JPH04372953A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To provide excellent carrier transportation capability, cyclic potential stability and high sensitivity by using a single polymer or a copolymer as polysilane, and using a specific compound as an antioxidant. CONSTITUTION:A single polymer or a copolymer with the cyclic unit expressed by the formula I and/or the formula II is used as polysilane on a conducting base, and a compound expressed by the formula III is used as an antioxidant, where R1-R4 indicate hydrogen atom, halogen atom, ether group, substituted or unsubstituted group, alkylsilyl group or allylsilyl group respectively, R5, R6 indicate alkyl group, alkenyl group, cycloalkyl group, allyl group or heterocyclic group respectively, and R7-R10 indicate hydrogen atom, halogen atom, alkyl group, alkenyl group, cycloalkyl group, allyl group, alkoxy group or alkylthio group respectively.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to an electrophotographic photoreceptor.
More specifically, the present invention relates to an electrophotographic photoreceptor having excellent carrier transport ability, high sensitivity, and high durability.

0002

[Prior Art] Conventionally, as an electrophotographic photoreceptor, selenium,
Inorganic photoreceptors provided with a photosensitive layer mainly composed of an inorganic photoconductive substance such as zinc oxide or cadmium sulfide have been widely used. However, such inorganic photoreceptors do not always satisfy the characteristics such as photosensitivity, thermal stability, moisture resistance, and durability required of electrophotographic photoreceptors for copying machines and the like.

In order to improve the drawbacks of such inorganic photoconductive materials, attempts have been made to use various organic photoconductive materials in the photosensitive layer of electrophotographic photoreceptors, and active research has been conducted in recent years. ing. For example, Japanese Patent Publication No. 50-10496 describes an organic photoreceptor having a photosensitive layer containing polyvinylcarbazole and trinitrofluorenone. However, this photoreceptor did not have sufficient sensitivity and durability. Therefore, a functionally separated electrophotographic photoreceptor has been developed in which the charge generation function and the charge transport function are assigned to different substances. For such functionally separated electrophotographic photoreceptors, materials with charge generation and charge transport functions can be selected from a wide range of materials, making it easy to obtain desired characteristics and producing organic photoreceptors with high sensitivity and excellent durability. You can get a body.

Charge-generating substances that perform the charge-generating function include various azo compounds, condensed polycyclic compounds, and phthalocyanine compounds, and charge-transporting substances that perform the charge-transporting function include, for example, Japanese Patent Application Laid-Open No. 1983-1996- No. 94829, No. 52-72231, No. 53-27033, No. 5
No. 5-52063, No. 58-65440, No. 58-1
Those proposed in various publications such as No. 98425 were used.

However, the functionally separated type photoreceptor constructed using the above-mentioned charge transport material does not have sufficient charge transport ability, and suffers from a decrease in sensitivity, especially when subjected to a high-speed copying process at a low environmental temperature. This has the disadvantage of causing an increase in residual potential. Further, even if the copying process is made easier by reducing the diameter of the photoreceptor drum, the charge transporting ability of conventional charge transport materials is not sufficient, so reducing the diameter of the drum inevitably leads to a reduction in the process speed.

[0006] Under these circumstances, a technique has recently been proposed for a photoreceptor using polysilane with a specific structure as a charge (hole) transport material (Japanese Patent Laid-Open No. 61-1
No. 0747, No. 62-269964, No. 63-285
(See No. 552). According to this polysilane, unlike the previously mentioned charge transport materials, it has self-forming properties, so it is possible to easily form a film-like photosensitive layer without combining it with other binders, and The mobility of is about 10-4 cm2/V
・It is on the order of sec or more, which is about one order of magnitude larger than that of conventional charge transport materials.

[0007]

However, photoreceptors using polysilane lack chemical stability against light, ozone, etc., and are susceptible to deterioration. This is thought to be due to the fact that the main chain of polysilane is cleaved, a -SiO- bond is formed at the end, photoconductivity is lost, and the residual potential increases. Antioxidants have been added to suppress the deterioration, but conventional antioxidants do not have sufficient ozone resistance and some may cause a decrease in sensitivity, making them undesirable. There has been a desire for an antioxidant that does not cause a decrease in sensitivity even for photoreceptors using polysilane and has excellent antioxidant ability.

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an electrophotographic photoreceptor having excellent carrier transport ability, high sensitivity, and excellent repeated potential stability. There is a particular thing.

As a result of extensive studies, the present inventors have found that by using the antioxidant according to the present invention in a polysilane-containing photoreceptor, it exhibits significantly superior ozone resistance compared to conventional ones, and improves other electrophotographic properties. However, it has been found that an excellent photoreceptor suitable for practical use without any adverse effects can be obtained.

0010

[Means for Solving the Problems] An object of the present invention is to provide an electrophotographic photoreceptor having a charge transport layer containing at least polysilane and an antioxidant on a conductive support, wherein the polysilane has the following general formula (I). and/or general formula (II)
It is a homopolymer or copolymer having a repeating unit represented by the following formula (II
This is achieved by an electrophotographic photoreceptor characterized by being a compound represented by I), (IV) or (V).

[0011]

[Chemical formula 7] (In the formula, R1, R2, R3 and R4 are each a hydrogen atom,
It represents a halogen atom, an ether group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, an alkylsilyl group, or an arylsilyl group. )

0012

[Image Omitted] (In the formula, R5 and R6 each represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R7, R8, R9 and R10 each represent a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxy group, alkylthio group,
It represents an aryloxy group, an arylthio group, an acyl group, an acylamino group, an alkylamino group, an alkoxycarbonyl group or a sulfonamide group. However, when R5 and R6 are both alkyl groups, the total number of carbon atoms in the alkyl groups is 3 or more. )

[0013]

embedded image (wherein R is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, R18CO-, R19SO2- or R20NH
represents CO-, R15 and R16 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, or an alkenoxy group; R17 represents a hydrogen atom;
Represents an alkyl group, alkenyl group or aryl group. However, R18, R19 and R20 each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. )

[0014]

(In the formula, R25 represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group, or an aryloxy group, and R26 and R27 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group. R1 is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, R28CO-, R2
9SO2- or R30NHCO-, R2 is a hydrogen atom, an alkyl group, an alkenyl group, R28CO-, R2
9SO2- or R30NHCO-. However, R28
, R29 and R30 each represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. )

The present invention will be explained in more detail below.

The electrophotographic photoreceptor of the present invention contains polysilane in the charge transport layer, and the polysilane has the following general formula (I).
and/or a homopolymer or copolymer having a repeating unit represented by general formula (II).

[0017]

[Chemical formula 11] (In the formula, R1, R2, R3 and R4 are each a hydrogen atom,
It represents a halogen atom, an ether group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, an alkylsilyl group, or an arylsilyl group. )

The alkyl group represented by R1 or R2 in the general formula (I) is a linear or branched alkyl group having 1 to 24 carbon atoms, preferably 1 to 8 carbon atoms, such as a methyl group or an ethyl group. , a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, a pentadecyl group, a stearyl group, a cycloalkyl group such as a cyclohexyl group, and the like.

The aryl group has 6 to 2 carbon atoms.
4 is preferred, and examples include phenyl group, naphthyl group, and anthryl group.

The alkoxy group has 1 to 1 carbon atoms.
10 is preferred, and examples thereof include methoxy, ethoxy, propoxy, and butoxy groups.

The alkenyl group has 2 to 2 carbon atoms.
10 is preferable, and examples thereof include vinyl group, allyl group, butenyl group, and the like.

As the alkylsilyl group, -SiH(C
H3)2, -Si(CH3)3, -Si(C2H5)3
, -Si(C3H7)3, -Si(C4H9)3, -S
i(CH3)2(C2H5), -Si(CH3)(C2
Examples include H5)2.

The arylsilyl group is -SiH(C6
H5)2, -Si(CH3)2(C6H5), -CH2
Examples include Si(CH3)2(C6H5).

[0024] The alkyl group represented by R1 or R2,
The aryl group or alkoxy group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an amino group, a nitro group, a cyano group, a halogen atom, and other substituents.

Preferred examples of the repeating unit represented by the general formula (I) are shown below. I will correct it.

[0026]

[Chemical formula 12]

[0027]

[Chemical formula 13]

[0028]

[Chemical formula 14]

[0029]

[Chemical formula 15]

In the present invention, those having a degree of polymerization and a weight average molecular weight Mw of 5,000 to 2,000,000 in terms of styrene are preferably used.

The alkyl group represented by R3 or R4 in the general formula (II) preferably has 20 or less carbon atoms, such as methyl group, ethyl group, n-propyl group, iso
-propyl group, n-butyl group, iso-butyl group, t-
Butyl group, n-pentyl group, neo-pentyl group, n-
Examples include hexyl group, n-octyl group, hexadecyl group, and the like. Further, examples of the halogen atom represented by R3 or R4 include chlorine, bromine, iodine, etc., examples of the aryl group include phenyl group, tolyl group, xylyl group, biphenyl group, or naphthyl group, and examples of the alkoxy group include Examples include methoxy group, ethoxy group, isopropoxy group, and phenoxy group. These groups may have a substituent, and examples of the substituent include a carboxyl group, an amino group, a halogen atom, a hydroxyl group, and an aldehyde group.

Examples of polysilanes preferably used in the present invention include cyclotetrasilanes, and specific examples thereof include decamethylbicyclo[2.2.0]
Hexasilane (Decamethyl bicyclo)
[2.2.0] hexasilane), decaisopropylbicyclo[2.2.0] hexasilane (Dec
aisopropyl bicyclo [2.2.0
] hexasilane), dodecamethyltricyclo[4.2.0.02,5]octasilane (Dodeca
methyl tricyclo [4.2.0.02
,5] octasilane), dodecaisopropyltricyclo[4.2.0.02,5]octasilane (D
odecaisopropyl tricyclo[
4.2.0.02,5] octasilane), tetradecaisopropyltetracyclo[6.2.0.0.
2,7.03,6] Decasilane
sopropyl tetracyclo [6.2.
0.0.2, 7.03, 6]
, hexadecaisopropyl pentacyclo [8.2.0.
02,9.03,8.04,7] Dodecasilane (Hex
adecaisopropyl pentacyclo
[8.2.0.02, 9.03, 8.04, 7] d
odecasilane),

[0033]

embedded image (wherein, iPr represents an isopropyl group, and Et represents an ethyl group).

In the present invention, polysilane having a degree of polymerization and a weight average molecular weight Mw of 1,000 to 2,000,000 in terms of styrene is preferably used.

In the present invention, the degree of polymerization n is n=10 to 20.
Preferably, it is in the range of 000.

Further, in the present invention, multidimensional copolymers such as random copolymers and block copolymers having appropriate repeating units are possible, as shown by the following general formula.

[0037]

embedded image In the formula, l, m and n each represent 0 or a positive integer, and R1' to R14' are each a hydrogen atom, a halogen atom, an ether group, an alkyl group, a hydroxyl group, an alkenyl group or an aryl group. . Also, the terminal groups R1', R2'
, R3', R4', R11', R12', R13', R
14' etc. are halogen atoms, hydroxyl groups, -O-Si(R')
3 (where R' is a substituent), an alkoxy group, an alkylthioether group, an arylthioether group, etc. are preferable, and new molecules may also be created by condensing these groups with other molecules.

The above-mentioned polysilane is described in, for example, Japanese Patent Application Laid-Open No. 1985-1985 and
138287 and JP-A-2-19853, or the method described in JP-A-61-170747, Journal of Organometallic Chemistry (R
．． West, J. Organomet. Chem. ,3
00, 327 (1986)), R. D. Miller
and J. Michl,Chemical Rev
iewsvol. 89, p. 1359 (1989).

The electrophotographic photoreceptor of the present invention has the above general formula (III), general formula (IV) or general formula (V) in the charge transport layer.
) Contains an antioxidant represented by:

In the general formula (III), R7, R8,
Examples of the halogen atom represented by R9 and R10 include fluorine, chlorine, bromine, and iodine. R5, R6
, R7, R8, R9, R10 may be linear or branched, but preferably have 1 to 32 carbon atoms, such as methyl, ethyl, butyl,
The alkenyl group is directly It may be chain or branched, and preferably has 2 to 32 carbon atoms, such as allyl, butenyl, octenyl, or oleyl. The cycloalkyl group preferably has 5 to 7 members, such as cyclopentyl. , cyclohexyl or cycloheptyl, the aryl group is preferably phenyl or naphthyl, and the heterocyclic group is preferably a 5- to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom, and/or a sulfur atom, such as furyl, Examples include pyranyl, tetrahydropyranyl, imidazolyl, pyrrolyl, pyrimidyl, pyrazinyl, triazinyl, thienyl, quinolyl, oxazolyl, thiazolyl, and pyridyl.

Examples of the alkoxy group represented by R7, R8, R9, R10 include methoxy, ethoxy, propoxy, t-butoxy, hexyloxy, dodecyloxy, octadecyloxy, docosyloxy, etc.
Examples of alkylthio groups include methylthio, butylthio, octylthio, dodecylthio, and docosylthio; examples of aryloxy groups include phenoxy and naphthoxy; examples of arylthio groups include phenylthio; examples of acyl groups include acetyl, butanoyl, octanoyl, dodecanoyl, benzoyl,
Examples of the acylamino group include cinnamoyl or naphthoyl; examples of the alkylamino group include acetylamino, octanoylamino, and benzoylamino;
For example, methylamino, ethylamino, diethylamino,
Mono- or dialkylamino groups such as isopropylamino, dioctylamino or didecylamino, alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, nonyloxycarbonyl, hexadecyloxycarbonyl or docosyloxycarbonyl, and sulfonamide groups include, for example. Examples include methylsulfonamide, octylsulfonamide, and phenylsulfonamide.

Furthermore, each of these groups may have a substituent, such as a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, an alkyl group (especially one having 1 to 32 carbon atoms), an alkenyl group, etc. groups (especially those having 2 to 32 carbon atoms), alkoxy groups, alkylthio groups, alkenyloxy groups, alkenylthio groups, aryl groups, aryloxy groups, arylthio groups, arylamino groups,
Alkylamino group, alkenylamino group, acyl group, acyloxy group, acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group or heterocyclic group (
In particular, those containing a 5- to 6-membered nitrogen atom, oxygen atom, and/or sulfur atom) can be mentioned. These substituents may be further substituted with the above-mentioned substituents.

In the general formula (III), R5 and R6 are each linear or branched and each has 1 carbon atom.
~32 alkyl groups or alkenyl groups are preferable, and substituents for these alkyl groups and alkenyl groups include hydroxyl groups, cyano groups, carboxyl groups, halogen atoms, aryl groups, alkoxy groups having 1 to 32 carbon atoms, and aryloxy. or an alkoxycarbonyl group having 1 to 32 carbon atoms. Also, R7, R8,
R9 and R10 are each preferably a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 32 carbon atoms, and the substituents for these alkyl groups and alkenyl groups are the same as those for R5 and R6. is preferred. In the present invention, it is particularly preferable that at least one of R5 and R6 is an alkyl group having 8 to 32 or more carbon atoms, and furthermore, at least two of R7, R8, R9 and R10 are an alkyl group or an alkenyl group, and the remaining Two of them are hydrogen atoms.

Typical specific examples of the antioxidant represented by the general formula (III) are shown below, but the present invention is not limited thereto.

[0045]

[Chemical formula 18]

[0046]

[Chemical formula 19]

[0047]

[C20]

[0048]

[C21]

[0049]

[C22]

[0050]

[C23]

[0051]

[C24]

[0052]

[C25]

[0053]

[C26]

[0054]

[C27]

[0055]

[C28]

[0056]

[C29]

These compounds were published in the Journal of the
Chemical Society (J.Chem.Soc.)
pp. 2904-2914 (1965) and The Journal of Organic Chemistry (J.Org.
．． Chem), Vol. 23, pp. 75-76.

The general formula (I) used in the present invention
II) (hereinafter referred to as the antioxidant I of the present invention)
The amount of addition (referred to as II) varies depending on the layer structure of the photoreceptor, the type of charge generating substance, etc., but it is 0.1 to 100% by weight, preferably 0.5 to 50% by weight, based on the polysilane.
It is used in a range of 1 to 25% by weight, particularly preferably 1 to 25% by weight.

In the general formula (IV), examples of the alkyl group represented by R include methyl, ethyl, propyl,
Groups such as t-octyl, benzyl, and hexadecyl; alkenyl groups include allyl, octenyl, and oleyl; aryl groups include phenyl and naphthyl; heterocyclic groups include tetrahydropyranyl and pyrimidinyl. The following groups can be mentioned. R is R18CO
-, R19SO2- or R20NHCO-, the alkyl group, alkenyl group, aryl group and heterocyclic group represented by R18, R19 and R20 include:
The same groups as those listed for R above can be mentioned. The halogen atoms represented by R15 and R16 include, for example, fluorine, chlorine, and bromine atoms; the alkoxy groups include, for example, methoxy, ethoxy, butoxy, and benzyloxy; and the alkenoxy groups include, for example, 2- Examples of groups such as propenyloxy and hexenyloxy, alkyl groups and alkenyl groups include the same groups as mentioned for R above. As for the alkyl group, alkenyl group and aryl group represented by R17, the same groups as those listed for R above can be mentioned. These alkyl groups, alkenyl groups, alkoxy groups, alkenoxy groups, aryl groups and heterocyclic groups may further have a substituent.

Typical specific examples of the compound represented by the general formula (IV) (hereinafter referred to as the antioxidant IV of the present invention) are shown below, but the present invention is not limited thereto.

[0061]

[C30]

[0062]

[Chemical formula 31]

These compounds have been published in the Journal of the Chemical Society (J.Chem.Soc.)
, 1934, p. 1678, 5,6,5',6'-tetrahydroxy-1,1'-
It can be easily synthesized by alkylating or esterifying a spirobiindane compound by a conventional method.

The amount of the antioxidant IV of the present invention to be added varies depending on the layer structure of the photoreceptor, the type of polysilane, etc., but is 0.1 to 100% by weight, preferably 0.5 to 50% by weight, based on the polysilane. It is used in a range of 1 to 25% by weight, particularly preferably 1 to 25% by weight.

In the general formula (V), examples of the alkyl group represented by R25 include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, i-pentyl,
Groups such as sec-pentyl, octyl, t-octyl, dodecyl, octadecyl, and eicosyl; alkenyl groups include allyl, octenyl, and oleyl; aryl groups include phenyl, naphthyl, and the like;
Examples of the alkoxy group include methoxy, ethoxy, butoxy, and dodecyloxy; examples of the alkenoxy group include allyloxy and hexenyloxy; and examples of the aryloxy group include phenyloxy.

Examples of the halogen atom represented by R26 or R27 include atoms such as fluorine, chlorine, and bromine; examples of the alkyl group, alkenyl group, and alkoxy group include the same groups as those described for R25 above. Examples of the cycloalkyl group represented by R1 include cyclopentyl, cyclohexyl, and cyclooctyl; examples of the heterocyclic group include imidazolyl, furyl, thiazolyl,
Examples of groups such as pyridyl, alkyl groups, and alkenyl groups include the same groups as those described for R25 above.

Examples of the alkyl group and alkenyl group represented by R2 include the same groups as those described for R25.

The alkyl group and aryl group represented by R28, R29 or R30 are the same as the group described for R25 above, and the cycloalkyl group and heterocyclic group are the same as the group described for R1 above. Examples include groups.

Further, these alkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenoxy groups, aryloxy groups, cycloalkyl groups and heterocyclic groups include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, It may be substituted with a substituent such as a cyano group, an acyloxy group, an alkoxycarbonyl group, an acyl group, a sulfamoyl group, a hydroxyl group, a nitro group, or an amino group.

In the present invention, the compound represented by the general formula (V) also includes the compound represented by the following general formula (VI).

[0071]

[C32]

In general formula (VI), R2, R25, R26
and R27 has the same meaning as in the general formula (V), X is a substituted or unsubstituted alkylene group, -O-, -S-, -NA- (A: hydrogen atom, (lower alkyl group, phenyl group, etc.), an alkylene group bonded via -SO2- or a phenylene group,
-CO-X'-CO-, -SO2-X'-SO2- or -CONX-X'-NHCO- (X' is an alkylene group, -O-, -S-, -NA −
(A: hydrogen atom, lower alkyl group, phenylene group, etc.) or an alkylene group or phenylene group bonded via -SO2-.

In the present invention, general formula (V) and (
In VI), R25 is a substituted or unsubstituted alkyl group,
It is an alkenyl group or an aryl group, and R26 and R27 are preferably hydrogen atoms or substituted or unsubstituted alkyl groups. However, the substituent represents the substituent described above.

Further, in the present invention, in general formulas (V) and (VI), R25 is an alkyl group or a phenyl group optionally substituted with an alkyl group, R26 and R2
7 is a hydrogen atom, R1 is an alkyl group, alkenyl group, cycloalkyl group, R28CO group, R29SO2 group or R30NHCO group, R28, R29 and R30 which may be substituted with a phenyl group or an alkoxycarbonyl group
is an alkyl group or a phenyl group which may be substituted with an alkyl group, and X is an alkylene group or -CO-X'-
Particularly preferred is CO- (X' represents an alkylene group).

Typical specific examples of the compounds represented by the general formula (V) or the general formula (VI) are shown below, but the present invention is not limited thereto.

[0076]

[Chemical formula 33]

[0077]

[C34]

These compounds are disclosed in Japanese Patent Publication No. 49-20977.
6,6'-dihydroxy-4 obtained by the method described in No.
, 4,4',4'-tetramethyl-2,2'-spirobichroman compound can be easily synthesized by alkylating or acylating it, and is disclosed in JP-A-53-2032.
It is also mentioned in number 7.

The amount of the compound represented by the general formula (V) or (VI) (hereinafter referred to as the antioxidant V of the present invention) is as follows:
Although it varies depending on the layer structure of the photoreceptor, the type of charge transport material, etc., it is 0.1 to 100% by weight, preferably 0.5 to 50% by weight, particularly preferably 1% by weight, based on the charge transport material.
It is used in a range of 25% by weight.

Examples of the charge generating substance used in the present invention include azo pigments, polycyclic quinone pigments, squarium pigments, perylene pigments, and phthalocyanine pigments. Among these, it is particularly preferable to use azo pigments, polycyclic quinone pigments, or phthalocyanine pigments.

The azo pigments used in the present invention are described in JP-A-1-179155, and include those represented by the following general formulas (a) to (c).

[0082]

embedded image (In the formula, Cp1 and Cp2 each represent a coupler residue, R1 and R2 each independently represent a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, or a hydroxyl group, and m1 and m2 respectively Represents an integer from 0 to 3. However, m1 R1 and m2 R2 may be the same or different.)

[0083]

embedded image (In the formula, Cp1 and Cp2 each represent a coupler residue.)

[0084]

embedded image (In the formula, Cp1 and Cp2 each represent a coupler residue.)

In the general formulas (a) to (c), Cp
Examples of the coupler residue represented by 1 or Cp2 include those represented by the following general formulas (1) to (11),
In each formula, Cp1 and Cp2 may be the same or different.

[0086]

[C38]

[0087]

embedded image In the formula, Z represents an atomic group necessary to form a polycyclic aromatic ring or a heterocycle by condensation with a benzene ring.

R1' and R2' are hydrogen atoms, alkyl groups,
It represents an aralkyl group, an aryl group, a heterocyclic group, or a substituted product thereof. Further, it may form a ring together with a nitrogen atom or a carbon atom.

R3' represents O, S, -NH.

R4' and R5' are hydrogen atoms, alkyl groups,
Represents an alkoxy group, nitro group, cyano group, halogen atom, or acetyl group.

Y represents an atomic group necessary to form a 5-membered ring or a 6-membered ring.

A represents a divalent group of a carbocyclic aromatic ring or a heterocyclic aromatic ring.

R6' represents an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, or a substituent thereof.

R7' represents a hydrogen atom, an alkyl group, a dialkylamino group, a diarylamino group, a dialkylamino group, a carbamoyl group, a carboxyl group or an ester group thereof.

R8' represents an aromatic ring group or a substituted product thereof.

Examples of the aromatic ring of Z include benzene and naphthalene, and examples of the heterocycle include indole, carbazole, benzofuran, and dibenzofuran. Z may have a substituent, and examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Alkyl groups (e.g. methyl, ethyl, propyl,
(butyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), and nitro group.

Specific examples of the coupler residues represented by the above general formulas (1) to (11) include, for example, Japanese Patent Application No. 2-27
Compound No. 7176, pages 72-75. 1-15
can be mentioned. Specific examples of azo pigments preferably used in the present invention include the compounds described on page 76 of Japanese Patent Application No. 2-277176, and representative examples are shown on the next page, but the present invention is not limited to these. It's not something you can do.

[0098]

[C40]

The polycyclic quinone pigments used in the present invention are described in JP-A-59-184349, and include, for example, those represented by the following general formulas (2) to (f). Among these, those represented by general formula (d) are particularly preferred.

[0100]

embedded image (In general formulas (2) to (f), X1 represents a halogen atom, nitro group, cyano group, acyl group, or carboxyl group, n1 represents an integer of 0 to 4, and n2 represents 0 to 6
represents an integer. )

Specific examples of polycyclic quinone pigments preferably used in the present invention include compounds (X-1) to (XII-1) described in Japanese Patent Application No. 2-277176, pages 79-80.
), Compounds 1 and 2 are mentioned.

Examples of the squarium pigment used in the present invention include those represented by the following general formula (g).

[0103]

embedded image (wherein R0', R1' and R2' each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group or NHY'. Y' is an optional alkyl group, a phenyl group or a hydrogen atom). R3' represents a substituted or unsubstituted alkyl group. X2 represents a group of carbon atoms necessary to form an at least 6-membered saturated or unsaturated monocyclic or polycyclic hydrocarbon. )

Examples of the substituent for R3' include a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, an ester group, an acyl group, a dialkylamino group, a dialkylamino group, a diarylamino group, and an aryl group. can.

Specific examples of squarium pigments preferably used in the present invention include Japanese Patent Application No. 2-27717.
Compounds XIII-1 to XII described in No. 6, pages 83 to 84
I-13 is mentioned.

Examples of perylene pigments preferably used in the present invention include those described in Japanese Patent Application No. 2-277176 No. 86-8.
Compound No. 7 described on page 7 Examples include P-1 to P-9.

As the phthalocyanine pigment, metal or metal-free phthalocyanine pigments can be used, and specifically, χ-type, τ-type metal-free phthalocyanine, α-type, β-type copper phthalocyanine, titanyl phthalocyanine, etc. are preferably used. It will be done. The titanyl phthalocyanine pigment preferably used in the present invention has the following general formula (H):
Examples include compounds represented by
No. 5246.

[0108]

[Chemical Formula 43] However, X1, X2, X3, and X4 represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and n, m,
l and k represent integers from 0 to 4.

[0109] The titanyl phthalocyanine pigment is (Cu
- At least 9.6° ± 0 of the Bragg angle 2θ in the X-ray diffraction spectrum for Kα rays (wavelength 1.541 Å)
．． It has peaks at 2° and 27.2°±0.2°, and 9
．． The peak intensity at 6°±0.2° is 27.2°±0.2°
It is in a crystalline state with a peak intensity of 40% or more.

[0110] Furthermore, preferably a crystalline state in which the peak intensity at 9.6°±0.2° is 60% or more of that at 27.2°±0.2° or The peak intensity is 50% or more of that of 27.2° ± 0.2°, and 6.
The peak intensity at 7°±0.2° is 27.2°±0.2°
titanyl phthalocyanine in a crystalline state that is less than 30% of that of titanyl phthalocyanine.

[0111] The X-ray diffraction spectrum was measured under the following conditions, and the peak here is an acute-angled pyramidal projection that is clearly different from noise.

[0112] X-ray tube Cu electron
Voltage 40.0 KV
Current: 100 mA Starting angle: 6.0 deg. Stop angle 35.0 deg. Step angle 0.02 deg. Measurement time
0.50 sec.

0113
] The above titanyl phthalocyanine can be produced by a generally well-known method. Although not limited to this, for example, titanium tetroxide and phthalodinitrile are
- Titanyl phthalocyanine is produced by hydrolyzing dichlorotitanium phthalocyanine obtained by reacting in an inert high-boiling solvent such as chlornaphthalene at a reaction temperature of 160 to 300°C, generally at 160 to 260°C with a base or water. can be obtained.

[0114] Another excellent method of synthesis is the use of an alkoxy titanate, a so-called titanium coupling agent.

As the titanium coupling agent, for example, a compound represented by the general formula (T) can be used.

[0116]

In the present invention, it is preferable that X1 to X4 are -OR1 from the viewpoint of reactivity, ease of handling, cost, etc.

Specific examples of titanium coupling agents preferably used in the present invention are shown below.

[0119]

[C44]

The reaction formula for synthesizing titanyl phthalocyanine is as follows. This method of using a titanium coupling agent is an excellent method that does not cause side reactions and can therefore easily obtain a highly purified product.

[0121]

embedded image In the formula, R1 to R16 are each a hydrogen atom, an alkyl group,
Represents an alkoxy group or a halogen atom.

Crystalline forms can be obtained, for example, directly from hydrolyzed titanyl phthalocyanine or from an amorphous form obtained by dissolving it in sulfuric acid and pouring it into water, by treating it with a water-immiscible organic solvent in the presence of water. You can get it by doing this.

[0123] As the apparatus used for the treatment, in addition to a general stirring apparatus, a homomixer, disperser, agitator, ball mill, sand mill, attritor, etc. can be used.

In the present invention, a charge transport substance (hereinafter also referred to as CTM) may be added as necessary, and in the general formula, the following (a), (b), (c), (d) or (e ), for details see Japanese Patent Application No. 2-27.
It is described in No. 7176.

[0125]

embedded image (In the formula, R3 represents a hydrogen atom, an alkyl group, or an aryl group, R4 represents a substituent, A1 represents a phenylene group or a naphthylene group, and Ar1 and Ar2 each represent an alkyl group, a phenyl group, or a naphthyl group. represents a group, Ar
3 represents a hydrogen atom, a phenyl group or a naphthyl group, and n
1 represents 0 or 1, and n2 represents an integer from 0 to 5. )

[0126]

embedded image (wherein R5, R6 and R7 each represent a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group,
R8 represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, m and l represent 1 or 2, and q represents 0 or 1. When m and l are 2, R5 and R6 may be the same or different. )

0127
]

embedded image (In the formula, Ar4 and Ar5 each represent an aryl group, Ar6 represents an arylene group, Ar7 represents a p-phenylene group or a naphthylene group, and R9 and R10 each represent an alkyl group.)

[0128]

(In the formula, R11 and R13 each represent a dialkylamino group, R12 and R14 each represent a halogen atom or a cyano group, Ar8 and Ar9 each represent a phenyl group or a naphthyl group, m1, m2, m3 and m4
represents 0 or 1, respectively. However, m1 and m3 are 0 at the same time
It will never become. )

[0129]

embedded image (wherein, R15 represents a hydrogen atom or a substituent, R16 represents a hydrogen atom, an alkyl group, or an aryl group, and Ar10
represents a hydrogen atom, a benzyl group, a phenyl group, or a naphthyl group, Ar11 represents a phenylene group or a naphthylene group, Ar12 represents an alkyl group, a phenyl group, or a naphthyl group, k1 represents an integer of 0 to 5, and k2 represents an integer of 0 to 5. Represents 0 or 1. )

The structure of the electrophotographic photoreceptor of the present invention is usually as shown in FIGS. 1(a) to 1(d). (A) and (B) are composed of a laminate of a conductive support 1, a charge generation layer 2 containing a charge generation substance, and a charge transport layer 3 containing polysilane and, if necessary, a charge transport substance. Photosensitive layers 4A and 4B are provided, and the stacking order of the charge generation layer 2 and charge transport layer 3 is different between (a) and (b). As shown in (c) and (d), these photosensitive layers 4A,
4B may be provided on the conductive support 1 via an intermediate layer 5 such as an adhesive layer or a barrier layer. Further, a protective layer may be provided as the outermost layer. In the present invention, a charge transport substance may be added to the charge generation layer in addition to the charge generation substance.

Any binder resin can be used for the photosensitive layer, protective layer, and intermediate layer, such as polystyrene, polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin,
Addition polymerization type resins, polyaddition type resins, polycondensation type resins such as vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, and these Examples include copolymer resins containing two or more of the repeating units of the above resins. In addition to these insulating resins, polymeric organic semiconductors such as poly-N-vinylcarbazole may also be used.

[0132] Next, as the conductive support for supporting the photosensitive layer, a metal plate made of aluminum or nickel, a metal drum, or a metal foil laminated, or a metal plate made of aluminum, nickel, etc.
A plastic film coated with tin oxide, indium oxide, or the like, or a film or drum made of paper or plastic coated with a conductive substance can be used.

[0133] In the present invention, the charge generation layer is typically formed by dipping a dispersion in which the charge generation substance described above and, if necessary, a charge transport substance are dispersed in a suitable dispersion medium alone or together with a suitable binder resin. It can be provided by a method of coating the support, subbing layer, or charge transport layer by spray coating, blade coating, roll coating, etc., and drying the coating. Further, in the present invention, a ball mill, a homomixer, a sand mill, an ultrasonic disperser, an attritor, etc. are used for dispersing the charge generating substance and the charge transporting substance.

Examples of the dispersion medium used in the present invention include hydrocarbons such as hexane, benzene, toluene, and xylene; methylene chloride, 1,2-dichloroethane,
Halogenated hydrocarbons such as sym-tetrachloroethane, 1,1,2-trichloroethane, and chloroform; Ketones such as acetone, methyl ethyl ketone, and cyclohexanone; Esters such as ethyl acetate and butyl acetate; methanol, ethanol, propanol, butanol , cyclohexanol, heptanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, acetic acid cellosolve and other alcohols and derivatives thereof; tetrahydrofuran, 1
Nitrogen compounds such as ethers and acetals such as , 4-dioxane, furan, and furfural; amines such as pyridine, butylamine, diethylamine, ethylenediamine, and isopropanolamine; and amides such as N,N-dimethylformamide can be used.

When the photoreceptor of the present invention has a laminated structure, the weight ratio of binder:carrier generating substance:carrier transporting substance in the carrier generating layer is 0 to 100:1 to 500:0 to 50.
0 is preferred.

If the content of the carrier generating substance is less than this, the sensitivity will be low and the residual potential will increase, and if it is more than this, the dark decay and acceptance potential will decrease.

The thickness of the carrier generation layer formed as described above is preferably 0.01 to 10 μm, particularly preferably 0.1 to 5 μm.

[0138] In the present invention, the charge transport layer can be formed by dissolving and dispersing polysilane and, if necessary, a charge transport substance in a suitable dispersion medium alone or together with the above-mentioned binder resin, followed by drying. . As the dispersion medium used, the dispersion medium used in dispersing the charge generating substance can be used.

[0139] In the present invention, polysilane and a charge transport substance added as necessary account for 40% of the total weight of the charge transport layer.
The content is preferably 60% or more, particularly preferably 60% or more.

The thickness of the charge transport layer to be formed is preferably 5 to 50 μm, particularly preferably 5 to 30 μm.

[0141] In the present invention, the intermediate layer is formed by dipping coating, roll coating, or spraying using an alcohol solution in which the binder and optional additives are dissolved in methanol, ethanol, butanol, etc. or in a solvent such as toluene. It can be obtained by coating on a substrate using a coating method such as a coating method, a wire bar coating method, a bead coating method, or a curtain coating method. However, the binder may be the same as the binder used in the carrier generation layer. The film thickness is generally 0.1 to 5 μm, preferably 0.5 to 3 μm. The amount of binder used is preferably 1 to 5% by weight, based on the solvent.

Further, in the photoreceptor of the present invention, a protective layer (protective film) may be formed on the surface of the photoreceptor in order to improve printing durability, for example, a synthetic resin film may be coated.

In the present invention, the charge generation layer contains, for the purpose of improving sensitivity, reducing residual potential or fatigue during repeated use, etc.
One or more types of electron-accepting substances can be contained. The addition ratio of the electron-accepting substance is a weight ratio of charge-generating substance:electron-accepting substance=100:0.01 to 200.
is preferable, and more preferably 100:0.1 to 100.

[0144] The electron-accepting substance may be added to the charge transport layer, and in this case, the ratio of the electron-accepting substance added is, by weight, the total charge-transporting substance:electron-accepting substance=100:0.01.
~100 is preferred, more preferably 100:0.1~
It is 50.

Examples of electron-accepting substances that can be used in the photoreceptor of the present invention include succinic anhydride, maleic anhydride, dibromaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, and 3-nitromaleic anhydride. Phthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, para Nitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, brumanil, 2-methylnaphthoquinone, dichlorodicyanoparabenzoquinone, anthraquinone, dinitroanthraquinone, trinitrofluorenone, 9-fluorenylidene [dicyanomethylenemalonodinitrile], polynitro-9- Fluorenylidene
[dicyanomethylenemalonodinitrile], picric acid,
Examples include o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and the like.

Furthermore, silicone oil may be present as a surface modifier. Further, an ammonium compound may be contained as a durability improver.

The photoreceptor of the present invention may also contain dyes for color sensitivity correction, if necessary.

[0148] As the light source used in the photoreceptor of the present invention, a halogen lamp, a fluorescent lamp, a tungsten lamp, a gas laser such as an argon laser or a helium-neon laser, a semiconductor laser, an LED, etc. are used.

[0149]

[Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited thereto.

Example 1-(1) Photoreceptor sample No. 1-1
1. An intermediate layer with a thickness of 0.1 μm made of vinyl chloride-vinyl acetate-maleic anhydride copolymer "S-LEC MF-10" (manufactured by Sekisui Chemical Co., Ltd.) was placed on a conductive support made of an aluminum vapor-deposited polyester base. Established.

4 represented by the following structural formula (CGM-1)
, 1 part by weight of 10-dibromoanthrone "Monolite Red 2Y" (manufactured by ICI) and 0.5 parts of polycarbonate resin "Panlite L-1250" (manufactured by Teijin Kasei).
1.2 parts by weight and 1.0 parts by weight of charge transport material CTM-I
- Mix with 100 parts by weight of dichloroethane and disperse in a ball mill for 24 hours to prepare a coating solution. Using this coating solution, coat the intermediate layer with a film thickness of 0.5 after drying by dipping method.
A charge generation layer was formed to have a thickness of μm.

[0152] Next, a coating solution was prepared by mixing polysilane and an antioxidant in toluene ((polysilane + antioxidant)/toluene = 15 W/V%), and a coating solution with a dry film thickness of 20 μm was formed on the charge generation layer. A charge transport layer was formed on the electrophotographic photoreceptor sample No. 1 to 11 were produced. However, polysilane and antioxidant were used as shown in Table 1.

[0153] The obtained sample No. Tests Nos. 1 to 11 were each evaluated using a modified Konica 1550MR (manufactured by Konica). Black paper potential VB0, white paper potential VW0,
After determining the residual potential VR0, evaluating the sensitivity, and repeating the evaluation for 100,000 copies, the black paper potential VB, the white paper potential VW, and the residual potential VR were determined. The results are shown in Table 1.

[0154]

[C51]

[0155]

[C52]

[0156]

[C53]

[0157]

[Table 1] As is clear from Table 1, the samples of the present invention were
Satisfactory values were obtained for all of the black paper potential, white paper potential, and residual potential after 10,000 copies, and there were no problems.

Example 1-(2) Photoreceptor samples were prepared in the same manner as in Example 1-(1) except that the type of antioxidant was changed, and the same evaluations were conducted. The results are shown in Table 2. However, polysilane and antioxidant were used as shown in Table 2.

[0159]

[Table 2] As is clear from Table 2, the samples of the present invention were
Satisfactory values were obtained for all of the black paper potential, white paper potential, and residual potential after 10,000 copies, and there were no problems.

[0160]

[C54] Antioxidant (comparison) AO-2: Same as AO-1 Polysilane: Same as shown in Example 1-(1)

0
Example 1-(3) Photoreceptor samples were prepared in the same manner as in Example 1-(1) except that the type of antioxidant was changed, and the same evaluations were conducted. The results are shown in Table 3. However, polysilane and antioxidant were used as shown in Table 3.

[0162]

[Table 3] As is clear from Table 3, the samples of the present invention were
Satisfactory values were obtained for all of the black paper potential, white paper potential, and residual potential after 10,000 copies, and there were no problems.

[0163]

[C55] Antioxidant (comparison) AO-3: Same as AO-1 Polysilane: Same as shown in Example 1-(1)

0
164 Example 2-(1) Photoreceptor sample No. 101-1
Preparation of No. 11 A 0.1 μm thick intermediate layer made of nylon copolymer X1874M (manufactured by Daicel Huls Co., Ltd.) was provided on a conductive support made of an aluminum vapor-deposited polyester base. 1 part by weight of a bisazo pigment represented by the following structural formula, 0.5 part by weight of polycarbonate resin "Panlite L-1300" (manufactured by Teijin Chemicals), and 1.0 part by weight of a charge transport substance CTM-II.
Part by weight was mixed with 100 parts by weight of tetrahydrofuran and dispersed in a ball mill for 24 hours to prepare a coating solution, and this coating solution was used to coat the intermediate layer with a film thickness of 0.4 μm after drying by a dipping method. The charge generation layer was formed so that the charge generation layer was as follows.

[0165] Next, a coating solution was prepared using the above-mentioned polysilane and antioxidant as shown in Table 4, and a charge transport layer having a dry thickness of 20 μm was formed on the charge generation layer. Photoreceptor sample No. 101 to 111 were produced. However, polysilane and antioxidant are TH without binder.
It was used after being dissolved in F (polysilane + antioxidant = 15 W/V%).

[0166] Obtained sample No. 101 to 111 were each evaluated using a modified Konica 5570MR (manufactured by Konica). Black paper potential VB0, white paper potential V
Determine W0 and residual potential VR0, evaluate the sensitivity, and
Black paper potential VB, white paper potential VW, residual potential V after 10,000 copies
R was evaluated. The results are shown in Table 4.

[0167]

[C56] Antioxidant (comparison) AO-4: Same as AO-1 Polysilane: Same as shown in Example 1-(1)

0
168]

[Table 4] As is clear from Table 4, the samples of the present invention were
Satisfactory values were obtained for all of the black paper potential, white paper potential, and residual potential after 10,000 copies, and there were no problems.

Example 2-(2) Photoreceptor samples were prepared in the same manner as in Example 2-(1) except that the type of antioxidant was changed, and the same evaluations were conducted. The results are shown in Table 5. However, polysilane and antioxidant were used as shown in Table 5.

[0170]

[Table 5] As is clear from Table 5, the samples of the present invention were
Satisfactory values were obtained for all of the black paper potential, white paper potential, and residual potential after 10,000 copies, and there were no problems.

[0171]

[C57] Antioxidant (comparison) AO-5: Same as AO-1 Polysilane: Same as shown in Example 1-(1)

0
Example 2-(3) Photoreceptor samples were prepared in the same manner as in Example 2-(1) except that the type of antioxidant was changed, and the same evaluations were conducted. The results are shown in Table 6. However, polysilane and antioxidant were used as shown in Table 6.

[0173]

[Table 6] As is clear from Table 6, the samples of the present invention were
Satisfactory values were obtained for all of the black paper potential, white paper potential, and residual potential after 10,000 copies, and there were no problems.

[0174]

[C58] Antioxidant (comparison) AO-6: Same as AO-1 Polysilane: Same as shown in Example 1-(1)

0
175 Example 3-(1) Synthesis of titanyl phthalocyanine 65 g of phthalodinitrile and 500 g of α-chlornaphthalene
After dropping 14.7 ml of titanium tetrachloride into the mixture under a nitrogen stream, the temperature was gradually raised to 200°C, the reaction temperature was maintained between 200°C and 220°C, and the reaction was stirred for 3 hours. Completed it. Thereafter, it was left to cool, and when the temperature reached 130°C, it was filtered while hot, washed with α-chlornaphthalene, washed several times with methanol, and further washed several times with hot water at 80°C.

After drying, 5 g of the solution was added to 100 g of 96% sulfuric acid, stirred at 3 to 5°C, filtered, and the obtained sulfuric acid solution was poured into 1.5 liters of water, and the precipitated crystals were collected by filtration. Next, washing with water was repeated until the washing solution became neutral.

1,2-dichloroethane was added to the Nutsche cake thus obtained, and the mixture was stirred at room temperature for 1 hour, filtered, and washed with methanol to obtain crystals of titanyl phthalocyanine. As shown in FIG. 2, this crystal has a maximum intensity peak at 27.3 degrees of Bragg angle 2θ, and 9.
Characteristic peaks were shown at 6°, 11.7°, and 24.1°.

Photoreceptor sample No. Preparation of 201 to 211 0 thickness made of copolyamide (CM-8000, manufactured by Toray Industries, Inc.) on a polyester base on which aluminum is vapor-deposited.
．． A 15 μm subbing layer was created. Then, the obtained Figure 2
Titanyl phthalocyanine 1 with an X-ray diffraction pattern of
(wt, same hereinafter), polyvinyl butyral "XYHL" (manufactured by Union Carbide) as binder resin
1 part and 100 parts of methyl ethyl ketone as a dispersion medium were dispersed using a sand mill, and this was applied onto the undercoat layer using a wire bar to form a charge generation layer having a thickness of 0.2 μm.

Next, a solution prepared by dissolving polysilane and antioxidant in 25 parts of toluene in a total amount of 7.5 parts was applied using a blade coater, and after drying, a film thickness of 15 μm was applied.
A charge transport layer was formed on the electrophotographic photoreceptor sample No. 201
-211 were produced. However, polysilane and antioxidant were used as shown in Table 7.

[0180] Obtained sample No. 201 to 211 were each evaluated using a modified Konica DC8010 (manufactured by Konica). The unexposed area potential VH0, the exposed area potential VL0, and the residual potential VR0 are determined to evaluate the sensitivity, and the unexposed area potential VH, the exposed area potential VL, after 100,000 copies,
The residual potential VR was evaluated. The results are shown in Table 7.

[0181]

[C59] Antioxidant (comparison) AO-7: Same as AO-1 Polysilane: Same as shown in Example 1-(1)

0
182]

[Table 7] As is clear from Table 7, the samples of the present invention were
After 00,000 copies, satisfactory values were obtained for all of the unexposed area potential, exposed area potential, and residual potential, and there were no problems.

Example 3-(2) Photoreceptor samples were prepared in the same manner as in Example 3-(1) except that the type of antioxidant was changed, and the same evaluations were conducted. The results are shown in Table 8. However, polysilane and antioxidant were used as shown in Table 8.

[0184]

[Table 8] As is clear from Table 8, the samples of the present invention were
After 10,000 copies, satisfactory values were obtained for all of the unexposed area potential, exposed area potential, and residual potential, and there were no problems.

[0185]

[C60] Antioxidant (comparison) AO-8: Same as AO-1 Polysilane: Same as shown in Example 1-(1)

0
Example 3-(3) Photoreceptor samples were prepared in the same manner as in Example 3-(1) except that the type of antioxidant was changed, and the same evaluations were conducted. The results are shown in Table 9. However, polysilane and antioxidant were used as shown in Table 9.

[0187]

[Table 9] 71 As is clear from Table 9, the samples of the present invention had satisfactory values in all of the unexposed area potential, exposed area potential, and residual potential at the initial stage and after 100,000 copies, and there were no problems. there were.

[0188]

[C61] Antioxidant (comparison) AO-9: Same as AO-1 Polysilane: Same as shown in Example 1-(1)

0
189]

[Effects of the Invention] As described in detail above, the present invention has made it possible to provide an electrophotographic photoreceptor that has excellent carrier transport ability, high sensitivity, and excellent repeated potential stability.

[Brief explanation of drawings]

FIGS. 1(a), (b), (c), and (d) are cross-sectional views each showing a configuration example of a photoreceptor of the present invention.

FIG. 2 is an X-ray diffraction diagram of titanyl phthalocyanine used in Examples.

[Explanation of symbols]

1 Conductive support 2 Charge generation layer 3 Charge transport layer 4A, 4B Photosensitive layer 5 Middle class

Claims (3)

[Claims] [Claim 1] An electrophotographic photoreceptor having a charge transport layer containing at least a polysilane and an antioxidant on a conductive support, wherein the polysilane is represented by the following general formula (I) and/or general formula (II). 1. An electrophotographic photoreceptor, which is a homopolymer or a copolymer having repeating units, and the antioxidant is a compound represented by the following general formula (III). [Chemical formula 1] (In the formula, R1, R2, R3 and R4 are each a hydrogen atom,
It represents a halogen atom, an ether group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, an alkylsilyl group, or an arylsilyl group. ) [Formula R5 and R6 each represent an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R7, R8, R9 and R10 each represent a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxy group, alkylthio group,
It represents an aryloxy group, an arylthio group, an acyl group, an acylamino group, an alkylamino group, an alkoxycarbonyl group or a sulfonamide group. However, when R5 and R6 are both alkyl groups, the total number of carbon atoms in the alkyl groups is 3 or more. ) 2. An electrophotographic photoreceptor having a charge transport layer containing at least a polysilane and an antioxidant on a conductive support, wherein the polysilane is represented by the following general formula (I) and/or general formula (II). 1. An electrophotographic photoreceptor, which is a homopolymer or a copolymer having a repeating unit, and the antioxidant is a compound represented by the following general formula (IV). [Chemical formula 3] (In the formula, R1, R2, R3 and R4 are each a hydrogen atom,
It represents a halogen atom, an ether group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, an alkylsilyl group, or an arylsilyl group. ) [Formula R is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, R18CO-, R19SO2- or R20NH
represents CO-, R15 and R16 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, or an alkenoxy group; R17 represents a hydrogen atom;
Represents an alkyl group, alkenyl group or aryl group. However, R18, R19 and R20 each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. ) 3. An electrophotographic photoreceptor having a charge transport layer containing at least a polysilane and an antioxidant on a conductive support, wherein the polysilane is represented by the following general formula (I) and/or general formula (II). 1. An electrophotographic photoreceptor, which is a homopolymer or copolymer having repeating units, and the antioxidant is a compound represented by the following general formula (V). [Chemical formula 5] (In the formula, R1, R2, R3 and R4 are each a hydrogen atom,
It represents a halogen atom, an ether group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, an alkylsilyl group, or an arylsilyl group. ) [In the formula, R25 represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group, or an aryloxy group, and R26 and R27 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an alkoxy group. represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, R28CO-, R2
9SO2- or R30NHCO-, R2 is a hydrogen atom, an alkyl group, an alkenyl group, R28CO-, R2
9SO2- or R30NHCO-. However, R28
, R29 and R30 each represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. )