted or unsubstituted six groups; alkylamino group, arylamino group, aralkylamino group , represents a cyclic hydrocarbon group, a fused polycyclic hydrocarbon group, or a heterocyclic group. R_4, R_5 and R_6 are substituted or unsubstituted four groups; alkyl group, phenyl group, alkoxy group,
Phenoxy group and cyano group, halogen atom, carboxyl group, acyl group, hydroxyl group, nitro group, amino group, and further substituted or unsubstituted 6 groups; alkylamino group, arylamino group, aralkylamino group, cyclic carbonization Represents a hydrogen group, a fused polycyclic hydrogen group, or a heterocyclic group. i, k, l represent an integer of 0 to 5, and j represents an integer of 0 to 4. ]