JPH0437762A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide the electrophotographic sensitive body which has a high sensitivity, the high mechanical durability of an electrophotographic sensitive layer and good surface smoothness and is less degraded in image quality and sensitivity by using specific monomers as the binder of the photosensitive layer. CONSTITUTION:The electrophotographic sensitive body which has excellent film properties and excellent electrophotographic characteristics, such as charge holding power and residual potential of sensitivity, and exhibits stable characteristics with lessened fatigue deterioration when subjected to repetitive use is formed by using a polymer contg. general formula (B1) as its main repeating unit or a copolymer contg. the general formula (B1) and general formula (B2) in its constituting compsn. as the main repeating unit. This photosensitive body exhibits an extremely improved effect in terms of sensitivity, durability and image quality, etc., if a fluorenone disazo pigment, fluorenilidene disazo pigment and polycyclic quinone are used as the carreir generating material of 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 Carlzin 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.

Conventionally, such functionally divided organic photoreceptors have been mainly used for negative charging, and as described in JP-A No. 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 a photoreceptor, bisphenol A type polycarbonate shown by the following structural formula exhibits good characteristics in terms of charging characteristics, sensitivity, residual potential, repeatability, etc. However, the present invention As a result of studies conducted by researchers, it was found that 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. ing. 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.

In order to solve the problem mentioned above, introduction of a substituent having fluorine on the carbon between the phenylene rings (Japanese Unexamined Patent Publication No. 63-65444
(No.), substitution of an alkyl group or halogen atom on the phenylene ring (Japanese Patent Application Laid-Open No. 148263/1982), or copolymers of monomers in which both phenylene rings are substituted with a phenyl group or a chlorohekynyl group (Japanese Patent Application Laid-open No. 1-269942). , 1-26
9943), or the combined use of distyryl as a carrier transport substance in bisphenol Z-type polycarbonate (Japanese Patent Application Laid-Open No. 64-32265).
It still lacks sufficient surface strength and surface smoothness, is susceptible to abrasion and scratches, and suffers from deterioration in image quality with repeated use, as well as a decrease in sensitivity due to a decrease in film thickness due to abrasion.

[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. ], or as the main repeating unit, the above general formula [B1] and the following general formula [B2]
contains a copolymer whose structural composition includes, and has the following general formula (
An electrophotographic photoreceptor comprising a compound represented by T).

General formula [B,] Numerical formula [B2] In the formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R3, R4Rs, Rs and Ry, Rg.

Rs and Rho are a hydrogen atom, a methyl group, and a chlorine atom.

However, not all of them are hydrogen atoms.

The degree of polymerization of the polymer or copolymer is 10 to 5,000, preferably 50 to 1,000.

In the present invention, a polymer having the above general formula (Bl) as a main repeating unit, or a polymer having the above general formula (Bl) as a main repeating unit,
By using a copolymer containing the general formula [B1] and the general formula [B, ] in its structural composition as a binder resin, the film has excellent physical properties,
It is possible to produce an electrophotographic photoreceptor that has excellent electrophotographic properties such as charge retention and sensitivity residual potential, and exhibits stable properties with little fatigue deterioration even when used repeatedly.

Furthermore, if necessary, other monomers may be mixed and used within a range that does not interfere with the intended effect. The mixing ratio at this time is preferably 50vt/% or less.

The polycarbonate resin of the present invention comprises the following (I) and (I)
It can be easily synthesized according to a conventional method using a phenolic compound selected from I).

In the formula, Ri and Rx represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Rs, R4Ri, Ra and Ry, Ra.

R1 and R16 are a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom. However, not all of them are hydrogen atoms.

Specifically, the method for producing the polycarbonate resin of the present invention includes adding an aqueous alkali solution or pyridine as an acid acceptor to the phenolic compound in the presence of an inert solvent such as methylene chloride or 1,2-dichloroethane, An example is a method of reacting 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.

In the present invention, the method of copolymerizing using two or more types of heptanoyl compounds includes (a) a method in which two or more types of heptanoyl compounds are first simultaneously reacted with phosgene and copolymerized; (b) A method in which one is first reacted with phosgene, and after a certain amount of reaction, the other is added and polymerized; (c) A method in which the two are reacted separately with phosgene and then polymerized, or any other method can be used.

Next, specific examples of the structures represented by the general formulas CB+) and (Bz) will be given.

Structure represented by general formula [B1]: B, -1 General formula [B! Structure shown by: Examples of copolymers having both of the above structures include copolymers having the following combinations.

Bl...(B, -1)/(i-1)B2...(B
l-2)/(Bl-1)B3... (Bl-3)/
(B, -1) Examples of binders that may be used in combination with the polycarbonate or carbonate copolymer 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) polymer, styrene-methyl methacrylate copolymer, etc.) (9) Acrylonitrile copolymer resin (e.g., vinylidene chloride-acrytronitrile copolymer, etc.) (10) Vinyl chloride-vinyl acetate copolymer ( 11) Vinyl chloride-vinyl acetate-maleic 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, the transport material (CTM) represented by the general formula (T) will be explained.

General formula (T) Ar+ Three unsubstituted groups; represents a fused polycyclic hydrocarbon group, a heterocyclic group, and a fused polycyclic heterocyclic group.

Three unsubstituted groups: a fused polycyclic hydrocarbon group, a heterocyclic group, and a fused polycyclic heterocyclic group.

Three unsubstituted groups; represent a fused polycyclic hydrocarbon group, a heterocyclic group, and a fused polycyclic heterocyclic group.

Three unsubstituted groups: Represents a fused polycyclic hydrocarbon group, a heterocyclic group, and a fused polycyclic heterocyclic group, and may form a ring in collaboration with Ar and Ars.

R8 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 six substituted or unsubstituted groups. : Represents an alkylamino group, an arylamino group, an aralkylamino group, a cyclic hydrocarbon group, a fused polycyclic hydrocarbon group, and a heterocyclic group.

R, R, and R6 are substituted or unsubstituted groups; alkyl group, phenyl group, alkoxy group, fenoquine group and/or ano 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. i, ni, i
represents an integer of 0 to 5, and j represents an integer of θ to 4.

The distyryl compound represented by the -formation (T) has good performance as a CTM and is advantageous for increasing sensitivity.

CI(.

T-15 CTMs that can be used in combination in the present invention are not particularly limited, but include, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidacilone derivatives, imidazolidine derivatives, Bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, amine derivatives, oxacilone derivatives,
benzothiazole derivatives, benzimidazole derivatives,
Quinapurine derivatives, benzofuran derivatives, acridine derivatives, heptanazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1 vinylpyrene,
Poly-9-vinylanthracene and the like.

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 (3) Anthraquinone derivatives, anthanthrone derivatives, and dibenzpyrenequinone derivatives , pyrantrone derivative,
Polycyclic quinone pigments such as violanthrone derivatives and inviolanthrone derivatives (4) Indigoid pigments such as indigo derivatives and thioindigo 1 conductors In particular, in the electrophotographic photoreceptor of the present invention, fluorenone-based disazo pigments, fluorenylidene-based disazo pigments, polycyclic It is preferable to use organic pigments such as quinone pigments. In particular, when the following fluorenone-based nosazo 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-based disazo pigment used in the present invention is represented by the following layer structure [F].

- Layering ['Fl] Xl and X2 each represent a halogen atom, an alkyl group, an alkoxy 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 x may be the same or different groups, respectively.

A represents a group represented by -stratified CF, -1) below.

General formula (F, -1:) Z In the formula, Ar represents a fluorinated hydrocarbon group or an aromatic carbocyclic group or an aromatic heterocyclic group serving as 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 an integer of 0°l or 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 No.

The fluorenone disazo pigment represented by the general formula [F,] 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 disazo pigment used in the present invention is represented by the following general formula [F1a].

General formula [F1a CN CN In the formula, A is: Substituted or unsubstituted two groups as shown below; atomic group necessary to constitute an aromatic carbocyclic ring, an aromatic heterocyclic ring, two elementary atoms, a hydroquine group, a carboxyne 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, Carboxy group or its ester group or cyano group Ar: Substituted or unsubstituted aryl group R2: Substituted or unsubstituted Synopsis Three groups; Represents an alkyl group, an aralkyl group, and an aryl group.

Specific examples of the disazo pigments represented by the general formula [F2] that are effective in the present invention include those represented by the following structural formula, but this limits the disazo pigments to be used in the present invention. It is not something that will be done.

F! The polycyclic non-pigment used in the present invention has the following layer structure [Q
1] to [Q,].

General formula [Q1] General formula (Q2): General formula CQI): In each formula, X represents a halogen atom, a nitro group, an acyl group, or a carboxy group, and n represents an integer of 0 to 4
m represents an integer of 0 to 6.

Specific examples of the polycyclic bovine non-pigment used in the present invention shown in the above-mentioned -layer structure [Q1] to [Q,] are shown below, but the pigment is not limited thereto.

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

Specific examples of the dibenzpyrenequinone pigment represented by Ql-I Q, -2 Q, -5 layer structure [Q2] are as follows.

Ql-3 The polycyclic quinone pigments represented by the above-mentioned stratification [Q1] to [Q,] used in the present invention of biracitron pigments represented by the general formula [Q,] 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 xylene, methylene chloride, methylene bromine,
．． 2-dichloroethane, 5yn-tetrachloroethane,
ClS-112-dichloroethylene, 11.2-trichloroethane, 1,1.1-1-dichloroethane, 1.
2-dichloropropane, chloroform, bromoform,
Halogenated hydrocarbons such as chlorobenzene, ketones such as acetone, methyl ethyl ketone, cyclohexanone, esters such as ethyl acetate, butyl acetate, methanol, ethanol, propatool, butanol, cyclohexanol, hexanol, ethylene glycol, ethyl cellosolve, ethyl Alcohols and their derivatives such as cellosolve and cellosolve acetate, tetrahydrofuran, ethers such as 4-dioxane, 7-ran, and furfural, acetals, amines such as pyridine, butylamine, diethylamine, ethylenediamine, and inpropatol amine, N, N - In addition to nitrogen compounds such as amides such as dimethylformamide, fatty acids and phenols, sulfur and phosphorus compounds such as carbon disulfide and triethyl phosphate, and the like.

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, tetracyanoquinodimethane, 0-dinitrobenzene, m-dinitrobenzene,
1.3.5-trinitrobenzene, paranitrobenzonitrile, vicryl chloride, quinone chlorimide, chloranil, brumanil, dichlorodicyanobarabenzoquinone, anthraquinone, dinitroanthraquinone, 21
7-cyclohexanone, 2,4.7-trinitrofluorenone, 2.4,5.7-tetranitrofluorenone,
9-fluorenylidene [dicyanomethylenemalonodinitrile], polynitro-9-fluorenylidene-[dinanomethylenemalonodinitrile], picric acid, 0-nitrobenzoic acid, p-nitrobenzoic acid, 3.5-dinitrobenzoic acid, penta Examples include fluorobenzoic 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 the organic pigment used in the present invention:electron-accepting substance-100 in weight ratio.
: 0.01-200, preferably 100 + 0.1
-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
The ratio is preferably 100:0.1 to 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.

Further, in the photosensitive layer of the present invention, an antioxidant may be added for the purpose of preventing ozone deterioration.

Typical examples of such antioxidants are shown below, but the invention is not limited thereto.

r-g, hindered phenols, ■-group, paraphenylenenoamines, I [I-group; hydroquinones,
■-group: Examples include organic sulfur compounds, ■-group, and organic phosphide metals.

These compounds are disclosed, for example, in JP-A-63-18354.

These compounds are known as antioxidants for rubber, plastics, oils and fats, and are easily available commercially.

The amount of antioxidant added is 0 per 100 parts by weight of CTM.
．． The amount is 1 to 100 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 5 to 25 parts by weight.

In addition, the photoreceptor of the present invention may also contain, if necessary, an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, 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 may be contained in an amount of less than 5 Qwt% 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.

l) 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 plastic film by coating or vapor deposition.

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

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 applied directly to 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 μm to 5 μm, more preferably 0.
05 μm to 3 μm.

Further, the thickness of the CTL 3 can be changed as necessary, but it is usually preferably 5 μm to 30 μm. This CTL
The composition ratio in 3 is preferably 0.1 to 5 parts by weight of the binder to 1 part by weight of CTM of the present invention, but when forming the photosensitive layer 4 in which fine particulate CGM is dispersed, 1 part by weight of CGM It is preferable to use the binder in an amount of 5 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 per 1 part by weight of C(:,M).

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 I Methanol EL specification of 800n+4 in which 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 500C. (manufactured by Kanto Kagaku Co., Ltd.) with stirring, and dissolved. After cooling to room temperature,
200 m+2 of l-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 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 dissolved in methyl ethyl ketone (EL standard, manufactured by Kanto Kagaku Co., Ltd.) 1000 +++ I2, and sand milled. At 2
Milling was performed for 4 hours to obtain a CGL coating liquid. This was coated by dip coating on the intermediate layer to form a CGL with a thickness of 0.3 μm.

Then, 120 g of the above (Exemplary CTM; T-2)
and Polymer B + 1165g were dissolved in 1,2-dichloroethane special grade (manufactured by Kanto Kagaku Co., Ltd.) 10100O, and C
A TL 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 μm. In this way, a photoreceptor was produced in which the intermediate layer-CGL-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-1.

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

As CGM, polycyclic quinone pigment: (Example compound: Q
, -3) 20 g and 10 g of polycarbonate resin L-1250 (manufactured by Ondai Kasei Co., Ltd.) as a binder were 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 if! A working solution was obtained. This was applied on the intermediate layer by dip coating to form a CGL having a thickness of 0.3 μl.

Next, CTM is exemplified, T-3 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 1.

Example 4 CTM is illustrated; T-13, CTL binder is copolymer B
A photoreceptor was produced in the same manner as in Example 1 except that -1 was used.

Example 5 12g of polyvinyl butyral resin (S-LEC BX-1゜manufactured by Fusui Kagaku Co., Ltd.) was mixed with methyl ethyl ketone 1000■Q
Exemplary compound Q13 as CGM;
5.7 g and 0.3 g of exemplified compound F r-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 Bisphenol A polycarpo, nate (Odai Kasei Panlite K-1300) was used as the CTL binder in Example 1.
A photoreceptor was prepared in the same manner except that .

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 unstable liquid was obtained.

Comparative Example 2 In Example 1, CTL/(Bisphenol Z
A photoreceptor was prepared in the same manner except that polycarbonate (Mitsubishi Gas Chemical Z-200) 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
4ix 2025J (manufactured by Konica), and performed 100,000 copies, and measured the surface potential before and after the actual copying.

Black paper potential2 Surface potential for an original with a reflection density of 1.3White paper potential: Surface potential for an original with a reflection density of 0.0Residual potential:Surface potential after static eliminationRegarding film depletion due to surface friction, 10,000 copies are completed before exposure to light. 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; It has extremely high printing durability as it has low friction and excellent abrasion resistance.

[Brief explanation of drawings]

FIGS. 1 to 6 are sectional views showing examples of the mechanical structure of the photoreceptor of the present invention, respectively. l... 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 of the photosensitive layer contains the following general formula [B_1] as a main repeating unit.
] or a copolymer whose structural composition includes the above general formula [B_1] and the following general formula [B_2] as main repeating units, and also contains a compound represented by the following general formula [T] An electrophotographic photoreceptor characterized by: General formula [B_1] -▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [B_2] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are hydrogen atoms and alkyl groups having 1 to 6 carbon atoms. represents. R_3, R_4, R_5, R_6 and R_7, R_8,
R_9 and R_1_0 are hydrogen atoms, methyl groups, chlorine atoms,
Bromine atoms, but not all 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 three groups; a fused polycyclic hydrocarbon group, a bare ring group, a fused polycyclic heterocyclic group, Ar
It may form a ring together with_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. ]