JP2001255674A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which can be produced by a method with no problem on safety and sanitation and has a surface photosensitive layer excellent in wear and scuffing resistances and capable of retaining its electrophotographic characteristics over a long period of time. SOLUTION: The electrophotographic photoreceptor is obtained by disposing a photosensitive layer containing a polycarbonate resin having a constituent unit comprising residues of 1,1-bis(4-hydroxyphenyl)propanes or 2,2-bis(4- hydroxyphenyl)butanes on an electrically conductive substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an electronic device which can be manufactured without problems in safety and hygiene while maintaining electrophotographic characteristics for a long time because the surface layer is excellent in abrasion resistance and printing durability. It relates to a photoreceptor.

[0002]

2. Description of the Related Art Conventionally, an electrophotographic photosensitive member using an inorganic photoconductive material such as selenium or α-silicon has been used. In recent years, however, an organic electrophotographic photosensitive member using an organic photoconductive material has been used. Significant improvements in body performance have led to an increase in their use. The organic electrophotographic photoreceptor is required to have predetermined sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process. And
In this electrophotographic photosensitive member, operations such as corona charging or contact charging, toner development, transfer to paper, and cleaning processing are repeatedly performed on the surface of the photosensitive layer. Therefore, each time these operations are performed, the surface of the photosensitive layer may be abraded or scratched due to friction.In corona charging or contact charging and transfer, surface deterioration due to active gas such as ozone or discharge may occur. May progress. Therefore, in order to maintain the image quality of electrophotography over a long period of time, the photosensitive layer provided on the surface of the electrophotographic photoreceptor is required to suppress the generation of these abrasions and scratches and the surface deterioration due to active gas or discharge. High durability is required.

In order to meet such demands, a binder resin, which is one of the materials for forming a photosensitive layer provided on the surface of an organic electrophotographic photosensitive member, has good compatibility with a charge transport material used for the photosensitive layer, and Polycarbonate resins having good optical properties have been used. And, as this polycarbonate resin, 2,2-bis (4-hydroxyphenyl)
Propane, 1,1-bis (4-hydroxyphenyl)
Polycarbonate resins using cyclohexane as a raw material have been used. In the photosensitive layer using these polycarbonate resins as a binder resin, optical properties and electrophotographic properties can be sufficiently satisfied, but abrasion resistance, scratch resistance and activity can be improved. Suppression of surface deterioration due to gas or electric discharge has not been sufficiently satisfactory.

In the production process of the organic electrophotographic photoreceptor, when forming the photosensitive layer, a polycarbonate resin as a binder resin is dissolved in a halogen-based solvent such as methylene chloride to prepare a coating solution. A method of forming a photosensitive layer by applying a coating solution and then volatilizing and solidifying a halogen-based solvent is employed. By the way, since halogen-based solvents such as methylene chloride have safety and health problems for the human body, switching to non-halogen-based solvents such as toluene and tetrahydrofuran has been promoted. Low solubility in non-halogen solvents. Also, when dissolved, there is a problem that the coating liquid crystallizes with the passage of time, or the photosensitive layer is whitened after coating and the transparency is reduced.

[0005] Under these circumstances, as a material for forming a photosensitive layer to be a surface layer of an organic electrophotographic photosensitive member, it is excellent in abrasion resistance and scratch resistance and causes deterioration of electrophotographic characteristics even after long-term use. There is a demand for the development of an organic electrophotographic photoreceptor which can be obtained by a production method which does not have any problems on human health and safety.

[0006]

SUMMARY OF THE INVENTION According to the present invention, the surface layer is excellent in abrasion resistance and scratch resistance, can maintain electrophotographic properties for a long period of time, and can be obtained by a production method free from safety and health problems. It is intended to provide a photographic photoreceptor.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that bis (4-hydroxyphenyl) butanes or bis (4-hydroxyphenyl) butanes and Other bisphenols,
The present inventors have found that the above object can be achieved by an electrophotographic photoreceptor in which a photosensitive layer contains a polycarbonate resin having a specific chemical structure obtained by copolymerization using a carbonate-forming compound. Based on the above, the present invention has been completed.

That is, the gist of the present invention is as follows. (1) In an electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, the photosensitive layer has the following general formula [1]:

[0009]

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[In the formula [1], R ¹ represents a hydrogen atom or a methyl group, and R ² each independently represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. A monovalent group selected from the group consisting of an aryl group, an aryl-substituted alkenyl group and a condensed polycyclic hydrocarbon group. m is each independently an integer of 0 to 4]. An electrophotographic photosensitive member comprising a polycarbonate resin having a repeating unit (1) represented by the following formula: (2) In an electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, the photosensitive layer has the above-mentioned general formula [1] and the following general formula [2]:

[0011]

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[In the formula [2], Ar represents the following general formula [2a]
~ [2e],

[0013]

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(In the formulas [2a] to [2e], each R ³ is independently a halogen atom, a substituted or unsubstituted alkyl group,
X represents a monovalent group selected from the group consisting of a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, an aryl group-substituted alkenyl group and a condensed polycyclic hydrocarbon group, and X represents a single bond, -O- , -CO-, -S-, -SO
_{-, - SO 2 -, -} CR 4 R 5 - ( provided that, R ^4, R ⁵
Are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group, a substituted or unsubstituted cycloalkylidene group having 6 to 12 carbon atoms, a substituted or unsubstituted α, having 2 to 12 carbon atoms. ω-alkylene group, 9,9-
Fluorenylidene group, 1,8-menthanediyl group, 2,
An 8-menthanediyl group, a substituted or unsubstituted pyradylidene group, or a substituted or unsubstituted arylene group having 6 to 12 carbon atoms), and Y ¹ each independently represents 2 carbon atoms.
The above alkylene group or an alkyleneoxyalkylene group having 2 or more carbon atoms, wherein Y ² is each independently an oxygen atom,
It represents an alkylene group having 2 or more carbon atoms or an alkyleneoxyalkylene group having 2 or more carbon atoms. M is each independently an integer of 0 to 4; n is each independently an integer of 0 to 200; p is each independently an integer of 0 to 6;
n4 is each independently an integer of 0 or 1 or more;
And the sum of 1 to n4 is an integer of 0 to 450). An electrophotographic photosensitive member comprising a polycarbonate resin having a repeating unit (2) represented by the following formula: (3) The above (1) or the above (1), wherein the reduced viscosity [η _SP / c] measured at 20 ° C. of a solution of a polycarbonate resin having a concentration of 0.5 g / deciliter using methylene chloride as a solvent is 0.1 deciliter / g or more. The electrophotographic photosensitive member according to (2).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The electrophotographic photoreceptor of the present invention comprises an electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein the photosensitive layer has a repeating unit (1) represented by the general formula [1]. The present invention relates to an electrophotographic photosensitive member containing a polycarbonate resin having the formula (1). Further, as the polycarbonate resin to be contained in the photosensitive layer of the electrophotographic photosensitive member in the present invention, a repeating unit (1) represented by the above general formula [1];
A polycarbonate resin containing the repeating unit (2) represented by the general formula [2] at an arbitrary ratio may be used. Furthermore, this polycarbonate resin
The repeating unit (1) and / or the repeating unit (2)
In addition to the basic structural units represented by, polycarbonate structural units having a chemical structure other than those defined by the general formula [1] or [2], polyester structural units, polyurethane structural units, polyether structural units, The polysiloxane structural unit may be contained within a range not to impair the object of the present invention.

In the above formula (1) of the polycarbonate resin, the halogen atom represented by R ² includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a substituted or unsubstituted alkyl group. As a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, i-butyl group, sec
-Butyl group, tert-butyl group, n-hexyl group, cyclohexyl group and the like. Examples of the substituted or unsubstituted alkoxy group include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy, and tert.
-Butoxy group, and the like. Furthermore, examples of the substituted or unsubstituted aryl group include a phenyl group, a tolyl group, and a xylyl group.

In the general formulas [2a] to [2e], specific examples of the alkyl group, alkoxy group and aryl group represented by R ³ , R ⁴ and R ⁵ are as follows:
The same groups as in the specific examples in the above general formula [1] can be mentioned. Further, in the general formula [2e], the alkylene group represented by Y ¹ and Y ² includes an ethylene group,
Examples include a trimethylene group, a tetramethylene group, a pentamethylene group, and the like, and examples of the alkyleneoxyalkylene group include an ethyleneoxyethylene group and a trimethyleneoxy trimethylene group.

The polycarbonate resin is
The above repeating unit (1) or this repeating unit (1)
Of a solution having a concentration of 0.5 g / deciliter using methylene chloride as a solvent.
The reduced viscosity [η _SP / c] measured at 0 ° C. is 0.1 deciliter / g or more, preferably 0.2 to 5.0 deciliter / g, more preferably 0.3 to 4.0 deciliter / g.
What is g is used suitably. If the reduced viscosity of the polycarbonate resin is less than 0.1 deciliter / g, the mechanical strength of the polycarbonate resin is not sufficient, and the wear resistance and scratch resistance of the photosensitive layer cannot be sufficiently obtained. There is.

Next, the method for producing this polycarbonate resin is described by the following general formula [A]:

[0020]

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R ¹ , R ² and m in the formula [A] have the same meanings as R ¹ , R ² and m in the general formula [1]. Used, or this bisphenol and the following general formula [B],

[0022]

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[Ar in the formula [B] is the same as the general formula [2]
Having the same meaning as Ar in the above), and reacting them with a carbonate-forming compound in the presence of a polymerization solvent, an acid acceptor, a terminal terminator, and a catalyst to carry out polymerization. You can depend on the method.

Here, the bisphenols represented by the above general formula [A] include, for example, 1,1-bis (4-hydroxyphenyl) propane and 1,1-bis (3-methyl-4-hydroxyphenyl) ) Propane, 1,1-bis (3-fluoro-4-hydroxyphenyl) propane,
1,1-bis (3-chloro-4-hydroxyphenyl)
Propane, 1,1-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, , 2-bis (3-fluoro-4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl) butane, 2,
2-bis (3-phenyl-4-hydroxyphenyl) butane and the like. Among these compounds, 1,1
-Bis (4-hydroxyphenyl) propane and 2,
2-bis (4-hydroxyphenyl) butane is a particularly preferred compound.

The bisphenols represented by the above general formula [B] include, for example, 4,4'-dihydroxybiphenyl, 3,3'-difluoro-4,4'-dihydroxybiphenyl, 3,3'- Dichloro-4,4'-dihydroxybiphenyl, 3,3'-dimethyl-4,4 '
-Dihydroxybiphenyl, 3,3'-diphenyl-
4,4'-dihydroxybiphenyl, 3,3'-dicyclohexyl-4,4'-dihydroxybiphenyl, 2,
2′-dimethyl-4,4′-dihydroxybiphenyl,
4,4′-dihydroxybiphenyls such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl; bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) phenylmethane, bis (3
-Methyl-4-hydroxyphenyl) methane, bis (3
-Nonyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) ) Methane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (2-tert-butyl-4-hydroxyphenyl) phenylmethane, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenyl ) Methane, bis (2-hydroxy-4)
Methylphenyl) methane, bis (2-hydroxy-4-
Methyl-6-tert-butylphenyl) methane, bis (2-hydroxy-4,6-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
1,2-bis (4-hydroxyphenyl) ethane, 1,
1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) ) -1-Phenylethane, 2- (4-hydroxy-3-methylphenyl) -2
-(4-hydroxyphenyl) -1-phenylethane,
1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1-phenyl-1,1
-Bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (2-hydroxy-4-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl)
Propane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2
-Bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 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 (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-
Bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5 -Difluorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (3-bromo-
4-hydroxy-5-chlorophenyl) propane, 2,
2-bis (4-hydroxyphenyl) -1,1,1,
3,3,3-hexafluoropropane, 2,2-bis (2-hydroxy-4-sec-butylphenyl) propane, 2,2-bis (2-hydroxy-4,6-dimethylphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 2,2- (3-methyl-4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis ( 2-
tert-butyl-4-hydroxy-5-methylphenyl) -2-methylpropane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane, 1,
1-bis (2-tert-butyl-4-hydroxy-5
-Methylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-pentylphenyl)
Butane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) butane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 1,
1-bis (4-hydroxyphenyl) -3-methylbutane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl ) Heptane, 2,2-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) Nonane, 2,2-bis (4
-Hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4
-Hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (3- Cyclohexyl-4-hydroxyphenyl) cyclohexane,
1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (3-methyl-4-hydroxyphenyl)
Bis (hydroxyphenyl) alkanes such as -3,3,5-trimethylcyclohexane; bis (4-hydroxyphenyl) ether such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether Bis (4-hydroxyphenyl) sulfides such as bis (4-hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl- Bis (4-hydroxyphenyl) sulfoxides such as 4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl)
Bis (4-hydroxyphenyl) sulfones such as sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone; and bis (4-hydroxyphenyl) sulfone such as 4,4′-dihydroxybenzophenone 4-hydroxyphenyl) ketones;
9,9-bis (4-hydroxyphenyl) fluorene,
9,9-bis (3-methyl-4-hydroxyphenyl)
Bis (hydroxyphenyl) fluorenes such as fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene; dihydroxy-p-terphenyls such as 4,4 "-dihydroxy-p-terphenyl;
Dihydroxy-p-quarterphenyls such as 4,4 ′ ″-dihydroxy-p-quarterphenyl;
5-bis (4-hydroxyphenyl) pyrazine, 2,5
-Bis (4-hydroxyphenyl) -3,6-dimethylpyrazine, 2,5-bis (4-hydroxyphenyl)-
Bis (hydroxyphenyl) pyrazines such as 2,6-diethylpyrazine; 1,8-bis (4-hydroxyphenyl) menthane, 2,8-bis (4-hydroxyphenyl) menthane, 1,8-bis (3- Bis (hydroxyphenyl) menthanes such as methyl-4-hydroxyphenyl) menthane and 1,8-bis (4-hydroxy-3,5-dimethylphenyl) menthane; 1,4-bis [2
-(4-hydroxyphenyl) -2-propyl] benzene, 1,3-bis [2- (4-hydroxyphenyl)-
Bis [2- (4-hydroxyphenyl) -2-propyl] benzenes such as 2-propyl] benzene; 1,3-
Dihydroxynaphthalenes such as dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; α, ω-dihydroxypolydimethylsiloxane, α, ω-bis [3- (2-
Polysiloxanes such as hydroxyphenyl) propyl] polydimethylsiloxane; 1,1,8,8-tetrahydro-1,8-dihydroxyperfluorooctane;
And dihydroperfluoroalkanes such as 1,1,6,6-tetrahydro-1,6-dihydroxyperfluorohexane.

Among these compounds, 1,1-bis (4
-Hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) 1,1-diphenylmethane, 1,1-
Bis (4-hydroxyphenyl) 1-phenylethane,
1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-
Phenylphenyl) propane, 4,4'-dihydroxybiphenyl, 2,7-dihydroxynaphthalene, bis (4-hydroxyfel) sulfone, 4,4 '-(3
3,5-trimethylcyclohexylidene) diphenol, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisphenol, α, ω-bis [3-
Compounds such as (2-hydroxyphenyl) propyl] polydimethylsiloxane are particularly preferably used.

As the solvent used in this reaction, those used in the production of ordinary polycarbonate resins can be used. For example, aromatic hydrocarbon solvents such as toluene and xylene, methylene chloride, chloroform, 1.1-dichloroethane, 1,2-
Dichloroethane, 1,1,1-trichloroethane, 1,
Suitable examples include halogenated hydrocarbons such as 1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, and chlorobenzene, and acetophenone. These solvents may be used alone or in combination of two or more. Furthermore, an interfacial polycondensation reaction may be performed using two kinds of solvents that are not mixed with each other.

Examples of the acid acceptor include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and pyridine. Organic bases or mixtures thereof can be used. The proportion of these acid acceptors to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. In particular,
One equivalent or a slightly excessive amount, preferably 1 to 5 equivalents of an acid binder may be used per 1 mol of hydroxyl group of the starting dihydric phenol.

Further, as the terminal terminator, a monovalent carboxylic acid and its derivative or a monovalent phenol can be used. For example, p-tert-butyl-phenol, p-phenylphenol, p-cumylphenol,
p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol, p-tert-perfluorobutylphenol, 1- (P-hydroxybenzyl)
Perfluorodecane, p- [2- (1H, 1H-perfluorotridodecyloxy) -1,1,1,3,3,3
-Hexafluoropropyl] phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p
-(1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H-perfluorononanoic acid, 1,
1,1,3,3,3-tetrafluoro-2-propanol and the like are preferably used.

As the catalyst, tertiary amines such as triethylamine and quaternary ammonium salts are preferably used. Further, as the above-mentioned carbonate-forming compound, various carbonyl halides such as phosgene, haloformates such as chloroformate, carbonate compounds and the like can be used. When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system can be suitably employed. The proportion of the carbonate-forming compound used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.

When producing a branched polycarbonate resin, various branching agents can be used. Specific examples of such a branching agent include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,6-
Dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 2,4-dimethyl-2,4,6-
Tris (4-hydroxyphenyl) heptane, 1,3
5-tris (2-hydroxyphenyl) benzene, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4- Screw [2-
Bis (4-hydroxyphenyl) -2-propyl] phenol, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4 -Dihydroxyphenyl)
Propane, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- (4-hydroxyphenylisopropyl) phenoxy] methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis (3
-Methyl-4-hydroxyphenyl) -2-oxo-
Suitable examples include 2,3-dihydroindole, 3,3-bis (4-hydroxyaryl) oxindole, 5-chloroisatin, 5,7-dichloroisatin, and 5-bromoisatin. Further, if desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added to the reaction system.

Next, regarding the reaction conditions for carrying out the polycondensation reaction, the reaction temperature is usually 0 to 150 ° C., preferably 5 to 40 ° C., and the reaction pressure is reduced pressure, normal pressure, or increased pressure. Either method may be used, but the reaction can be usually performed under normal pressure or under pressure of about the self-pressure of the reaction system. The reaction time depends on the reaction temperature, but is about 0.5 minute to 10 hours, preferably about 1 minute to 2 hours. In addition, this reaction may be performed by any of a continuous method, a semi-continuous method, and a batch method.

The molecular weight of the polycarbonate resin can be adjusted within the above-mentioned numerical range of the reduced viscosity by, for example, selecting reaction conditions and increasing or decreasing the amount of a terminal terminator or a branching agent. In some cases, the obtained polycarbonate resin is subjected to physical treatment (mixing, fractionation, etc.).
Or a chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate resin having a desired reduced viscosity. Further, the polycarbonate-based resin obtained by this reaction can obtain a high-purity polycarbonate-based resin by a known separation and purification method.

Next, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor in which a photosensitive layer is provided on a conductive substrate, and has a surface layer containing the above-mentioned polycarbonate resin in the photosensitive layer. Things. The structure of the electrophotographic photosensitive member is not particularly limited, and can be formed in various known forms such as a single layer type and a laminated type. For example, a laminated electrophotographic photoreceptor in which a photosensitive layer has one charge generation layer and one charge transport layer forming a surface layer is preferable.
It is preferable that the above-mentioned polycarbonate resin is used as a binder resin or further as a surface protective layer in the charge transport layer.

When the above-mentioned polycarbonate resin is used as a binder resin in the electrophotographic photoreceptor of the present invention, the polycarbonate resin may be used alone or in combination of two or more. A resin component such as another polycarbonate resin may be used in combination as long as the object of the present invention is not hindered.

As the conductive substrate used for the electrophotographic photosensitive member of the present invention, various known substrates can be used. Specifically, aluminum, nickel, chromium,
Palladium, titanium, molybdenum, indium, gold, platinum, silver, copper, zinc, brass, stainless steel, lead oxide, tin oxide, indium oxide, indium tin oxide (ITO),
Examples include plates, drums and sheets made of indium tin zinc oxide or graphite. Further, glass, cloth, paper, plastic film, sheet, seamless belt, etc., which have been subjected to a conductive treatment by coating by a vapor deposition method, a sputtering method, a coating method, or the like may be used. Etc. can be used.

The charge generation layer of the multi-layer type electrophotographic photoreceptor is a layer containing at least a charge generation substance, and the charge generation layer is formed on a substrate as a base by a vacuum evaporation method, a chemical evaporation method, or a sputtering method. It can be obtained by forming a layer of a charge generating substance or forming a layer formed by binding the charge generating substance on a layer serving as a base using a binder resin. The method for forming the charge generation layer using the binder resin can be a known method. For example, a method in which a coating liquid in which a charge generating substance is dispersed or dissolved in a suitable solvent together with a binder resin is applied to a layer serving as a base and dried is preferably used.
The thickness of the charge generation layer thus formed is 0.01
To 2.0 μm, preferably 0.1 to 0.8 μm.
If the thickness of the charge generation layer is less than 0.01 μm, it is difficult to form a layer having a uniform thickness, and if the thickness exceeds 2.0 μm, the electrophotographic characteristics are degraded. Because there is.

As the charge generating material used here, for example, JP-A-8-225639 and JP-A-11-17
Various compounds known in JP-A-2003-2003 and the like can be used. Specific compounds include selenium alone such as amorphous selenium and trigonal selenium, tellurium alone, selenium alloys such as selenium-tellurium alloy, selenium-arsenic alloy, As ₂ S
selenium compound or selenium-containing compositions, such as e _3, zinc oxide, cadmium sulfide, antimony sulfide, zinc sulfide,
Alloys such as CdS-Se, inorganic materials composed of Group 12 and Group 16 elements, oxide semiconductors such as titanium oxide,
Silicon-based materials such as amorphous silicon, metal-free phthalocyanine pigments such as τ-type metal-free phthalocyanine, χ-type metal-free phthalocyanine, α-type copper phthalocyanine, β-type copper phthalocyanine, γ-type copper phthalocyanine, ε-type copper phthalocyanine, X-type copper phthalocyanine A-type titanyl phthalocyanine, B-type titanyl phthalocyanine, C-type titanyl phthalocyanine, D-type titanyl phthalocyanine, E-type titanyl phthalocyanine, F-type titanyl phthalocyanine, G-type titanyl phthalocyanine, H-type titanyl phthalocyanine, K-type titanyl phthalocyanine, L-type titanyl phthalocyanine , M-type titanyl phthalocyanine, N-type titanyl phthalocyanine, Y-type titanyl phthalocyanine,
Oxo titanyl phthalocyanine, metal phthalocyanine pigments such as titanyl phthalocyanine showing a strong diffraction peak at a Bragg angle 2θ of 27.3 ± 0.2 degrees in the X-ray diffraction diagram, cyanine dye, anthracene pigment, bisazo pigment, pyrene pigment, polycyclic quinone Pigments, quinacridone pigments,
Indigo pigment, perylene pigment, pyrylium dye, squarium pigment, anthantrone pigment, benzimidazole pigment, azo pigment, thioindigo pigment, quinoline pigment, lake pigment, oxazine pigment, dioxazine pigment,
Examples include triphenylmethane pigments, azurenium dyes, triarylmethane dyes, xanthine dyes, thiazine dyes, thiapyrylium dyes, polyvinylcarbazole, bisbenzimidazole pigments, and the like. These compounds
One type may be used alone, or two or more types may be used in combination as a charge generating substance.

The binder resin used in the charge generation layer is not particularly limited, and various known resins can be used. For example, polystyrene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, alkyd resin, acrylic resin, polyacrylonitrile, polycarbonate, polyurethane, epoxy resin, phenol resin, polyamide, polyketone, polyacrylamide, Butyral resin, polyester resin, vinylidene chloride-vinyl chloride copolymer, methacrylic resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone -Alkyd resin, phenol-
Formaldehyde resin, styrene-alkyd resin, melamine resin, polyether resin, benzoguanamine resin, epoxy acrylate resin, urethane acrylate resin, poly-N-vinyl carbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, Nitrocellulose, carboxy-methylcellulose, vinylidene chloride polymer latex, acrylonitrile-butadiene copolymer, vinyltoluene-styrene copolymer, soybean oil-modified alkyd resin, nitrated polystyrene, polymethylstyrene, polyisoprene, polythiocarbonate, poly Arylate, polyhaloarylate, polyallyl ether, polyvinyl acrylate, polyester acrylate And the like. As the binder resin in the charge generation layer, the above-mentioned polycarbonate-based resin can also be used.

Next, as for the charge transport layer of the electrophotographic photoreceptor of the present invention, a layer containing the above-mentioned polycarbonate resin and a charge transport material is formed on a layer serving as a base, for example, a charge generation layer. Can be obtained.
As a method for forming the charge transport layer, various methods can be used.A charge transport material and the above-mentioned polycarbonate-based resin, or an appropriate amount of the binder resin used in the charge generation layer, are dispersed or dissolved in a solvent. It is preferable to adopt a method in which a coating liquid is applied onto a predetermined base layer and dried. In this case, the mixing ratio of the charge transport material and the polycarbonate resin is 2% by mass ratio.
0: 80-80: 20, preferably 30; 70-70:
30. The thickness of the charge transport layer is 5 to 10
0 μm, preferably 10 to 30 μm. If the thickness is less than 5 μm, the initial potential will be lowered, and if it exceeds 100 μm, the electrophotographic characteristics may be reduced.

As the charge transporting substance, various known compounds can be used. For example, carbazole compounds, indole compounds, imidazole compounds, oxazole compounds, pyrazole compounds, oxadiazole compounds, pyrazoline compounds, thiadiazole compounds, aniline compounds, hydrazone compounds, aromatic amine compounds,
Aliphatic amine compounds, stilbene compounds, fluorenone compounds, butadiene compounds, quinone compounds, quinodimethane compounds, thiazole compounds, triazole compounds, imidazolone compounds, imidazolidine compounds, bisimidazolidin compounds, oxazolone compounds, benzothiazole compounds, benzimidazole compounds, quinazolines Compound, benzofuran compound, acridine compound, phenazine compound, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-vinylphenylanthracene, pyrene-
A formaldehyde resin, an ethyl carbazole resin, or a polymer having these structures in the main chain or side chain is suitably used. Among these compounds, Japanese Patent Application Laid-Open No.
The compounds specifically exemplified in 172003 are particularly preferably used. These compounds may be used alone or in combination of two or more.

In the electrophotographic photosensitive member of the present invention, an undercoat layer can be provided between the conductive substrate and the photosensitive layer. As the undercoat layer, fine particles such as titanium oxide, aluminum oxide, zirconia, titanic acid, zirconic acid, lanthanum lead, titanium black, silica, lead titanate, barium titanate, tin oxide, indium oxide, and silicon oxide, polyamide Resin, phenolic resin, casein, melamine resin, benzoguanamine resin, polyurethane resin,
It can be formed using an epoxy resin, cellulose, nitrocellulose, polyvinyl alcohol, polyvinyl butyral resin, or the like. As the resin for the undercoat layer, the binder resin used in the charge generation layer may be used, or the polycarbonate resin of the present invention may be used. These fine particles and resin may be used alone or in various mixtures. When these are used as a mixture,
It is preferable to use inorganic fine particles and a resin in combination, since a film having good smoothness is formed. And the thickness of this undercoat layer is 0.01 to 10 μm, preferably 0.01 to 10 μm.
1 μm. When this thickness is less than 0.01 μm,
It is difficult to form an undercoat layer uniformly, and 10
If it exceeds μm, electrophotographic properties may be degraded.

Further, between the conductive substrate and the photosensitive layer,
A blocking layer may be provided. As this blocking layer, a resin of the same type as the binder resin described above can be used. Further, the polycarbonate resin of the present invention may be used. The thickness of this blocking layer is 0.01 to
It is 20 μm, preferably 0.1 to 10 μm. If the thickness is less than 0.01 μm, it is difficult to form a blocking layer uniformly, and if it exceeds 20 μm, electrophotographic properties may be degraded.

Further, in the electrophotographic photosensitive member of the present invention, a protective layer may be laminated on the photosensitive layer. For this protective layer, the same kind of resin as the binder resin described above can be used. It is particularly preferable to use the polycarbonate resin of the present invention. The thickness of this protective layer is 0.01
To 20 μm, preferably 0.1 to 10 μm. The protective layer contains the charge generation material, the charge transport material, additives, and conductive materials such as metals and oxides, nitrides, salts, alloys, carbon black, and organic conductive compounds thereof. Is also good.

Further, in order to improve the performance of the electrophotographic photosensitive member, a binder, a plasticizer, a curing catalyst, a fluidity-imparting agent, a pinhole controlling agent, and a spectral sensitivity-enhancing agent are provided in the charge generation layer and the charge transport layer. A sensitizer (sensitizing dye) may be added. Additives such as various chemical substances, antioxidants, surfactants, anti-curl agents, and leveling agents are used to prevent increase in residual potential, decrease in charge potential, and decrease in sensitivity to repeated use. Can be added.

As the binder, silicone resin, polyamide resin, polyurethane resin, polyester resin,
Epoxy resin, polyketone resin, polycarbonate resin, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene resin, polyisobrene resin, melamine resin, benzoguanamine resin, polychloroprene resin, polyacrylonitrile resin, ethylcellulose resin, nitrocellulose resin, urea resin, Phenol resin, phenoxy resin, polyvinyl butyral resin, formal resin, vinyl acetate resin, vinyl acetate
Examples thereof include a vinyl chloride copolymer resin and a polyester carbonate resin. Further, a thermosetting resin or a photocurable resin can also be used. The binder may be a resin that is electrically insulating and can form a film in a normal state. The compounding ratio of these binders is 1 to 1 with respect to the polycarbonate resin.
Preferably it is 200% by mass, and 10 to 100% by mass
Is more preferred. If the compounding ratio of the binder is less than 1% by mass, the film of the photosensitive layer tends to be non-uniform and the image quality tends to be poor. If it exceeds 200% by mass, the sensitivity is lowered and the residual potential is sometimes increased.

Specific examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, halogenated paraffin, dimethylnaphthalene, dimethylphthalate,
Dibutyl phthalate, dioctyl phthalate, diethylene glycol phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate, dimethyl glycol phthalate, methyl naphthalene, benzophenone, polypropylene, polystyrene, fluoro Hydrocarbons and the like.

Specific examples of the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, and the like. Examples of the fluidity-imparting agent include Modaflow and Acronal 4F.
Examples of the pinhole control agent include benzoin and dimethyl phthalate. These plasticizers, curing catalysts, fluidity-imparting agents, and pinhole controlling agents are preferably used in an amount of 5% by mass or less based on the charge transport material.

When a sensitizing dye is used as the spectral sensitivity sensitizer, for example, triphenylmethane dyes such as methyl violet, crystal violet, night blue and Victoria blue, erythrosine, rhodamine B, rhodamine 3R Acridine dyes such as acridine orange and frappeosin, thiazine dyes such as methylene blue and methylene green, oxazine dyes such as capri blue and meldra blue, cyanine dyes, merocyanine dyes, styryl dyes, pyrium salt dyes, and thiopyrilum salt dyes are suitable. I have.

An electron-accepting substance can be added to the photosensitive layer for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue upon repeated use. Specific examples thereof include succinic anhydride, maleic anhydride, dibromomaleic anhydride,
Phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, melitic anhydride,
Tetracyanoethylene, tetracyanoquinodimethane, o
-Dinitrobenzene, m-dinitrobenzene, 1,3
5-trinitrobenzene, p-nitrobenzonitrile,
Picryl chloride, quinone chlorimide, chloranil, bromanyl, benzoquinone, 2,3-dichlorobenzoquinone, dichlorodicyanoparabenzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4 '-Dinitrobenzophenone, 4-nitrobenzalmalone dinitrile,
ethyl α-cyano-β- (p-cyanophenyl) acrylate, 9-anthracenylmethylmalondinitrile, 1
-Cyano- (p-nitrophenyl) -2- (p-chlorophenyl) ethylene, 2,7-dinitrofluorenone,
2,4,7-trinitrofluorenone, 2,4,5,7
-Tetranitrofluorenone, 9-fluorenylidene-
(Dicyanomethylene malononitrile), polynitro-9
-Fluorenylidene- (dicyanomethylenemalonodinitrile), picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid Compounds having a high electron affinity, such as phthalic acid, phthalic acid and melitic acid are preferred. These compounds may be added to any of the charge generation layer and the charge transport layer, and the compounding ratio is 0.01 to 20 with respect to the charge generation substance or the charge transport substance.
0 mass%, preferably 0.1 to 50 mass%.

For improving the surface properties, ethylene tetrafluoride resin, ethylene trifluoride chloride resin, ethylene tetrafluoride hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluoride dichloride Ethylene resins, their copolymers, and fluorine-based graft polymers may be used. The compounding ratio of these surface modifiers is 0.1 to 60% by mass, preferably 5 to 4% by mass, based on the binder resin.
0% by mass. If the blending ratio is less than 0.1% by mass, surface modification such as surface durability and surface energy reduction is not sufficient. If the blending ratio is more than 60% by mass, electrophotographic properties may be deteriorated.

The antioxidants include hindered phenol antioxidants, aromatic amine antioxidants, hindered amine antioxidants, sulfide antioxidants,
Organic phosphoric acid antioxidants are preferred. Among these antioxidants, the compounds specifically exemplified in JP-A-11-172003 can be particularly preferably used. The mixing ratio of these antioxidants is usually 0.01 to 10% by mass, and preferably 0.1 to 5% by mass, based on the charge transport material. These antioxidants may be used alone or as a mixture of two or more. Furthermore, in addition to the photosensitive layer,
It may be used by adding to a surface protective layer, an undercoat layer, or a blocking layer.

Examples of the solvent used for forming the charge generation layer and the charge transport layer include aromatic solvents such as benzene, toluene, xylene, chlorobenzene and anisole; ketones such as acetone, methyl ethyl ketone and cyclohexanone; Alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl acetate and ethyl cellosolve; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, and tetrachloroethane; ethers such as tetrahydrofuran and dioxane; dimethylformamide; dimethyl sulfoxide ,
Diethylformamide and the like. These solvents may be used alone or as a mixture of two or more.

Next, as a method for forming the charge transport layer, a coating solution prepared by dispersing or dissolving the charge transport material, additives, and a polycarbonate resin used as a binder resin in a solvent is prepared. Is applied on, for example, the charge generation layer serving as a base for forming a charge transport layer in a form in which the polycarbonate resin coexists with a charge transport material as a binder resin.

As a method of preparing the coating liquid, the above-mentioned prepared raw material can be dispersed or dissolved by using a ball mill, an ultrasonic wave, a paint shaker, a red devil, a sand mill, a mixer, an attritor, or the like. About the method of applying using the coating liquid obtained in this way, dip coating, electrostatic coating, powder coating,
Spray coating method, roll coating method, applicator coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor blade coating method, wire bar coating method, knife coater coating method, attritor coating method A construction method, a spinner coating method, a bead coating method, a blade coating method, a curtain coating method, or the like can be adopted.

The photosensitive layer of the single-layer type electrophotographic photosensitive member is formed by using the above-mentioned polycarbonate resin, charge generation material, additive, charge transport material and other binder resins. In this case, the coating liquid is prepared and its coating method,
The formulation of the additives and the like are the same as in the formation of the photosensitive layer in the laminated electrophotographic photosensitive member. Further, in this single-layer type electrophotographic photoreceptor, an undercoat layer, a blocking layer, and a surface protective layer may be provided in the same manner as described above. When forming these layers, it is preferable to use the above-mentioned polycarbonate resin.

The thickness of the photosensitive layer in the single-layer type electrophotographic photoreceptor is 5 to 100 μm, preferably 8 to 50 μm. When the thickness is less than 5 μm, the initial potential tends to decrease. May decrease.

The ratio of the charge generating substance to the binder resin used in the production of this single-layer type electrophotographic photoreceptor is 1:99 to 30:70 by mass, preferably 3:97 to 15: 8.
5 The ratio of the charge transporting material to the polycarbonate resin is from 20:80 to 80:20, preferably from 30:70 to 70:30 by mass.

The electrophotographic photoreceptor of the present invention thus obtained is a photoreceptor having excellent abrasion resistance and maintaining excellent printing durability and electrophotographic properties for a long period of time. It is suitably used in various electrophotographic fields such as monochrome, multi-color, full-color; analog, digital), printers (laser, light-emitting diode, liquid crystal shutter), facsimile, and plate-making machine.

In using the electrophotographic photoreceptor of the present invention, for charging, corona discharge (corotron, scorotron), contact charging (charging roll, charging brush) and the like are used. Further, for the exposure, any of a halogen lamp, a fluorescent lamp, a laser (semiconductor, He-Ne), a light emitting diode, and a photoconductor internal exposure method may be adopted. For the development, a dry development method such as a cascade development, a two-component magnetic brush development, a one-component insulating toner development, a one-component conductive toner development, or a wet development method using a liquid toner is used. Further, for the transfer, an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method is used. For fixing, heat roller fixing, radiant flash fixing, open fixing, pressure fixing and the like are used. Further, a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, and the like are used for cleaning and static elimination.

[0061]

[Example 1]

(1) Production of polycarbonate resin 92 g of 2,2-bis (4-hydroxyphenyl) butane
To a solution prepared by dissolving 550 ml of a 2 N aqueous sodium hydroxide solution was mixed 350 ml of methylene chloride, and while stirring, phosgene gas was blown into the solution at a rate of 950 ml / min for 30 minutes under cooling. Then, the reaction solution was allowed to stand and separated to obtain a methylene chloride solution of a polycarbonate oligomer having a degree of polymerization of 2 to 4 in an organic phase and having a chloroformate group at a molecular terminal.

To this methylene chloride solution of the polycarbonate oligomer, methylene chloride was further added to adjust the total amount to 60.
After 0 ml, 2,2-bis (4-
A solution prepared by dissolving 27 g of (hydroxyphenyl) butane in 200 ml of a 2 N aqueous solution of sodium hydroxide was added, and 1.2 g of p-tert-butylphenol was further added as a molecular weight regulator. Next, while vigorously stirring this mixture, 2 ml of a 7% by mass aqueous solution of triethylamine was added as a catalyst, and the mixture was reacted at 25 ° C. with stirring for 1.5 hours.

After completion of the reaction, the reaction product was treated with methylene chloride 1
Diluted with liter, then twice with 1.5 liter of water,
Once with 1 liter of hydrochloric acid of 0.01N concentration,
After washing with liter twice, the organic layer was poured into methanol and purified by reprecipitation to obtain a polycarbonate resin.

With respect to the polycarbonate resin thus obtained, a concentration of 0.5 g using methylene chloride as a solvent was used.
Reduced viscosity [ηsp / c] measured at 20 ° C./deciliter solution (under the same conditions in the following examples)
Was 1.2 deciliter / g. To measure the reduced viscosity, an automatic viscosity measuring device VMR-042 manufactured by Rigo Co., Ltd. was used.
Ubbelohde improved viscometer for automatic viscosity (RM
(Type). From the result of ¹ H-NMR spectrum analysis of the polycarbonate resin, it was confirmed that the chemical structure of the polycarbonate resin obtained here was as follows.

[0065]

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(2) Production of Electrophotographic Photoreceptor A polyethylene terephthalate resin film on which aluminum metal was vapor-deposited was used as a conductive substrate.
An electrophotographic photoreceptor having a laminated photosensitive layer formed by sequentially laminating a charge generation layer and a charge transport layer was manufactured.

0.5 parts by mass of oxotitanium phthalocyanine was used as the charge generating material, and 0.5 parts by mass of butyral resin was used as the binder resin. These were added to 19 parts by mass of methylene chloride as a solvent, dispersed by a ball mill, and the resulting dispersion was applied to the surface of the conductive substrate film by a bar coater and dried to obtain a charge having a thickness of about 0.5 μm. A generating layer was formed.

Next, as a material for forming the charge transport layer, a charge transport material described below is used.

[0069]

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Compound 0.5 having a chemical structure represented by the following formula:
g and 0.5 g of the polycarbonate resin obtained in the above (1), and these were dissolved in 10 ml of tetrahydrofuran to prepare a coating liquid. Then, the coating solution was applied on the charge generation layer by an applicator and dried to form a charge transport layer having a thickness of about 20 μm, thereby producing an electrophotographic photosensitive member.

(3) Evaluation of Electrophotographic Photoreceptor The electrophotographic characteristics of the thus obtained electrophotographic photoreceptor were measured using an electrostatic charging tester [EPA-8100, manufactured by Kawaguchi Electric Works, Ltd.]. . The measurement conditions here were that a corona discharge was performed at −6 kv, an initial surface potential (V ₀ ) at that time, a residual potential (V _R ) 5 seconds after light irradiation at 10 lux, and a half-life exposure (E _1/2 ) was measured.

The abrasion resistance of the charge transport layer of the electrophotographic photosensitive member was measured using a wear tester [NUS-I manufactured by Suga Test Instruments Co., Ltd.].
SO-3 type]. As a condition of the abrasion test, abrasion paper (containing alumina particles having a particle diameter of 3 μm) under a load of 500 g was brought into contact with the surface of the photosensitive layer and reciprocated 2000 times to measure the amount of decrease in mass. Table 1 shows the measurement results.

Example 2 (1) Production of polycarbonate resin 92 g of 2,2-bis (4-hydroxyphenyl) butane
To a solution prepared by dissolving 550 ml of a 2 N aqueous sodium hydroxide solution was mixed 350 ml of methylene chloride, and while stirring, phosgene gas was blown into the solution at a rate of 950 ml / min for 30 minutes under cooling. Then, the reaction solution was allowed to stand and separated to obtain a methylene chloride solution of a polycarbonate oligomer having a degree of polymerization of 2 to 4 in an organic phase and having a chloroformate group at a molecular terminal.

To this methylene chloride solution of the polycarbonate oligomer, methylene chloride was further added to adjust the total amount to 60%.
Then, 21 g of 4,4'-biphenol was added to 20 ml of a 2 N aqueous solution of sodium hydroxide.
A solution dissolved in 0 ml was added, and 1.2 g of p-tert-butylphenol was further added as a molecular weight regulator.
Was added. Next, while stirring this mixture vigorously,
As a catalyst, a 7% by mass aqueous triethylamine solution was used.
Milliliter was added, and the reaction was carried out at 25 ° C. with stirring for 1.5 hours.

After completion of the reaction, the reaction product was treated with methylene chloride 1
Diluted with liter, then twice with 1.5 liter of water,
Once with 1 liter of hydrochloric acid of 0.01N concentration,
After washing with liter twice, the organic layer was poured into methanol and purified by reprecipitation to obtain a polycarbonate resin.

The reduced viscosity [ηsp / c] of the polycarbonate resin thus obtained was 1.1 deciliter / g. From the result of ¹ H-NMR spectrum analysis of the polycarbonate resin, it was confirmed that the chemical structure of the polycarbonate resin obtained here was as follows.

[0077]

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(2) Production of Electrophotographic Photoreceptor An electrophotographic photosensitive member was produced in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used as a material for forming the charge transport layer. Body manufactured. (3) Evaluation of electrophotographic photoreceptor The electrophotographic photoreceptor obtained in the above (2) was evaluated in the same manner as in (3) of Example 1. Table 1 shows the evaluation results.

Example 3 (1) Production of polycarbonate resin 92 g of 2,2-bis (4-hydroxyphenyl) butane
To a solution prepared by dissolving 550 ml of a 2 N aqueous sodium hydroxide solution was mixed 350 ml of methylene chloride, and while stirring, phosgene gas was blown into the solution at a rate of 950 ml / min for 30 minutes under cooling. Then, the reaction solution was allowed to stand and separated to obtain a methylene chloride solution of a polycarbonate oligomer having a degree of polymerization of 2 to 4 in an organic phase and having a chloroformate group at a molecular terminal.

To this methylene chloride solution of the polycarbonate oligomer, methylene chloride was further added to adjust the total amount to 60%.
After making the volume 0 ml, 9,9-bis (4-
A solution prepared by dissolving 42 g of (hydroxy-methylphenyl) fluorene in 200 ml of a 2 N aqueous potassium hydroxide solution was added, and pt was added as a molecular weight regulator.
1.0 g of tert-butylphenol was added. Next,
While stirring this mixture vigorously, 7% by mass as a catalyst was used.
2 ml of an aqueous triethylamine solution having a concentration of
The reaction was carried out at 25 ° C. with stirring for 1.5 hours.

After completion of the reaction, the reaction product was treated with methylene chloride 1
Diluted with liter, then twice with 1.5 liter of water,
Once with 1 liter of hydrochloric acid of 0.01N concentration,
After washing with liter twice, the organic layer was poured into methanol and purified by reprecipitation to obtain a polycarbonate resin.

The reduced viscosity [ηsp / c] of the polycarbonate resin thus obtained was 1.2 deciliter / g. From the result of ¹ H-NMR spectrum analysis of the polycarbonate resin, it was confirmed that the chemical structure of the polycarbonate resin obtained here was as follows.

[0083]

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(2) Production of Electrophotographic Photoreceptor The electrophotography was performed in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used as a material for forming the charge transport layer. A photoreceptor was manufactured. (3) Evaluation of electrophotographic photoreceptor The electrophotographic photoreceptor obtained in the above (2) was evaluated in the same manner as in (3) of Example 1. Table 1 shows the evaluation results.

Example 4 (1) Production of polycarbonate resin 1,1-bis (4-hydroxyphenyl) propane 87
g in a solution of 550 ml of a 2N aqueous sodium hydroxide solution, 350 ml of methylene chloride was mixed and stirred, and while cooling, phosgene gas was blown into the solution at a rate of 950 ml / min for 30 minutes. . Then, the reaction solution was allowed to stand and separated to obtain a methylene chloride solution of a polycarbonate oligomer having a degree of polymerization of 2 to 4 in an organic phase and having a chloroformate group at a molecular terminal.

Methylene chloride was further added to the methylene chloride solution of the polycarbonate oligomer to adjust the total amount to 60.
After making 0 ml, 1,1-bis (4-
(Hydroxyphenyl) propane 25 g and the following structural formula:

[0087]

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A solution prepared by dissolving 1.2 g of the phenol-containing polydimethylsiloxane represented by the above formula in 200 ml of a 2 N aqueous sodium hydroxide solution was added. In addition, p-tert-butylphenol 1.
0 g was added.

Next, while vigorously stirring these mixed liquids, 2 ml of a 7% by mass aqueous solution of triethylamine was added as a catalyst, and the mixture was reacted at 25 ° C. with stirring for 1.5 hours.

After completion of the reaction, the reaction product was treated with methylene chloride 1
Diluted with liter, then twice with 1.5 liter of water,
Once with 1 liter of hydrochloric acid of 0.01N concentration,
After washing with liter twice, the organic layer was poured into methanol and purified by reprecipitation to obtain a polycarbonate resin.

The reduced viscosity [ηsp / c] of the polycarbonate resin thus obtained was 1.2 deciliter / g. From the result of ¹ H-NMR spectrum analysis of the polycarbonate resin, it was confirmed that the chemical structure of the polycarbonate resin obtained here was as follows.

[0092]

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(2) Production of Electrophotographic Photoreceptor An electrophotographic photosensitive member was produced in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used as a material for forming the charge transport layer. Body manufactured. (3) Evaluation of electrophotographic photoreceptor The electrophotographic photoreceptor obtained in the above (2) was evaluated in the same manner as in (3) of Example 1. Table 1 shows the evaluation results.

Example 5 (1) Production of polycarbonate resin 1,1-bis (4-hydroxyphenyl) propane 87
g in a solution of 550 ml of a 2N aqueous sodium hydroxide solution, 350 ml of methylene chloride was mixed and stirred, and while cooling, phosgene gas was blown into the solution at a rate of 950 ml / min for 30 minutes. . Then, the reaction solution was allowed to stand and separated to obtain a methylene chloride solution of a polycarbonate oligomer having a degree of polymerization of 2 to 4 in an organic phase and having a chloroformate group at a molecular terminal.

To the methylene chloride solution of the polycarbonate oligomer, methylene chloride was further added to adjust the total amount to 60.
After adjusting to 0 ml, a solution prepared by dissolving 18 g of 2,7-dihydroxynaphthalene and 1 g of the same phenol-containing polydimethylsiloxane as in Example 3 in 200 ml of a 2 N aqueous sodium hydroxide solution was added thereto. 1.1 g of p-tert-butylphenol was added as a regulator. Next, while vigorously stirring this mixture, 2 ml of a 7% by mass aqueous solution of triethylamine was added as a catalyst, and the mixture was reacted at 25 ° C. with stirring for 1.5 hours.

After completion of the reaction, the reaction product was treated with methylene chloride 1
Diluted with liter, then twice with 1.5 liter of water,
Once with 1 liter of hydrochloric acid of 0.01N concentration,
After washing with liter twice, the organic layer was poured into methanol and purified by reprecipitation to obtain a polycarbonate resin.

The reduced viscosity [ηsp / c] of the polycarbonate resin thus obtained was 1.1 deciliter / g. From the result of ¹ H-NMR spectrum analysis of the polycarbonate resin, it was confirmed that the chemical structure of the polycarbonate resin obtained here was as follows.

[0098]

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(2) Production of Electrophotographic Photoreceptor An electrophotographic photosensitive member was produced in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used as a material for forming the charge transport layer. Body manufactured. (3) Evaluation of electrophotographic photoreceptor The electrophotographic photoreceptor obtained in the above (2) was evaluated in the same manner as in (3) of Example 1. Table 1 shows the evaluation results.

Comparative Example 1 As a material for forming the charge transport layer, a polycarbonate resin using 1,1-bis (4-hydroxyphenyl) cyclohexane as a raw material (reduced viscosity;
An electrophotographic photoreceptor was manufactured and evaluated in the same manner as in Example 1, except that 0.5 g of (1.0 deciliter / g) and 0.5 g of the charge transporting substance used in Example 1 were used. Table 1 shows the evaluation results.

Comparative Example 2 As a material for forming the charge transport layer, a polycarbonate resin using 2,2-bis (4-hydroxyphenyl) propane as a raw material (reduced viscosity: 1.1
An electrophotographic photoreceptor was manufactured and evaluated in the same manner as in Example 1, except that 0.5 g (deciliter / g) and 0.5 g of the charge transporting substance used in Example 1 were used.

Table 1 shows the results of these evaluations.

[0103]

[Table 1]

[0104]

The electrophotographic photoreceptor of the present invention can maintain electrophotographic properties for a long period of time because its surface layer is excellent in abrasion resistance and scratch resistance, and can also form the photosensitive layer with a non-halogen type photoreceptor. Since it is formed by a coating solution using a solvent, an electrophotographic photoreceptor can be obtained by a production method having no problem in safety and health.

Claims (3)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein the photosensitive layer has the following general formula [1]: [In the formula (1), R ¹ represents a hydrogen atom or a methyl group;
R ² is independently selected from the group consisting of a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, an aryl group-substituted alkenyl group and a condensed polycyclic hydrocarbon group. Represents a monovalent group represented by m is each independently an integer of 0 to 4]. An electrophotographic photosensitive member comprising a polycarbonate resin having a repeating unit (1) represented by the following formula: 2. An electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, wherein the photosensitive layer has the above general formula [1] and the following general formula [2]: [In the formula [2], Ar represents the following general formulas [2a] to [2
e], embedded image (In the formulas [2a] to [2e], R ³ is each independently a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, an aryl group-substituted alkenyl group, X represents a monovalent group selected from the group of condensed polycyclic hydrocarbon groups, and X represents a single bond, -O-, -CO-, -S-, -SO-, -SO
_2- , -CR ⁴ R ^5- (where R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a trifluoromethyl group, a substituted or unsubstituted Cycloalkylidene group, substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, 9,9-fluorenylidene group, 1,8-menthanediyl group, 2,8-menthanediyl group, substituted or unsubstituted pyradylidene group Or a substituted or unsubstituted arylene group having 6 to 12 carbon atoms), Y ¹ each independently represents an alkylene group having 2 or more carbon atoms or an alkyleneoxyalkylene group having 2 or more carbon atoms, and Y ² represents It independently represents an oxygen atom, an alkylene group having 2 or more carbon atoms or an alkyleneoxyalkylene group having 2 or more carbon atoms. M is each independently an integer of 0 to 4; n is each independently an integer of 0 to 200;
Are each independently an integer of 0 to 6, n1 to n4 are each independently an integer of 0 or 1 or more, and the sum of n1 to n4 is an integer of 0 to 450) Two or more groups are shown. ] (2)
An electrophotographic photosensitive member containing a polycarbonate resin having the formula: 3. A solution of a polycarbonate resin having a concentration of 0.5 g / deciliter using methylene chloride as a solvent at 20 ° C.
3. The electrophotographic photosensitive member according to claim 1, wherein the reduced viscosity [η _SP / c] measured at 0.1 or more is 0.1 deciliter / g or more.