JPH1090927A - Electrophotographic photoreceptor and coating liquid for charge transportation layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which has a high sensitivity and a low residual potential and coating liquid for charge transportation of the electrophotographic photoreceptor. SOLUTION: In an electrophotographic photoreceptor having both a charge generating layer including a charge generating substance and a charge transporting layer including a charge transporting substance, on a conductive base material; the charge generating substance contains a phthalocyanine compound including phthalocyanine and the charge transporting substance contains both the electrophotographic photosensitive body including the benzidine derivative expressed by the formula and the charge liquid for charge transportation making the benzidine derivative expressed by the formula as the charge transporting substance. In the formula, R<1> denotes independently a hologen atom, alkyl group, alkoxy group, aryl group, fluoroalkyl group, or fluoroalkoxy group; and two R<2> s denote independently hydrogen atoms or alkyl groups, and m is an integer from 0 to 5, and a plurality of R<1> s may be the same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photosensitive member and a coating solution for a charge transport layer.

[0002]

2. Description of the Related Art As a conventional electrophotographic photosensitive member, selenium (S) of about 50 μm is formed on a conductive substrate such as aluminum.
e) Some films are formed by a vacuum evaporation method, but this Se photoreceptor has a problem that it has sensitivity only up to a wavelength of about 500 nm. Also, 50μ on the conductive substrate
There is a photoreceptor in which a Se layer of about m is formed, and a selenium-tellurium (Se-Te) alloy layer of several μm is further formed thereon, and this photoreceptor has a Te content of the above Se-Te alloy. The higher the spectral sensitivity, the longer the spectral sensitivity extends to longer wavelengths. However, as the amount of Te added increases, the surface charge retention characteristics become poor, and there is a serious problem that the photoconductor can not be practically used.

Further, a charge generation layer is formed by coating a chlorocyan blue or squarylium acid derivative of about 1 μm on an aluminum substrate, and a mixture of a polyvinyl carbazole or pyrazoline derivative having high insulation resistance and a polycarbonate resin is formed thereon. , 10-20 μm
There is also a so-called composite two-layer type photoreceptor in which a charge transport layer is formed by coating, but in reality this photoreceptor does not have sensitivity to light of 700 nm or more.

In recent years, in this composite two-layer type photoreceptor,
The above-mentioned disadvantage has been improved, that is, the semiconductor laser oscillation region 80
Many photoreceptors having sensitivity around 0 nm have been reported,
Many of these use a phthalocyanine pigment as a charge generation material, and provide an insulation between a polyvinyl carbazole, a pyrazoline derivative or a hydrazone derivative and a polycarbonate resin or a polyester resin on a charge generation layer having a thickness of about 0.5 to 1 μm. Mix high resistance mixtures
A charge transport layer is formed by coating with a thickness of 20 μm to form a composite two-layer type photoreceptor.

Examples of the charge transporting material used in the charge transporting layer include hydrazone derivatives described in JP-B-55-42380, enamine derivatives described in JP-A-62-237458, JP-B-59-9049, and JP-A-59-9049. 55-7
940 and JP-A-61-295558, stilbene derivatives of JP-A-58-198043, and triphenylamine derivatives of JP-B-58-32372 and JP-A-61-132555. Etc. are known.

[0006] Benzidine derivatives include N, N,
N ', N'-tetraphenylbenzidine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -benzidine, N, N, N', N'-tetrakis (4-methylphenyl)- Benzidine, N, N'-diphenyl-
N, N'-bis (4-methoxyphenyl) -benzidine, N, N, N ', N'-tetrakis (4-methylphenyl) -tolidine and the like are known, but these benzidine derivatives are relatively Although it has good charge transport ability, it has the disadvantages of low solubility in organic solvents and relatively easy oxidation. That is, it is difficult to prepare a coating solution for forming a charge transport layer due to low solubility in an organic solvent and / or a binder, or crystals of a benzidine derivative are precipitated during coating film formation. There is. Further, even if the charge transport layer can be formed as a good coating film by visual observation, fine crystals of these benzidine derivatives precipitate in the charge transport layer, and as a result, there is a disadvantage that image characteristics are poor.

Therefore, Japanese Patent Laid-Open No. 5-6010 discloses that
High sensitivity and good image using a fluorine-containing N, N, N ', N'-tetraarylbenzidine derivative which is a novel compound which is excellent in solubility in organic solvents and compatibility with a binder such as polycarbonate resin. Electrophotographic photosensitive members having characteristics have been proposed. However, for a laser beam printer or the like that is used for such purpose, an electrophotographic photoreceptor having higher sensitivity, lower residual potential, and good image characteristics has been demanded with higher image quality and higher definition.

[0008] Charge-generating substances in combination with these charge-transporting substances include metal-free phthalocyanines, copper phthalocyanines, aluminum chloride phthalocyanines, chloroindium phthalocyanines, titanyl phthalocyanines,
And metal phthalocyanines such as vanadyl phthalocyanine.

Phthalocyanines not only have different absorption spectra and photoconductivity depending on the type of the central metal, but also have different physical properties depending on the crystal type. Several examples have been reported that have been selected for electrophotographic photoreceptors.
For example, it is reported that titanyl phthalocyanine has various crystal forms, and there is a large difference in chargeability, dark decay rate, sensitivity, and the like depending on the crystal form.

JP-A-59-49544 discloses a crystal form of titanyl phthalocyanine having a Bragg angle (2
θ ± 0.2 degrees), 9.2 degrees, 13.1 degrees, 20.7 degrees,
It is shown that those giving strong diffraction peaks at 26.2 degrees and 27.1 degrees are preferable, and an X-ray diffraction spectrum is shown. The electrophotographic characteristics of the photoreceptor using this crystalline form of titanyl phthalocyanine as a charge generating substance have a dark decay rate (DDR) of 85% and a sensitivity (E _1/2 ) of 0.57 lux · sec. Also, JP-A-59-1669
No. 59, a deposited film of titanyl phthalocyanine was left in saturated steam of tetrahydrofuran for 1 to 24 hours,
The charge generation layer is formed by changing the crystal type.

The X-ray diffraction spectrum has a small number of peaks and a wide width, and has a Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees, 12.6 degrees, 13.0 degrees, and 25.4 degrees. , 2
It is shown to give strong diffraction peaks at 6.2 degrees and 28.6 degrees. The electrophotographic characteristics of a photoreceptor using this crystalline form of titanyl phthalocyanine as a charge generating substance are as follows:
86% dark decay rate (DDR), 0.7 l sensitivity (E _1/2 )
ux · sec.

Japanese Patent Application Laid-Open No. 2-198452 discloses that a crystal form of titanyl phthalocyanine having a main diffraction peak at 27.3 degrees of Bragg angle (2θ ± 0.2 degrees) has high sensitivity (1). 0.7 mJ / m ² ), and as a production method thereof, in a mixed solution of water and o-dichlorobenzene,
Heat stirring at 60 ° C. for 1 hour is shown. Japanese Patent Application Laid-Open No. 2256059/1990 discloses that the crystal form of titanyl phthalocyanine has a Bragg angle (2θ ± 0.
Those having a main diffraction peak at 27.3 ° (2 °) have high sensitivity (0.62 lux · sec), and as a production method, stirring in 1,2-dichloroethane at room temperature was shown. I have. Japanese Patent Application Laid-Open No. Sho 62-194257 discloses that two or more phthalocyanines are used as a mixture, and for example, a mixture of titanyl phthalocyanine and a metal-free phthalocyanine is used as a charge generating substance.

Therefore, in Japanese Patent Application Laid-Open No. 6-17.5382, a phthalocyanine mixture containing titanyl phthalocyanine and a metal phthalocyanine whose trivalent metal is a trivalent metal is precipitated in water by an acid pasting method, and then precipitated with an organic solvent. C, characterized by processing
In the X-ray diffraction spectrum of uKα, the Bragg angle (2
θ ± 0.2 degrees) of 7.5 degrees, 22.5 degrees, 24.3 degrees,
A novel phthalocyanine composition having major diffraction peaks at 25.3 degrees and 28.6 degrees and a method for producing the same have been proposed. JP-A-8-41373 discloses that a phthalocyanine mixture containing titanyl phthalocyanine and a trivalent halogenated metal phthalocyanine as a central metal is precipitated in water by an acid pasting method, and then treated with an organic solvent. In the X-ray diffraction spectrum of CuKα, the Bragg angle (2θ ± 0.2 degrees)
A novel phthalocyanine composition having major diffraction peaks at 9.3 degrees, 13.1 degrees, 15.0 degrees, and 26.2 degrees, and a method for producing the same have been proposed.

These phthalocyanine compositions give a charge-generating substance having high sensitivity and excellent characteristics due to crystal form conversion. However, in a laser beam printer or the like for which the phthalocyanine composition is used, high image quality and high definition are advanced. There is a need for an electrophotographic photoreceptor having higher sensitivity characteristics.

In Japanese Patent Application Laid-Open No. 6-271786, in the X-ray diffraction spectrum of CuKα, the Bragg angles (2θ ± 0.2 degrees) of 7.5 °, 24.2 ° and 2 °
A phthalocyanine composition having a main diffraction peak at 7.3 degrees and a method for producing the same have been proposed, and exhibit higher sensitivity characteristics.

As described above, the electrophotographic characteristics of phthalocyanines greatly differ depending on the crystal type, and the crystal type is an important factor which affects the performance as an electrophotographic photoreceptor. It provides a charge generating material that is very sensitive and exhibits excellent properties. However, in laser beam printers and the like, which are used for such applications, high image quality and high definition have been further advanced, and sensitivity has been further increased.
There is a need for an electrophotographic photoreceptor having low residual potential and good image characteristics. It is also known that the dark decay rate, sensitivity, and residual potential change significantly depending on the combination of a charge generating substance and a charge transporting substance, and in order to find an electrophotographic photoreceptor having these properties balanced, It is necessary to study the combination of the charge generation material and the charge transport material.

[0017]

An object of the present invention is to provide an electrophotographic photosensitive member having high sensitivity and low residual potential. The invention described in claim 2 is claim 1
An object of the present invention is to provide an electrophotographic photoreceptor having the effects of the invention described, exhibiting higher sensitivity and lower residual potential, and further having excellent image characteristics. The third aspect of the present invention is to provide an electrophotographic photoreceptor having the effects of the first aspect of the invention, exhibiting higher sensitivity and lower residual potential, and having better dark decay rate and image characteristics. . The invention described in claim 4 provides the effects of the invention described in claim 1 and provides an electrophotographic photoreceptor that can arbitrarily adjust the sensitivity and has better image characteristics. The invention according to claim 5 provides a coating solution for a charge transport layer of an electrophotographic photoreceptor, which exhibits high sensitivity and low residual potential.

[0018]

According to the present invention, there is provided an electrophotographic photoreceptor having a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance on a conductive substrate.
The charge generating substance contains (A) a phthalocyanine composition containing phthalocyanine, and the charge transporting substance contains (B) a general formula [I]

Embedded image (Wherein, R ¹ each independently represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, and two R ^{2 s} each independently represent a hydrogen atom or an alkyl group Wherein m is an integer of 0 to 5, and a plurality of R ^{1 s} may be the same or different.)

Further, according to the present invention, the phthalocyanine composition (A) has a Bragg angle (2θ ± 0.2 degrees) of 7.5 °, 24.2 ° and 27.3 ° in the X-ray diffraction spectrum of CuKα. And an electrophotographic photoreceptor having a main diffraction peak. In addition, the present invention provides (A) a phthalocyanine composition having a Bragg angle (2θ ± 0.2 degrees) of 17.9 degrees in the X-ray diffraction spectrum of CuKα;
The present invention relates to the electrophotographic photoreceptor having main diffraction peaks at 4.0 degrees, 26.2 degrees and 27.2 degrees. Further, according to the present invention, the charge generation substance has a Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees, 22.5 degrees, 24.3 degrees, 25.3 degrees, and an X-ray diffraction spectrum of CuKα. 2
In the X-ray diffraction spectra of the phthalocyanine composition having a main diffraction peak at 8.6 degrees and CuKα, the Bragg angles (2θ ± 0.2 degrees) of 17.9 degrees, 24.0 degrees,
2. The electrophotographic photosensitive member according to claim 1, comprising a phthalocyanine composition having main diffraction peaks at 6.2 degrees and 27.2 degrees. Further, the present invention relates to a coating liquid for a charge transport layer containing the benzidine derivative (B) represented by the general formula [I] as a charge transport substance.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The electrophotographic photoreceptor of the present invention comprises, on a conductive substrate, a charge generation layer containing a charge generation material containing a phthalocyanine composition containing (A) phthalocyanine; [I]

Embedded image (Wherein, R ¹ each independently represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, and two R ^{2 s} each independently represent a hydrogen atom or an alkyl group Wherein m is an integer of 0 to 5, and a plurality of R ^{1 s} may be the same or different), and has a charge transporting layer containing a charge transporting material containing a benzidine derivative represented by the following formula: is there.

As the conductive base material in the present invention, for example, a metal plate (aluminum, aluminum alloy, steel,
Iron, copper, etc.), metal compound plates (tin oxide, indium oxide, chromium oxide, etc.), conductive particles (carbon black,
A substrate obtained by coating plastic on a plastic together with a suitable binder together with an appropriate binder, etc., or a material obtained by imparting conductivity to a plastic, paper, glass, or the like by vapor deposition, sputtering, or the like. Further, as the shape of these substrates, for example,
Although a cylindrical shape, a sheet, etc. are mentioned, their shape, dimensions, surface roughness and the like are not particularly limited.

The charge generating material in the present invention contains (A) a phthalocyanine composition containing phthalocyanine.
As the raw material phthalocyanine constituting the phthalocyanine composition, a conventionally known phthalocyanine can be used. In the phthalocyanine composition containing (A) phthalocyanine in the present invention, for example, (a) titanyl phthalocyanine as phthalocyanine and (b) 3
A phthalocyanine mixture containing a divalent metal halide phthalocyanine is precipitated in water by an acid pasting method, and a characteristic diffraction peak at a Bragg angle (2θ ± 0.2 degrees) of 27.2 degrees in the X-ray diffraction spectrum of CuKα. After obtaining a precipitate having
It can be obtained by treating in an organic solvent or a mixed solvent of an aromatic organic solvent and water.

In general, a phthalocyanine mixture is a mere physical mixture of two or more phthalocyanines used as raw materials, and the X-ray diffraction pattern of the phthalocyanine mixture is the peak pattern of each phthalocyanine used alone as a raw material. It consists of superposition.
On the other hand, the phthalocyanine composition containing phthalocyanine (A) in the present invention is a mixture of phthalocyanine used as a raw material at a molecular level, and an X-ray diffraction pattern shows a peak pattern of each phthalocyanine used alone as a raw material. This shows a different pattern from the superposition.

[0024] The titanyl phthalocyanine (a) in the present invention is not particularly limited, and known ones can be used. For example, those prepared as follows can be used. 18.4 g of phthalonitrile (0.
144 mol) in 120 ml of α-chloronaphthalene, and 4 ml (0.0364) of titanium tetrachloride under a nitrogen atmosphere.
Mol) was added dropwise, and the temperature was raised and 200 to 2 with stirring.
Reaction at 20 ° C. for 3 hours, then hot filtration at 100-130 ° C., washing with α-chloronaphthalene and then methanol. Next, hydrolysis was carried out with 140 ml of ion-exchanged water (at 90 ° C. for 1 hour), and this operation was repeated until the solution became neutral. After washing with methanol, it was thoroughly washed with N-methylpyrrolidone at 100 ° C. Followed by washing with methanol. The compound obtained in this way is
It is possible to obtain titanyl phthalocyanine by drying by heating under vacuum at ℃ (46% yield).

In the present invention, (b) the trivalent metal phthalocyanine having a central metal of trivalent metal as the central metal includes, for example, In, Ga, Al and the like. Cl, Br and the like. Further, the phthalocyanine ring may have a substituent such as halogen. These compounds are known compounds. For example, a method for synthesizing a monohalogenated metal phthalocyanine and a monohalogenated metal phthalocyanine is described in Inorganic Chemistry [Inorganic Chemistry].
Chemistry], 19, 3131 (1980) and JP-A-59-440.
No. 54, etc.

The monohalogenated metal phthalocyanine can be produced, for example, as follows. 78.2 mmol of phthalonitrile and 15.8 metal trihalides
Millimol was placed in 100 ml of quinoline purified by double distillation, heated to reflux for 0.5 to 3 hours, subsequently cooled to room temperature, filtered, washed with toluene, acetone, and then methanol. This is washed with methanol using a Soxhlet extractor, and then dried by heating under vacuum at 60 ° C. to obtain a monohalogenated metal phthalocyanine.

The monohalogenated metal halogen phthalocyanine can be produced, for example, as follows. After mixing 156 mmol of phthalonitrile and 37.5 mmol of metal trihalide, melting at 300 ° C., and heating for 0.5 to 3 hours, a composition of monohalogenated metal halogen phthalocyanine was obtained. The product is washed with α-chloronaphthalene using a Soxhlet extractor to obtain a monohalogenated metal halide phthalocyanine.

The amount of each component in the phthalocyanine mixture containing (a) titanyl phthalocyanine and (b) a trivalent halogenated metal phthalocyanine as the central metal in the present invention depends on the electrophotographic characteristics such as chargeability, dark decay and sensitivity. From the viewpoint, (a) the compounding amount of titanyl phthalocyanine is
The total amount of the components (a) and (b) is preferably 20 to 95 parts by weight based on 100 parts by weight, and 50 to 9 parts by weight.
It is more preferably 0 parts by weight, particularly preferably 65 to 90 parts by weight, and very preferably 7.5 to 90 parts by weight.

The above components (a) and (b) in the present invention
The phthalocyanine mixture containing the components is precipitated in water by an acid pasting method and is made amorphous. For example, 1 g of a phthalocyanine mixture is mixed with 50 ml of concentrated sulfuric acid.
After stirring at room temperature, the mixture is dropped into 1 liter of ion-exchanged water cooled with ice water for about 1 hour, preferably 40 to 50 minutes, and the precipitate which has been made amorphous by filtration is recovered. . Thereafter, the substrate is washed with ion-exchanged water. The pH of the washing water after the washing is preferably pH 2 to 5, more preferably pH 3, and the conductivity is 5 to 5.
The precipitate is repeatedly washed until it becomes 00 μS / cm, then thoroughly washed with methanol, and then dried by heating under vacuum at 60 ° C. to obtain a powder.

The precipitate powder composed of the component (a) and the component (b) thus produced has a Bragg angle (2θ ± 0.
2)), except that it shows a clear diffraction peak at 27.2 degrees.
The peak is broad and its value cannot be clearly defined. When the pH of the washing water after the washing exceeds 5, the characteristic peak intensity of the Bragg angle (2θ ± 0.2 degrees) of 27.2 degrees decreases in the X-ray diffraction spectrum of CuKα. The phthalocyanine composition of the present invention can be obtained even if the powder is subjected to crystal transformation using a mixed solvent of an aromatic organic solvent and water, with a peak intensity higher than the peak intensity of 27.2 degrees at 6.8 degrees. When the pH of the washing water after washing is less than 2 or more than 5, the chargeability, dark decay rate, sensitivity and the like tend to be inferior.
Also, the conductivity of the washing water after washing is less than 5 μS / cm or 50 μS / cm.
If it exceeds 0 μS / cm, the chargeability, dark decay rate, sensitivity and the like tend to be inferior.

Then, the powder of the precipitate (amorphized phthalocyanine) obtained above is treated in an organic solvent or a mixed solvent of an aromatic organic solvent and water to change the crystal form, The (A) phthalocyanine composition of the present invention can be obtained. Examples of the organic solvent used in the conversion of the crystal form in the treatment in an organic solvent include N-methyl-2-pyrrolidone, methyl ethyl ketone, diethyl ketone, pyridine, tetrahydrofuran, benzene, toluene, xylene, o-dichlorobenzene and the like. The crystal form conversion treatment in an organic solvent is performed, for example, by adding 100 parts by weight of an organic solvent to 5 to 30 parts by weight of a precipitate, heating at a temperature of 80 to 150 ° C., and treating for 2 to 6 hours.
It can be performed by performing heat treatment for a long time.

[0032] Examples of the organic solvent used in the conversion of the crystal type to be treated in a mixed solvent of an aromatic organic solvent and water include benzene, toluene, xylene, o-dichlorobenzene and the like. At this time, the ratio of the aromatic organic solvent and water is such that the ratio of the aromatic organic solvent / water is 1/99 to 99.
/ L (weight ratio), preferably from 95/5 to 5 /
More preferably, it is 95. The crystal form conversion treatment in a mixed solvent of an aromatic organic solvent and water is performed, for example, at 40 ° C.
100 parts by weight of a mixed solvent of an aromatic organic solvent and water at a temperature of
It can be performed by, for example, contacting 5 parts by weight for 1 to 24 hours.

As a contact method, for example, by performing heating stirring, pulverization and heating stirring at the same time, stable electrophotographic characteristics can be obtained when used as a charge generating substance of an electrophotographic photosensitive member. Examples of the method of simultaneously performing pulverization and heating and stirring include heating milling, homogenizing, paint shaking, and the like.
From the point that more stable electrophotographic characteristics can be obtained,
Heat milling is preferred. As a medium used for a pulverizing treatment such as a heat milling treatment, for example, beads using a material having a specific gravity of 3 or more, such as zirconia beads and alumina beads, are preferable.
３3 mm, more preferably ０．５0.5-2 mm, particularly preferably ０．８0.8-1.5 mm.

The phthalocyanine composition (A) according to the present invention which can be obtained by the above-mentioned method is, for example, a Bragg angle (in the X-ray diffraction spectrum of CuKα) which can be obtained by heating and stirring as a contact method. 7.5 degrees of 2θ ± 0.2 degrees), 22.5 degrees,
In the X-ray diffraction spectrum of the phthalocyanine composition having the main diffraction peaks at 24.3 degrees, 25.3 degrees and 28.6 degrees, CuKα has a Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees, 24 degrees. A phthalocyanine composition having major diffraction peaks at 2 ° and 27.3 °, Bragg angle (2θ ±
0.2 degrees) of 9.3 degrees, 13.1 degrees, 15.0 degrees and 2
A phthalocyanine composition or the like having a main diffraction peak at 6.2 ° is mentioned as a preferable one in terms of sensitivity and the like. Further, as the contact method, in the X-ray diffraction spectrum of CuKα, which can be obtained by simultaneously performing pulverization and heating and stirring, the Bragg angles (2θ ± 0.2 degrees) of 17.9 degrees, 24.0 degrees, and 26 degrees Phthalocyanine compositions having major diffraction peaks at 0.2 degrees and 27.2 degrees are more preferable in terms of sensitivity and the like.

Also, since the sensitivity can be finely adjusted easily,
In the X-ray diffraction spectrum of CuKα among the above phthalocyanine compositions as a charge generating substance, a Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees, 22.5 degrees,
In the X-ray diffraction spectra of the phthalocyanine composition having the main diffraction peaks at 4.3 degrees, 25.3 degrees and 28.6 degrees and CuKα, the Bragg angles (2θ ± 0.2 degrees) of 17.9 degrees and 24 degrees It is preferable to use a phthalocyanine composition having main diffraction peaks at 0.0, 26.2, and 27.2 degrees in combination. In this case, the ratio of the former to the latter (weight ratio) is 1 / It is preferably from 99 to 99/1, more preferably from 10/90 to 90/10.

The charge generating material in the present invention is, if necessary, a charge generating material other than the phthalocyanine composition of component (A), as long as the characteristics of the electrophotographic photoreceptor of the present invention are not deteriorated. Can be used.

Examples of the charge-generating substance (organic pigment that generates charge) other than the component (A) include, for example, azoxybenzene-based, disazo-based, trisazo-based, benzimidazole-based, polycyclic quinone-based, indigoid-based, and quinacridone-based substances. ,
Perylene, methine, α-type, β-type, γ-type, δ-type, ε
Pigments that are known to generate electric charges, such as metal-free or metal-type phthalocyanine, having various crystal structures such as type and type 型.

These pigments are described, for example, in JP-A-47-3
JP-A-7543, JP-A-47-37544, JP-A-47-18543, JP-A-47-18544, JP-A-48-43942, JP-A-48-7
0538, JP-A-49-1231, JP-A-49-105536, JP-A-50-75214, JP-A-53-44028, JP-A-54-1
No. 7,732, and the like.

Further, τ, τ ′, η and η ′ type metal-free phthalocyanines disclosed in JP-A-58-182640 and EP-A-92,255 can also be used. In addition to these, any organic pigment that generates charge carriers by light irradiation can be used. When a charge-generating substance other than the component (A) is used in combination, the amount thereof is preferably 100 parts by weight or less based on 100 parts by weight of the component (A). When the amount is more than 100 parts by weight, the characteristics and the like of the electrophotographic photoreceptor of the present invention tend to be deteriorated.

The above-described charge generating substance containing the phthalocyanine composition (A) and the charge generating substance other than the component (A) used in the present invention are dispersed or dissolved uniformly in a solvent, if necessary. It can be a charge generation layer coating liquid.

It is preferable to add a binder to the coating liquid for the charge generation layer. The binder is not particularly limited as long as it is an insulating resin capable of forming a film in a normal state and a resin which is cured by heat and / or light to form a film. For example, a silicone resin, a polyamide resin, polyurethane Resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polycarbonate copolymer, polyester carbonate resin, polyformal resin, poly (2,6-dimethylphenylene oxide), polyvinyl butyral resin, polyvinyl acetal resin, styrene-acrylic Copolymer, polyacrylic resin, polystyrene resin, melamine resin, styrene-butadiene copolymer, polymethyl methacrylate resin, polyvinyl chloride, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyacryl Bromide resins, polyvinyl carbazole, polyvinyl pyrazoline, polyvinyl pyrene, and the like. Further, a thermosetting resin and a photocurable resin which are crosslinked by heat and / or light can also be used. These binders are used alone or in combination of two or more.

When the binder is compounded, the compounding amount is (A)
The amount is preferably 0 to 500 parts by weight, more preferably 30 to 500 parts by weight, based on 100 parts by weight of the components and the charge generating substance other than the component (A) used as required.

When a binder is blended in the coating solution for the charge generation layer, if necessary, a plasticizer, a fluidity-imparting agent, a pinhole inhibitor, an antioxidant, an ultraviolet absorber and the like may be added. Agents can be added.

Examples of the plasticizer include biphenyl,
3,3 ', 4,4'-tetramethyl-1,1'-biphenyl, 3,3 ", 4,4" -tetramethyl-p-terphenyl, 3,3 ", 4,4" -tetramethyl -M-terphenyl, halogenated paraffin, dimethylnaphthalene, dibutylphthalate and the like. Examples of the fluidity-imparting agent include Modaflow (manufactured by Monsanto Chemical), Acronal 4F (manufactured by Bazfu) and the like. Examples of pinhole inhibitors include, for example, benzoin,
Dimethyl phthalate and the like can be mentioned.

Examples of antioxidants and ultraviolet absorbers include 2,6-di-tert-butyl-4-methylphenol, 2,4-bis (n-octylthio) -6- (4-hydroxy-3, 5-di-t-butylanilino) -1,
3,5-triazine, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2- (5-tert-butyl-2-
(Hydroxyphenyl) benzotriazole, 2- [2-
Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2Hbenzotriazole, Antigen FR (manufactured by Ouchi Shinko Chemical Co., Ltd.) and the like. These additives can be appropriately selected and used. The amount of the additives is 5 parts by weight based on 100 parts by weight of the total amount of the component (A) and the charge generating substance other than the component (A) used as needed. It is preferable that the content be not more than part by weight.

Examples of the solvent used in the coating liquid for the charge generating layer include aromatic solvents (toluene, xylene, anisole, etc.), ketone solvents (cyclohexanone, methylcyclohexanone, etc.), halogenated hydrocarbon solvents (chloride, etc.). Methylene, carbon tetrachloride, etc., alcohol solvents (methanol, ethanol, propanol, 1-methoxy-2)
-Propanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.), ether solvents (tetrahydrofuran, 1,3-dioxolan,
1,4-dioxane, etc.). These solvents are used alone or in combination of two or more.

The amount of the solvent used in the coating solution for the charge generation layer is 100 parts (A) and, if necessary, the total amount of the charge generation material other than the component (A), the binder and the additive.
It is preferably 900 to 10000 parts by weight, more preferably 1900 to 8000 parts by weight, based on parts by weight. If the amount used is less than 900 parts by weight, it tends to be difficult to form a charge generation layer having a preferable upper limit of 1 μm or less, and if it exceeds 10,000 parts by weight, the thickness of the charge generation layer is increased. It tends to be difficult to form a charge generation layer having a lower limit of 0.01 μm or more. Further, in order to uniformly dissolve the component (A) and the charge generating substance other than the component (A), the binder and the additives, which are used as needed, in a solvent, the same as in the case of the coating liquid for the charge transport layer, The powder can be dissolved using a paint shaker, mechanical stirring, a homogenizer, a homomixer, or the like.

The charge transporting material according to the present invention has the general formula [I]

Embedded image (Wherein, R ¹ each independently represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, and two R ^{2 s} each independently represent a hydrogen atom or an alkyl group Wherein m is an integer of 0 to 5, and a plurality of R ^{1 s} may be the same or different.)

The benzidine derivative (B) of the present invention represented by the general formula [I] can be produced, for example, as follows. General formula (II)

Embedded image (Wherein, R ² each independently represents a hydrogen atom or an alkyl group, and X represents iodine or bromine), and a general formula [III]

Embedded image (Wherein, R ¹ independently represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, m is an integer of 0 to 5, and a plurality of R ¹ And a phenylnaphthylamine compound represented by the following formula (1), a copper-based catalyst (copper compound such as copper powder, copper oxide and copper halide) and a basic compound (potassium carbonate, sodium carbonate, water). In the presence of a carbonate or hydroxide of an alkali metal such as potassium oxide or sodium hydroxide, no solvent or an organic solvent (nitrobenzene, dichlorobenzene, quinoline, N,
N-dimethylformamide, N-methyl-2-pyrrolidone, sulfolane, etc.)
After heating and stirring for 30 hours, the reaction mixture was dissolved in an organic solvent such as methylene chloride or toluene, insolubles were separated, and the solvent was distilled off. The residue was purified using an alumina column or the like, and re-used with hexane, cyclohexane, etc. By crystallizing (B)
The benzidine derivative represented by the general formula [I] can be produced.

The amount of the halogenated biphenyl derivative, the phenylnaphthylamine compound, the copper-based catalyst and the basic compound may be generally used in stoichiometric amounts. It is preferable to use 2 to 3 moles of a naphthylamine compound, 0.5 to 2 moles of a copper catalyst, and 1 to 2 moles of a basic compound.

In the general formula [I], examples of the halogen atom include a chlorine atom and a bromine atom. Examples of the alkyl group include a methyl group having 1 to 6 carbon atoms, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a tert-butyl group. Examples of the alkoxy group include a methoxy group having 1 to 6 carbon atoms, an ethoxy group, an n-propoxy group, and an iso-propoxy group. Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms, a tolyl group, a biphenyl group, a terphenyl group, and a naphthyl group. Examples of the fluoroalkyl group include a trifluoromethyl group having 1 to 6 carbon atoms, a trifluoroethyl group, a heptafluoropropyl group, and the like. Examples of the fluoroalkoxy group include a trifluoromethoxy group having 1 to 6 carbon atoms, a 2,2-difluoroethoxy group, a 2,2,2
-Trifluoroethoxy group, 1H, 1H-pentafluoropropoxy group, hexafluoro-iso-propoxy group, 1H, 1H-pentafluorobutoxy group, 2,2,2
3,4,4,4-hexafluorobutoxy group, 4,4
A fluoroalkoxy group such as a 4-trifluorobutoxy group is exemplified.

Specific examples of the benzidine derivative (B) represented by the general formula (I) in the present invention include the following compounds No. 1 to No. 10.

[0053]

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[0054]

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[0055]

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Among these, No. 3, No. 4, N
The compound No. 7 is preferred, and the compound No. 3 is more preferred. In addition, as a specific production example of the benzidine derivative (B) represented by the general formula [I] in the present invention, for example, the compound of No. 3 can be synthesized as follows.

Under a nitrogen stream, a 100 ml glass round bottom flask equipped with a condenser with a water separator, a thermometer and a stirrer was charged with 2
-25.4 g (176 mmol) of naphthol, 21.1 g (197 mmol) of m-methylaniline and 2.1 g (11 mmol) of p-toluenesulfonic acid hydrate were added, and 190 ° C / 1 hour, 220 ° C / 2 hours and 250 ° C
/ Heat for 1 hour. After cooling to room temperature, the mixture is dissolved in hot acetone, and the filtrate is poured into ice water (acetone / water = 1/1 to 1).
1/2 volume ratio). The deposited precipitate is separated by filtration, and methanol /
After washing with water (1/1 volume ratio), it was dried, and milky white powder m-methylphenyl-2-naphthylamine 40.8
g (174 mmol) are obtained.

Then, under a nitrogen stream, 10.2 g (2,4'-diiodobiphenyl) was placed in a 100 ml glass round bottom flask equipped with a condenser with a water separator, a thermometer and a stirrer.
5.1 mmol), m-methylphenyl-2-naphthylamine 17.6 g (75.4 mmol), potassium carbonate 5.3 g (38.3 mmol) and copper powder 2.1 g (3
3 mmol), heated at 210 ° C. for 20 hours, cooled to room temperature, dissolved in hot toluene, neutral alumina, and developed solution by column chromatography using toluene / cyclohexane = 1/4 to 1/3 volume ratio. Separation gives a pale yellow solid. The obtained pale yellow solid was recrystallized from methylcyclohexane to obtain white crystalline bis-N, N '-(3
-Methylphenyl) -N, N'-bis (2-naphthyl)
10.5 g (17 mmol) of-[1,1'-biphenyl] -4,4'-diamine (Exemplary Compound No. 3) is obtained (yield = 68%). The N, N'-bis (3-methylphenyl) -N, N'-bis (2-naphthyl)-[1,1'-biphenyl] -4,4'-diamine (Exemplified Compound No. .3) (measured by Hitachi, Ltd., Model 270-30 Infrared Spectrophotometer) is shown in FIG.

The charge-transporting substance containing the benzidine derivative (B) in the present invention may be, if necessary, a charge-transporting substance other than the component (B) as long as the characteristics of the electrophotographic photoreceptor of the present invention are not deteriorated. Can be used in combination.

As the charge transporting substance other than the component (B),
For example, in the polymer compound, poly-N-vinyl carbazole, halogenated poly-N-vinyl carbazole, polyvinyl pyrene, polyvinyl indoloquinoxaline, polyvinyl benzothiophene, polyvinyl anthracene, polyvinyl acridine, polyvinyl pyrazoline, and the like, For low molecular weight compounds, fluorenone, fluorene,
2,7-dinitro-9-fluorenone, 4H-indeno (1,2,6 thiophen-4-one, 3,7-dinitro-dibenzothiophen-5-oxide, 1-bromopyrene, 2-phenylpyrene, carbazole, N-ethylcarbazole, 3-phenylcarbazole, 3- (N-
Methyl-N-phenylhydrazone) methyl-9-ethylcarbazole, 2-phenylindole, 2-phenylnaphthalene, oxadiazole, 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminostyryl) -5- (4
-Diethylaminophenyl) pyrazolin, 1-phenyl-3- (p-diethylaminophenyl) pyrazolin, p
-(Dimethylamino) -stilbene, 2- (4-dipropylaminophenyl) -4- (4-dimethylaminophenyl) -5- (2-chlorophenyl) -1,3-oxazole, 2- (4-dimethylamino Phenyl) -4-
(4-dimethylaminophenyl) -5- (2-fluorophenyl) -1,3-oxazole, 2- (4-diethylaminophenyl) -4- (4-dimethylaminophenyl) -5- (2-fluorophenyl) -1,3-oxazole, 2- (4-dipropylaminophenyl) -4-
(4-dimethylaminophenyl) -5- (2-fluorophenyl) -1,3-oxazole, imidazole, chrysene, tetraphen, acridene, triphenylamine, derivatives thereof, 4-N ', N'-diphenylamino Benzaldehyde-N, N-diphenylhydrazone,
4-N ', N'-ditolylaminobenzaldehyde-
N, N-diphenylhydrazone, N, N, N ', N'-
Tetraphenylbenzidine, N, N'-diphenyl-
N, N'-bis (3-methylphenyl) -benzidine,
N, N'-diphenyl-N, N'-bis (4-methylphenyl) -benzidine, N, N, N ', N'-tetrakis (3-methylphenyl) -benzidine, N, N,
N ', N'-tetrakis (4-methylphenyl) -benzidine, N, N'-diphenyl-N, N'-bis (4-
Methoxyphenyl) -benzidine, N, N, N ', N'
-Tetrakis (4-methylphenyl) -tolidine, 1,
Examples thereof include 1-bis (4-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene and derivatives thereof.

When a charge transport material other than the component (B) is used in combination, the amount thereof is preferably 100 parts by weight or less based on 100 parts by weight of the component (B). When the amount is more than 100 parts by weight, the characteristics and the like of the electrophotographic photoreceptor of the present invention tend to be deteriorated.

The coating liquid for a charge transport layer of the present invention is obtained by uniformly dispersing the charge transport material containing the benzidine derivative (B) and the charge transport material other than the component (B) used in the present invention in a solvent. Alternatively, it can be prepared by dissolving.

The coating solution for a charge transport layer of the present invention may contain a binder. The binder is not particularly limited as long as it is an insulating resin capable of forming a film in a normal state and a resin which is cured by heat and / or light to form a film. For example, a silicone resin, a polyamide resin, polyurethane Resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polycarbonate copolymer, polyester carbonate resin, polyformal resin, poly (2,6-dimethylphenylene oxide), polyvinyl butyral resin, polyvinyl acetal resin, styrene-acrylic Copolymer, polyacrylic resin, polystyrene resin, melamine resin, styrene
Butadiene copolymer, polymethyl methacrylate resin, polyvinyl chloride, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyacrylamide resin,
Polyvinyl carbazole, polyvinyl pyrazoline, polyvinyl pyrene and the like. Further, a thermosetting resin and a photocurable resin which are crosslinked by heat and / or light can also be used. These binders are used alone or in combination of two or more.

When the binder is blended, the blending amount is (B)
The amount is preferably 0 to 500 parts by weight, more preferably 30 to 500 parts by weight, based on 100 parts by weight of the total of the components and the charge transport material other than the component (B) used as required. When the charge transporting substance other than the component (B) and the component (B) used as required is a low molecular weight compound, the compounding amount of the binder is determined based on the component (B) and the component (B) used as needed. 100) Total amount of charge transport material other than component 100
It is preferable that the amount be 50 to 500 parts by weight based on parts by weight.

In addition, additives such as a plasticizer, a fluidity-imparting agent, a pinhole inhibitor, an antioxidant, and an ultraviolet absorber may be added to the coating solution for a charge transport layer of the present invention, if necessary. Can be. Examples of the plasticizer include biphenyl,
3,3 ', 4,4'-tetramethyl-1,1'-biphenyl, 3,3 ", 4,4" -tetramethyl-p-terphenyl, 3,3 ", 4,4" -tetramethyl -M-terphenyl, halogenated paraffin, dimethylnaphthalene, dibutylphthalate and the like. Examples of the fluidity-imparting agent include Modaflow (manufactured by Monsanto Chemical), Acronal 4F (manufactured by Bazfu) and the like. Examples of pinhole inhibitors include, for example, benzoin,
Dimethyl phthalate and the like can be mentioned.

Examples of the antioxidant and the ultraviolet absorber include 2,6-di-tert-butyl-4-methylphenol, 2,4-bis (n-octylthio) -6- (4-hydroxy-3, 5-di-t-butylanilino) -1,
3,5-triazine, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2- (5-tert-butyl-2-
(Hydroxyphenyl) benzotriazole, 2- [2-
Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2Hbenzotriazole, Antigen FR (manufactured by Ouchi Shinko Chemical Co., Ltd.) and the like.

These additives can be appropriately selected and used, and the amount of the additives is based on 100 parts by weight of the total amount of the component (B) and the charge transporting substance other than the component (B) used if necessary. It is preferable that the content be 5 parts by weight or less.

Examples of the solvent used in the coating solution for the charge transport layer of the present invention include aromatic solvents (toluene, xylene, anisole, etc.), ketone solvents (cyclohexanone, methylcyclohexanone, etc.), halogenated hydrocarbons Solvents (methylene chloride, carbon tetrachloride, etc.), ether solvents (tetrahydrofuran, 1,3-dioxolan, 1,
4-dioxane) and the like. These solvents are used alone or in combination of two or more.

The amount of the solvent used in the coating solution for the charge transport layer of the present invention is determined by the amount of the component (B)
The amount is preferably from 250 to 1,000 parts by weight, more preferably from 250 to 700 parts by weight, based on 100 parts by weight of the total amount of the charge transporting substance, the binder and the additives other than the component (B). If the amount is less than 250 parts by weight, it tends to be difficult to form a charge transporting layer having a preferable upper limit of 50 μm or less of the thickness of the charge transporting layer. It tends to be difficult to form a charge transport layer having a lower limit of 5 μm or more. Also,
In order to uniformly dissolve the charge transport material in the solvent, the charge transport material can be dissolved using a shaking machine, a paint shaker, mechanical stirring, a homogenizer, a homomixer, or the like.

The electrophotographic photoreceptor of the present invention comprises a charge generation layer containing a charge generation material containing the (A) phthalocyanine composition of the present invention on the conductive substrate and the (B) of the present invention. A charge transport layer containing a charge transport material containing a benzidine derivative; (A) a charge generation layer containing a charge generation material containing a phthalocyanine composition; and (B) a charge transport layer containing a benzidine derivative. By having a charge transport layer containing a substance, an electrophotographic photoreceptor exhibiting good characteristics such as high sensitivity and low residual potential can be obtained.

In the electrophotographic photoreceptor of the present invention, the method for forming the charge generation layer and the charge transport layer on the conductive substrate includes, for example, the above-mentioned coating solution for the charge generation layer and the charge transport layer of the present invention. A method of applying the coating liquid for a layer on a conductive substrate and drying the coating liquid may be used.

The method for applying the coating solution for the charge generation layer and the coating solution for the charge transport layer of the present invention on a conductive substrate includes, for example, a spin coating method and a dip coating method. As a spin coating method, the coating liquid for a charge generation layer or the coating liquid for a charge transport layer of the present invention is used, and the number of rotations is 500 to 4000 rp.
m, and the dip coating method includes dipping a conductive substrate in the coating solution for the charge generation layer or the coating solution for the charge transport layer of the present invention. Drying performed after application is usually 80 to 140 ° C.
For 5 to 90 minutes.

The thickness of the charge generation layer in the electrophotographic photosensitive member of the present invention is preferably 0.01 to 1 μm,
More preferably, the thickness is 0.1 to 0.5 μm. If the thickness of the charge generation layer is less than 0.01 μm, it tends to be difficult to form the charge generation layer uniformly, and if it exceeds 1 μm, the electrophotographic properties tend to be reduced. The thickness of the charge transport layer in the electrophotographic photosensitive member of the present invention is 5 to 50 μm.
And more preferably 15 to 30 μm. When the thickness of the charge transport layer is less than 5 μm, the initial potential tends to decrease, and when it exceeds 50 μm, the sensitivity tends to decrease.

The charge generating layer and the charge transport layer are formed on the electrophotographic photosensitive member of the present invention as described above. In this case, either of the charge generation layer and the charge transport layer may be an upper layer, and the charge generation layer may be sandwiched between two charge transport layers. The electrophotographic photoreceptor of the present invention may further have a thin adhesive layer or barrier layer immediately above the conductive substrate, and may have a protective layer on the surface.

[0075]

The present invention will be described below with reference to examples. Production Example 1 (Preparation of (A) phthalocyanine composition (I)) A phthalocyanine mixture 48 g composed of 36 g of titanyl phthalocyanine and 12 g of indium phthalocyanine was dissolved in 2.4 liters of sulfuric acid, and stirred at room temperature for 30 minutes.
This was added to 48 liters of ion-exchanged water cooled with ice water.
It was added dropwise over 0 minutes and reprecipitated. In addition, 3 under cooling
After stirring for 0 minutes, a precipitate was separated by filtration. As the first washing, 4 liters of ion-exchanged water was added to the precipitate as washing water, stirred, and then the precipitate was collected by filtration. The same washing operation was further continued four times, and in the fifth operation, the pH and conductivity of the filtered washing water (ie, washing water after washing) were measured (23 ° C.).

The pH of the washing water is 3.4 and the conductivity is 6
It was 5.0 μS / cm. The pH was measured using Model PH51 manufactured by Yokogawa Electric Corporation, and the conductivity was measured using Model SC-17A manufactured by Shibata Scientific Instruments.

Thereafter, the precipitate was washed with 4 liters of methanol three times, and dried by heating under vacuum at 60 ° C. for 4 hours, and the obtained precipitate was dried. As a result of measuring the X-ray diffraction spectrum of the obtained dried product, it was determined that the Bragg angle (2θ ± 0.2 degrees) was 27.
It showed a clear peak twice. The X-ray diffraction spectrum is shown in FIG. The X-ray diffraction spectrum was measured using RAD-IIIA manufactured by Rigaku Corporation.

Next, 100 ml of 1-methyl-2-pyrrolidone was added to 10 g of the dried product, and the mixture was heated with stirring at 150 ° C. for 1 hour, cooled, filtered, washed thoroughly with methanol, and then at 60 ° C. for 4 hours. It was dried by heating under vacuum to obtain (A) crystals of the phthalocyanine composition (I). As a result of measuring the X-ray diffraction spectrum of the crystal of the obtained phthalocyanine composition (I) (A), a Bragg angle (2θ ± 0.2 degrees) of 7.5 was obtained.
Degrees, 22.5 degrees, 24.3 degrees, 25.3 degrees and 28.6 degrees
Each time showed a major diffraction peak. The X-ray diffraction spectrum is shown in FIG.

Preparation Example 2 (Preparation of (A) Phthalocyanine Composition (II)) Preparation Example 1
The precipitate was dried in the same manner as in Production Example 1 except that 60 g of a phthalocyanine mixture consisting of 45 g of titanyl phthalocyanine and 15 g of indium chloride phthalocyanine was dissolved in 1.2 liter of sulfuric acid.
to 100 g of 1-methyl-2-pyrrolidone,
The mixture was heated and stirred at 50 ° C. for 1 hour, cooled, filtered, washed sufficiently with methanol, and dried by heating under vacuum at 60 ° C. for 4 hours to obtain a crystal of (A) phthalocyanine composition (II).
X of the crystal of the obtained (A) phthalocyanine composition (II)
As a result of measuring the X-ray diffraction spectrum, the Bragg angle (2θ ±
0.2 degrees) of 9.3 degrees, 13.1 degrees, 15.0 degrees and 2
A major diffraction peak was shown at 6.2 degrees. Note that this X
The line diffraction spectrum is shown in FIG.

Production Example 3 (Preparation of (A) Phthalocyanine Composition (III)) The precipitate was dried in the same manner as in Production Example 1, and 2 g of the dried product
140 g of ion-exchanged water and 50 g of toluene were added, and
The mixture was heated and stirred at -70 ° C for 5 hours, centrifuged, and the supernatant was removed. After thoroughly washing with methanol, drying by heating under vacuum at 60 ° C for 4 hours, (A) phthalocyanine composition (II)
The crystals of I) were obtained. As a result of measuring the X-ray diffraction spectrum of the crystal of the obtained phthalocyanine composition (III) (A), a Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees and 24 degrees.
Main diffraction peaks were shown at 2 degrees and 27.3 degrees. The X-ray diffraction spectrum is shown in FIG.

Production Example 4 (Preparation of (A) Phthalocyanine Composition (IV)) Production Example 1
The precipitate is dried in the same manner as described above.
700 g of ion-exchanged water, 250 g of toluene and 1 kg of 1 mmφ zirconia beads were added, and the mixture was pulverized and heated and stirred at 60 to 70 ° C. for 5 hours. After cooling, filtration and centrifugation were performed. Vacuum heating and drying at 60 ° C for 4 hours, (A) phthalocyanine composition (IV)
Was obtained. As a result of measuring the X-ray diffraction spectrum of the crystal of the obtained phthalocyanine composition (IV) (A), the Bragg angle (2θ ± 0.2 degrees) was 17.9 degrees and 24.0 degrees.
, 26.2 and 27.2 degrees. The X-ray diffraction spectrum is shown in FIG.

Production Example 5 (Preparation of Coating Liquid (1) for Charge Generating Layer) 1.5 g of the crystal of the phthalocyanine composition (I) (A) obtained in Production Example 1, a polyvinyl butyral resin (Eslec BL-S ( 0.9 g of melamine resin (ML365 (trade name of Hitachi Chemical Co., Ltd., solid content 60% by weight)) 0.1
67 g, 50 g of 2-ethoxyethanol and 50 g of tetrahydrofuran were mixed and dispersed by a ball mill to prepare a coating liquid (1) for a charge generation layer.

Production Example 6 (Preparation of coating liquid (2) for charge generation layer)
(A) Phthalocyanine composition (I) obtained in Production Example 1
The charge generation layer coating liquid (2) was prepared in the same manner as in Production Example 5, except that the crystal of (1) was replaced with the crystal of the phthalocyanine composition (II) obtained in Production Example 2.

Production Example 7 (Preparation of Coating Solution (3) for Charge Generating Layer)
(A) Phthalocyanine composition (I) obtained in Production Example 1
The charge generation layer coating liquid (3) was prepared in the same manner as in Production Example 5, except that the crystal of (1) was replaced with the crystal of the phthalocyanine composition (III) (A) obtained in Production Example 3.

Production Example 8 (Preparation of coating liquid (4) for charge generation layer)
(A) Phthalocyanine composition (I) obtained in Production Example 1
Was prepared in the same manner as in Production Example 5, except that the crystals of (A) were replaced with the crystals of (A) phthalocyanine composition (IV) obtained in Production Example 4.

Example 1 (Preparation of coating liquid (1) for charge transport layer) 15 g of a benzidine derivative (B) of Exemplified Compound No. 3, a polycarbonate copolymer BPPC (manufactured by Idemitsu Kosan, number average molecular weight = 50,000)
0) 15 g of tetrahydrofuran and 130 g of tetrahydrofuran were blended and uniformly dissolved using a mechanical stirrer to prepare a charge transport layer coating liquid (1).

Example 2 (Preparation of coating liquid (2) for charge transport layer)
Except that the (B) benzidine derivative of Exemplified Compound No. 3 was replaced with the (B) benzidine derivative of Exemplified Compound No. 4,
In the same manner as in Example 1, a charge transport layer coating liquid (2) was prepared.

Example 3 (Preparation of coating liquid (3) for charge transport layer)
Except that the (B) benzidine derivative of Exemplified Compound No. 3 was replaced with the (B) benzidine derivative of Exemplified Compound No. 7,
In the same manner as in Example 1, a coating liquid (3) for a charge transport layer was prepared.

Comparative Example 1 (Preparation of Coating Solution for Charge Transport Layer ())
Except that the (B) benzidine derivative of Exemplified Compound No. 3 was replaced with the following butadiene derivative T-1, a coating solution () for a charge transport layer was prepared in the same manner as in Example 1.

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Comparative Example 2 (Preparation of Coating Liquid () for Charge Transport Layer)
A coating liquid () for a charge transport layer was prepared in the same manner as in Example 1 except that the benzidine derivative (B) of Exemplified Compound No. 3 was replaced with the following benzidine derivative T-2.

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Comparative Example 3 (Preparation of coating liquid () for charge transport layer)
A coating liquid () for a charge transport layer was prepared in the same manner as in Example 1, except that the benzidine derivative (B) of Exemplified Compound No. 3 was changed to the following fluorine-containing benzidine derivative T-3.

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Example 4 (Preparation of Electrophotographic Photoreceptor (A)) [Formation of Undercoat Layer] Alcohol-soluble polyamide resin (M
1276 (trade name, manufactured by Nihon Rilsan Co., Ltd.)) 26.6 parts by weight, melamine resin (ML2000 (trade name, manufactured by Hitachi Chemical Co., Ltd., solid content 50% by weight)) 52.3 parts by weight, and trimellitic anhydride 2.8 parts by weight (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 620 parts by weight of ethanol and 930 parts by weight of 1,1,2-trichloroethane to prepare a coating solution. The obtained coating solution is applied on an aluminum plate (conductive substrate, 10 mm × 100 mm × 0.1 mm) by a dip coating method,
After drying at 140 ° C. for 30 minutes, an undercoat layer having a thickness of 0.3 μm was formed.

[Formation of Charge Generating Layer] Next, the coating liquid (1) for a charge generating layer obtained in Production Example 5 was applied on the undercoat layer of the aluminum substrate by a dip coating method.
After drying at 20 ° C. for 30 minutes, a charge generation layer having a thickness of 0.2 μm was formed. [Formation of charge transport layer] Next, the coating liquid for charge transport layer (1) obtained in Example 1 was applied on the charge generation layer of the aluminum substrate by a dip coating method, and dried at 120 ° C for 30 minutes. Thus, a charge transport layer having a thickness of 23 μm was formed, and an electrophotographic photosensitive member (A) was produced.

The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (A) were measured, and the results are shown in Table 1. In addition, the electrophotographic characteristics are Cynthia 30HC
(Midoriya Electric Co., Ltd.), the photoconductor is charged to −650 V by a corona charging method, and monochromatic light of 780 nm is emitted for 25 ms.
The photoreceptor was exposed and measured. The definition of the above characteristics is
It is as follows. Sensitivity (E _1/2 ): Initial charging potential -650 V, exposure 0.
This is the irradiation energy amount (mJ / m ² ) of the monochromatic light of 780 nm required to reduce by half after 2 seconds. Residual potential (VL _t): exposing the monochromatic light of 20 mJ / m ² of the same wavelength, which is the potential remaining on the surface of the photoreceptor after exposure after t seconds (-V). The dark decay rate (DDR _t ) is calculated by (V _t / 650) × 100 using the initial charging potential of the photoreceptor −650 V and the surface potential V _t (−V) after the initial charging and left in a dark place for t seconds. (%)
Defined.

Example 5 (Preparation of electrophotographic photoreceptor (B)) In Example 4, the coating liquid (1) for a charge generation layer obtained in Production Example 5 was replaced with Production Example 6
An electrophotographic photoreceptor (B) was produced in the same manner as in Example 4, except that the coating liquid for charge generation layer (2) obtained in the above was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (B) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Example 6 (Preparation of Electrophotographic Photoreceptor (C)) In Example 4, the coating liquid (1) for a charge generation layer obtained in Production Example 5 was replaced with Production Example 7
An electrophotographic photoreceptor (C) was produced in the same manner as in Example 4, except that the coating solution for charge generation layer (3) obtained in the above was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (C) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Example 7 (Preparation of Electrophotographic Photoreceptor (D)) In Example 4, the coating liquid (1) for a charge generation layer obtained in Production Example 5 was replaced with Production Example 8
An electrophotographic photoreceptor (D) was produced in the same manner as in Example 4 except that the coating liquid for charge generation layer (4) obtained in was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photoreceptor (D) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Example 8 (Preparation of Electrophotographic Photoreceptor (E)) In Example 6, the coating liquid (1) for a charge transport layer obtained in Example 1 was replaced with Example 2
An electrophotographic photoreceptor (E) was produced in the same manner as in Example 6, except that the coating liquid for charge transport layer (2) obtained in was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (E) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Example 9 (Preparation of Electrophotographic Photoreceptor (F)) In Example 6, the coating liquid (1) for a charge transport layer obtained in Example 1 was replaced with Example 3
An electrophotographic photoreceptor (F) was produced in the same manner as in Example 6, except that the coating liquid for a charge transport layer (3) obtained in was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photoreceptor (F) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Example 10 (Preparation of Electrophotographic Photoreceptor (G)) In Example 7, the charge transport layer coating liquid (1) obtained in Example 1 was replaced with Example 2
An electrophotographic photoreceptor (G) was produced in the same manner as in Example 7, except that the coating liquid for charge transport layer (2) obtained in was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (G) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Example 11 (Preparation of Electrophotographic Photoreceptor (H)) In Example 7, the coating liquid (1) for a charge transport layer obtained in Example 1 was replaced with Example 3
An electrophotographic photoreceptor (H) was prepared in the same manner as in Example 7, except that the coating liquid for charge transport layer (3) obtained in was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (H) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Comparative Example 4 (Preparation of Electrophotographic Photoreceptor (a)) In Example 6, the coating liquid (1) for a charge transport layer obtained in Example 1 was used.
An electrophotographic photoreceptor (a) was prepared in the same manner as in Example 6, except that the coating liquid () for a charge transport layer obtained in (1) was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (a) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Comparative Example 5 (Preparation of Electrophotographic Photoreceptor (b)) In Example 6, the charge transport layer coating liquid (1) obtained in Example 1 was replaced with Comparative Example 2
An electrophotographic photoreceptor (b) was produced in the same manner as in Example 6, except that the coating liquid () for a charge transport layer obtained in (1) was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (b) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Comparative Example 6 (Preparation of electrophotographic photoreceptor (c)) In Example 6, the coating solution (1) for a charge transport layer obtained in Example 1 was replaced with Comparative Example 3
An electrophotographic photoreceptor (c) was produced in the same manner as in Example 6, except that the coating liquid () for a charge transport layer obtained in (1) was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (c) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Comparative Example 7 (Preparation of Electrophotographic Photoreceptor (d)) In Example 7, the charge transport layer coating liquid (1) obtained in Example 1 was replaced with Comparative Example 1
An electrophotographic photoreceptor (d) was produced in the same manner as in Example 7, except that the coating liquid () for a charge transport layer obtained in (1) was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photoreceptor (d) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Comparative Example 8 (Preparation of Electrophotographic Photoreceptor (e)) In Example 7, the coating liquid (1) for a charge transport layer obtained in Example 1 was replaced with Comparative Example 2
An electrophotographic photoreceptor (e) was produced in the same manner as in Example 7, except that the coating liquid () for a charge transport layer obtained in (1) was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (e) were measured in the same manner as in Example 4, and the results are shown in Table 1.

Comparative Example 9 (Preparation of Electrophotographic Photoreceptor (f)) In Example 7, the coating liquid (1) for a charge transport layer obtained in Example 1 was replaced with Comparative Example 3
An electrophotographic photoreceptor (f) was prepared in the same manner as in Example 7, except that the coating liquid () for a charge transport layer obtained in (1) was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (f) were measured in the same manner as in Example 4, and the results are shown in Table 1.

[0108]

[Table 1]

From the results shown in Table 1, it can be seen that all of the electrophotographic photoreceptors of the present invention (Examples 4 to 11) show high sensitivity, low residual potential and good dark decay rate. Further, the electrophotographic photoreceptor of Comparative Example 4 had a low dark decay rate, and the electrophotographic photoreceptors of Comparative Examples 6 and 9 had a higher residual potential and were inferior to the electrophotographic photoreceptor of the present invention. Was.
The electrophotographic photoreceptors of Comparative Example 5, Comparative Example 7, and Comparative Example 8 exhibited the same electrophotographic characteristics as those of the examples.

(Evaluation of Image Characteristics and Repetition Characteristics of Electrophotographic Photoreceptor) Example 6, Example 7, Comparative Example 5, Comparative Example 7
Using the electrophotographic photosensitive member produced in Comparative Example 8, changes in characteristics (chargeability, dark decay rate, residual potential, and image characteristics) during repeated use were evaluated as described below. Using an electrophotographic property evaluation device Cynthia 99HC (Gentec), the charge-dark decay rate measurement-discharge-charge-exposure (measurement of residual potential) -discharge cycle is defined as one cycle, and this cycle is repeated. Changes in characteristics during use were examined, and the evaluation results are shown in Tables 2 and 3.

Specifically, a corona voltage of -5 kV is applied to the photoreceptor to charge it up to a charging potential (V ₀ ). From the surface potential (V ₁ ) left for one second in a dark place, the dark decay rate (DDR) ₁ = (V
₁ / V ₀ ) × 100). Next, after performing static elimination, a corona voltage of −5 kV was applied again to charge, and 78
A monochromatic light of 20 nm (20 mJ / m ² ) was exposed, and a residual potential (VL _0.2 ) remaining on the surface of the photoreceptor was measured 0.2 seconds after the exposure. The evaluation of image characteristics is performed by using an image evaluation device (negative charging,
(Reversal development method), the surface potential was -700 V, the bias potential was -600 V, and fog, black spots, white spots,
The measurement was performed according to the image density at the time of black solid printing. Black spots and white spots were visually determined. Fog and black solid image densities were measured using a Macbeth reflection densitometer (A division of
(Kollmergen Corporation).

[0112]

[Table 2]

[0113]

[Table 3]

From the results shown in Tables 2 and 3, the electrophotographic photoreceptor of the present invention (Examples 6 and 7) has high sensitivity, low residual potential and high dark decay rate even in the repetition characteristics. Further, it can be seen that good image characteristics are exhibited. In the electrophotographic photoreceptors of Comparative Examples 5, 7 and 8, relatively good values were obtained for the sensitivity, the residual potential, and the dark decay rate. It can be seen that the change is large and the image characteristics in the repetition characteristics are inferior.

(Thermal analysis of the charge transport layer coating film) An aluminum plate (conductive base material, 10 mm × 1 mm) was prepared by dip coating using the charge transport layer coating liquid prepared in Example 1 and Comparative Example 2.
(00 mm × 0.1 mm) and dried at 120 ° C. for 30 minutes to form a charge transport layer having a thickness of 23 μm. Next, the charge transport layer coating film was peeled off from the aluminum plate, and a differential scanning calorimeter DS manufactured by Seiko Electronic Industry Co., Ltd. was used.
Using a C-200, the thermal analysis of the charge transport layer coating film was performed in air under the measurement conditions of a temperature rising rate of 5 ° C./min. FIG. 7 shows differential scanning calorimetry data of the charge transport layer coating film using the charge transport layer coating liquid prepared in Example 1, and the charge transport layer using the charge transport layer coating liquid prepared in Comparative Example 2. FIG. 8 shows the differential scanning calorimetry data of the coating film.

In FIG. 7, in the charge transport layer containing the benzidine derivative (Exemplary Compound No. 3) in the present invention, only an endothermic change which is considered to be derived from the glass transition of the charge transport layer is observed. (A) It was suggested that the benzidine derivative (Exemplary Compound No. 3) did not undergo phase separation in the charge transport layer. Further, in FIG. 8, the charge transport layer coating film containing the benzidine derivative (T-2) is not only an endothermic change indicating a glass transition of the charge transport layer, but also a sharp one thought to be derived from the benzidine derivative (T-2). An endothermic change was observed, suggesting that fine crystals of the benzidine derivative (T-2) were precipitated in the charge transport layer.

Production Example 9 (Preparation of coating liquid (5) for charge generation layer)
(A) Phthalocyanine composition (I) obtained in Production Example 1
The crystals of (A) were prepared as follows: (A) Crystals of phthalocyanine composition (I)
A charge generation layer coating liquid (5) was prepared in the same manner as in Production Example 5, except that a mixture of 35 g and 0.15 g of crystals of the phthalocyanine composition (IV) (A) was used.

Production Example 10 (Preparation of coating liquid (6) for charge generation layer)
(A) Phthalocyanine composition (I) obtained in Production Example 1
The crystals of (A) were prepared from the crystals of (A) phthalocyanine composition (I).
A charge generation layer coating liquid (6) was prepared in the same manner as in Production Example 5, except that the mixture was changed to a mixture of 75 g and 0.75 g of the crystals of the phthalocyanine composition (IV) (A).

Production Example 11 (Preparation of coating liquid (7) for charge generation layer)
(A) Phthalocyanine composition (I) obtained in Production Example 1
The crystals of (A) were prepared from the crystals of (A) phthalocyanine composition (I).
3 g and crystals of (A) phthalocyanine composition (IV)
Except having replaced with 2 g of mixture, it carried out similarly to manufacture example 5, and
A coating solution (7) for a charge generation layer was prepared.

Example 12 (Preparation of electrophotographic photoreceptor (I)) In Example 4, the coating solution (1) for a charge generation layer obtained in Production Example 5 was replaced with Production Example 9
The electrophotographic photoreceptor (I) was produced in the same manner as in Example 4, except that the coating liquid for charge generation layer (5) obtained in the above was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photoreceptor (I) were measured in the same manner as in Example 4, and the results are shown in Table 4.

Example 13 (Preparation of Electrophotographic Photoreceptor (J)) In Example 4, the coating liquid (1) for a charge generation layer obtained in Production Example 5 was replaced with Production Example 9
An electrophotographic photoreceptor (J) was produced in the same manner as in Example 4, except that the coating liquid for charge generation layer (6) obtained in the above was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (J) were measured in the same manner as in Example 4, and the results are shown in Table 4.

Example 14 (Preparation of Electrophotographic Photoreceptor (K)) In Example 4, the coating liquid (1) for a charge generation layer obtained in Production Example 5 was replaced with Production Example 9
An electrophotographic photoreceptor (K) was produced in the same manner as in Example 4, except that the coating liquid (7) for a charge generation layer obtained in was used. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate) of the obtained electrophotographic photosensitive member (K) were measured in the same manner as in Example 4, and the results are shown in Table 4.

[0123]

[Table 4]

From the results in Table 4, it was found that CuKα was added to the CGL composition.
In the X-ray diffraction spectrum, the Bragg angle (2θ ±
0.2 degrees) 7.5 degrees, 22.5 degrees, 24.3 degrees, 2
In the X-ray diffraction spectra of the phthalocyanine composition having the main diffraction peaks at 5.3 degrees and 28.6 degrees and CuKα, the Bragg angle (2θ ± 0.2 degrees) of 17.9 degrees,
By using a mixture of phthalocyanine compositions having main diffraction peaks at 24.0 degrees, 26.2 degrees, and 27.2 degrees, the sensitivity can be arbitrarily maintained while maintaining a low residual potential and a good dark decay rate. It can be seen that it can be adjusted.

(Evaluation of Image Characteristics and Repetition Characteristics of Electrophotographic Photoreceptor) The characteristics (chargeability, dark decay) of the electrophotographic photoreceptors produced in Examples 12, 13 and 14 during repeated use were evaluated. Of the electrophotographic photosensitive member obtained in Example 6 described above using an electrophotographic property evaluation apparatus Cynthia 99HC (manufactured by Gentec) in the same manner as in the case of the electrophotographic photosensitive member obtained in Example 6 described above. did. Table 5 shows the evaluation results.

[0126]

[Table 5]

From the results shown in Table 5, the electrophotographic photoreceptors of the present invention (Examples 12, 13 and 14) have a low residual potential and a high dark decay rate in the repetition characteristics, and the sensitivity is low. It can be seen that it can be adjusted arbitrarily and shows good image characteristics.

[0128]

The electrophotographic photoreceptor according to the first aspect exhibits high sensitivity and low residual potential. The electrophotographic photoreceptor according to the second aspect exhibits the effects of the electrophotographic photoreceptor according to the first aspect, exhibits higher sensitivity and lower residual potential, and has better image characteristics. The electrophotographic photoreceptor according to the third aspect has the effects of the electrophotographic photoreceptor according to the first aspect, exhibits higher sensitivity and lower residual potential, and further has excellent dark decay rate and image characteristics.
The electrophotographic photoreceptor according to the fourth aspect has the effects of the first aspect of the present invention, provides an electrophotographic photoreceptor having a sensitivity that can be arbitrarily adjusted, and further having excellent image characteristics.
The coating liquid for a charge transporting layer according to claim 5 is suitable for forming a charge transporting layer of an electrophotographic photoreceptor having high sensitivity and low residual potential.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a benzidine derivative (Exemplary Compound No. 3) obtained by synthesis (B).

FIG. 2 is an X-ray diffraction spectrum of a dried product obtained in Production Example 1.

FIG. 3 is an X-ray diffraction spectrum of a crystal of the phthalocyanine composition (I) obtained in Production Example 1.

FIG. 4 is an X-ray diffraction spectrum of a crystal of (A) phthalocyanine composition (II) obtained in Production Example 2.

FIG. 5 is an X-ray diffraction spectrum of a crystal of (A) phthalocyanine composition (III) obtained in Production Example 3.

6 is an X-ray diffraction spectrum of a crystal of (A) a phthalocyanine composition (IV) obtained in Production Example 4. FIG.

FIG. 7 shows differential scanning calorimetry data of a charge transport layer coating film using the charge transport layer coating liquid prepared in Example 1.

FIG. 8 shows differential scanning calorimetry data of a charge transport layer coating film using the charge transport layer coating liquid prepared in Comparative Example 2.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeru Hayashida 48 Wadai, Tsukuba, Ibaraki Prefecture Within Tsukuba Development Laboratory, Hitachi Chemical Co., Ltd. Chemical Industry Co., Ltd. Yamazaki Plant

Claims (5)

[Claims] 1. An electrophotographic photoreceptor having a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance on a conductive substrate, wherein the charge generating substance contains (A) phthalocyanine. The charge transport material containing a phthalocyanine composition is represented by the following general formula (I): (Wherein, R ¹ independently represents a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, and two R ^{2 s} each independently represent a hydrogen atom or an alkyl group. Wherein m is an integer of 0 to 5, and a plurality of R ^{1 s} may be the same or different.) 2. The method according to claim 1, wherein (A) the phthalocyanine composition is CuK.
In the X-ray diffraction spectrum of α, the Bragg angle (2θ ±
2. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member has main diffraction peaks at 7.5 degrees, 24.2 degrees and 27.3 degrees (0.2 degrees). 3. The method according to claim 1, wherein (A) the phthalocyanine composition is CuK
In the X-ray diffraction spectrum of α, the Bragg angle (2θ ±
The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor has main diffraction peaks at 17.9 degrees, 24.0 degrees, 26.2 degrees and 27.2 degrees (0.2 degrees). 4. The X-ray diffraction spectrum of CuKα, wherein the charge generating substance has a Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees, 22.5 degrees, 24.3 degrees, 25.3 degrees, and 2 degrees.
In the X-ray diffraction spectra of the phthalocyanine composition having a main diffraction peak at 8.6 degrees and CuKα, the Bragg angles (2θ ± 0.2 degrees) of 17.9 degrees, 24.0 degrees,
2. The electrophotographic photoreceptor according to claim 1, comprising a phthalocyanine composition having main diffraction peaks at 6.2 degrees and 27.2 degrees. 5. A coating solution for a charge transport layer, comprising (B) the benzidine derivative represented by the general formula [I] as a charge transport material.