JPH0580548A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To improve the adhesive property of the photosensitive layer of a single layer type electrophotographic sensitive body to the electric conductive substrate and to prolong the service life of the sensitive body by using specified polycarbonate resin as a resin binder in the photosensitive layer. CONSTITUTION:Polycarbonate resin consisting of repeating units represented by formulae I, II in 0.01-0.9 molar ratio of the units represented by the formula I to the units represented by the formulae I, II is used as a resin binder in a photosensitive layer. In the formulae I, II, each of R<1>-R<4> is H, halogen, 1-6C alkyl, etc., X is -CR<5>R<6> (each of R<5> and R<6> is H, trifluoromethyl, 1-6C alkyl, etc.), 5-11C 1,1-cycloalkylene or 2-10C alpha, beta-alkylene and each of (o)-(r) is an integer of 0-4 independently.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, and more specifically, it is a single layer type which can maintain excellent mechanical strength and electrophotographic characteristics for a long time and can be suitably used in various electrophotographic fields. The present invention relates to an electrophotographic photoreceptor.

[0002]

2. Description of the Related Art In a recent electrophotographic photosensitive member, a laminated electrophotographic photosensitive member, that is, a photosensitive layer is a charge generating layer (CGL) which generates a charge upon exposure and a charge transport layer (CTL) which transfers a charge. ) And a single-layer type electrophotographic photosensitive member (OPC) having at least two layers with a single layer type in which the photosensitive layer has one layer in which a charge generating material and a charge transporting material are dispersed in a binder resin. Proposed and used. As a binder resin for the charge transport layer of the laminated electrophotographic photoreceptor and the binder layer of the photosensitive layer of the single-layer electrophotographic photoreceptor, a polycarbonate resin containing bisphenol A as a raw material is widely used.

Polycarbonate resin using bisphenol A as a raw material has good compatibility with a charge transporting substance, and therefore has good electrical characteristics when manufactured as a photoconductor and has a relatively large mechanical strength. is doing.

However, it has been revealed that the following problems occur when a photosensitive layer is formed by using a polycarbonate resin prepared from bisphenol A or bisphenol Z as a binder resin. When a photosensitive layer is applied during the production of a photoreceptor, the coating solution may be whitened (gelled) or the photosensitive layer may be easily crystallized depending on the solvent used. In the part where this crystallization has occurred, there is no light attenuation, the electric charge remains as a residual potential, and it appears as a defect in terms of image quality. The photosensitive layer using the polycarbonate resin made of bisphenol A or bisphenol Z as a raw material has poor adhesion to the base and is easily peeled off, or is scratched due to insufficient surface hardness, and the surface is worn to shorten the printing life. There is a drawback. In this case, the base is usually
In the single-layer type photoreceptor, it means a conductive substrate.

[0005]

The present invention has been made based on the above circumstances. The object of the present invention is to solve the above-mentioned problems found in conventional electrophotographic photoreceptors using a polycarbonate resin prepared from bisphenol A or bisphenol Z as a binder resin for the photosensitive layer.
The coating liquid does not whiten (gel) during the production of the electrophotographic photoreceptor, and has excellent surface hardness for a long period of time.
An object of the present invention is to provide an electrophotographic photoreceptor that is remarkably excellent in practical use and maintains mechanical strength such as adhesiveness and electrophotographic characteristics.

[0006]

As a result of intensive studies to solve the above problems, the present inventors have found that an electrophotographic photoreceptor using a polycarbonate resin having a specific structure as a binder resin for a photosensitive layer is There is no problem as described above that is observed in a conventional electrophotographic photoreceptor using a polycarbonate resin made of bisphenol A or bisphenol Z as a binder resin, and the coating liquid is whitened (gelled) during the production of the photoreceptor. It has been found that the mechanical strength such as surface hardness and adhesiveness and the electrophotographic characteristics are maintained over a long period of use without any trouble, and the present invention has been completed based on this finding.

That is, the present invention provides a single-layer type electrophotographic photosensitive member having a photosensitive layer composed of a single layer on a conductive substrate, and the following general formula (I) is used as a binder resin for the photosensitive layer.
And (II)

[0008]

[Chemical 2]

[Wherein R ¹, R ², R ³And R ^FourEach is independent
A hydrogen atom, a halogen atom, an alkyl having 1 to 6 carbon atoms
Group, cycloalkyl group having 5 to 7 carbon atoms or 6 to 1 carbon atoms
2 is an aryl group, and X is —CR ^FiveR ⁶− (However,
R ^FiveAnd R ⁶Are each independently a hydrogen atom, trifluoromethyl
Group, an alkyl group having 1 to 6 carbon atoms or an alkyl group having 6 to 12 carbon atoms
It is an aryl group. ), 1,1-siku having 5 to 11 carbon atoms
Roalkylene group, α, ω-alkylene having 2 to 10 carbon atoms
Group, -O-, -S-, -SO- or -SO ₂−,
o, p, q, and r are each independently an integer of 0 to 4. ]
A repeating unit represented by the general formula (I)
The content ratio of the repeating unit represented by the general formula (I)
And a repeating unit represented by the general formula (II)
A polycarbonate resin having a molar ratio with respect to the total of the following is expressed by the following formula: 0.01 ≦ [(I) / {(I) + (II)}] ≦ 0.9.
And an electrophotographic photosensitive member.

The polycarbonate resin used in the electrophotographic photosensitive member of the present invention comprises a repeating unit represented by the above general formula (I) and a repeating unit represented by the above general formula (II). The molar ratio of the repeating unit represented by formula (I) to the total of the repeating unit represented by formula (I) and the repeating unit represented by formula (II) is represented by the following formula 0.01 ≦ [(I) /{(I)+(II)}]≦0.9.

When the molar ratio of the repeating unit represented by the general formula (I) is less than 0.01, the effect of the present invention cannot be obtained, and the coating solution is whitened (gelled) and the charge transport layer is crystallized. It is impossible to prevent the deterioration of printing life and the improvement of printing life. on the other hand,
When this molar ratio exceeds 0.9, crystallization occurs in a part of the polycarbonate resin, which makes it unsuitable as a binder resin for an electrophotographic photoreceptor.

The content ratio of the repeating unit represented by the formula (I) is preferably 0.05 ≦ [(I) / {(I) + (II)}] ≦ 0.5.

The polycarbonate resin used in the present invention may have other repeating units other than those mentioned above within the range not impairing the object of the present invention, and may contain other polycarbonate components or additives. It is also possible to appropriately add and blend it.

The polycarbonate resin used in the present invention has a reduced viscosity [η _sp / c] of a solution of methylene chloride at a concentration of 0.5 g / dl at 20 ° C., preferably 0.2 to 5.0 dl / g, more preferably 0.3 to
It is in the range of 3.0 dl / g. When the reduced viscosity [η _sp / c] is less than 0.2 dl / g, the mechanical strength of the polycarbonate resin is low, and in particular, the surface hardness of the layer using this polycarbonate resin as a binder resin is insufficient, and the photoreceptor wears and resists abrasion. Printing life may be shortened. On the other hand, the reduced viscosity [η
_{When sp} / c] exceeds 5.0 dl / g, the solution viscosity of the polycarbonate resin increases, and it may be difficult to manufacture the photoreceptor by the solution coating method.

The polycarbonate resin used in the present invention has the following general formula (III):

[Chemical 3](In the formula, R ¹, R ², O and p have the same meaning as described above.
Have a taste. ) 4,4'-dihydroxybif
And a general formula (IV) below.

[Chemical 4](In the formula, R ³, R ^Four, X, q and r are the same as described above.
Has the meaning. ) Bisphenol compounds
And a carbonic acid ester-forming compound such as phosgene,
Polycondensation in the presence of acid binder, or 4,4 '
-Dihydroxybiphenyl compound (III) and bisphenol
Enol compound (IV) and bisaryl carbonate
Can be obtained by a method such as transesterification of
It

4,4 'represented by the general formula (III)
As typical examples of the dihydroxybiphenyl compound, specifically, 4,4′-dihydroxybiphenyl, 4,
4'-dihydroxy-3,3'-dimethylbiphenyl,
4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl, 4,4'- Dihydroxy-3,
3'-diphenyl biphenyl etc. are mentioned. Particularly preferably, 4,4'-dihydroxybiphenyl is used.

Specific examples of the bisphenol compound represented by the general formula (IV) include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane and 1,2-bis. (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl)
Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-
Hydroxyphenyl) -1-phenylethane, 1,1-
Bis (4-hydroxyphenyl) -1-phenylmethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane, 1,1-bis (4-
Hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2
-(3-Methyl-4-hydroxyphenyl) -2- (4
-Hydroxyphenyl) -1-phenylethane, bis (3-methyl-4-hydroxyphenyl) sulfide,
Bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (2 -Methyl-4-
Hydroxyphenyl) propane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane,
1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1,1-bis (2-t
ert-Butyl-4-hydroxy-5-methylphenyl) propane, 1,1-bis (2-tert-butyl-)
4-hydroxy-5-methylphenyl) butane, 1,1
-Bis (2-tert-butyl-4-hydroxy-5-
Methylphenyl) isobutane, 1,1-bis (2-te
rt-Butyl-4-hydroxy-5-methylphenyl)
Heptane, 1,1-bis (2-tert-butyl-4-
Hydroxy-5-methylphenyl) -1-phenylmethane, 1,1-bis (2-tert-amyl-4-hydroxy-5-methylphenyl) butane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane,
2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) ) Propane, 2,2-
Bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-)
4-hydroxy-5-chlorophenyl) propane, 2,
2-bis (3,5-dichloro-4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 1-phenyl-1,1-bis (3-fluoro- 4-hydroxyphenyl) ethane,
Examples thereof include bis (3-fluoro-4-hydroxyphenyl) ether and 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane. These bisphenol compounds may be used alone or in combination of both. Particularly preferably, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1,1
-Diphenylmethane, 2,2-bis (3-methyl-4-)
Hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are used.

Typical examples of the carbonic acid ester-forming compound include various carbonyl dihalides such as phosgene, haloformates such as chloroformate compounds, and carbonic acid ester compounds.

The proportion of the carbonic acid ester forming compound used is
It may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent amount) of the reaction. When a gaseous carbonic acid ester-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably adopted.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide,
An alkali metal carbonate such as sodium carbonate or potassium carbonate, an organic base such as pyridine, or a mixture thereof is used. The proportion of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent weight) of the reaction, similarly to the above.
Specifically, 2 equivalents or slightly excess amount of the acid is used with respect to the total number of moles of 4,4'-dihydroxybiphenyl compound (III) and bisphenol compound (IV) used (usually 1 mole corresponds to an equivalent amount). It is preferable to use a binder.

As the solvent, various solvents such as those used in the production of known polycarbonates may be used alone or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. The interfacial polycondensation reaction may be carried out using two kinds of solvents that are immiscible with each other.

Further, in order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt, and to adjust the degree of polymerization,
It is desirable to carry out the reaction by adding a molecular weight modifier such as p-tert-butylphenol or phenylphenol. Further, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added.
The reaction is usually carried out at a temperature in the range of 0 to 150 ° C, preferably 5 to 40 ° C. The reaction pressure may be any of reduced pressure, normal pressure, and increased pressure, but normally, normal pressure or the self-pressure of the reaction system is suitable. The reaction time depends on the reaction temperature and the like, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours.

First, the 4,4'-dihydroxybiphenyl compound (III) and the bisphenol compound (I
It is also possible to use a two-step method in which a part of the reaction raw material consisting of V) is reacted with a carbonic acid ester forming substance to form an oligomer, and then the remaining reaction raw materials are added to complete the polycondensation. According to such a two-step method, the reaction can be easily controlled, and the molecular weight can be controlled with high accuracy.

When the latter transesterification method of 4,4'-dihydroxybiphenyl compound (III) and bisphenol compound (IV) and bisaryl carbonate is used, the reaction mode is a melt polycondensation method or a solid phase polycondensation method. Etc. are suitable. When performing the melt polycondensation method, the above 3
The seed monomers are mixed and allowed to react in a molten state at high temperature under reduced pressure. The reaction is usually performed at a temperature in the range of 150 to 350 ° C, preferably 200 to 300 ° C.
When the solid phase polycondensation method is carried out, the above-mentioned three kinds of monomers are mixed, and the polycondensation is carried out by heating to a temperature not higher than the melting point of the produced polycarbonate resin in the solid phase state. In any case, the degree of vacuum is preferably 1 mm at the final stage of the reaction.
The phenols derived from the above bisaryl carbonate produced by the transesterification reaction are distilled out of the system to Hg or less. Although the reaction time depends on the reaction temperature and the degree of reduced pressure, it is usually about 1 to 4 hours. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon, and if desired, the reaction may be carried out by adding the above-mentioned molecular weight modifier or antioxidant.

The reduced viscosity [η _sp / c] of the obtained polycarbonate resin can be controlled by various methods such as selection of the reaction conditions and adjustment of the amount of the molecular weight modifier used. .. In addition, in some cases, the obtained polycarbonate resin is appropriately subjected to physical treatment (mixing,
Fractionation) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.)
It can also be obtained as a polycarbonate resin of _sp / c].

The obtained reaction product (crude product) can be recovered as a polycarbonate resin having a desired purity (purification degree) by subjecting to various post-treatments such as a known separation and purification method.

The electrophotographic photoreceptor of the present invention can be used not only in the known various types of electrophotographic photoreceptors, but also in any known electrophotographic photoreceptors, as long as the above-mentioned polycarbonate resin is used as a binder resin for the photosensitive layer in the single-layer type photoreceptor. It may be one.

In the electrophotographic photosensitive member of the present invention, the polycarbonate resin of the present invention may be used alone or in combination of two or more. If desired, other binder resin components such as polycarbonate may be contained within the range not impairing the object of the present invention. Further, additives such as antioxidants may be included.

As the conductive substrate material used in the electrophotographic photosensitive member of the present invention, various materials such as known materials can be used. Specifically, for example, aluminum,
Conductive by coating a conductive material such as aluminum, nickel, chromium, palladium, graphite on the metal plate of brass, copper, nickel, steel, etc., drum or metal sheet, plastic sheet by vapor deposition, sputtering, coating, etc. It is possible to use those which have been subjected to a chemical treatment, those whose metal drum surface has been subjected to a metal oxide treatment such as electrode oxidation, or those whose substrates such as glass, plastic plate, cloth and paper have been subjected to a conductive treatment. ..

The photosensitive layer contains at least a charge-generating material and a charge-transporting material in the polycarbonate as a binder resin, and various methods such as known methods can be used for forming the photosensitive layer. However, usually, for example, a method of applying a coating solution in which a charge generating material and a charge transporting material are dispersed or dissolved together with a binder resin in an appropriate solvent onto a predetermined base substrate and drying it is preferably used. can do.

The charge generating material is not known.
Various types can be used, specifically, for example
For example, selenium simple substances such as amorphous selenium and trigonal selenium, selenium
Alloy of selenium such as nickel-tellurium, As ₂Se ₃Selenium compounds such as
Alternatively, selenium-containing composition, zinc oxide, CdS-Se, etc.
Inorganic material consisting of Group II and Group IV elements, titanium oxide
Oxide-based semiconductors such as Silica and amorphous silicon
Various inorganic materials such as Cone-based materials, metal or metal-free materials
Tarocyanine, cyanine, anthracene, pyrene, peri
Len, pyrylium salt, thiapyrylium salt, polyvinyl alcohol
Various organic materials such as Lubazole and Squarium pigment
Can be mentioned. These are used alone
Or you can mix two or more,
It can also be used together.

Further, to the extent that the object of the present invention is not impaired,
It is also possible to use other binder resins together with the polycarbonate resin of the present invention.

Examples of the charge transport material that can be used in the present invention include conventionally used electron transport materials and hole transport materials. Specific examples of the electron transporting substance include, for example, chloroanyl, bromoanyl,
Tetracyanoethylene, tetracyanoquinodimethane,
2,4,7-trinitro-9-fluorenone, 2,4
5,7-tetranitro-9-tetrafluorenone, 2,
4,7-Trinitro-9-dicyanomethylenefluorenone, 2,4,5,7-tetranitroxanthone, 2,
There are electron withdrawing substances such as 4,9-trinitrothioxanthone and those obtained by polymerizing these electron withdrawing substances. These may be used alone or in combination of two or more.

As the hole transporting substance, pyrene, N-ethylcarbazole, N-isopropylcarbazole, N
-Methyl-N-phenylhydrazino-3-methylidene-
9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N, N
-Diphenylhydrazino-3-methylidene-10-ethylphenothiazine, N, N-diphenylhydrazino-3
-Methylidene-10-ethylphenoxazine, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-diethylaminobenzaldehyde-N-α
-Naphthyl-N-phenylhydrazone, p-pyrrolidinobenzaldehyde-N, N-diphenylhydrazone,
1,3,3-Trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 1-phenyl-1,2,3,4- Hydrazones such as tetrahydroquinoline-6-carboxaldehyde-1 ′, 1′-diphenylhydrazone, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- ( p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [quinolyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [lepidil (2 )]-3- (p-
Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [6-methoxy-pyridyl (2)]-3- (p-diethylaminostyryl) -5-
(P-Diethylaminophenyl) pyrazoline, 1- [pyridyl (5)]-3- (p-diethylaminophenyl)
Pyrazoline, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3- (p
-Diethylaminostyryl) -4-methyl-5- (p-
Diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3- (α-methyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (p-diethylaminostyryl)- 4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (α-benzyl-
Pyrazolines such as p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and spiropyrazoline, 2- (p-diethylaminostyryl) -δ-
Oxazole compounds such as diethylaminobenzoxazole, 2- (p-diethylaminophenyl) -4- (p-dimethylaminophenyl) -5- (2-chlorophenyl) oxazole, 2- (p-diethylaminostyryl) -6-diethylaminobenzo Thiazole-based compounds such as thiazole, triarylmethane-based compounds such as bis (4-diethylamino-2-methylphenyl) -phenylmethane, 1,1-bis (4-N, N-diethylamino-)
Polyarylamines such as 2-methylphenyl) heptane and 1,1,2,2-tetrakis (4-N, N-dimethylamino-2-methylphenyl) ethane, N, N′-diphenyl-N, N ′ -Bis (methylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (ethylphenyl) benzidine, N, N'-diphenyl-N, N '
-Bis (propylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (butylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (isopropylphenyl) benzidine, N, N ' -Diphenyl-
N, N'-bis (secondary butylphenyl) benzidine,
N, N'-diphenyl-N, N'-bis (tertiary butylphenyl) benzidine, N, N'-diphenyl-N,
Benzidine compounds such as N'-bis (chlorophenyl) benzidine, triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-vinylphenylanthracene, pyrene-formaldehyde resin, ethylcarbazole- Formaldehyde resin etc. can be mentioned. In addition, these may be used individually by 1 type, or may be used together, such as mixing 2 or more types.

Specific examples of the solvent used for forming the photosensitive layer include aromatic solvents such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, methanol, ethanol and isopropanol. Alcohol, etc.
Examples include esters such as ethyl acetate and ethyl cellosolve, carbon tetrachloride, carbon tetrabromide, halogenated hydrocarbons such as chloroform, dichloromethane and tetrachloroethane, ethers such as tetrahydrofuran and dioxane, dimethylformamide, dimethylsulfoxide and diethylformamide. You can These solvents may be used alone or in combination of two or more as a mixed solvent.

Coating of the photosensitive layer can be carried out by using various coating devices such as known ones. Specifically, for example,
Applicator, spray coater, bar coater, tip coater, roll coater, dip coater, doctor blade and the like can be used.

The electrophotographic photosensitive member of the present invention does not cause whitening (gelation) of the coating liquid during its preparation, and has excellent mechanical strength and electrophotographic characteristics even when it is repeatedly used for a long time. It is a remarkably excellent electrophotographic photosensitive member that maintains the above properties, and can be suitably used in various electrophotographic fields.

[0038]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples, and various modifications can be made without departing from the spirit of the present invention. And application is possible. Example 1 2,2-bis (4-hydroxyphenyl) propane 74
550 ml of phosgene gas in the liquid while cooling, while stirring a solution of g dissolved in 550 ml of a 6% concentration aqueous sodium hydroxide solution and 250 ml of methylene chloride.
Blow for 15 minutes at a rate of / minute. Then, the reaction solution was separated by standing to obtain a methylene chloride solution of an oligomer having a degree of polymerization of 2 to 4 in the organic phase and having a chloroformate group at the molecular end.

Methylene chloride was added to the obtained oligomer solution to bring the total amount to 450 ml, and then 24 g of 4,4'-dihydroxybiphenyl was mixed with a solution prepared by dissolving 150 ml of an 8% strength aqueous sodium hydroxide solution. 3.0 g of p-tert-butylphenol which is a regulator
Was added. Then, while vigorously stirring this mixed solution, 2 ml of a 7% aqueous solution of triethylamine was added as a catalyst, and the reaction was carried out at 28 ° C. for 1.5 hours with stirring.

After completion of the reaction, the reaction product was converted into methylene chloride 1
Dilute with liters, then twice with 1.5 liters of water,
0.01N hydrochloric acid 1 liter once, water 1 liter 2
Wash in the order of times and re-precipitate by throwing the organic phase into methanol.
Purified. The polymer thus obtained is methyl chloride.
Solution of 0.5 g / dl in solvent at 20 ° C
Reduced viscosity [η_sp/ c] is 0.82 dl / g
It was The structure and composition of the obtained polymer are ¹H-
When analyzed by NMR spectrum, the polymer was
Polycarbonate consisting of the following repeating units and compositions
It was confirmed to be a polymer.

[0041]

[Chemical 5]

A coating solution was prepared by dissolving 1 g of this polycarbonate, 0.1 g of oxotitanium phthalocyanine as a charge generating substance and 1 g of the following hydrazone compound as a charge transporting substance in 8 ml of tetrahydrofuran. Even when the coating solution was allowed to stand for 1 month, no white turbidity or gel was observed.

Charge transport material (1-phenyl-1,2,
3,4-tetrahydroquinoline-6-carboxaldehyde-1 ', 1'-diphenylhydrazone)

[Chemical 6]

Using aluminum as a conductive substrate, the above coating liquid was applied by a dip coating method, and after drying, a single-layer type electrophotographic photoreceptor having a photosensitive layer thickness of 20 μm was prepared. The photosensitive layer was not crystallized during coating. The abrasion resistance of this photosensitive layer was evaluated using a Suga abrasion tester NUS-ISO-3 type (manufactured by Suga Testing Instruments Co., Ltd.). Test condition is 200g
The sample was reciprocated a certain number of times on the worn paper under the load, and the change in the amount of wear thereafter was measured. The results of reciprocating 1200 times are shown in Table 1. Further, the adhesiveness between the photosensitive layer and the conductive substrate was evaluated by a peeling test using a Scotch tape, and the results are shown in Table 1. In addition, as the evaluation criteria of the adhesiveness in Table 1, those having a binding retention rate of 80% or more in the peeling test are “good” and
Those with less than% were regarded as “bad”.

Example 2 The same operation as in Example 1 was performed except that 4,4'-dihydroxybiphenyl used in Example 1 was changed to 27 g of 4,4'-dihydroxy-3,3'-dimethylbiphenyl, and the following procedure was performed. A polycarbonate polymer ([η _sp /c]=0.75 dl / g) having a repeating unit of was obtained.

[0046]

[Chemical 7]

Using this polycarbonate polymer, a single-layer type electrophotographic photosensitive member was prepared in the same manner as in Example 1.
The stability of the coating liquid and the evaluation results of crystallization during coating were the same as in Example 1. Table 1 shows the evaluation results of abrasion resistance and adhesiveness.

Comparative Example 1 Polycarbonate ([η _sp /c]=0.78 dl) composed of the following repeating unit using commercially available 2,2-bis (4-hydroxyphenyl) propane (bisphenol A)
/ G) in the same manner as in Example 1 to produce a single-layer type electrophotographic photosensitive member. As a result, the coating liquid became cloudy on the second day and gel was generated. In addition, part of the charge transport layer was crystallized (whitened) during coating. Table 1 shows the evaluation results of abrasion resistance and adhesiveness.

[0049]

[Chemical 8]

Comparative Example 2 74 g of 2,2-bis (4-hydroxyphenyl) propane used in Example 1 was added to 87 g of 1,1-bis (4-hydroxyphenyl) cyclohexane, and 24 g of 4,4'-dihydroxybiphenyl was added. A polycarbonate polymer ([η _sp /c]=0.84 dl / g) consisting of the following repeating unit was prepared in the same manner as in Example 1 except that 35 g of 1,1-bis (4-hydroxyphenyl) cyclohexane was used.
Got

[0051]

[Chemical 9]

Using this polycarbonate polymer as a binder resin, a single-layer type electrophotographic photosensitive member was prepared in the same manner as in Example 1. The stability of the coating liquid and the evaluation results of crystallization during coating were the same as in Example 1. Table 1 shows the results of evaluation of abrasion resistance and adhesiveness of this electrophotographic photosensitive member.

[0053]

[Table 1]

[0054]

According to the present invention, since a polycarbonate resin having a specific structure is used as a binder resin for the photosensitive layer of a single-layer type electrophotographic photoreceptor, the coating liquid is whitened during the production of the electrophotographic photoreceptor. (Gelling), the adhesiveness between the conductive substrate and the photosensitive layer is improved, the life of the electrophotographic photosensitive member is extended, and the surface hardness of the photosensitive member surface, that is, abrasion resistance is improved. It is possible to provide an electrophotographic photosensitive member having excellent printing durability that maintains excellent electrophotographic characteristics even after repeated use for a long time.

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[Procedure amendment]

[Submission date] October 16, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

As the conductive substrate material used in the electrophotographic photosensitive member of the present invention, various materials such as known materials can be used. Specifically, for example, aluminum,
Brass, copper, nickel, steel and other metal plates, drums or metal sheets, aluminum on plastic sheets,
Nickel, chromium, palladium, graphite or other conductive material that has been subjected to a conductive treatment by coating it by vapor deposition, sputtering, coating, etc., or a metal drum surface that has been subjected to metal oxide treatment such as electrode oxidation, or Substrates such as glass, plastic plates, cloth, and paper that have been subjected to a conductive treatment can be used.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

As the charge generating material, various materials such as known materials can be used. Specifically, for example, selenium simple substance such as amorphous selenium and trigonal selenium, and selenium such as selenium-tellurium. Alloy, selenium compound such as As ₂ Se ₃ or selenium-containing composition, zinc oxide, CdS-
Inorganic materials composed of Group II and Group IV elements such as Se,
Oxide semiconductors such as titanium oxide, various inorganic materials such as silicon-based materials such as amorphous silicon, metal or metal-free phthalocyanines, cyanines, bisazo compounds,
Examples thereof include various organic materials such as anthracene, pyrene, perylene, pyrylium salts, thiapyrylium salts, polyvinylcarbazole, and squarylium pigments. It should be noted that these may be used alone, or 2
It is also possible to use them in combination, such as by mixing two or more species.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0033

[Correction method] Change

[Correction content]

Examples of the charge transport material that can be used in the present invention include conventionally used electron transport materials and hole transport materials. Specific examples of the electron transporting substance include, for example, chloroanyl, bromoanyl,
Tetracyanoethylene, tetracyanoquinodimethane,
2,4,7-trinitro-9-fluorenone, 2,4
5,7-Tetranitro-9- fluorenone , 2,4,7
-Trinitro-9-dicyanomethylenefluorenone,
2,4,5,7-tetranitroxanthone, 2,4,9
-Trinitrothioxanthone or 3,5-dimethyl
-3 ', 5'-di-t-butyl-4,4'-diphenoxy
There are electron withdrawing substances such as diphenoquinone derivatives such as non and those obtained by polymerizing these electron withdrawing substances. In addition,
These may be used alone or in combination of two or more.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

As the hole transporting substance, pyrene, N-ethylcarbazole, N-isopropylcarbazole, N
-Methyl-N-phenylhydrazino-3-methylidene-
9-ethylcarbazole, N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N, N
-Diphenylhydrazino-3-methylidene-10-ethylphenothiazine, N, N-diphenylhydrazino-3
-Methylidene-10-ethylphenoxazine, p-diethylaminobenzaldehyde-N, N-diphenylhydrazone, p-diethylaminobenzaldehyde-N-α
-Naphthyl-N-phenylhydrazone, p-pyrrolidinobenzaldehyde-N, N-diphenylhydrazone,
1,3,3-Trimethylindolenine-ω-aldehyde-N, N-diphenylhydrazone, p-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 1-phenyl-1,2,3,4- Hydrazones such as tetrahydroquinoline-6-carboxaldehyde-1 ′, 1′-diphenylhydrazone, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- ( p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [quinolyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [lepidil (2 )]-3- (p-
Diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [6-methoxy-pyridyl (2)]-3- (p-diethylaminostyryl) -5-
(P-Diethylaminophenyl) pyrazoline, 1- [pyridyl (5)]-3- (p-diethylaminophenyl)
Pyrazoline, 1- [pyridyl (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3- (p
-Diethylaminostyryl) -4-methyl-5- (p-
Diethylaminophenyl) pyrazoline, 1- [pyridyl (2)]-3- (α-methyl-p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (p-diethylaminostyryl)- 4-methyl-5- (p-diethylaminophenyl) pyrazoline, 1-phenyl-3- (α-benzyl-
Pyrazolines such as p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and spiropyrazoline, 2- (p-diethylaminostyryl) -δ-
Oxazole compounds such as diethylaminobenzoxazole, 2- (p-diethylaminophenyl) -4- (p-dimethylaminophenyl) -5- (2-chlorophenyl) oxazole, 2- (p-diethylaminostyryl) -6-diethylaminobenzo Thiazole-based compounds such as thiazole, triarylmethane-based compounds such as bis (4-diethylamino-2-methylphenyl) -phenylmethane, 1,1-bis (4-N, N-diethylamino-)
Polyarylamines such as 2-methylphenyl) heptane and 1,1,2,2-tetrakis (4-N, N-dimethylamino-2-methylphenyl) ethane, N, N′-diphenyl-N, N ′ -Bis (methylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (ethylphenyl) benzidine, N, N'-diphenyl-N, N '
-Bis (propylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (butylphenyl) benzidine, N, N'-diphenyl-N, N'-bis (isopropylphenyl) benzidine, N, N ' -Diphenyl-
N, N'-bis (secondary butylphenyl) benzidine,
N, N'-diphenyl-N, N'-bis (tertiary butylphenyl) benzidine, N, N'-diphenyl-N,
Benzidine compounds such as N'-bis (chlorophenyl) benzidine, butadiene compounds, triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-vinylphenylanthracene, organic poly
Examples thereof include silane, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin and the like. In addition, these may be used individually by 1 type, or may be used together, such as mixing 2 or more types.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

Coating of the photosensitive layer can be carried out by using various coating devices such as known ones. Specifically, for example,
Applicator, spray coater, bar coater,
It can be performed using a roll coater, a dip coater, a doctor blade, or the like.

Claims (1)

[Claims] 1. A photosensitive layer consisting of a single layer on a conductive substrate.
In the provided single-layer type electrophotographic photosensitive member,
Of the following general formulas (I) and (II)[In the formula, R ¹, R ², R ³And R ^FourAre independently hydrogen
Child, halogen atom, alkyl group having 1 to 6 carbon atoms, carbon number
5-7 cycloalkyl group or C6-C12 aryl
Is a radical and X is --CR ^FiveR ⁶-(However, R ^FiveAnd R ⁶
Are each independently a hydrogen atom, trifluoromethyl group, carbon
Alkyl group having 1 to 6 carbon atoms or aryl group having 6 to 12 carbon atoms
Is. ), 1,1-cycloalkyl having 5 to 11 carbon atoms
Group, an α, ω-alkylene group having 2 to 10 carbon atoms, —O
-, -S-, -SO- or -SO ₂−, O, p,
q and r are each independently an integer of 0 to 4. ]]
A repeating unit represented by the general formula (I)
Repetition in which the content ratio of the return unit is represented by the general formula (I)
Of the repeating unit represented by the general formula (II)
A polycarbonate resin having a molar ratio with respect to the total in the range represented by the following formula 0.01 ≦ [(I) / {(I) + (II)}] ≦ 0.9 is used.
And an electrophotographic photoreceptor.