JP3445854B2 - Electrophotographic photoreceptor - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more specifically, it retains excellent mechanical strength and electrophotographic characteristics for repeated use over a long period of time and is suitable for various electrophotographic fields. The present invention relates to a usable electrophotographic photoreceptor.

[0002]

2. Description of the Related Art In the recent electrophotographic field, a laminated electrophotographic photosensitive member, that is, a photosensitive layer has a charge generating layer (CGL) for generating charges upon exposure and a charge transporting layer (CTL) for transferring charges. And a single-layer type electrophotographic photosensitive member (OPC) of a laminate type having at least two layers, and a single-layer type electrophotographic photosensitive member in which the photosensitive layer is a single layer in which a charge generating substance and a charge transporting substance are dispersed in a binder resin. Proposed and used.

On the other hand, the electrophotographic photosensitive member is required to have predetermined sensitivity, electrical characteristics, and optical characteristics according to the electrophotographic process to which it is applied. In particular, for a photoreceptor that is repeatedly used, the surface layer of the photoreceptor, that is, the layer that is located farthest from the substrate (usually a conductive substrate), has corona charging, toner development, transfer to paper, and cleaning treatment. At the time of, etc., electrical and mechanical external force is directly applied,
Durability against them is required. Specifically, it is required to have durability against abrasion and scratches on the surface due to friction and deterioration of the surface due to ozone generated during corona charging under high temperature. Therefore, in order to meet such demands, the binder resin for the charge transport layer of the laminated electrophotographic photoreceptor or the photosensitive layer of the single-layer electrophotographic photoreceptor has good compatibility with the charge transport substance. In addition, polycarbonate resins made from bisphenol A or bisphenol Z, which have high mechanical strength, have been widely used. However, this bisphenol A and bisphenol Z
Even a polycarbonate resin prepared from the above is not sufficient to satisfy the above requirements.

That is, when a polycarbonate resin containing bisphenol A or bisphenol Z as a raw material is dissolved in a solvent to prepare a coating liquid for forming a photosensitive layer, the coating liquid is whitened or gelled, and the coating liquid is applied. , The photosensitive layer after drying may be crystallized. In the part where this crystallization has occurred, there is no light attenuation, and the charge remains as a residual potential,
It appears as a defect in terms of image quality.

Further, a photoreceptor using a polycarbonate resin containing bisphenol A or bisphenol Z as a raw material is inferior in durability due to abrasion and scratches due to insufficient surface hardness.

[0006]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances, and has the above-mentioned problems found in an electrophotographic photoreceptor using a polycarbonate containing bisphenol A or bisphenol Z as a binder resin. In addition to solving the problems, it has good compatibility with charge transport materials,
An electrophotographic photosensitive member which does not cause whitening or gelation even when dissolved in a solvent, and is made of a polycarbonate having high surface hardness and abrasion resistance and which maintains excellent electrophotographic characteristics for a long period of time. The purpose is to provide.

[0007]

As a result of intensive studies to solve the above problems, the present inventor has found that a polycarbonate-based graft copolymer synthesized by using an allyl group-containing polycarbonate or a maleic anhydride-modified polycarbonate as a trunk polymer. When the combination is used as a binder resin, it is found that the coating liquid does not whiten or gel during the preparation of the photoreceptor, and that it retains excellent electrophotographic characteristics and durability over a long period of use, The present invention has been completed based on these findings.

That is, the present invention provides an electrophotographic photosensitive member comprising a conductive substrate provided with a photosensitive layer containing a charge generating substance, a charge transporting substance and a binder resin .
A laminated electrophotographic image sensor in which the surface layer of the photoconductor is a charge transport layer.
An optical body, which comprises an allyl group-containing polycarbonate and maleic anhydride as a binder resin in the charge transport layer.
Reaction of anhydrous maleic acid-modified polycarbonate obtained by heating with a radical initiator with an acid anhydride
It is intended to provide an electrophotographic photoreceptor characterized by using a polycarbonate-based graft copolymer obtained by reacting a compound having a possible functional group .

[1] Polycarbonate-based graft copolymer The polycarbonate-based graft copolymer used as a binder resin in the electrophotographic photoreceptor of the present invention is usually a solution of 0.5 g / dl in methylene chloride as a solvent. The reduced viscosity at 20 ° C. is preferably 0.1 to 20 dl / g. If the reduced viscosity is less than 0.1 dl / g, the surface hardness is insufficient and the surface of the electrophotographic photosensitive member is easily worn. On the other hand, the reduced viscosity is 20 dl / g.
If it exceeds g, the solution viscosity of the polycarbonate-based graft copolymer may increase, which may make it difficult to manufacture the photoreceptor by applying the coating liquid. More preferably, 0.
It is 2 to 5 dl / g.

This polycarbonate-based graft copolymer is synthesized using an allyl group-containing polycarbonate or a maleic anhydride-modified polycarbonate as a trunk polymer. The synthesis method will be described below.

[1-1] Synthesis of Allyl Group-Containing Polycarbonate The degree of polymerization of the allyl group-containing polycarbonate used as a trunk polymer in the synthesis of the polycarbonate-based graft copolymer is usually 0. The reduced viscosity of the 5 g / dl solution at 20 ° C. is 0.
It is preferably 1 to 20 dl / g. When the reduced viscosity is less than 0.1 dl / g, the mechanical strength and surface strength of the polycarbonate-based graft copolymer may be insufficient, while the reduced viscosity is 20 dl / g.
When it exceeds the above, the solution viscosity of the allyl group-containing polycarbonate or the polycarbonate-based graft copolymer increases, and the production itself becomes difficult, or the production of the photoconductor by applying the coating solution of the polycarbonate-based graft copolymer. Can be difficult. More preferably,
It is 0.2-5 dl / g.

The above allyl group-containing polycarbonate may be linear or cyclic, and by using an end terminating agent or a branching agent during synthesis, a special terminal structure or a special terminal is added to the polymer terminal. A branched structure may be introduced.

The above allyl group-containing polycarbonate is synthesized, for example, by reacting a divalent phenol having an allyl group, a divalent phenol having an allyl group and a divalent phenol having no allyl group with a carbonic acid ester forming compound. be able to. As a synthetic method, for example, using phosgene or the like as a carbonic acid ester forming compound, polycondensation with the dihydric phenols in the presence of a suitable acid binder, or using a bisaryl carbonate as a carbonic acid ester forming compound, A method of performing a transesterification reaction may be mentioned.

Examples of the dihydric phenol having an allyl group include those represented by the following general formula (I)

[0015]

[Chemical 1]

(Wherein W ¹ is a single bond, —O—, —CO
-, - S -, - SO -, - SO 2 -, - CR 50 R 51 -
(R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or a carbon atom having 6 to 1 carbon atoms.
2 is a substituted or unsubstituted aryl group. ), A 1,1-cycloalkylidene group having 5 to 11 carbon atoms or an α, ω-alkylene group having 2 to 12 carbon atoms. ) Is included.

Specific examples of the dihydric phenol having an allyl group represented by the general formula (I) include, for example, 3,3'-
Diallyl-4,4'-dihydroxybiphenyl, bis (3-allyl-4-hydroxyphenyl) methane, 1,
1-bis (3-allyl-4-hydroxyphenyl) ethane, 1,2-bis (3-allyl-4-hydroxyphenyl) ethane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-allyl-4)
-Hydroxyphenyl) butane, 2,2-bis (3-allyl-4-hydroxyphenyl) octane, 4,4-bis (3-allyl-4-hydroxyphenyl) heptane,
1,1-bis (3-allyl-4-hydroxyphenyl)
-1,1-diphenylmethane, 1,1-bis (3-allyl-4-hydroxyphenyl) -1-phenylethane,
1,1-bis (3-allyl-4-hydroxyphenyl)
-1-phenylmethane, bis (3-allyl-4-hydroxyphenyl) ether, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-)
Hydroxyphenyl) sulfone, 1,1-bis (3-allyl-4-hydroxyphenyl) cyclopentane, 1,
1-bis (3-allyl-4-hydroxyphenyl) cyclohexane, 3,3'-diallyl-4,4'-dihydroxybenzophenone and the like can be mentioned.

Among the allyl group-containing dihydric phenols (I) mentioned above, W ¹ is preferably a single bond, a methylene group, a dimethylmethylene group or a cyclohexylidene. A group such as 3,3′-diallyl-4,4′-dihydroxybiphenyl, bis (3-allyl-4-hydroxyphenyl) methane, 2,2-bis (3-allyl-4-).
Examples include hydroxyphenyl) propane and 1,1-bis (3-allyl-4-hydroxyphenyl) cyclohexane. Particularly, 2,2-bis (3-allyl-4-hydroxyphenyl) propane is preferably used.

These dihydric phenols having an allyl group may be used alone or in combination of two or more.

When synthesizing the above-mentioned allyl group-containing polycarbonate, only the above-mentioned dihydric phenol having an allyl group may be used as the dihydric phenol, but another dihydric phenol having no allyl group is copolymerized. You may use it as a dihydric phenol. The other dihydric phenol is not particularly limited, but is usually the following general formula (I
I)

[0021]

[Chemical 2]

(In the formula, R ⁵² and R ⁵³ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. Represents a group, W ² is a single bond, —O—, —CO
-, - S -, - SO -, - SO 2 -, - CR 54 R 55 -
(R ⁵⁴ and R ⁵⁵ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or a carbon atom having 6 to 1 carbon atoms.
2 is a substituted or unsubstituted aryl group. ), A 1,1-cycloalkylidene group having 5 to 11 carbon atoms or an α, ω-alkylene group having 2 to 12 carbon atoms, and A and B each independently represent an integer of 0 to 4. Those represented by) are preferably used.

Specific examples of the dihydric phenol (II) represented by the general formula (II) include, for example, 4,4'-dihydroxybiphenyl and 3,3'-difluoro-4,4'-.
Dihydroxybiphenyl, 4,4'-dihydroxy-
4,4'-Dihydroxybiphenyls such as 3,3'-dimethylbiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl; bis ( 4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) ), 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, 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) 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-tert-
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-tert-butyl-4-hydroxy-5-methylphenyl) heptane,
1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane, 1,1
-Bis (4-hydroxy-2-methyl-5-tert-
Pentylphenyl) 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 (alias: tetrafluorobisphenol A), 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane (alias: tetrachlorobisphenol A), 2,2-bis (3,5) -Dibromo-4-hydroxyphenyl) propane (also known as tetrabromobisphenol A), 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, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-hydroxyphenyl) -1,1,1, 3,3,3-hexafluoropropane, 2,2-bis (3-phenyl-4-
Bis (4-hydroxyphenyl) alkanes such as hydroxyphenyl) propane and 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane; bis (4
-Hydroxyphenyl) ether, bis (4-hydroxyphenyl) ether such as bis (3-fluoro-4-hydroxyphenyl) ether; bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) Bis (4-hydroxyphenyl) sulfides such as sulfides; bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone and other bis (4-hydroxyphenyl) sulfones; 4,4′-dihydroxybenzophenone and the like can be mentioned.

Among these, dihydric phenols having no allyl group which are preferably used are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis ( 4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane,
2,2-bis (4-hydroxy-3-methylphenyl)
Propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 4,4'-dihydroxybiphenyl and bis (4-hydroxyphenyl) sulfone, especially 2,2-bis (4-hydroxyphenyl) propane Is preferably used.

These dihydric phenols having no allyl group may be used alone or in combination of two or more.

When the divalent phenol (I) having an allyl group represented by the above general formula (I) and the divalent phenol having no allyl group are used in combination, the divalent phenol (I) having an allyl group is used. , 1-50 mol%, preferably 1-30, relative to the total moles of the dihydric phenol (I) having an allyl group and the dihydric phenol having no allyl group.
It is preferable to use mol%. If the amount of the dihydric phenol (I) having an allyl group is less than 1 mol%, the introduction of the branch polymer at the time of synthesizing the polycarbonate-based graft copolymer will be insufficient, and the effect of the present invention will not be obtained. It may be impossible to achieve the improvement of the printing life. On the other hand, the proportion of the dihydric phenol (I) having an allyl group is 50 mol%
If it exceeds, the solubility of the polycarbonate-based graft copolymer in a solvent at the time of preparing a coating solution and the stability of the solution may decrease.

In addition to the above-mentioned dihydric phenol having an allyl group and dihydric phenol having no allyl group as a raw material, a branching agent or a terminal terminator may be used if necessary.

As the branching agent, a trivalent or higher valent phenol or carboxylic acid can be used.

Examples of branching agents are phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,4-
Dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 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-
(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, 1,4-bis (4 ', 4 "-
Dihydroxytriphenylmethyl) benzene, 2,4-
Dihydroxybenzoic acid, trimesic acid, cyanuric acid,
3,3-bis (3-methyl-4-hydroxyphenyl)
-2-oxo-2,3-dihydroindole, 3,3-
Bis (4-hydroxyaryl) oxindole, 5
-Chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like can be mentioned.

Among these, phloroglysin, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane and the like are preferably used.

As the terminal terminator, monovalent carboxylic acid and its derivative, and monovalent phenol can be used.

Specific examples include phenol, α-naphthol, β-naphthol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,
4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, p-ethylphenol, p-propylphenol, p-butylphenol, p-pentylphenol,
p-hexylphenol, p-heptylphenol, p
-Octylphenol, p-nonylphenol, p-decylphenol, p-undecylphenol, p-dodecylphenol, p-isopropylphenol, pt
ert-butylphenol, 2,6-dimethyl-pt
ert-butylphenol, 2-tert-pentyl-
4-methylphenol, 3-methyl-6-tert-butylphenol, 2-methyl-4,6-di-tert-
Butylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-tert-pentylphenol, 2,
4,6-Tri-tert-butylphenol, p-phenylphenol, 2,6-di-tert-butyl-4-
Phenylphenol, 2,6-di-sec-butyl-4
-Methylphenol, o-anisole, m-anisole, p-anisole, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, p-ethoxyphenol , O-aminophenol,
m-aminophenol, p-aminophenol, p-cyanophenol, p-nitrophenol, 3-methyl-
6-isopropylphenol, 2-methyl-5-isopropylphenol, perfluorobutanoic acid, perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, Perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorotetradecanoic acid, perfluoropentadecanoic acid, perfluorohexadecanoic acid, perfluorooctadecanoic acid, 2H, 2H-perfluoropentanic acid, 2H, 2H- Perfluorohexanoic acid, 2H, 2H
-Perfluoroheptanoic acid, 2H, 2H-perfluorooctanoic acid, 2H, 2H-perfluorononanoic acid, 2
H, 2H-perfluorodecanoic acid, 2H, 2H-perfluoroundecanoic acid, 2H, 2H-perfluorododecanoic acid, 2H, 2H-perfluorotridecanoic acid, 2H,
2H, 3H, 3H-perfluorohexanoic acid, 2H, 2
H, 3H, 3H-perfluoroheptanoic acid, 2H, 2
H, 3H, 3H-perfluorooctanoic acid, 2H, 2
H, 3H, 3H-perfluorononanoic acid, 2H, 2H,
3H, 3H-perfluorodecanoic acid, 2H, 2H, 5H
-Perfluoropentanoic acid, 2H, 2H, 6H-perfluorohexanoic acid, 2H, 2H, 7H-perfluoroheptanoic acid, 2H, 2H, 8H-perfluorooctanoic acid,
2H, 2H, 9H-perfluorononanoic acid, 2H, 2
H, 10H-perfluorodecanoic acid, 2H, 2H, 11
H-perfluoroundecanoic acid, 2H, 2H, 12H-
Perfluorododecanoic acid, 2H, 2H, 13H-perfluoroundecanoic acid, or acid halides thereof, p
-(Perfluoropentyl) phenol, p- (perfluorohexyl) phenol, p- (perfluoroheptyl) phenol, p- (perfluorooctyl) phenol, p- (perfluorononyl) phenol, p-
(Perfluorodecyl) phenol, p- (perfluoroundecyl) phenol, p- (perfluorododecyl) phenol, p- (perfluorotridecyl) phenol, p- (perfluorotetradecyl) phenol, p- (per) Fluoropentadecyl) phenol, p
-(Perfluorobutyloxy) phenol, p- (perfluoropentyloxy) phenol, p- (perfluorohexyloxy) phenol, p- (perfluoroheptyloxy) phenol, p- (perfluorooctyloxy) phenol, p -(Perfluorononyloxy) phenol, p- (perfluorodecyloxy) phenol, p- (perfluoroundecyloxy) phenol, p- (perfluorododecyloxy)
Phenol, p- (perfluorotridecyloxy) phenol, p- (perfluorotetradecyloxy) phenol, p- (perfluoropentadecyloxy) phenol, 4-perfluorooctyl-2,3,5,6
-Tetrafluorophenol, 4-perfluorononyl-2,3,5,6-tetrafluorophenol, 4-perfluorodecyl-2,3,5,6-tetrafluorophenol, 4-perfluoroundecyl-2, 3, 5,
6-tetrafluorophenol, 4-perfluorododecyl-2,3,5,6-tetrafluorophenol, 4
-Perfluorotridecyl-2,3,5,6-tetrafluorophenol, 4-perfluorotetradecyl-
2,3,5,6-tetrafluorophenol, 4-perfluoropentadecyl-2,3,5,6-tetrafluorophenol, p-tert-perfluorobutylphenol, 3-methyl-4-perfluorononylphenol, p -(2- (1H, 1H-perfluorooctyloxy) -1,1,1,3,3,3-hexafluoro-2
-Propyl) phenol, p- (2- (1H, 1H-perfluorononyloxy) -1,1,1,3,3,3-
Hexafluoro-2-propyl) phenol, p- (2
-(1H, 1H-perfluorodecyloxy) -1,
1,1,3,3,3-hexafluoro-2-propyl)
Phenol, p- (2- (1H, 1H-perfluoroundecyloxy) -1,1,1,3,3,3-hexafluoro-2-propyl) phenol, p- (2- (1
H, 1H-perfluorododecyloxy) -1,1,
1,3,3,3-hexafluoro-2-propyl) phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, p- (1H, 1H-perfluoropentyloxy) phenol, p- (1H, 1H-perfluorohexyloxy) phenol, p- (1H,
1H-perfluoroheptyloxy) phenol, p-
(1H, 1H-perfluorooctyloxy) phenol, p- (1H, 1H-perfluorononyloxy) phenol, p- (1H, 1H-perfluorodecyloxy) phenol, p- (1H, 1H-perfluorounoxy) Decyloxy) phenol, p- (1H, 1H-perfluorododecyloxy) phenol, p- (1H, 1H
-Perfluorotridecyloxy) phenol, perfluoropentyl p-hydroxybenzoate, perfluorohexyl p-hydroxybenzoate, perfluoroheptyl p-hydroxybenzoate, perfluorooctyl p-hydroxybenzoate, p-hydroxybenzoic acid Perfluorononyl, perfluorodecyl p-hydroxybenzoate, perfluoroundecyl p-hydroxybenzoate,
Perfluorododecyl p-hydroxybenzoate, (p-
(Hydroxybenzyl) perfluorohexane, (p-hydroxybenzyl) perfluoroheptane, (p-hydroxybenzyl) perfluorooctane, (p-hydroxybenzyl) perfluorononane, (p-hydroxybenzyl) perfluorodecane, (p- Examples thereof include hydroxybenzyl) perfluoroundecane and (p-hydroxybenzyl) perfluorododecane.

Among these, p- is preferably used.
(Tert-butyl) phenol, p-phenylphenol, p- (perfluorolononylphenyl) phenol, p- (perfluoroxylphenyl) phenol,
p-tert-perfluorobutylphenol, 1-
(P-hydroxybenzyl) perfluorodecane, p-
(2- (1H, 1H-perfluorotridecyloxy)
-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, etc. Is mentioned.

The terminal terminator and the branching agent are used by coexisting with the above dihydric phenol. The method is as follows: by coexisting with the dihydric phenol having an allyl group and the dihydric phenol having no allyl group from the beginning. A method of increasing the molecular weight by carrying out a reaction, a method of forming an oligomer composed of a dihydric phenol having an allyl group or a dihydric phenol having no allyl group, and then making both of them coexist when increasing the molecular weight, allyl After making an oligomer composed of a dihydric phenol having a group or a dihydric phenol having no allyl group, a terminal terminator is coexisted in the oligomer to react with the oligomer, and then a branching agent is coexisted to increase the molecular weight. Method, after preparing an oligomer composed of a dihydric phenol having an allyl group or a dihydric phenol having no allyl group, first, an oligomer is prepared. Coexist branching agent is reacted with the oligomer, then the method the molecular weight of the coexistence of terminating agent or the like, it is possible to adopt various methods.

The reaction in which polycondensation is carried out in the presence of an acid binder by using various carbonyl dihalides such as phosgene, haloformates such as chloroformates, carbonic acid ester compounds and the like as carbonic acid ester forming compounds, Usually, it is carried out in a solvent. 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.

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.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate,
An organic base such as pyridine or a mixture thereof is used.

The ratio of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalent amount) of the reaction. Specifically, 2 equivalents or an excess thereof, preferably 2 equivalents or more, based on the total number of moles of the divalent phenol having an allyl group and the divalent phenol having no allyl group (usually 1 mole corresponds to 2 equivalents). It is preferred to use 2 to 10 equivalents of acid 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. As a typical example, for example, a hydrocarbon solvent such as toluene or xylene,
Examples thereof include halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene. The interfacial polycondensation reaction may be carried out using two types of solvents that are immiscible with each other.

In order to accelerate the polycondensation reaction, it is desirable to add a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt to carry out the reaction. If desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added. The reaction is
Usually, it is 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, it can be suitably carried out at normal pressure or the self-pressure of the reaction system. The reaction time depends on the reaction temperature and the like, but is usually 0.5 minutes to 10 hours, preferably about 1 minute to 2 hours.

Further, first, a part of a reaction raw material composed of a dihydric phenol having an allyl group and a dihydric phenol having no allyl group is reacted with a carbonic acid ester forming substance to form an oligomer, and then the remaining reaction raw material. It is also possible to use a two-step method in which is 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.

Examples of the latter bisaryl carbonate used in the transesterification method of an allyl group-containing divalent phenol or an allyl group-free divalent phenol and a bisaryl carbonate include, for example, diphenyl carbonate and di-p-tolyl carbonate. , Phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate and the like.

The reaction type of this transesterification method is as follows:
A melt polycondensation method, a solid phase polycondensation method, etc. are suitable. When carrying out the melt polycondensation method, a dihydric phenol having an allyl group and a bisaryl carbonate having no allyl group are mixed and reacted in a molten state at high temperature under reduced pressure.
The reaction is usually 150 to 350 ° C., preferably 200 to 3
It is carried out at temperatures in the range of 00 ° C. When performing the solid-phase polycondensation method, the dihydric phenol having an allyl group, the dihydric phenol having no allyl group and the bisaryl carbonate are mixed and heated to a temperature below the melting point of the produced polycarbonate in the solid state. And polycondensation is performed. In any case, the degree of vacuum is preferably 1 m at the final stage of the reaction.
The phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system to mHg 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 of the obtained allyl group-containing polycarbonate can be controlled by various methods such as selection of the reaction conditions and adjustment of the amounts of the branching agent and the terminal terminator used. it can. In some cases, the obtained allyl group-containing polycarbonate is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a predetermined reduced viscosity. It can also be obtained as the allyl group-containing polycarbonate.

[1-2] Synthesis of Maleic Anhydride-Modified Polycarbonate As the maleic anhydride-modified polycarbonate, any polycarbonate having a structure derived from maleic anhydride in the polycarbonate structure may be used without particular limitation. You can

Examples of the maleic anhydride-modified polycarbonate preferably used in the present invention include those synthesized by heating and reacting the above allyl group-containing polycarbonate with maleic anhydride in the presence of a radical initiator.

The amount of maleic anhydride used is usually 1 mol based on 1 mol of the allyl group in the allyl group-containing polycarbonate.
It is desirable that the amount be ˜100 mol, preferably 1-50 mol.

Examples of the radical initiator include peroxide radical initiators such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide and dicumyl peroxide, and azo compound radicals such as azobisisobutyronitrile. An initiator is preferably used.

The amount of the radical initiator used is preferably 0.01 to 2 mol, and more preferably 0.01 to 1 mol, per 1 mol of maleic anhydride.

The reaction between the allyl group-containing polycarbonate and maleic anhydride is preferably carried out in a solution state or a molten state, but it is usually preferable to carry out the reaction in a solution state. When the reaction is carried out in a solution state, it is preferable to use a solvent that easily dissolves polycarbonate, for example, a hydrocarbon solvent such as toluene and xylene, a methylene chloride, chloroform, a halogenated hydrocarbon solvent such as chlorobenzene, and the like. A ketone solvent such as cyclohexanone or tetrahydrofuran is preferably used.

The reaction is usually carried out at a temperature in the range of 20 to 100 ° C, preferably 40 to 80 ° C. The reaction pressure is
Any of reduced pressure, normal pressure and increased pressure is possible, but normally, it can be suitably carried out under normal pressure or the self pressure of the reaction system. The reaction time depends on the reaction temperature and the like, but is usually 0.5
~ 8 hours, preferably about 0.5-5 hours.

After the reaction, it is preferable to remove unreacted maleic anhydride, a homopolymer of maleic anhydride, etc. from the product by a fractional precipitation method or a solvent extraction method.

[1-3] Synthesis of Polycarbonate Graft Copolymer from Polycarbonate Containing Allyl Group Polycarbonate containing allyl group, for example, the above [1-
A polycarbonate-based graft copolymer can be obtained by polymerizing (graft-polymerizing) a radical-polymerizable monomer in the presence of the allyl group-containing polycarbonate obtained by the synthesis method [1].

As the radical-polymerizable monomer, various substituted ethylene derivatives including vinyl compounds can be used. Examples thereof include styrenes such as styrene and α-methylstyrene, methyl acrylate and methyl methacrylate. Unsaturated carboxylic acid esters such as ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 1,1,1-trifluoromethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, vinyl chloride, acetic acid Vinyl esters such as vinyl, acrylic acid such as acrylonitrile and acrylamide, methacrylic acid derivatives, vinyl naphthalenes, vinyl ketones such as vinyl methyl ketone, N such as N-vinylpyrrolidone
-Vinyl compounds are preferably used. Among them, styrene, methyl methacrylate, 2,2,2- trifluoroethyl methacrylate and the like are preferably used.

These radical-polymerizable monomers may be used alone or in combination of two or more.

The amount of the radically polymerizable monomer used is usually 1 to 1000 mol, preferably 10 to 5 mol, based on 1 mol of the allyl group in the allyl group-containing polycarbonate.
It is preferred to use 00 mol. If the amount of the radical-polymerizable monomer used is less than 1 mol, grafting of the allyl group-containing polycarbonate may be insufficient, while if it exceeds 1000 mol, a large amount of a homopolymer of the radical-polymerizable monomer is formed. As a result, the mechanical strength of the polycarbonate-based graft copolymer may be impaired.

A radical initiator is used in this graft polymerization, and for example, benzoyl peroxide, acetyl peroxide,
Peroxide type radical initiators such as lauroyl peroxide and dicumyl peroxide, and azo compound type radical initiators such as azobisisobutyronitrile are preferably used.

The amount of the radical initiator used is preferably 0.01 to 50% by weight, and more preferably 0.01 to 10% by weight, based on the amount of the radically polymerizable monomer used.

Graft polymerization of the allyl group-containing polycarbonate and the radical-polymerizable monomer is usually carried out preferably in a solution state, and it is preferable to use a solvent which easily dissolves the polycarbonate, for example, toluene or xylene. And the like, halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene, ketone solvents such as cyclohexanone, and cyclic oxy compounds such as tetrahydrofuran.

The reaction is usually carried out at a temperature in the range of 20 to 100 ° C, preferably 40 to 80 ° C. The reaction pressure is
Any of reduced pressure, normal pressure and increased pressure is possible, but normally, it can be suitably carried out under normal pressure or the self pressure of the reaction system. The reaction time depends on the reaction temperature and the like, but is usually 0.5
~ 8 hours, preferably about 0.5-5 hours.

After the reaction is completed, it is preferable to remove the unreacted radical-polymerizable monomer or the homopolymer of the radical-polymerizable monomer from the product by a fractional precipitation method or a solvent extraction method.

[1-4] Synthesis of Polycarbonate Graft Copolymer from Maleic Anhydride-Modified Polycarbonate Maleic anhydride-modified polycarbonate, for example, maleic anhydride-modified polycarbonate obtained by the synthesis method of [1-2] above, A polycarbonate-based graft copolymer can be obtained by reacting a compound having a functional group capable of reacting with an acid anhydride.

As the compound having a functional group capable of reacting with an acid anhydride, for example, a polymer having an amino group at the end of the polymer chain is preferably used. For example, terminal aminated polysiloxanes such as terminal aminated polysiloxanes, terminal aminated polymethyl methacrylate, terminal aminated polyacrylates or methacrylates such as terminal aminated poly (2,2,2-trifluoroethyl methacrylate), etc. Is preferably used. As such a polymer,
Usually, the molecular weight is 500 to 100,000, preferably 50.
It is preferable to use one of 0 to 50,000. These compounds may be used alone or in combination of two or more.

The amount of the compound having a functional group capable of reacting with an acid anhydride is usually 1 to 10 mol, preferably 1 to 1 mol of the group derived from maleic anhydride in the maleic anhydride modified polycarbonate. It is preferred to use ~ 5 mol. When the amount of the compound having a functional group capable of reacting with an acid anhydride is less than 1 mol, grafting of the maleic anhydride-modified polycarbonate may be insufficient, while when it exceeds 10 mol, unreacted. A large amount of the compound having a functional group capable of reacting with the acid anhydride may remain, and the mechanical strength of the polycarbonate-based graft copolymer may be impaired.

The reaction between this maleic anhydride-modified polycarbonate and the compound having a functional group capable of reacting with an acid anhydride is usually suitably carried out in a solution state, and the solvent is
It is preferable to use a solvent that easily dissolves the maleic anhydride-modified polycarbonate, and examples thereof include hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene, and ketone solvents such as cyclohexanone and tetrahydrofuran. It is preferably used.

The reaction is usually carried out at a temperature in the range of 20 to 200 ° C, preferably 40 to 100 ° C. The reaction pressure may be any of reduced pressure, normal pressure and increased pressure, but normally, it can be suitably carried out at normal pressure or at about the self pressure of the reaction system.
The reaction time depends on the reaction temperature, etc.
It is about 0.5 to 10 hours, preferably about 0.5 to 8 hours.

After the completion of the reaction, it is preferable to remove the unreacted compound from the product by a fractional precipitation method or a solvent extraction method.

By using polycarbonate as a graft copolymer as described above, a copolymer having excellent mechanical properties and surface hardness can be obtained. Due to the improved surface hardness, these copolymers can be resins having excellent abrasion resistance. When a siloxane-containing polymer such as the above terminal aminated polysiloxane or a fluorine atom-containing polymer such as the above terminal aminated poly (2,2,2-trifluoroethylmethacrylate) is grafted,
In addition to excellent mechanical properties and surface hardness, a polycarbonate-based graft copolymer excellent in water repellency and releasability can be obtained.

[2] Electrophotographic Photoreceptor The electrophotographic photoreceptor of the present invention contains in the photosensitive layer at least one of the above polycarbonate-based graft copolymers as a binder resin, a charge generating substance and a charge transporting substance. It is a thing.

The electrophotographic photoreceptor of the present invention is not particularly limited in its structure as long as such a photosensitive layer is formed on a conductive substrate, and various known layers such as a single layer type and a laminated type are known. Any type of electrophotographic photoreceptor, including a charge transport layer in a laminated electrophotographic photoreceptor, in which the photosensitive layer has at least one charge generation layer and at least one charge transport layer, It is preferably used as a binder resin.

In the electrophotographic photosensitive member of the present invention, the above-mentioned polycarbonate-based graft copolymer may be used alone as the binder resin, or may be used in combination of two or more kinds. If desired, other resin components such as polycarbonate may be contained within a range that does not impair the achievement of the object of the present invention.

As the material of the conductive substrate used in the electrophotographic photosensitive member of the present invention, various materials such as known materials can be used, and specifically, aluminum, nickel, chromium, palladium, titanium, gold. , Silver, copper, zinc,
Plates, drums and sheets of stainless steel, molybdenum, indium, platinum, brass, lead oxide, tin oxide, indium oxide, ITO or graphite, and glass, cloth, and paper that have been electrically conductive by coating by vapor deposition, sputtering, coating, etc. Or plastic films, sheets and seamless belts, plastic films, sheets and seamless belts laminated with metal foil such as aluminum, film-like sheets and seamless belts of metal plates, and metal drums that have been metal-oxidized by electrode oxidation etc. Can be used.

The charge generating layer of the multi-layer electrophotographic photosensitive member contains at least a charge generating substance, and the charge generating layer is formed on the base substrate, which is vacuum deposition, sputtering method, CV.
It can be obtained by forming a layer of the charge generating substance by the D method or the like, or by forming a layer obtained by binding the charge generating substance using a binder resin on the layer as the base thereof. As the method for forming the charge generation layer using the binder resin, various methods such as a known method can be used. Usually, for example, a coating liquid in which the charge generation substance is dispersed or dissolved together with the binder resin in a suitable solvent. Is preferably applied on a layer serving as a predetermined base and dried.

As the charge generating substance, various substances such as known substances can be used. Specifically, selenium simple substance such as amorphous selenium and trigonal selenium, tellurium simple substance,
Selenium alloys such as selenium-tellurium alloys and selenium-arsenic alloys, selenium compounds such as As ₂ Se ₃ or selenium-containing compositions, alloys such as zinc oxide, cadmium sulfide, antimony sulfide, zinc sulfide, CdS-Se, 12th Inorganic materials made of Group 16 and Group 16 elements, oxide semiconductors such as titanium oxide, various inorganic materials such as silicon-based materials such as amorphous silicon, and metal-free phthalocyanines such as τ-type metal-free phthalocyanine and χ-type metal-free phthalocyanine Pigment, 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 H type titanyl phthalocyanine,
G-type titanyl phthalocyanine, K-type titanyl phthalocyanine, L-type titanyl phthalocyanine, M-type titanyl phthalocyanine, N-type titanyl phthalocyanine, titanyl phthalocyanine showing a strong diffraction peak at a black angle 2θ of 27.3 ± 0.2 degrees in an X-ray diffraction pattern. Metal phthalocyanine pigments, cyanine dyes, anthracene pigments, bisazo pigments, pyrene pigments, polycyclic quinone pigments, quinacridone pigments, indigo pigments, perylene pigments, pyrylium dyes, thiapyrylium dyes, polyvinylcarbazole, squarium pigments, anthanthrone pigments, Benzimidazole pigment, azo pigment, thioindigo pigment, bisbenzimidazole pigment, quinoline pigment, lake pigment, oxazine pigment, dioxazine pigment, triphenylmethane pigment, azurenium dye , Squarium dye, triarylmethane dye, xanthine dye, thiazine dye and the like.

For example, a compound represented by the following general formula is preferably used.

[0076]

[Chemical 3]

[Wherein Z ¹ , Z ² , Z ³ and Z ⁴ are each independently two carbon atoms on the pyrrole ring together with an aromatic hydrocarbon ring or heterocycle which may have a substituent. Represents an atomic group capable of forming, and M represents a metal atom or a metal compound which may have two hydrogen atoms or a ligand. ]

[0078]

[Chemical 4]

[Wherein, Ar ⁶ represents a t-valent residue having a conjugated system which may contain an aromatic hydrocarbon ring or a heterocycle, t is a positive number of 1 or more, and Cp is an aromatic group. Represents a coupler residue having a group hydroxyl group, and when t is 2 or more,
Each Cp may be the same or different. ]

[0080]

[Chemical 5]

[Wherein, X ² , X ³ , X ⁴ and X ⁵ each independently represent an oxygen atom, a sulfur atom or a selenium atom, and R ¹⁶ and R ¹⁷ are an alkyl group having 1 to 12 carbon atoms or It represents an aryl group, and X ² or X ³ and R ¹⁶ and X ⁴ or X ⁵ and R ¹⁷ may form a heterocyclic ring which may have a substituent. ] Examples of the fluorene-based disazo pigment are as follows.

[0082]

[Chemical 6]

[0083]

[Chemical 7]

[0084]

[Chemical 8]

The following are examples of perylene pigments.

[0086]

[Chemical 9]

[0087]

[Chemical 10]

Examples of the polycyclic quinone pigment are as follows.

[0089]

[Chemical 11]

Examples of the anthanthrone pigment are as follows.

[0091]

[Chemical 12]

Examples of the dibenzpyrenequinone pigment are as follows.

[0093]

[Chemical 13]

Examples of pyranthrone pigments are as follows.

[0095]

[Chemical 14]

These pigments may be used alone or in admixture of two or more.

The thickness of the charge generation layer is 0.01 to 2.0 μm.
m is preferable, and 0.1 to 0.8 μm is more preferable.
If it is less than 0.01 μm, it is difficult to uniformly form the charge generation layer, and if it exceeds 2.0 μm, the electrophotographic characteristics tend to deteriorate.

The binder resin used in the charge generating layer is not particularly limited, and various known resins can be used. Specifically, 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, vinylidene chloride-vinyl chloride copolymer, methacrylic resin, polystyrene, 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, poly-N-vinylcarbazole, polyvinyl butyral, polyvinyl formal, Resulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, nitrocellulose, carboxy-methyl cellulose, vinylidene chloride polymer latex, acrylonitrile-butadiene copolymer, vinyltoluene-styrene copolymer, soybean oil modified alkyd resin, nitrated polystyrene, poly Methyl styrene, polyisoprene, polythiocarbonate, polyarylate, polyhaloarylate, polyallyl ether, polyvinyl acrylate,
Thermosetting resins such as melamine resin, polyether resin, benzoguanamine resin, epoxy acrylate resin, urethane acrylate resin and polyester acrylate can be used.

The above polycarbonate-based graft copolymer can also be used as the binder resin in the above charge generation layer.

Next, the charge-transporting layer can be obtained by forming a layer obtained by binding a charge-transporting substance with a binder resin on a base layer (for example, a charge-generating layer).

As the method for forming the charge transport layer, various methods such as known methods can be used. Usually, the above charge transport material is dispersed in a suitable solvent together with the above polycarbonate graft copolymer or A method of applying the dissolved coating liquid on a layer serving as a predetermined base and drying it is used. The blending ratio of the charge transporting substance and the polycarbonate-based graft copolymer in the charge transporting layer is preferably 20:80 to 80:20 by weight, more preferably 30:70 to 70:30.

In the charge transport layer, the above polycarbonate-based graft copolymer may be used alone or in a mixture of two or more kinds. Further, other resins such as those mentioned as the binder resin used for the charge generation layer may be used in combination with the above polycarbonate-based copolymer within a range that does not impair the achievement of the object of the present invention.

As the charge transport substance, various substances such as known substances can be used. For example, carbazole compound, indole compound, imidazole compound, oxazole compound, pyrazole compound, oxadiazole compound, pyrazoline compound, thiadiazole compound,
Aniline compounds, hydrazone compounds, aromatic amine compounds, aliphatic amine compounds, stilbene compounds, fluorenone compounds, quinone compounds, quinodimethane compounds, thiazole compounds, triazole compounds, imidazolone compounds, imidazolidine compounds, bisimidazolidine compounds, oxazolone compounds , Benzothiazole compound, benzimidazole compound, quinazoline compound, benzofuran compound, acridine compound, phenazine compound, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9
-Vinylphenylanthracene, pyrene-formaldehyde resin, ethylcarbazole resin, or a polymer having these in the main chain or side chain is used, and preferably a compound represented by the following general formula is used.

[0104]

[Chemical 15]

[Wherein Ar ¹ , Ar ² and Ar ³ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a carbon number. 6-12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic hetero group Represents a cyclic group, Ar ¹ and Ar ² , Ar ² and Ar ³
And Ar ³ and Ar ¹ may form a ring. ]

[0106]

[Chemical 16]

[Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group or an arylamino group. Group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycycle Represents a formula hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, and a, b, c and d are each 0 to 5 each independently
Is an integer. ]

[0108]

[Chemical 17]

[Wherein Ar ¹ and Ar ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a carbon number. 6-12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic hetero group It represents a cyclic group, and Ar ¹ and Ar ² may form a ring. R ¹ is a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, R ⁵ Represents an ethylene group or an ethenylene group, and e is an integer of 0-4. ]

[0110]

[Chemical 18]

[Wherein Ar ¹ and Ar ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a carbon number. 6-12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic hetero group It represents a cyclic group, and Ar ¹ and Ar ² may form a ring. R ¹ is a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, R ⁶ And R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and e is an integer of 0 to 4. ]

[0112]

[Chemical 19]

[Wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted alkyl group having 7 to 13 carbon atoms] Or an unsubstituted aralkyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic hetero group Represents a cyclic group or a condensed polycyclic heterocyclic group, Ar
⁶ and Ar ⁷ are each independently a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl compound having 6 to 12 carbon atoms, a polycyclic hydrocarbon, a substituted or unsubstituted condensed compound. Represents a divalent residue of a polycyclic hydrocarbon, a heterocyclic compound, a polycyclic heterocyclic compound or a condensed polycyclic heterocyclic compound, wherein Ar ¹ and Ar ² and Ar ³ and Ar ⁴ may form a ring. Good. ]

[0114]

[Chemical 20]

[Wherein Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 13 carbon atoms] Aralkyl group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group Or a condensed polycyclic heterocyclic group, Ar ¹ and Ar ²
And Ar ³ and Ar ⁴ may form a ring. R ⁸ and R ⁹ are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, e and f is 0 to 4 independently
Is an integer. ]

[0116]

[Chemical 21]

[Wherein Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 13 carbon atoms] Aralkyl group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group Or a condensed polycyclic heterocyclic group, Ar ¹ and Ar ²
And Ar ³ and Ar ⁴ may form a ring. R ¹ , R ² and R ³ are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, and a carbon number of 1 to 1. A substituted or unsubstituted alkyl group having 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted It represents a condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, and e, f and g are each independently an integer of 0 to 4. X ¹ is -O-, -S-, -Se
-, - Te -, - CR 10 R 11 -, - SiR 10 R 11 -, -
NR ¹⁰ - or -PR ¹⁰ - (wherein, each independently R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom, an alkylamino group, an arylamino group, aralkylamino group, having 1 to 10 carbon atoms
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group,
It represents a substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or fused polycyclic heterocyclic group. ) Represents. ]

[0118]

[Chemical formula 22]

[Wherein, Ar ¹ and Ar ² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, or a carbon number. 6-12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic hetero group It represents a cyclic group, and Ar ¹ and Ar ² may form a ring. R ¹ is a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted fused polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a fused polycyclic heterocyclic group, and a is It is an integer of 0-5. ]

[0120]

[Chemical formula 23]

[In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted alkyl group having 7 to 13 carbon atoms. Or an unsubstituted aralkyl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic hetero group Represents a cyclic group or a condensed polycyclic heterocyclic group, R ¹
And R ² are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, a substituted or unsubstituted group having 1 to 10 carbon atoms. Substituted alkyl group, C7-13 substituted or unsubstituted aralkyl group, C6-12 substituted or unsubstituted aryl group, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic carbon group Represents a hydrogen group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, Ar ¹ and Ar ² and Ar
³ and Ar ⁴ may form a ring. f and e are each independently an integer of 0 to 4. ]

[0122]

[Chemical formula 24]

[In the formula, Ar ¹ is a hydrogen atom and has 1 to 1 carbon atoms.
A substituted or unsubstituted alkyl group having 0 to 7 carbon atoms
Substituted or unsubstituted aralkyl group having 6 to 12 carbon atoms
, A substituted or unsubstituted aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group And R ¹ , R ² and R ³ are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, a carbon atom. A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, substituted or An unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic heterocyclic group, n is 0 or 1, a, b and c are each independently It is an integer of 0-5. ]

[0124]

[Chemical 25]

[Wherein Ar ¹ , Ar ² and Ar ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms. Group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed Represents a polycyclic heterocyclic group, R ¹ and R ³ are each independently cyano group, halogen atom, carboxyl group, acyl group, hydroxyl group, nitro group, amino group, alkylamino group, arylamino group, aralkyl Amino group,
A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substitution Or an unsubstituted condensed polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group or condensed polycyclic heterocyclic group, wherein R ² ′ is a hydrogen atom, a cyano group, a halogen atom or a carboxyl group. Group, acyl group, hydroxyl group,
Nitro group, amino group, alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, and 6 to carbon atoms 12 substituted or unsubstituted aryl groups, polycyclic hydrocarbon groups, substituted or unsubstituted condensed polycyclic hydrocarbon groups, heterocyclic groups, polycyclic heterocyclic groups or condensed polycyclic heterocyclic groups Represents a group, n is 0 or 1, e is an integer of 0 to 4, and h is an integer of 0 to 3. ]

[0126]

[Chemical formula 26]

[Wherein Ar ¹ and Ar ² are each independently a hydrogen atom, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms. A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic group. It represents a cyclic heterocyclic group, and Ar ¹ and Ar ² may form a ring. ]

[0128]

[Chemical 27]

[Wherein Ar ¹ , Ar ² and Ar ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms. A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic group. It represents a cyclic heterocyclic group, and Ar ¹ and Ar ² may form a ring. ]

[0130]

[Chemical 28]

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁸ and R ⁹
Are each independently a cyano group, a halogen atom, a carboxyl group, an acyl group, a hydroxyl group, a nitro group, an amino group,
Alkylamino group, arylamino group, aralkylamino group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 13 carbon atoms, substituted or unsubstituted having 6 to 12 carbon atoms Represents an aryl group, a polycyclic hydrocarbon group, a substituted or unsubstituted condensed polycyclic hydrocarbon group, a heterocyclic group, a polycyclic heterocyclic group or a condensed polycyclic heterocyclic group, a, b, c, d, i and j are each independently an integer of 0-5. ]

[0132]

[Chemical 29]

[Wherein Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 13 carbon atoms] Aralkyl group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group Or a condensed polycyclic heterocyclic group, Ar ⁶ is a substituted or unsubstituted alkylene group having 1 to ⁶ carbon atoms or a substituted or unsubstituted aryl compound having 6 to 12 carbon atoms, a polycyclic hydrocarbon, A substituted or unsubstituted condensed polycyclic hydrocarbon, heterocyclic compound, polycyclic heterocyclic compound or divalent residue of condensed polycyclic heterocyclic compound, wherein Ar ¹ and Ar ² and Ar
³ and Ar ⁴ may form a ring, and n is 0 or 1. ]

[0134]

[Chemical 30]

[Wherein R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 7 to 13 carbon atoms] Aralkyl group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, polycyclic hydrocarbon group, substituted or unsubstituted fused polycyclic hydrocarbon group, heterocyclic group, polycyclic heterocyclic group Alternatively, it represents a condensed polycyclic heterocyclic group. ] Specifically, the following compounds are used.

[0136]

[Chemical 31]

[0137]

[Chemical 32]

[0138]

[Chemical 33]

[0139]

[Chemical 34]

[0140]

[Chemical 35]

[0141]

[Chemical 36]

[0142]

[Chemical 37]

[0143]

[Chemical 38]

[0144]

[Chemical Formula 39]

[0145]

[Chemical 40]

[0146]

[Chemical 41]

[0147]

[Chemical 42]

[0148]

[Chemical 43]

[0149]

[Chemical 44]

[0150]

[Chemical formula 45]

[0151]

[Chemical formula 46]

[0152]

[Chemical 47]

[0153]

[Chemical 48]

[0154]

[Chemical 49]

[0155]

[Chemical 50]

[0156]

[Chemical 51]

[0157]

[Chemical 52]

[0158]

[Chemical 53]

[0159]

[Chemical 54]

[0160]

[Chemical 55]

[0161]

[Chemical 56]

[0162]

[Chemical 57]

[0163]

[Chemical 58]

[0164]

[Chemical 59]

[0165]

[Chemical 60]

[0166]

[Chemical formula 61]

[0167]

[Chemical formula 62]

[0168]

[Chemical formula 63]

[0169]

[Chemical 64]

[0170]

[Chemical 65]

[0171]

[Chemical formula 66]

[0172]

[Chemical formula 67]

[0173]

[Chemical 68]

[0174]

[Chemical 69]

[0175]

[Chemical 70]

[0176]

[Chemical 71]

[0177]

[Chemical 72]

[0178]

[Chemical formula 73]

[0179]

[Chemical 74]

[0180]

[Chemical 75]

[0181]

[Chemical 76]

The above charge transport materials can be used alone or in admixture of two or more. The thickness of the charge transport layer is 5
100 μm is preferable, and 10 to 30 μm is more preferable. If it is less than 5 μm, the initial potential will be low and 100
If it exceeds μm, the electrophotographic characteristics tend to deteriorate.
A well-known subbing layer as commonly used can be provided between the conductive substrate and the photosensitive layer. As the undercoat layer,
Fine particles of titanium oxide, aluminum oxide, zirconia, titanic acid, zirconic acid, lead lanthanum, titanium black, silica, lead titanate, barium titanate, tin oxide, indium oxide, silicon oxide, etc., polyamide resin, phenol resin, casein, Melamine resin, benzoguanamine resin, polyurethane resin, epoxy resin, cellulose,
Components such as nitrocellulose, polyvinyl alcohol, and polyvinyl butyral resin can be used. These fine particles and resins can be used alone or in admixture of two or more. Especially when fine particles are used, the resin is adsorbed on the fine particles and a smooth film can be obtained. Therefore, it is desirable to use the fine particles and the resin together. The binder resin can be used for the undercoat layer. Further, the above polycarbonate-based graft copolymer can also be used.

The thickness of the undercoat layer is usually 0.01-10.
It is 0 μm, preferably 0.01 to 1.0 μm. If the thickness is less than 0.01 μm, it may be difficult to uniformly form the undercoat layer, and if it is more than 10.0 μm, the electrophotographic properties may deteriorate. Further, a known blocking layer which is usually used can be provided between the conductive substrate and the photosensitive layer. The binder resin can be used in the blocking layer. The thickness of the blocking layer is usually 0.01 to 20.0 μm, preferably 0.1 to 10.0 μm. This thickness is 0.01
If it is less than μm, it may be difficult to uniformly form the blocking layer, and if it exceeds 20.0 μm, the electrophotographic properties may deteriorate.

In the electrophotographic photosensitive member of the present invention, a protective layer may be laminated on the photosensitive layer. The thickness of the protective layer is 0.01 to
20 μm is possible, and more preferably 0.1 to 10 μm.
m. The binder resin can be used for the protective layer. The protective layer may contain a conductive material such as the above-mentioned charge generating substance, charge transporting substance, additive, metal and oxides, nitrides, salts, alloys and carbon thereof.

Further, in order to improve the performance of the electrophotographic photoreceptor of the present invention, a binder, a plasticizer, a curing catalyst, a fluidizing agent, a pinhole control agent, an electrophotographic agent are added to the charge generation layer and the charge transport layer. In addition to the spectral sensitivity sensitizer (sensitizing agent) for improving sensitivity and the spectral sensitivity sensitizer, the purpose is to prevent an increase in residual potential, a decrease in charging potential, and a decrease in sensitivity with repeated use. Additives such as various chemical substances, antioxidants, surfactants, anti-curl agents, leveling agents and the like can be added.

Specific examples of the binder include silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polystyrene resin, polymethacrylate resin, polyacrylamide resin, polybutadiene resin, polyisoprene. Resin, melamine resin, benzoguanamine resin, polychloroprene resin, polyacrylonitrile resin, ethyl cellulose resin, nitrocellulose resin, urea resin, phenol resin, phenoxy resin, polyvinyl butyral resin, formal resin, vinyl acetate resin, vinyl acetate / vinyl chloride copolymer Examples include coalescing and polyester carbonate resins. Further, a heat and / or light curable resin can also be used. In any case, there is no particular limitation as long as it is an electrically insulating resin that can form a film in a normal state.

The binder is 5 to 20 relative to the charge transport material.
It is preferable to add 0% by weight, and 10 to 100% by weight
Is more preferable. If it is less than 5% by weight, the film of the photosensitive layer tends to be non-uniform and the image quality tends to be poor. If it exceeds 20% by weight, the sensitivity tends to decrease and the residual potential tends to increase. Specific examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, halogenated paraffin,
Dimethyl naphthalene, dimethyl phthalate, 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, various fluorohydrocarbons, and the like.

Specific examples of the curing catalyst include methanesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid and the like. Examples of the fluidizing agent include modaflow and acronal 4F. Examples of the pinhole control agent include benzoin and dimethyl phthalate.

The plasticizer, curing catalyst, fluidizing agent, and pinhole control agent are preferably used in an amount of 5% by weight or less based on the charge transport material. Specific examples of the sensitizing dye include triphenylmethane dyes represented by methyl violet, crystal violet, night blue, and Victoria blue, erythrosine, rhodamine B, rhodamine 3R, acridine orange, and flapeosin. Acridine dyes, thiazine dyes represented by methylene blue, methylene green, etc., oxazine dyes represented by capri blue, meldra blue, etc., and other cyanine dyes, merocyanine dyes, styryl dyes, pyrylium salt dyes, thiopyrylium salt dyes and the like. .

An electron-accepting substance can be added to the photosensitive layer for the purpose of improving sensitivity and reducing residual potential to fatigue during repeated use. Examples of the electron accepting substance include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, and anhydrous. Pyromellitic acid, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide, Chloranil, bromanil, benzoquinone, 2,3-dichlorobenzoquinone, dichlorodicyanoparabenzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone,
1-chloroanthraquinone, dinitrotroanthraquinone, 4-nitrobenzophenone, 4,4-nitrobenzophenone, 4-nitrobenzalmalondinitrile, α-
Ethyl 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- [dicyanomethylene malonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid , Phthalic acid, mellitic acid, and other compounds with high electron affinity.

This electron-accepting substance may be added to either the charge-transporting layer or the charge-generating layer, and is usually 0.01 to 200% by weight, more preferably 0.1 to 200% by weight based on the charge-transporting substance or the charge-generating substance. ˜50% by weight. In order to improve the surface property, tetrafluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluorodichloroethylene resin. Also, a copolymer thereof or a fluorine-based graft polymer may be used.

These surface modifiers are contained in the binder resin in an amount of 0.1 to 60% by weight, preferably 5 to 40% by weight.
It is blended by weight%. If it is less than 0.1% by weight, surface modification such as abrasion resistance, surface durability and reduction of surface energy is not sufficient, and if it is more than 60% by weight, electrophotographic properties may be deteriorated. Examples of the antioxidant include hindered phenol-based antioxidants, aromatic amine-based antioxidants, hindered amine-based antioxidants, sulfide-based antioxidants, organic phosphoric acid-based antioxidants and the like.

These antioxidants are usually used in an amount of 0.01 to 10% by weight, more preferably 0.1 to 10% by weight based on the charge transport material.
2% by weight is blended. The following are examples of hindered phenolic antioxidants.

[0194]

[Chemical 77]

[0195]

[Chemical 78]

[0196]

[Chemical 79]

The following are examples of aromatic amine antioxidants.

[0198]

[Chemical 80]

As the hindered amine-based antioxidant,
There are the following examples.

[0200]

[Chemical 81]

Examples of the sulfide-based antioxidant are as follows.

[0202]

[Chemical formula 82]

Examples of organic phosphoric acid type antioxidants are as follows.

[0204]

[Chemical 83]

Examples of the antioxidant having a hindered phenol structural unit and a hindered amine structural unit in the molecule are as follows.

[0206]

[Chemical 84]

These additives may be used alone or in combination of two or more. These additives may be added to the protective layer, the undercoat layer and the blocking layer. The charge generation layer, specific examples of the solvent used in the formation of the charge transport layer, for example, benzene, toluene, xylene, aromatic solvents such as chlorobenzene, acetone, methyl ethyl ketone, ketone such as cyclohexanone, methanol, Ethanol, alcohols such as isopropanol, ethyl acetate, esters such as ethyl cellosolve, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane and tetrachloroethane, ethers such as tetrahydrofuran and dioxane,
Examples thereof include dimethylformamide, dimethylsulfoxide, diethylformamide and the like.

These solvents may be used alone or in combination of two or more.
As a method of forming a photoreceptor, the charge generating substance, the charge transporting substance, the additive and the binder resin are dispersed in a solvent,
Alternatively, the dissolved solution is applied to a substrate as a predetermined base, a layer, a dip coating method, an electrostatic coating method, a powder coating method, a spray coating method, a roll coating method, an applicator coating method, a spray coater coating method, a bar coater coating method. , Roll coater coating method,
Coating using dip coater coating method, doctor blade coating method, wire bar coating method, knife coater coating method, attritor coating method, spinner coating method, bead coating method, blade coating method, curtain coating method, etc. It can be dried and formed.

The dispersion method includes ball mill, ultrasonic wave, paint shaker, red devil, sand mill,
A mixer, an attritor or the like can be used. Also in the single-layer type electrophotographic photoreceptor, the binder resin can be used in the photosensitive layer. The charge generating substance and the charge transporting substance described above can be used for the photosensitive layer of the single-layer type photoreceptor. Further, the above-mentioned additives may be used in order to improve the electrophotographic characteristics of the photosensitive layer. Also a protective layer,
An undercoat layer and a blocking layer may be provided.

The film thickness of the single-layer type photoreceptor is usually 5 to 100 μm.
Is preferable, and 8-50 micrometers is more preferable. If it is less than 5 μm, the initial potential tends to be low, and if it exceeds 50 μm, the electrophotographic properties tend to deteriorate. The ratio by weight of the charge generating substance: polycarbonate graft copolymer in the photosensitive layer of the single-layer type electrophotographic photosensitive member is preferably 2
0:80 to 80:20, more preferably 30:70 to
It is 60:40. The ratio of the charge transport material: polycarbonate-based graft copolymer by weight is preferably 20:80 to 80:20, more preferably 30: 7.
It is 0 to 70:30. The ratio of the charge generating substance to the charge transporting substance by weight is preferably 20:80 to 7.
It is 0:30, more preferably 30:70 to 60:40.

Further, other resins may be used in combination with the polycarbonate-based graft copolymer of the present invention within a range that does not impair the achievement of the object of the present invention. The layer structure of the photosensitive layer of the electrophotographic photosensitive member of the present invention is preferably such that the layer containing the above-mentioned polycarbonate-based graft copolymer serves as the surface layer of the photosensitive layer. The electrophotographic photoreceptor of the present invention thus obtained has a high surface hardness,
It is a photoconductor that maintains excellent printing durability and good cleaning properties for a long period of time, and is a copying machine (monochrome, multi-color, full-color; analog, digital), printer (laser, LED, liquid crystal shutter), FAX, plate making machine. It can be suitably used in various electrophotographic fields such as.

In using the electrophotographic photosensitive member of the present invention, a corona discharge (corotron, scotron), contact charging (charging roll, charging brush) or the like is used as a charger. The exposure is performed by a halogen lamp, a fluorescent lamp, a laser (semiconductor, He-Ne), an LED, and a photoconductor internal exposure method. As the developing process, a dry developing method such as cascade developing, two-component magnetic brush developing, one-component insulating toner developing, and one-component conductive toner developing, a wet developing method, or the like is used. In the transfer step, an electrostatic transfer method such as corona transfer, roller transfer, belt transfer, a pressure transfer method, or an adhesive transfer method is used. For fixing, heat roller fixing, radiant flash fixing, oven fixing, pressure fixing and the like are used. A brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, etc. are used for cleaning and charge removal.

[0213]

The present invention will be described in more detail below with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples. Reference Example 1 Synthesis of Polycarbonate Containing Allyl Group 2,2-Bis (4-hydroxyphenyl) propane 74
550 ml of 6% by weight aqueous sodium hydroxide solution
A solution of phosgene gas (95 ml) was mixed with 250 ml of methylene chloride while stirring with cooling.
Bubbling was carried out for 15 minutes at a rate of 0 ml / min. Next, this reaction solution is allowed to stand to separate the organic layer, and bisphenol A (2,2-bis (4-hydroxyphenyl) propane) having a degree of polymerization of 2 to 4 and a chloroformate group at the molecular end. A methylene chloride solution of the polycarbonate oligomer of was obtained. The structure, degree of polymerization and terminal group of the produced oligomer were confirmed by ¹ H-NMR, MS and GPC.

Methylene chloride was added to a methylene chloride solution of the above oligomer to bring the total volume to 450 ml, and then 2,2-
10.8 g of bis (3-allyl-4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl)
16.0 g of propane was mixed with a solution of 150 ml of an aqueous solution of sodium hydroxide having a concentration of 8% by weight, and p-tert-butylphenol 3.0 as a molecular weight regulator was added thereto.
g was added. Next, while vigorously stirring this mixed solution, 2 ml of a 7 wt% concentration triethylamine aqueous solution 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 diluted with 1 liter of methylene chloride, and then twice with 1.5 liter of water to give a 0.1.
It was washed with 1 liter of 01N hydrochloric acid once and twice with 1 liter of water in that order, the organic layer was put into methanol, and the precipitated polymer was filtered and dried.

The concentration of the thus obtained allyl group-containing polycarbonate in methylene chloride was 0.5 g.
The reduced viscosity [η _sp / c] of the solution of / dl at 20 ° C was 0.89 dl / g. The reduced viscosity can be measured by
Using an automatic kinematic viscosity measuring device VMR-042 manufactured by Riaisha,
It was measured by an automatic Ubbelohde viscometer (RM type) for viscosity.

Reference Example 2 Synthesis of Maleic Anhydride Modified Polycarbonate The polymer obtained in Reference Example 1, ie, 10 g of an allyl group-containing polycarbonate, 10 g of maleic anhydride and 0.5 g of benzoyl peroxide were dissolved in 50 ml of cyclohexanone,
The mixture was reacted at 80 ° C. for 5 hours with stirring. After the reaction,
The reaction solution was poured into a large amount of methanol, and the precipitated polymer was filtered and dried.

Example 1 (Reference Example) Allyl group-containing polycarbonate 10 obtained in Reference Example 1
g, methyl methacrylate 10 g, benzoyl peroxide 0.
1 g was dissolved in 50 ml of cyclohexanone and reacted with stirring at 80 ° C. for 8 hours. After the reaction, this solution was put into a large amount of methanol, and the precipitated polymer was filtered and dried. The yield of the obtained product was 18.5 g.
This was stirred and washed in toluene at room temperature, insoluble materials were filtered and dried, and 16.1 g of a polycarbonate-based graft copolymer (PC-1) was obtained.

The reduced viscosity [η _sp of a solution of the thus obtained polycarbonate-based graft copolymer in methylene chloride at a concentration of 0.5 g / dl was measured at 20 ° C.
/ C] was 0.85 dl / g. (C-1) was used as the charge transport material, and (PC-
1) and C-1: PC-1: methylene chloride = 1:
A 1: 8 (weight ratio) solution was prepared and used as a coating liquid. Even when the coating solution was allowed to stand for 1 month, no cloudiness or gel formation was observed. A dispersion liquid of oxotitanium phthalocyanine: butyral resin: methylene chloride = 1: 1: 38 (weight ratio) was applied on a conductive substrate made of aluminum by a dip coating method, and an oxotitanium phthalocyanine layer (about 0.5 μm) was charged. Formed as a generation layer, the coating liquid is applied onto the charge generation layer by a dip coating method, and dried,
A charge transporting layer having a thickness of about 20 μm was formed to prepare a laminated electrophotographic photosensitive member. The charge transport layer did not crystallize during coating.

[0219]

[Chemical 85]

The electrophotographic characteristics of the obtained electrophotographic photosensitive member were evaluated by using an electrostatic charging test apparatus EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.) to carry out corona discharge of -6 kV to obtain an initial surface potential (V ₀ ), Light irradiation (10 Lux) 5
The residual potential (V _R ) and the half-exposure amount (E _1/2 ) after 2 seconds were measured. The results are shown in Table 1. Furthermore, the abrasion resistance of the charge transport layer was evaluated using a Suga abrasion tester NUS-ISO-3 type (manufactured by Suga Test Instruments Co., Ltd.). The test conditions were evaluated by reciprocating the sample of the above laminated electrophotographic photosensitive member 1200 times on a worn paper loaded with 200 g and measuring the change in the amount of decrease. The results are shown in Table 2.

Example 2 (Reference Example) The same operation as in Example 1 was carried out except that 10 g of styrene was used instead of the methyl methacrylate used in Example 1.
15.8 g of polycarbonate-based graft copolymer (P
C-2) was obtained. The reduced viscosity [η of a solution of the polycarbonate-based graft copolymer thus obtained having a concentration of 0.5 g / dl in methylene chloride as a solvent at 20 ° C.
_sp / c] was 0.93 dl / g.

PC instead of PC-1 used in Example 1
-2 was used to prepare a photoconductor in the same manner as in Example 1, and the same method was used to prepare an initial surface potential (V ₀ ) and light irradiation (1).
Residual potential (V _R ), half-exposure amount (E) after 5 seconds
_1/2 ) and the amount of decrease in the charge transport layer due to abrasion were measured.
The results are shown in Tables 1 and 2. Example 3 (Reference Example) Instead of the methyl methacrylate used in Example 1, 2,
The same operation as in Example 1 was performed except that 10 g of 2,2- trifluoroethyl methacrylate was used to obtain 16.8 g of a polycarbonate-based graft copolymer (PC-3).

The reduced viscosity [η _sp of a solution of the thus obtained polycarbonate-based graft copolymer in methylene chloride at a concentration of 0.5 g / dl was measured at 20 ° C.
/ C] was 0.91 dl / g. A photoreceptor was prepared in the same manner as in Example 1 except that PC-3 was used in place of PC-1 used in Example 1, and the initial surface potential (V ₀ ) and light irradiation (10 Lux) were prepared in the same manner. ) The residual potential (V _R ) after 5 seconds, the half-exposure amount (E _1/2 ) and the reduction amount of the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Example 4 10 g of the maleic anhydride-modified polycarbonate obtained in Reference Example 2 was dissolved in 30 ml of methylene chloride, 3 g of terminal aminated polysiloxane (molecular weight about 10,000) was added, and the mixture was stirred at room temperature for 8 hours for reaction. It was This solution is then added to a large volume of n.
-Introduced into hexane and the precipitated polymer was recovered.
This was further washed with methanol and then dried,
11.8 g of a polycarbonate-based graft copolymer (P
C-4) was obtained.

The reduced viscosity [η _sp of a solution of the thus obtained polycarbonate-based graft copolymer in methylene chloride at a concentration of 0.5 g / dl was measured at 20 ° C.
/ C] was 0.87 dl / g. A photoreceptor was prepared in the same manner as in Example 1 except that PC-4 was used instead of PC-1 used in Example 1, and the initial surface potential (V ₀ ) and light irradiation (10 Lux) were prepared in the same manner. ) The residual potential (V _R ) after 5 seconds, the half-exposure amount (E _1/2 ) and the reduction amount of the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Example 5 The same operation as in Example 4 except that 3 g of terminal aminated methacrylic resin (terminal aminated methyl methacrylate: molecular weight of about 10,000) was used in place of the terminal aminated polysiloxane used in Example 4. Then, 12.2 g of a polycarbonate-based graft copolymer (PC-5) was obtained.

The reduced viscosity [η _sp of a solution of the thus obtained polycarbonate-based graft copolymer in a concentration of 0.5 g / dl in methylene chloride as a solvent [η _sp
/ C] was 0.85 dl / g. A photoconductor was prepared in the same manner as in Example 1 except that PC-5 was used instead of PC-1 used in Example 1, and the initial surface potential (V ₀ ) and light irradiation (10 Lux) were prepared in the same manner. ) The residual potential (V _R ) after 5 seconds, the half-exposure amount (E _1/2 ) and the reduction amount of the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Example 6 In place of the terminal aminated polysiloxane used in Example 4, 3 g of terminal aminated poly (2,2,2- trifluoroethyl methacrylate) (molecular weight about 12,000) was used. The same operation as in Example 4 was performed to obtain 10.8 g of a polycarbonate-based graft copolymer (PC-6).

The reduced viscosity [η _sp of a solution of the thus obtained polycarbonate-based graft copolymer in a concentration of 0.5 g / dl using methylene chloride as a solvent [η _sp
/ C] was 0.86 dl / g. A photoreceptor was prepared in the same manner as in Example 1 except that PC-6 was used in place of PC-1 used in Example 1, and the initial surface potential (V ₀ ) and light irradiation (10 Lux) were prepared in the same manner. ) The residual potential (V _R ) after 5 seconds, the half-exposure amount (E _1/2 ) and the reduction amount of the charge transport layer due to abrasion were measured. The results are shown in Tables 1 and 2.

Comparative Example 1 Using bisphenol Z as a raw material, a polycarbonate (reduced viscosity: 0.84 dl / g) consisting of the following repeating units was used as a binder resin, and (C-1
An electrophotographic photosensitive member was produced in the same manner as in Example 1 using 1). The results are shown in Tables 1 and 2.

[0231]

[Chemical 86]

[0232]

[Table 1]

[0233]

[Table 2]

[0234]

EFFECT OF THE INVENTION The electrophotographic photoreceptor of the present invention uses a polycarbonate-based graft copolymer which is resistant to crystallization and gelation and has excellent abrasion resistance as a binder resin in the photosensitive layer. The coating liquid does not whiten (gel) during the production of the photoconductor, the adhesion between the conductive substrate and the photoconductor layer and the abrasion resistance of the photoconductor surface are improved, and the electrophotographic photoconductor has a long life. In addition, the excellent electrophotographic characteristics can be maintained even after repeated use for a long time.

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Claims (3)

(57) [Claims] 1. An electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer containing a charge generating substance, a charge transporting substance and a binder resin, wherein the surface layer of the electrophotographic photosensitive member is charged.
A laminated electrophotographic photoreceptor comprising a transport layer, the electrophotographic photoreceptor comprising:
As a binder resin in the load transport layer , an allyl group-containing polycarbonate and maleic anhydride are used as radical initiators.
The maleic anhydride-modified polycarbonate obtained by heating and reacting in the presence of water has a functional group capable of reacting with an acid anhydride.
An electrophotographic photoreceptor comprising a polycarbonate-based graft copolymer obtained by reacting a compound . 2. An allyl group-containing polycarbonate is used for divalent phenols having an allyl group, divalent phenols having an allyl group and divalent phenols having no allyl group,
The electrophotographic photoreceptor of claim 1, wherein is obtained by reacting a carbonic acid ester-forming compound. 3. The dihydric phenol containing an allyl group is 2,2-bis (3-allyl-4-hydroxyphenyl).
Propane, the dihydric phenol having no allyl group is 2,2-bis (4-hydroxyphenyl) propane, and the compound having a functional group capable of reacting with an acid anhydride is a terminal aminated polysiloxane or a terminal amino group. The electrophotographic photosensitive member according to claim 2, which is a polymethylmethacrylate or an aminated poly (2,2,2-trifluoroethylmethacrylate).