JPH11143098A - Electrophotographic photoreceptor - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To provide an electrophotographic photosensitive member having high sensitivity to a long-wavelength light source near 700 nm and maintaining high stability. SOLUTION: On a conductive support, at least 7.5 °, 8.3 ° of Bragg angle in X-ray diffraction spectrum,
A charge generating material containing a titanium phthalocyanine compound having a main peak at either 9.5% or 27.2%, and a compound represented by the general formula (I): (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a substituent Represents a good alkoxy group or a halogen atom, and represents Ar ¹ , Ar ² , Ar ³ and Ar ⁴
Represents a phenyl group which may have a substituent. An electrophotographic photoreceptor having a photoconductive layer containing a charge transport material containing a distyryl compound represented by the formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copier, an LD printer, and an LED using a long-wavelength light source near 700 nm.
The present invention relates to an electrophotographic photosensitive member used for a printer or the like.

[0002]

2. Description of the Related Art In recent years, with the increasing demand for higher sensitivity and higher durability of electrophotographic photosensitive members, a function-separated type in which the charge generation function and the charge transport function of the electrophotographic photosensitive member are shared by different materials. The development of electrophotographic photoreceptors has been active.

In addition, semiconductor lasers (LDs) and light emitting diodes (LEDs) have been developed along with the development of the electronics industry.
As materials used for electrophotographic photoreceptors such as copiers, LD printers, and LED printers using a long wavelength light source near 00 nm, phthalocyanine compounds sensitive to these light sources have attracted attention.

A phthalocyanine compound is used for the photoconductive layer, and as an electrophotographic photoreceptor having excellent sensitivity and repetition characteristics, for example, JP-A-6-118674 and JP-A-8-292588 disclose a charge transporting agent. An electrophotographic photoreceptor having a photoconductive layer containing a distyryl compound substituted with an amino group and titanyloxyphthalocyanine as a charge generating substance has been proposed.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies in view of the above situation, and as a result, have found that an electrophotographic photosensitive member comprising a photoconductive layer containing a specific charge generating material and a specific charge transport material is provided. The inventors have found that the body exhibits excellent sensitivity and potential stability, and have completed the present invention.

That is, in order to solve the above-mentioned problems, the present invention provides an electrophotographic photosensitive member having a photoconductive layer containing a charge generating material and a charge transporting material on a conductive support, wherein the charge generating material is Cu-Kα. At least a Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum of
A charge-transporting material containing a titanium phthalocyanine compound having a main peak at any of 5 °, 8.3 °, 9.5 °, and 27.2 °;

[0007]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, Represents an optionally substituted alkoxy group or a halogen atom, Ar ¹ , Ar ² , Ar
³ and Ar ⁴ represent a phenyl group which may have a substituent. The present invention provides an electrophotographic photoreceptor characterized by containing a distyryl compound represented by the formula (1):

Further, the charge generation material has a Bragg angle (2θ ± 0.2) in the X-ray diffraction spectrum of Cu-Kα.
2)) containing a titanium phthalocyanine compound having a main peak at least in any one of 7.5 °, 8.3 °, 9.5 °, and 27.2 °, and wherein the charge transporting material has the general formula (I)

[0010]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, Represents an optionally substituted alkoxy group or a halogen atom, Ar ¹ , Ar ² , Ar
³ and Ar ⁴ represent a phenyl group which may have a substituent. ), And further comprising (1) a general formula (II)

[0012]

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Wherein Ar ⁵ and Ar ⁶ each independently represent a phenyl group which may have a substituent; or (2) a compound represented by the general formula (III)

[0014]

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(Where R⁷, R⁸And R⁹Are independent
Hydrogen atom, an alkyl group which may have a substituent,
An alkoxy group or a halogen atom which may have a substituent
Represents a child, R^TenAnd R¹²Are each independently substituted
An optionally substituted alkyl group, R ¹¹And R¹³Are independent
An alkyl group or a substituent which may have a substituent
Represents a phenyl group which may be possessed, and n is 1 to 4
Represents an integer. Contains a distyryl compound represented by)
To provide an electrophotographic photoreceptor.

In an electrophotographic photosensitive member having a photoconductive layer containing a charge generating material and a charge transporting material on a conductive support, the charge generating material has a Bragg angle (2θ ± 2) in an X-ray diffraction spectrum with respect to Cu-Kα. 0.2 °) of at least 7.5 °, 8.3 °, 9.5 ° and 27.2
チ containing a titanium phthalocyanine compound having a main peak, and wherein the photoconductive layer has a Bragg angle (2θ ± 0.
2}) has a main peak at least at any of 7.5 °, 8.3 °, 9.5 ° and 27.2 °, and the charge transporting material has the general formula (I)

[0017]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, Represents an optionally substituted alkoxy group or a halogen atom, Ar ¹ , Ar ² , Ar
³ and Ar ⁴ represent a phenyl group which may have a substituent. The present invention provides an electrophotographic photoreceptor characterized by containing a distyryl compound represented by the formula (1):

Further, the charge generation material has a Bragg angle (2θ ± 0.2 in the X-ray diffraction spectrum of Cu-Kα).
2}) contains a titanium phthalocyanine compound having a main peak at least in any one of 7.5 °, 8.3 °, 9.5 ° and 27.2 °, and the photoconductive layer is formed of Cu—K
In the X-ray diffraction spectrum for α, the Bragg angle (2
θ ± 0.2 °) at least 7.5 °, 8.3 °, 9.
Having a main peak at either 5 ° or 27.2 °,
The charge transport material has the general formula (I)

[0020]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, Represents an optionally substituted alkoxy group or a halogen atom, Ar ¹ , Ar ² , Ar
³ and Ar ⁴ represent a phenyl group which may have a substituent. ), And further comprising (1) a general formula (II)

[0022]

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Wherein Ar ⁵ and Ar ⁶ each independently represent a phenyl group which may have a substituent, or (2) a compound represented by the general formula (III)

[0024]

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Where R⁷, R⁸And R⁹Are independent
Hydrogen atom, an alkyl group which may have a substituent,
An alkoxy group or a halogen atom which may have a substituent
Represents a child, R^TenAnd R¹²Are each independently substituted
An optionally substituted alkyl group, R ¹¹And R¹³Are independent
An alkyl group or a substituent which may have a substituent
Represents a phenyl group which may be possessed, and n is 1 to 4
Represents an integer. Contains a distyryl compound represented by)
To provide an electrophotographic photoreceptor.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrophotographic photoreceptor of the present invention will be described in detail below.

The titanium phthalocyanine compound used in the present invention is a compound having a phthalocyanine ring having a titanium atom as a central metal, and specifically, a compound represented by the general formula (IV) in which various ligands are bonded to a titanium atom.

[0028]

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Wherein the hydrogen atom of the phthalocyanine ring is
X may be substituted with a halogen atom, a lower alkyl group, a nitro group, etc., X represents an alkoxy group which may have a substituent, a halogen atom, an oxygen atom, and n is 1 or 2
Represents an integer. However, when X is a dialcolate coordinated to a titanium atom with two oxygen atoms, or when it is an oxygen atom, n represents 1. ).

Among these titanium phthalocyanine compounds, titanium phthalocyanine compounds in which an oxygen atom or an alkoxy group is coordinated to a titanium atom as a central metal, wherein the phthalocyanine ring has no substituent or is partially substituted with a halogen atom Preferred are titanium phthalocyanine compounds. The titanium phthalocyanine compound to which an alkoxy group is coordinated may be a compound represented by the general formula (V) having a cyclic butylene glycolate structure:

[0031]

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(Wherein the hydrogen atom of the phthalocyanine ring may be substituted by a halogen atom, a lower alkyl group, a nitro group, etc.) and the general formula (VI)

[0033]

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(Wherein the hydrogen atom of the phthalocyanine ring may be substituted with a halogen atom, a lower alkyl group, a nitro group or the like).

Further, the titanium phthalocyanine compound used in the present invention has an X-ray diffraction spectrum with respect to Cu-Kα of at least 7.5 with a Bragg angle (2θ ± 0.2 °).
{1, 8.3}, 9.5} and 27.2}.

The main peak of the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum for Cu-Kα in the present invention means that the Bragg angle (2θ ± 0.2 °) is at least in the range of 7 to 30 °. Preferably, in the X-ray diffraction spectrum measured in the range of 3 ° to 35 °, the intensity of the diffraction intensity of 50% or more with respect to the peak having the highest diffraction intensity and the peak having the highest diffraction intensity excluding background noise. And preferably a peak having the highest diffraction intensity. In this case, the tube voltage, tube current, scanning speed, slit width, and the like of the X-ray diffraction spectrum measuring device can be appropriately selected and measured.

The method for producing the titanium phthalocyanine compound used in the present invention is not particularly limited. For example, a titanium compound such as titanium tetrahalide or titanium tetraalkoxide, an o-phthalonitrile derivative or diiminoiso The titanium phthalocyanine compound obtained by the coupling reaction with the indolenine derivative can be produced by hydrolyzing, reacting with an alcohol, or the like, if necessary.

Further, if necessary, the synthesized titanium phthalocyanine compound is purified by recrystallization, solvent washing, hot suspension, solvent extraction, sublimation, acid slurry, acid paste, or the like, or the particle size is reduced by grinding or the like. It may be controlled or crystal converted by a physical method or a chemical method.

As a method of crystal transformation, a method of sublimating, pulverizing, pulverizing a titanium phthalocyanine compound by an acid slurry, an acid paste, or the like, followed by an organic solvent treatment, and, if necessary, in the presence of an organic substance or an inorganic salt. Examples of the method include a method of mechanical grinding, a method of performing crystal conversion by a reaction between a titanium phthalocyanine compound and an organic compound, and the like, but are not necessarily limited to these examples.

In the X-ray diffraction spectrum of Cu-Kα used in the present invention, the Bragg angle (2θ ± 0.2 °)
A method for producing a titanium phthalocyanine compound having a main peak at 7.5 °
No. 21050, which can be produced by hydrolyzing dichlorotitanium phthalocyanine obtained by reacting titanium tetrachloride and phthalodinitrile in an α-chloronaphthalene solvent with concentrated aqueous ammonia or the like,
Subsequently, a method of treating with an electron-donating solvent such as 2-ethoxyethanol, diglyme, dioxane, tetrahydrofuran, N, N-dimethylformaldehyde, N-methylpyrrolidone, pyridine, morpholine and the like can be mentioned. By using the titanium phthalocyanine compound obtained by this method as a charge generation material, the photoconductive layer on the conductive support has a Bragg angle (2θ ± 0.2 °) of 7, in the X-ray diffraction spectrum of Cu-Kα. 5
An electrophotographic photoreceptor having a main peak can be produced.

In the X-ray diffraction spectrum of Cu-Kα used in the present invention, the Bragg angle (2θ ± 0.
As a method for producing a titanium phthalocyanine compound having a main peak at 8.3% in 2)), for example, a method described in JP-A-8-82942, namely, 20 parts by weight of α-form titanyl phthalocyanine and (2R, 3R) −2,3-
A method in which 2.2 parts by weight of butanediol is reacted in α-chloronaphthalene while heating and stirring, and the resulting crystals are washed with benzene, methanol, dimethylformamide and water in that order, and then dried under reduced pressure. By using the titanium phthalocyanine compound obtained by this method as a charge generating material, the photoconductive layer on the conductive support has a Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum of Cu-Kα. An electrophotographic photoreceptor having a main peak at 3 ° can be produced.

In the X-ray diffraction spectrum of Cu-Kα used in the present invention, the Bragg angle (2θ ± 0.
The method for producing a titanium phthalocyanine compound having a main peak at 9.5 ° in 2)) includes, for example, (1)
The method described in JP-A-3-200790, that is, dichlorotitanium phthalocyanine is produced by reacting titanium tetrachloride and phthalodinitrile in an inert solvent such as α-chloronaphthalene at 160 to 300 ° C. Titanium phthalocyanine obtained by hydrolyzing dichlorotitanium phthalocyanine with a base or water can be immiscible with water, such as dichloroethane, in the presence of water, directly or from amorphous obtained by dissolving in sulfuric acid and pouring into water. Treatment with a neutral organic solvent,

(2) The method described in JP-A-5-320167, that is, titanium tetrachloride and phthalodinitrile are converted to α
-In an insoluble high boiling solvent such as chloronaphthalene
A method of hydrolyzing dichlorotitanium phthalocyanine obtained by reacting at 300 ° C. with a base or water,

(3) The method described in JP-A-8-82942, ie, 20 parts by weight of α-form titanyl phthalocyanine and 4.4 parts by weight of (2R, 3R) -2,3-butanediol or (2S, 3S) A method comprising reacting 4.4 parts by weight of 2,3-butanediol in α-chloronaphthalene with heating and stirring, washing the crystals obtained in this order with benzene, methanol, dimethylformamide and water, and then drying under reduced pressure. And the like. By using the titanium phthalocyanine compound obtained by these methods as a charge generation material, the photoconductive layer on the conductive support is
An electrophotographic photosensitive member having a main peak at 9.5 ° of the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum with respect to Kα can be produced.

In the X-ray diffraction spectrum of Cu-Kα used in the present invention, the Bragg angle (2θ ± 0.
As a method for producing a titanium phthalocyanine compound having a main peak at 27.2 ° in 2)), for example, a method described in JP-A-1-17066, that is, α-type titanyl phthalocyanine is subjected to 50 to 180 ° C., preferably 60 to 180 ° C. ~
For example, a method of milling with stirring or mechanical strain for a time sufficient for crystal transformation at 130 ° C. may be used. By using the titanium phthalocyanine compound obtained by this method as a charge generation material, the photoconductive layer on the conductive support has a Bragg angle (2θ ± 0.2 °) of 2 in the X-ray diffraction spectrum for Cu-Kα.
An electrophotographic photosensitive member having a main peak at 7.2 ° can be produced.

In the electrophotographic photoreceptor of the present invention, a titanium phthalocyanine compound is used as a charge generating material, but other charge generating materials may be used as long as the characteristics of high sensitivity to a long wavelength light source near 700 nm are not impaired. Can also be used in combination therewith.

Other charge generating materials include, for example, metal-free phthalocyanine compounds, aluminum, indium,
Gallium, magnesium, copper, metal phthalocyanine compounds such as vanadium, azo pigments, anthraquinone pigments, perylene pigments, polycyclic quinone pigments, squarium pigments and the like, but are not limited to these examples Not something.

In the distyryl compound represented by the general formula (I) used in the present invention, R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ and R ⁶ are a hydrogen atom; a methyl group, an ethyl group, n-
Propyl group, iso-propyl group, n-butyl group, is
an alkyl group such as an o-butyl group; an alkyl group having a substituent such as a methoxymethyl group and an ethoxymethyl group; an alkoxy group such as a methoxy group and an ethoxy group; a halogen atom such as a chlorine atom and a bromine atom. Among these, a hydrogen atom, a methyl group and a methoxy group are particularly preferred. Also,
A in the distyryl compound represented by the general formula (I)
Examples of the substituent of the phenyl group which may have a substituent represented by r ¹ , Ar ² , Ar ³ and Ar ⁴ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group,
alkyl groups such as n-butyl group and iso-butyl group; alkyl groups having a substituent such as methoxymethyl group and ethoxymethyl group; alkoxy groups such as methoxy group and ethoxy group; halogen atoms such as chlorine atom and bromine atom Of these, a methyl group, an ethyl group, an n-propyl group, a methoxy group, and a chlorine atom are particularly preferable.

The method for producing the distyryl compound represented by the general formula (I) used in the present invention is disclosed in
U.S. Pat. No. 3,873,3 corresponding to US Pat.
As described in the specification of No. 12, there may be mentioned a method in which a corresponding alkyl phosphite is reacted with an appropriate aldehyde in the presence of a strong base to synthesize a distyryl compound. However, it is not limited to this synthesis method.

Representative distyryl compounds represented by the general formula (I) used in the present invention are shown in Table 1 below.
To (Table 4), but are not limited to these exemplified compounds. In addition, n-Pr in the following table
Represents an n-propyl group, and the numbers described in the table represent the numbers of the exemplified compounds.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

[Table 7]

[0058]

[Table 8]

[0059]

[Table 9]

[0060]

[Table 10]

As the charge transporting material used in the photoconductive layer of the electrophotographic photosensitive member of the present invention, at least one kind of the compound represented by the above general formula (I) is used, provided that the characteristics thereof are not impaired. Other charge transport materials can be used in combination.

Examples of charge transport materials that can be used in combination include arylamine, hydrazone, pyrazoline, and the like.
Oxazole, oxadiazole, thiazole,
Examples thereof include carbazole-based, diphenoquinone-based, arylmethane-based compounds, and polymerizable compounds such as poly-N-vinylcarbazole and polysilane. Among these charge-transporting materials that can be used in combination, an arylamine-based compound having a terphenyl skeleton and / or an arylamine having a specific distyryl skeleton are preferable. Specifically, the following general formula (II)

[0063]

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(Wherein Ar ⁵ and Ar ⁶ each independently represent a phenyl group which may have a substituent) and a compound represented by the general formula (III)

[0065]

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(Where R⁷, R⁸And R⁹Are independent
Hydrogen atom, an alkyl group which may have a substituent,
An alkoxy group or a halogen atom which may have a substituent
Represents a child, R^TenAnd R¹²Are each independently substituted
An optionally substituted alkyl group, R ¹¹And R¹³Are independent
An alkyl group or a substituent which may have a substituent
Represents a phenyl group which may be possessed, and n is 1 to 4
Represents an integer. The compounds of the formula (1) are particularly preferred.

In the compound represented by the general formula (II), the phenyl group which may have a substituent represented by Ar ⁵ and Ar ⁶ may be a methyl group, an ethyl group,
n-propyl group, iso-propyl group, n-butyl group,
alkyl groups such as an iso-butyl group; alkyl groups having a substituent such as a methoxymethyl group and an ethoxymethyl group; alkoxy groups such as a methoxy group and an ethoxy group; halogen atoms such as a chlorine atom and a bromine atom; Among them, a methyl group, an ethyl group, an n-propyl group, a methoxy group and a chlorine atom are particularly preferable.

R ⁷ , R ⁸ and R ⁹ in the distyryl compound represented by the general formula (III) are a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group,
alkyl groups such as n-butyl group and iso-butyl group; alkyl groups having a substituent such as methoxymethyl group and ethoxymethyl group; alkoxy groups such as methoxy group and ethoxy group; halogen atoms such as chlorine atom and bromine atom. is there.
Among these, a hydrogen atom, a methyl group and a methoxy group are particularly preferred.

Further, R ¹⁰ and R ¹² in the distyryl compound represented by the general formula (III) represent a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and an iso-butyl group. Alkyl group; an alkyl group having a substituent such as a methoxymethyl group or an ethoxymethyl group. Among them, methyl group, ethyl group, n-
A propyl group, an iso-propyl group and an n-butyl group are particularly preferred. R ¹¹ and R ¹³ in the distyryl compound represented by the general formula (III) are alkyl groups such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group and iso-butyl group; An alkyl group having a substituent such as a methoxymethyl group or an ethoxymethyl group; a phenyl group; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group or an iso-butyl group; A methyl group, an alkyl group having a substituent such as an ethoxymethyl group, a methoxy group,
It is a phenyl group substituted by an alkoxy group such as an ethoxy group, or a halogen atom such as a chlorine atom or a bromine atom. Among these, a phenyl group; a phenyl group substituted by a methyl group, an ethyl group, an n-propyl group, a methoxy group, or the like is particularly preferable.

As a method for producing the compound represented by the general formula (II), for example, a method described in JP-A-7-48324, that is, a terphenyl halide and an appropriate arylamine are reacted with a copper catalyst and a base React in the presence,
And a method of preparing a terphenyl derivative. However, it is not limited to this synthesis method.

As a method for producing the compound represented by the general formula (III), as described in US Pat. No. 3,873,312 corresponding to JP-A-50-31773, And a method of reacting an alkyl phosphite with a suitable aldehyde in the presence of a strong base to synthesize a distyryl compound. However, it is not limited to this synthesis method.

Typical compounds represented by the general formula (II) used in the electrophotographic photoreceptor of the present invention are shown in the following (Table 5), and typical compounds represented by the general formula (III) are shown below. These are shown in the following (Table-6) to (Table-17), but are not limited to these examples. In the table below, n-Pr represents an n-propyl group, and the numbers described in the table represent the numbers of the exemplified compounds.

[0073]

[Table 11]

[0074]

[Table 12]

[0075]

[Table 13]

[0076]

[Table 14]

[0077]

[Table 15]

[0078]

[Table 16]

[0079]

[Table 17]

[0080]

[Table 18]

[0081]

[Table 19]

[0082]

[Table 20]

[0083]

[Table 21]

[0084]

[Table 22]

[0085]

[Table 23]

[0086]

[Table 24]

[0087]

[Table 25]

[0088]

[Table 26]

[0089]

[Table 27]

[0090]

[Table 28]

[0091]

[Table 29]

[0092]

[Table 30]

[0093]

[Table 31]

[0094]

[Table 32]

[0095]

[Table 33]

[0096]

[Table 34]

[0097]

[Table 35]

[0098]

[Table 36]

When these charge transporting materials are used in combination with the distyryl compound represented by the general formula (I), the content of the distyryl compound represented by the general formula (I) in the total charge transporting material is determined by weight. A range of 20-90% is preferred, and a range of 50-80% is particularly preferred. In this case, the total content of the compounds represented by the general formulas (II) and (III) in the entire charge transporting material is 1% by weight.
A range of 0 to 80% is preferable, and a range of 20 to 50% is particularly preferable.

The electrophotographic photoreceptor of the present invention comprises a photoconductive layer containing a charge generating material and a charge transporting material formed on a conductive support. The structure may take various structures. it can. Examples thereof are shown in FIGS.

The electrophotographic photoreceptor shown in FIGS. 1 and 2 has a charge generation layer 2 mainly composed of a charge generation material on a conductive support 1,
A photoconductive layer 4a or 4b comprising a charge transport layer 3 containing a charge transport material is provided. The electrophotographic photoreceptor of FIG. 3 has a photoconductive layer 4c in which a charge generation material 5 is dispersed in a charge transfer medium 6 on a conductive support 1.

In the case of the electrophotographic photosensitive members shown in FIGS. 1 and 2, the charge generation material contained in the charge generation layer 2 generates charges, while the charge transport layer 3 receives injection of charges and transports them. That is, the charge necessary for light attenuation is generated by the charge generating material, and the charge is transported by the charge transport medium.
In the case of the electrophotographic photoreceptor of FIG. 3, the charge generating material generates a charge with respect to light, and the charge is transferred by the charge transfer medium.

The electrophotographic photoreceptor shown in FIG. 1 has a charge generation layer composed of a vapor deposition film of a charge generation material or a fine particle of the charge generation material in a solvent in which a binder resin is dissolved, if necessary, on a conductive support. A charge generation layer obtained by coating and drying a dispersion obtained by dispersing the charge transport material is applied, and a solution in which the charge transport material is dissolved in a solvent or a binder resin solution as required is coated on the charge generation layer. And by forming a charge transport layer by drying.

The electrophotographic photoreceptor shown in FIG. 2 is obtained by applying a solution of a charge transporting material in a solvent or, if necessary, a binder resin solution on a conductive support, applying the solution on the conductive support, and drying the solution. Forming a charge transport layer, and on the charge transport layer,
Forming a charge generation layer composed of a vapor deposition film of a charge generation material, or a charge generation layer obtained by applying and drying a dispersion obtained by dispersing fine particles of a charge generation material in a solvent or a binder resin solution. Can be manufactured.

The electrophotographic photosensitive member shown in FIG. 3 is obtained by dispersing fine particles of a charge generating material in a solution in which a charge transporting material is dissolved in a solvent or, if necessary, a binder resin solution, on a conductive support.
It can be manufactured by applying and drying this on a conductive support to form a photoconductive layer.

In the case of the electrophotographic photosensitive members shown in FIGS. 1 and 2, the thickness of the photoconductive layer is preferably 5 μm or less, more preferably 0.01 to 2 μm.
The thickness of the charge transport layer is preferably in the range of 3 to 50 μm,
A range of 5 to 35 μm is particularly preferred. In the case of the electrophotographic photoreceptor of FIG. 3, the thickness of the photoconductive layer is preferably in the range of 3 to 50 μm, particularly preferably in the range of 5 to 35 μm.

The proportion of the charge transporting material in the charge transporting layer in the electrophotographic photosensitive members shown in FIGS. 1 and 2 is preferably in the range of 10 to 100% by weight, particularly preferably in the range of 30 to 80% by weight. The ratio of the binder resin in the charge transport layer of the electrophotographic photosensitive member of FIGS. 1 and 2 is preferably in the range of 0 to 90% by weight, and particularly preferably in the range of 20 to 70% by weight. The ratio of the charge generation material in the charge generation layer of the electrophotographic photosensitive member of FIGS. 1 and 2 is preferably in the range of 5 to 100% by weight,
A range of 80% by weight is particularly preferred. The ratio of the charge transport material in the photoconductive layer of the electrophotographic photoreceptor in FIG. 3 is preferably in the range of 5 to 80% by weight, and the ratio of the binder resin in the photoconductive layer is
The range of 0 to 94% by weight is preferable, and the ratio of the charge generation material in the photoconductive layer is preferably in the range of 1 to 70% by weight.
Particularly preferred is a range of ５０50% by weight. 1 to 3
In any of the above electrophotographic photoreceptors, a plasticizer and a sensitizer can be used together with the binder resin.

The conductive support used in the electrophotographic photosensitive member of the present invention includes, for example, aluminum, copper, zinc,
Stainless steel, chrome, titanium, nickel, molybdenum,
Metals or alloys such as vanadium, indium, gold, platinum, etc.
Alternatively, a conductive compound such as a conductive polymer or indium oxide; paper, a plastic film, ceramics or the like coated, vapor-deposited or laminated with a metal or alloy such as aluminum, palladium, or gold, and the like; The body surface may be subjected to a chemical or physical treatment.

Although the shape of the electrophotographic photosensitive member of the present invention varies depending on the support used, various shapes such as a drum shape, a flat plate shape, a sheet shape, and a belt shape are possible.

The binder resin used as necessary for the charge transport layer of the electrophotographic photosensitive member of the present invention is preferably a high molecular polymer which is hydrophobic and can form an electrically insulating film. Examples of such a high-molecular polymer include polycarbonate, polyarylate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, and 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,
And polysulfone.

Among these binder resins, polycarbonate and polyarylate are preferable because they can form a highly durable photoconductive layer. Particularly, (1) the general formula (VI)
I)

[0112]

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(Wherein the hydrogen atom on the aromatic ring may be substituted with a halogen atom or a substituted or unsubstituted alkyl group;
R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group. (2) a polycarbonate having a repeating unit represented by the general formula (VIII):

[0114]

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(Wherein the hydrogen atom on the aromatic ring may be substituted with a halogen atom or a substituted or unsubstituted alkyl group;
Z represents a group of atoms necessary to form a substituted or unsubstituted carbon ring and a substituted or unsubstituted heterocyclic ring. And (3) a repeating unit represented by formula (VII) and a repeating unit represented by formula (I)
X)

[0116]

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(Wherein the hydrogen atom on the aromatic ring may be substituted with a halogen atom or a substituted or unsubstituted alkyl group). The copolymerized polycarbonate having a repeating unit represented by the formula (I) Is more preferable as a resin that dissolves the compound.

These binder resins can be used alone or as a mixture of two or more kinds.

The binder resin used in the charge generation layer of the electrophotographic photoreceptor of the present invention, if necessary, is preferably a polymer compound which is hydrophobic and can form an electrically insulating film. The same binder resin as obtained by dissolving the material is preferable.

Further, the film forming property, flexibility,
In order to improve the mechanical strength, well-known additives such as a plasticizer and a surface modifier can be used together with these binder resins.

Examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, p-terphenyl,
Dibutyl phthalate, diethyl glycol phthalate,
Examples include dioctyl phthalate, triphenylphosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, various fluorohydrocarbons, and the like.

Examples of the surface modifier include silicone oil, fluororesin and the like.

As the sensitizer used as necessary in the photoconductive layer, any known sensitizer can be used.

Examples of the sensitizer include chloranil, tetracyanoethylene, methyl violet, rhodamine B, cyanine dye, merocyanine dye, pyrylium dye, and thiapyrylium dye.

Further, in the electrophotographic photoreceptor of the present invention, in order to improve the storage stability, durability and environmental resistance, the photoconductive layer contains a deterioration inhibitor such as an antioxidant or a light stabilizer. It can also be done. Examples thereof include phenol compounds, hydroquinone compounds, and amine compounds.

Further, in the electrophotographic photoreceptor of the present invention, in order to improve the adhesion between the conductive support and the photoconductive layer, or to prevent the injection of free charges from the conductive support into the photoconductive layer. If necessary, an adhesive layer or a barrier layer may be provided between the conductive support and the photoconductive layer.

The materials used for these layers include, in addition to the high molecular compounds used for the binder resin, casein, gelatin, ethyl cellulose, nitrocellulose,
Carboxy-methylcellulose, vinylidene chloride-based polymer latex, styrene-butadiene-based polymer latex, polyvinyl alcohol, polyamide, polyurethane, phenolic resin, aluminum oxide, tin oxide,
Titanium oxide and the like are mentioned, and the film thickness is desirably 1 μm or less.

When the laminated electrophotographic photosensitive member is formed by coating, the solvent for dissolving the binder resin varies depending on the type of the binder resin, but it is desirable to select a solvent that does not dissolve the lower layer. Examples of specific organic solvents include:
For example, alcohols such as methanol, ethanol and n-propanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; tetrahydrofuran, dioxane, methyl cellosolve and the like Ethers; esters such as methyl acetate and ethyl acetate;
Sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane; aliphatic halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and trichloroethane; and aromatics such as benzene, toluene, xylene, monochlorobenzene and dichlorobenzene.

As the coating method, for example, a coating method such as a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, and a curtain coating method may be used. it can.

The electrophotographic photoreceptor of the present invention provided with a photoconductive layer containing a specific charge generating material and a specific charge transporting material has the above-described structure, and is apparent from the following examples. As described above, the electrophotographic photoreceptor is excellent in high sensitivity and stability of electric characteristics during repeated use.

[0131]

EXAMPLES Hereinafter, examples of the synthesis of the charge generating material and the charge transport material used in the present invention and examples of the electrophotographic photoreceptor of the present invention will be described, but the present invention is limited to the following examples. is not. In the following examples, “parts” means “parts by weight” unless otherwise specified.

<< Synthesis of Titanium Phthalocyanine Compound >><Synthesis Example 1> A method described in JP-A-61-239248, ie, phthalodinitrile 40 g, titanium tetrachloride 18
g and α-chloronaphthalene in a mixture of 500 ml were heated and stirred at 240 to 250 ° C. for 3 hours in a nitrogen stream to complete the reaction. The reaction mixture was filtered to obtain dichlorotitanium phthalocyanine. The obtained dichlorotitanium phthalocyanine was mixed with 300 ml of concentrated aqueous ammonia and pyridine 3
The mixture was heated and refluxed together with 00 ml for 1 hour to obtain an oxytitanium phthalocyanine compound having a spectrum shown in FIG. 4 in powder X-ray diffraction using Cu-Kα ray.

<Synthesis Example 2> A method described in JP-A-5-320167, that is, 50.9 parts of titanium tetrachloride and 135 parts of orthophthalonitrile were converted to α-chloronaphthalene 11
React at 90-220 ° C for 3 hours in 90 parts, 130 ° C
And washed with α-chloronaphthalene, methanol and hot water to synthesize oxytitanium phthalocyanine.
The synthesized oxytitanium phthalocyanine was subjected to concentrated acid sulfate paste treatment and wet milling treatment in ortho-dichlorobenzene to obtain an oxytitanium phthalocyanine compound having a spectrum shown in FIG. 5 in powder X-ray diffraction by Cu-Kα ray.

<Synthesis Example 3> The method described in JP-A-8-82942, that is, 20 parts of oxytitanium phthalocyanine obtained in Synthesis Example 1 and 4.4 parts of (2R, 3R) -2,3-butanediol were used. And 240 hours of α-chloronaphthalene while stirring at 195 to 205 ° C. for 1.5 hours. The reaction mixture was cooled to room temperature, filtered, and the residue was washed with benzene, methanol, dimethylformamide (hereinafter, referred to as DMF) and water in that order, and dried under reduced pressure to obtain a powder X by Cu-Kα radiation. A titanium phthalocyanine compound showing the spectrum of FIG. 6 in the line diffraction was obtained.

<Synthesis Example 4> 20 parts of oxytitanium phthalocyanine obtained in Synthesis Example 1 and 2.2 parts of (2R, 3R) -2,3-butanediol obtained in the method described in JP-A-8-82942 were used. And 240 hours of α-chloronaphthalene at 195 to 205 ° C. with stirring for 1.5 hours. After cooling the reaction mixture to room temperature, it was filtered off, and the residue was washed with benzene, methanol, DMF, and water in this order,
By drying under reduced pressure, a titanium phthalocyanine compound having a spectrum shown in FIG. 7 in powder X-ray diffraction by Cu-Kα ray was obtained.

<Synthesis Example 5> The method described in JP-A-2-28265, that is, 7.6 parts of titanium tetrachloride and 20.4 parts of orthophthalonitrile were reacted in 50 parts of quinoline at 200 ° C. for 2 hours. After the completion of the reaction, the solvent was removed, and the residue was purified with an aqueous hydrochloric acid solution and an aqueous sodium hydroxide solution, and washed with methanol and dimethylformamide to obtain oxytitanium phthalocyanine. The oxytitanium phthalocyanine thus obtained is treated with concentrated sulfuric acid paste and treated with tetrahydrofuran (hereinafter, referred to as THF) to obtain an oxytitanium phthalocyanine compound having a spectrum shown in FIG. 8 in powder X-ray diffraction by Cu-Kα radiation. I got

<< Synthesis of Distyryl Compound Represented by General Formula (I) >><Synthesis Example 6> (Synthesis of Exemplified Compound (I-3)) The method described in JP-A-50-31773, that is, α,
13.3 g of α'-dibromo-m-xylene and 33.3 g of triethyl phosphite were removed from 90 to 90 while removing low boiling components.
Heat at 120 ° C. for 6 hours. Excess triethyl phosphite was distilled off from the reaction mixture, and 10.7 g of an alkyl phosphite derivative was obtained by distillation under reduced pressure. 3 g of the alkyl phosphite derivative and 5.6 g of 4- (N, N-bis (4-methylphenyl) amino) benzaldehyde are dissolved in 42 g of dehydrated dimethylformamide, and the solution is dissolved in a water bath.
While keeping the temperature at not more than ° C, 2.1 g of potassium tert-butoxide was gradually added. After stirring at room temperature for 10 hours,
The solution was poured into 400 g of ion-exchanged water. The yellow precipitate was collected by suction filtration and collected by filtration, washed with water, dried and then concentrated in a solvent to obtain 5.7 g of a fluorescent yellow solid. The compound was purified by silica gel column chromatography (developing solvent = methylene chloride / hexane mixed solvent) to give Exemplified Compound (I-3).
3.6 g were obtained.

<Synthesis Example 7> According to Synthesis Example 6, α, α ′
4,6-bis (chloromethyl) -m-xylene is used instead of -dibromo-m-xylene, and 4- (N, 4,4) is used instead of 4- (N, N-bis (4-methylphenyl) amino) benzaldehyde. The exemplary compound (I-59) was synthesized using N-bis (4-methylphenyl) amino) -2-methylbenzaldehyde. FIG. 9 shows an infrared spectrum of the exemplified compound (I-59), and FIG. 1 shows a ¹ H-NMR spectrum thereof.
0.

<Example 1> 2 parts of the titanium phthalocyanine compound obtained in Synthesis Example 1 and 2 parts of butyral resin ("ESLEC BH-3" manufactured by Sekisui Chemical Co., Ltd.) were mixed with 66 parts of methylene chloride and 1,1,2. The mixture was added to a mixed solvent consisting of 99 parts of trichloroethane, dispersed and mixed with a paint conditioner to obtain a charge generation material dispersion.

FIG. 11 shows an X-ray diffraction spectrum of a thin film having a thickness of 5 μm obtained by dip-coating the thus-obtained dispersion of the charge-generating material on a thin metal plate and drying.

The thus-obtained charge-generating material dispersion was applied onto a polyester film on which aluminum had been vapor-deposited using a wire bar so that the film thickness after drying was 0.3 μm. A generating layer was formed.

On this charge generation layer, 8 parts of the charge transport material of the exemplified compound (I-59) obtained in Synthesis Example 7 and the following structural formula (X)

[0143]

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Polycarbonate having a repeating unit represented by the formula (Iupilon Z20 manufactured by Mitsubishi Gas Chemical Company, Inc.)
0 ") A charge transport layer forming coating solution in which 10 parts were dissolved in a mixed solvent consisting of 54 parts of methylene chloride and 36 parts of chlorobenzene was applied so that the film thickness after drying was 20 μm, and dried to dry the charge transport. The layers were formed to obtain an electrophotographic photosensitive member having the layer configuration shown in FIG.

<Example 2> In Example 1, 6 parts of Exemplified Compound (I-41) and 6 parts of Exemplified Compound (II-I) were used in place of 8 parts of Exemplified Compound (I-59) used as the charge transporting material.
5) Using 2 parts, instead of 10 parts of a polycarbonate having a repeating unit represented by the structural formula (X) (“Iupilon Z200” manufactured by Mitsubishi Gas Chemical Company), the structural formula (X)
I)

[0146]

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Polycarbonate having a repeating unit represented by the formula (“PANLITE C140” manufactured by Teijin Chemicals Limited)
0 "), and instead of 36 parts of chlorobenzene, 1,1,2-
An electrophotographic photosensitive member was obtained in the same manner as in Example 1, except that 36 parts of trichloroethane was used.

<Example 3> In Example 1, 6 parts of the exemplified compound (I-59) and 6 parts of the exemplified compound (III) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
-32) An electrophotographic photosensitive member was obtained in the same manner as in Example 1, except for using 2 parts.

Example 4 In Example 1, 6 parts of the exemplified compound (I-59) and 6 parts of the exemplified compound (III) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
-152) An electrophotographic photosensitive member was obtained in the same manner as in Example 1, except that 2 parts were used.

Example 5 In Example 1, 7 parts of the exemplified compound (I-59) and 7 parts of the exemplified compound (III) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
-150) An electrophotographic photosensitive member was obtained in the same manner as in Example 1, except that 1 part was used.

Example 6 In Example 1, the titanium phthalocyanine compound obtained in Synthesis Example 2 was used instead of the titanium phthalocyanine compound obtained in Synthesis Example 1 used as a charge generation material, and used as a charge transporting material. Instead of 8 parts of the exemplary compound (I-59), the exemplary compound (I-4)
1) An electrophotographic photosensitive member was obtained in the same manner as in Example 1 except that 8 parts were used.

The dispersion of the charge generation material used in Example 6 was dip-coated on a thin metal plate and dried to obtain a film having a thickness of 5 μm.
The X-ray diffraction spectrum of the thin film of m is shown in FIG.

Example 7 In Example 6, 6 parts of the exemplified compound (I-59) and 6 parts of the exemplified compound (III) were used instead of 8 parts of the exemplified compound (I-41) used as the charge transporting material.
-32) Using two parts, instead of a polycarbonate having a repeating unit represented by the structural formula (X) (“Iupilon Z200” manufactured by Mitsubishi Gas Chemical Company), the following structural formula (XI)
I)

[0154]

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An electrophotographic photoreceptor was prepared in the same manner as in Example 6 except that a copolymerized polycarbonate having a repeating unit represented by the formula (XI) and a repeating unit represented by the structural formula (XI) in a ratio of 86:14 was used. Obtained.

<Example 8> In Example 1, the titanium phthalocyanine compound obtained in Synthesis Example 3 was replaced with 2 parts of the titanium phthalocyanine compound obtained in Synthesis Example 1 used as a charge generation material, and a structural formula (X ), The repeating unit represented by the structural formula (XII) and the repeating unit represented by the structural formula (XI) are 86 to 14 in place of the polycarbonate (“Iupilon Z200” manufactured by Mitsubishi Gas Chemical Company). Except for using a copolymerized polycarbonate having a ratio of
An electrophotographic photosensitive member was obtained.

The dispersion of the charge generation material used in Example 8 was dip-coated on a thin metal plate and dried to obtain a film having a thickness of 5 μm.
X-ray diffraction spectrum of the thin film of m is shown in FIG.

Example 9 In Example 8, 6 parts of the exemplified compound (I-59) and 6 parts of the exemplified compound (II-I) were used in place of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
5) An electrophotographic photosensitive member was obtained in the same manner as in Example 8, except that 2 parts were used.

<Example 10> In Example 8, 6 parts of the exemplified compound (I-59) and 6 parts of the exemplified compound (III) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
-152) An electrophotographic photosensitive member was obtained in the same manner as in Example 8, except that 2 parts were used.

<Example 11> In Example 8, 4 parts of the exemplified compound (I-41) and 4 parts of the exemplified compound (III) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
-132) An electrophotographic photosensitive member was obtained in the same manner as in Example 8, except that 4 parts were used.

Example 12 Example 8 was repeated, except that the titanium phthalocyanine compound obtained in Synthesis Example 4 was used in place of the titanium phthalocyanine compound obtained in Synthesis Example 3 used as the charge generation material. In the same manner as in the above, an electrophotographic photoreceptor was obtained.

Further, the charge generation material dispersion liquid used in Example 12 was dip-coated on a thin metal plate and dried to obtain a film thickness of 5 μm.
FIG. 14 shows the X-ray diffraction spectrum of the μm thin film.

<Example 13> In Example 12, 6 parts of the exemplified compound (I-59) and 6 parts of the exemplified compound (II) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
-5) In the same manner as in Example 12 except that 2 parts were used,
An electrophotographic photosensitive member was obtained.

Example 14 In Example 12, 6 parts of the exemplified compound (I-59) and 6 parts of the exemplified compound (II) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
I-32) An electrophotographic photosensitive member was obtained in the same manner as in Example 12, except that 2 parts were used.

Example 15 Example 8 was repeated, except that the titanium phthalocyanine compound obtained in Synthesis Example 5 was used in place of the titanium phthalocyanine compound obtained in Synthesis Example 3 used as the charge generating material. An electrophotographic photoreceptor was obtained in the same manner as described above.

The dispersion of the charge generation material used in Example 15 was dip-coated on a thin metal plate and dried to obtain a film having a thickness of 5 μm.
The X-ray diffraction spectrum of the μm thin film is shown in FIG.

Example 16 In Example 15, 4 parts of the exemplified compound (I-59) and 4 parts of the exemplified compound (II) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
I-5) An electrophotographic photoreceptor was obtained in the same manner as in Example 15, except that 4 parts were used.

<Comparative Example 1> In Example 1, the compound represented by the structural formula (XIII) was used in place of the exemplified compound (I-59) used as the charge transporting material.

[0169]

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A charge transporting material represented by
An electrophotographic photoreceptor was obtained in the same manner as in Example 1, except for using (described in No. 125941).

Comparative Example 2 The procedure of Example 1 was repeated, except that the X-type metal-free phthalocyanine was used in place of the titanium phthalocyanine compound obtained in Synthesis Example 1 used as the charge generating material. Thus, an electrophotographic photosensitive member was obtained.

Comparative Example 3 In Example 1, the compound represented by the structural formula (XIV) was used in place of the exemplified compound (I-59) used as the charge transporting material.

[0173]

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An electrophotographic photosensitive member was obtained in the same manner as in Example 1 except that the monostyryl compound represented by the following formula was used.

Comparative Example 4 In Example 1, the compound represented by the structural formula (XV) was used in place of the exemplary compound (I-59) used as the charge transporting material.

[0176]

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An electrophotographic photoreceptor was obtained in the same manner as in Example 1 except that the para-substituted distyryl compound represented by the following formula was used.

In Comparative Example 4, the solubility of the charge transporting material of the structural formula (XV) in the solution for dissolving the charge transporting material was low. Was not obtained.

<Comparative Example 5> In Example 1, a β-type oxytitanium phthalocyanine was used in place of the titanium phthalocyanine compound obtained in Synthesis Example 1 used as a charge generating material, and an example compound (I) was used as a charge transporting material.
-59) In place of 8 parts, the structural formula (XVI)

[0180]

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A distyryl compound represented by
An electrophotographic photoreceptor was obtained in the same manner as in Example 1 except that the compound of Formula IA-17 of JP-118674A) was used.

(Electrophotographic Characteristics) The electrophotographic photoreceptors obtained in Examples 1 to 16 and Comparative Examples 1 to 3 and 5 were subjected to an electrostatic copying paper tester ("EPA 810" manufactured by Kawaguchi Electric Works, Ltd.).
0 ") using a charged by corona discharge -6KV the electrophotographic photosensitive member in the dark to measure the surface potential V ₀ electrophotographic photosensitive member when the (V). Next, leave it in the dark for 10 minutes.
Surface potential V of the electrophotographic photosensitive member when left for 2 seconds
₁₀ (V) was measured. From V ₀ and V ₁₀ , potential holding ratio (%) of the surface potential of the electrophotographic photosensitive member: (V ₁₀ / V ₀ ) × 10
0) was calculated. Furthermore, the wavelength with respect to the surface potential V ₁₀ 78
0 nm, subjected to exposure with light of exposure energy 1μW / cm ^2, the surface potential was determined half decay exposure than the time to half E _1/2 (μJ / cm ²⁾ of V _10. Furthermore, the surface potential 15 seconds after the start of exposure, that is, the residual potential V _R (V)
Was measured.

Table 18 shows the measurement results of darkness and light decay of the surface potential. Table 18 also shows the measurement results immediately after repeating the process of charging, leaving in a dark place for 1 second, exposing for 1 second, and removing static electricity by 300 lux of white light for 0.1 second 100 times.

[0184]

[Table 37]

[0185]

[Table 38]

[0186]

[Table 39]

[0187]

[Table 40]

From the results shown in Table 18, the electrophotographic photoreceptor of the present invention has excellent characteristics such as high potential holding ratio, high sensitivity to a long wavelength light source of 780 nm, and low residual potential. Therefore, it can be understood that the repetition stability is high.

Example 17 A coating material was obtained by dissolving 1 part of a polyamide resin ("Amilan CM-8000" manufactured by Toray Industries, Ltd.) in a mixed solvent consisting of 7 parts of methanol and 7 parts of n-butanol. This coating material was applied on the outer peripheral surface of an aluminum drum having a diameter of 30 mm by a dip coating method so that the film thickness after drying was 1 μm, and dried to form a barrier layer.

Next, a charge generation layer having a thickness of 0.4 μm after drying was formed on the barrier layer by dip coating the charge generation material dispersion used in Example 1.

On this charge generation layer, the exemplary compound (I-
59), 8 parts of the charge transporting material, 0.2 parts of 2,6-di-t-butyl-p-cresol and a polycarbonate having a repeating unit represented by the structural formula (X) (manufactured by Mitsubishi Gas Chemical Company, Inc.). "Iupilon Z200") is coated with a coating material for forming a charge transporting material layer by dissolving 10 parts in a mixture of 54 parts of methylene chloride and 36 parts of chlorobenzene so as to have a dry film thickness of 20 μm. Work,
The resultant was dried to form a charge transport layer, thereby obtaining a drum-shaped electrophotographic photosensitive member.

Example 18 In Example 17, 6 parts of the exemplified compound (I-41) and 6 parts of the exemplified compound (II) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
-5) In the same manner as in Example 17 except that 2 parts were used,
A drum-shaped electrophotographic photosensitive member was obtained.

<Example 19> In Example 17, 4 parts of the exemplified compound (I-59) and 4 parts of the exemplified compound (II) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
I-32) A drum-shaped electrophotographic photosensitive member was obtained in the same manner as in Example 17, except that 4 parts were used.

<Comparative Example 6> In Example 17, the compound (I-59) used as the charge transport material was replaced with the compound (I-59),
Structural formula (XVII)

[0195]

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A drum-shaped electrophotographic photosensitive member was obtained in the same manner as in Example 17 except that the compound represented by the following formula was used.

(Electrical Characteristics) The drum-shaped electrophotographic photosensitive members obtained in Examples 17 to 19 and Comparative Example 6 were mounted on a commercially available laser printer modified machine equipped with a surface electrometer, and the temperature and humidity were changed. To evaluate the potential characteristics.

Table 19 shows the results of the evaluation. 0 in the table
% Potential, 50% potential is 0% halftone dot of laser printer, 50% potential.
% Indicates the surface potential on the electrophotographic photosensitive member at the output of halftone dot.

[0199]

[Table 41]

From the results shown in Table 19, it can be understood that the electrophotographic photoreceptor of the present invention has high sensitivity and stable charging potential and exposure potential due to environmental changes.

<Example 20> In Example 17, the charge generation material dispersion used in Example 1 was used instead of Example 1.
Using the charge generation material dispersion liquid used in 2 above, instead of 10 parts of a polycarbonate having a repeating unit of the above structural formula (X) ("Iupilon Z200" manufactured by Mitsubishi Gas Chemical Company), represented by the above structural formula (XII) Of the repeating unit represented by the formula (XI) and 86: 1
A drum-shaped electrophotographic photosensitive member was obtained in the same manner as in Example 17, except that a copolymerized polycarbonate having a ratio of 4 was used.

<Example 21> In Example 18, 6 parts of the exemplified compound (I-59) and 6 parts of the exemplified compound (II) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
-5) In the same manner as in Example 18 except that 2 parts were used,
A drum-shaped electrophotographic photosensitive member was obtained.

Example 22 In Example 18, 5 parts of the exemplified compound (I-59) and 5 parts of the exemplified compound (II) were used instead of 8 parts of the exemplified compound (I-59) used as the charge transporting material.
I-32) A drum-shaped electrophotographic photosensitive member was obtained in the same manner as in Example 18 except for using 3 parts.

<Comparative Example 7> In Example 18, except that 8 parts of the exemplified compound (I-59) used as the charge transporting material was replaced by 5 parts of the compound represented by the structural formula (XV), In the same manner as in Example 18, a drum-shaped electrophotographic photosensitive member was obtained.

(Image Characteristics) The drum-shaped electrophotographic photosensitive members obtained in Examples 20 to 22 and Comparative Example 7 were mounted on a commercially available laser printer (trade name "LaserJet 4" manufactured by Hewlett-Packard Company) to supply toner. Continuous printing was performed while evaluating the image state. Table 20 summarizes the evaluation results at the initial stage and after the 10,000-sheet printing test.

[0206]

[Table 42]

From the results shown in Table 20, it can be understood that the electrophotographic photosensitive member of the present invention can provide stable and high-quality images in an electrophotographic printer using a semiconductor laser as a light source.

[0208]

The electrophotographic photoreceptor of the present invention has a thickness of 700 nm.
It has high sensitivity to nearby long-wavelength light sources and also maintains high potential stability, which is extremely effective in practice.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view illustrating an example of a layer configuration of an electrophotographic photosensitive member according to the present invention.

FIG. 2 is a schematic cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member according to the present invention.

FIG. 3 is a schematic cross-sectional view illustrating an example of a layer configuration of an electrophotographic photosensitive member according to the present invention.

FIG. 4 is a powder X-ray diffraction spectrum of the titanium phthalocyanine compound obtained in Synthesis Example 1 by Cu-Kα radiation.

FIG. 5 is an X-ray powder diffraction spectrum of the titanium phthalocyanine compound obtained in Synthesis Example 2 by Cu-Kα radiation.

FIG. 6 is a powder X-ray diffraction spectrum of the titanium phthalocyanine compound obtained in Synthesis Example 3 by Cu-Kα radiation.

FIG. 7 is an X-ray powder diffraction spectrum of the titanium phthalocyanine compound obtained in Synthesis Example 4 by Cu-Kα radiation.

FIG. 8 is a powder X-ray diffraction spectrum of the oxytitanium phthalocyanine compound obtained in Synthesis Example 5 by Cu-Kα radiation.

9 is an infrared spectrum diagram of an exemplary compound (I-59) obtained in Synthesis Example 7. FIG.

[10] exemplified compound obtained in Synthesis Example 7 (I-59) ¹
It is an H-NMR spectrum figure.

FIG. 11 is an X-ray diffraction spectrum of a thin film obtained by dip-coating a charge generating material dispersion containing a titanium phthalocyanine compound prepared in Example 1 on a thin metal plate, using Cu-Kα radiation.

FIG. 12 is an X-ray diffraction spectrum of a thin film obtained by dip coating a charge generating material dispersion containing a titanium phthalocyanine compound prepared in Example 6 on a thin metal plate, using Cu-Kα radiation.

FIG. 13 is an X-ray diffraction spectrum of a thin film obtained by dip-coating a charge generating material dispersion containing a titanium phthalocyanine compound prepared in Example 8 on a thin metal plate, using Cu-Kα radiation.

FIG. 14 is an X-ray diffraction spectrum of a thin film obtained by dip-coating a charge generating material dispersion containing a titanium phthalocyanine compound prepared in Example 12 on a thin metal plate, using Cu-Kα radiation.

FIG. 15 is an X-ray diffraction spectrum of a thin film obtained by dip coating a charge generating material dispersion containing a titanium phthalocyanine compound prepared in Example 15 on a thin metal plate, using Cu-Kα radiation.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2 Charge carrier generation layer 3 Charge transport layer 4a Photoconductive layer 4b Photoconductive layer 4c Photoconductive layer 5 Charge carrier generating material 6 Charge transfer medium 7 Electrophotographic photoreceptor

Claims (11)

[Claims] 1. An electrophotographic photosensitive member having a photoconductive layer containing a charge generating material and a charge transporting material on a conductive support, wherein the charge generating material has a Bragg angle (2θ ± 2) in an X-ray diffraction spectrum with respect to Cu-Kα. 0.2%) containing a titanium phthalocyanine compound having a main peak at least in any of 7.5%, 8.3%, 9.5% and 27.2%, and wherein the charge transporting material has the general formula (I) Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a substituent Represents a good alkoxy group or a halogen atom, and represents Ar ¹ , Ar ² , Ar ³ and Ar ⁴
Represents a phenyl group which may have a substituent. An electrophotographic photoreceptor comprising a distyryl compound represented by the formula (1): 2. The method according to claim 1, wherein the charge generation material is X-to-Cu-α.
2. The electrophotographic photoreceptor according to claim 1, wherein the line diffraction spectrum is a titanium phthalocyanine compound having a main peak at 7.5 ° at a Bragg angle (2θ ± 0.2 °). 3. The electron according to claim 1, wherein the charge generation material is a titanium phthalocyanine compound having an X-ray diffraction spectrum with respect to Cu-Kα having a main peak at 8.3 ° at a Bragg angle (2θ ± 0.2 °). Photoreceptor. 4. The X-ray diffraction spectrum of the charge generating material for Cu-Kα shows a Bragg angle (2θ ± 0.2
2. The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor is a titanium phthalocyanine compound having a main peak of 9.5) of ゜). 5. The X-ray diffraction spectrum of the charge generation material for Cu-Kα, the Bragg angle (2θ ± 0.2
2. The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor is a titanium phthalocyanine compound having a main peak at 27.2}. 6. The photoconductive layer has a Bragg angle (2θ ± 0.2 °) of at least 7.5 °, 8.3 °, 9.5 ° and 27.2 ° in an X-ray diffraction spectrum for Cu-Kα. 2. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor has any main peak. 7. The electrophotographic photoreceptor according to claim 2, wherein the photoconductive layer has a main peak at a Bragg angle (2θ ± 0.2 °) of 7.5 ° in an X-ray diffraction spectrum of Cu-Kα. 8. The electrophotograph according to claim 3, wherein the photoconductive layer has a main peak at a Bragg angle (2θ ± 0.2 °) of 8.3 ° in an X-ray diffraction spectrum of Cu-Kα. Photoconductor. 9. The electrophotographic photosensitive material according to claim 4, wherein the photoconductive layer has a main peak at 9.5 ° of Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum with respect to Cu-Kα. body. 10. The X-ray diffraction spectrum of the photoconductive layer for Cu-Kα, the Bragg angle (2θ ± 0.2 °)
7. The electrophotographic photoreceptor according to claim 5, which has a main peak at 27.2 °. 11. The charge transport material further comprises (1) a general formula
(II)(Wherein, Ar^FiveAnd Ar⁶Are each independently substituted
Represents a phenyl group which may be substituted. )
Compound or (2) General formula (III)(Where R⁷, R⁸And R⁹Are independently hydrogen sources
A substituent, an alkyl group which may have a substituent,
Represents an optionally substituted alkoxy group or a halogen atom
Then R^TenAnd R¹²Are each independently having a substituent
A good alkyl group, R ¹¹And R¹³Are each independently substituted
Having an optionally substituted alkyl group or substituent
Represents a phenyl group which may be substituted, and n represents an integer of 1 to 4
I forgot. ).
1, 2, 3, 4, 5, 6, 7, 8, 9 or 10
The electrophotographic photosensitive member according to the above.