JP2003270863A - Electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having a high electrification potential and high sensitivity and capable of showing stable performance without changing various kinds of characteristics even when it is repeatedly used. <P>SOLUTION: The electrophotographic photoreceptor having a photosensitive layer containing a charge generating substance and a charge transfer substance as structural components on a conductive supporting body, is characterized in that the photoreceptor contains at least one kind of phthalocyanines as the charge generating substance and at least one kind of compound expressed by general formula (1) as the charge transfer substance. In general formula (1), R<SP>1</SP>represents an alkyl group, R<SP>2</SP>represents hydrogen atom, an alkyl group or a halogen atom, and each of Ar<SP>1</SP>and Ar<SP>2</SP>represents an aryl group or a heterocyclic group which may have a substituent. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor containing a specific compound and a phthalocyanine compound.

[0002]

2. Description of the Related Art In recent years, the use of electrophotography has spread not only to the field of copying machines but also to fields in which photographic technology has been used in the past, such as printing plate materials, slide films, and microfilm, and lasers, LEDs, and CRTs. Applications to high-speed printers that use a light source are also under consideration. Therefore, the demand for electrophotographic photoreceptors is becoming more sophisticated and wider.
Inorganic photoconductive substances such as selenium, cadmium sulfide, zinc oxide, and silicon have been known as electrophotographic photoreceptors, and have been widely studied and put to practical use. While these inorganic materials have many advantages, they also have various drawbacks. For example, selenium has drawbacks that it is difficult to produce under conditions and is easily crystallized by heat or mechanical shock, and cadmium sulfide and zinc oxide have poor moisture resistance and durability. It has been pointed out that silicon has insufficient chargeability and is difficult to manufacture. Furthermore, selenium and cadmium sulfide have toxicity problems.

On the other hand, organic photoconductive materials have good film-forming properties, excellent flexibility, light weight, good transparency, and are sensitized to a wide range of wavelengths by a suitable sensitizing method. Because of its advantages such as easy body design, its practical application is gradually gaining attention.

By the way, the photosensitive member used in the electrophotographic technique is generally required to have the following basic properties. That is, (1) high chargeability against corona discharge in the dark, (2) little leakage (dark decay) of the obtained charged charge in the dark, and (3) charge charging by light irradiation. The light is rapidly dissipated (4), and (4) there is little residual charge after light irradiation.

However, much research has been conducted on photoconductive polymers such as polyvinylcarbazole as an organic photoconductive substance, but these are not necessarily sufficient in film formability, flexibility and adhesiveness. In addition, it is difficult to say that the photoconductor has the basic properties described above.

On the other hand, regarding the organic low-molecular-weight photoconductive compound, by selecting a binder or the like used for forming the photoconductor, the photoconductor having excellent mechanical strength such as film-forming property, adhesive property and flexibility. However, it is difficult to find a compound suitable for retaining the highly sensitive property.

In order to improve such a point, an organic photoreceptor having higher sensitivity characteristics has been developed, in which different substances have a charge generating function and a charge transporting function. A characteristic of such a photoconductor, which is called a function-separated type, is that materials suitable for each function can be selected from a wide range, and many studies have been carried out because a photoconductor having arbitrary performance can be easily produced. Has been promoted.

Of these, various substances such as phthalocyanine pigments, squarium dyes, azo pigments, and perylene pigments have been investigated as substances in charge of the charge generation function. Among them, azo pigments can have various molecular structures. In addition, since high charge generation efficiency can be expected, it has been widely studied and put into practical use. However, in this azo pigment, the relationship between the molecular structure and the charge generation efficiency has not yet been clarified. The reality is that we are conducting an enormous amount of synthetic research to search for the optimal structure, but those that fully satisfy the basic properties and high durability required for the photoreceptors listed above are , Not yet obtained.

Further, in recent years, laser beam printers and the like, which have advantages of high speed, high image quality and non-impact using laser light as a light source instead of conventional white light, have come into widespread use together with the progress of information processing systems. There is a demand for the development of materials that can meet the demands. Particularly, in recent years, semiconductor lasers, whose applications to compact discs, optical discs and the like have been increased and whose technological progress has been remarkable, have been actively applied in the printer field as compact and highly reliable light source materials. In this case, since the wavelength of the light source is around 780 nm, a photoconductor having high sensitivity to long wavelength light around 780 nm is suitable, and its development is strongly desired. Among them, particularly, a photoconductor using phthalocyanine having light absorption in the near infrared region has been actively developed, but a satisfactory one has not been obtained yet.

On the other hand, there are a hole transporting substance and an electron transporting substance as the substances in charge of the charge transporting function. Various substances such as hydrazone compounds and styryl compounds are considered as hole transporting substances, and various substances such as 2,4,7-trinitro-9-fluorenone and diphenoquinone derivatives are considered as electron transporting substances.
Although it is being put to practical use, the fact is that it is also conducting an enormous amount of synthetic research to search for the optimal structure. In fact, many improvements have been made so far, but none of them have sufficiently obtained the basic properties and high durability required for the above-mentioned photoreceptor.

As described above, various improvements have been made in the production of the electrophotographic photosensitive member, but the basic properties and high durability required for the photosensitive member listed above are sufficiently satisfied. The current situation is that nothing has been obtained yet.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member which has a high charging potential and high sensitivity, and which can exhibit stable performance without changing various characteristics even after repeated use. .

[0013]

Means for Solving the Problems As a result of research conducted by the inventors to achieve the above object, Japanese Patent Application No. 2001-3271
The inventors have found that a photoconductor having extremely good sensitivity and durability can be obtained by combining a compound having a specific structure described in No. 73 with phthalocyanines, and completed the present invention. Here, the compound having a specific structure is a compound represented by the following general formula (1).

[0014]

[Chemical 2]

In the general formula (1), R ¹ represents an alkyl group, and R ² represents a hydrogen atom, an alkyl group or a halogen atom. Ar ¹ and Ar ² each represent an aryl group or a heterocyclic group which may have a substituent.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), specific examples of R ¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. Linear alkyl group such as isopropyl group, sec-butyl group, tert-butyl group, isobutyl group, isopentyl group, neopentyl group, tert.
-Pentyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, isohexyl group, 1-methypentyl group, 1-ethylbutyl group, 1,3-dimethylbutyl group, 1 -Ethyl-2
-Methylpropyl group, 1,1-dimethylbutyl group, 2-
Methylpentyl group, 3-methylpentyl group, 1,2-dimethylbutyl group, 1-ethyl-1-methylpropyl group,
Branched alkyl groups such as 2,2-dimethylbutyl group, 1,2,2-trimethylpropyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, and 1,1,2-trimethylpropyl group, Examples thereof include a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and an alkyl group in which the above-described linear alkyl group, branched alkyl group, and cycloalkyl group are further bonded. . Specific examples of R ² include a hydrogen atom, the above-mentioned alkyl group, a halogen atom such as a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.

Specific examples of Ar ¹ and Ar ² are:
Aryl group such as phenyl group and naphthyl group, pyridyl group,
Heterocyclic groups such as thienyl group and furyl group can be mentioned. Ar ¹ and Ar ² may have a substituent, and specific examples thereof include the above-mentioned alkyl group and halogen atom.

Specific examples of the compound represented by the general formula (1) according to the present invention are shown below, but the invention is not limited thereto.

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

[0030]

[Chemical 14]

[0031]

[Chemical 15]

The compound represented by the general formula (1) according to the present invention can be produced by the method described in the previously proposed Japanese Patent Application No. 2001-327173.

As the phthalocyanines, many compounds are known as pigments for general color materials or electrophotography, and any of these compounds can be used in the present invention. As a specific example thereof, Japanese Patent Laid-Open No. 51-108847.
No. 51-117637 and No. 56-696.
44, 57-211149, 58-1.
58649, 58-215655, and 5
9-44053, 59-44054, 59-128544, 59-133550, 59-133551 and 59-17484.
6, gazette 60-2061 gazette, gazette 61-2034.
No. 61, No. 61-217050, No. 62-2
No. 75272, No. 62-296150, No. 6
No. 3-17457, No. 63-286857,
No. 63-95460, JP-A No. 1-144057, JP-A No. 64-38753, and JP-A 1-20.
No. 4968, No. 1-2221459, and No. 1-2.
47469, 1-268763, 1-
No. 312551, No. 2-289657, No. 3
No. 227372, No. 4-277562, No. 4-360150, No. 5-45914, No. 5-66594, No. 5-93366, No. 7
Examples thereof include phthalocyanine compounds described in JP-A-53892. Among these, metal-free phthalocyanines, any one of titanium atom, copper atom, aluminum atom, gallium atom, germanium atom, indium atom, magnesium atom, tin atom, vanadium atom, zinc atom, cobalt atom or nickel atom as the central metal atom. More preferred are phthalocyanines containing

Among the metal-free phthalocyanines, particularly preferable examples in the present invention are Bragg angles (2θ ± 0.2 °) of 7.6 ° and X-ray of CuKα1.541 Å in the X-ray diffraction spectrum. 2 °, 1
Metal-free phthalocyanine (τ type metal-free phthalocyanine) showing major peaks at 6.8 °, 17.4 °, 20.4 °, and 20.9 °, 7.5 °, 9.1 °, 16.8 ° 1
7.3 °, 20.3 °, 20.8 °, 21.4 °, 2
Metal-free phthalocyanine (τ'-type metal-free phthalocyanine) showing a major peak at 7.4 °, 7.5 °, 9.1
Metal-free phthalocyanine (X-type metal-free phthalocyanine) showing major peaks at 1 °, 16.7 °, 17.3 °, 22.3 °, 7.6 °, 9.2 °, 16.8 °, 17. Four
°, 28.5 ° or 7.6 °, 9.2 °, 16.8
Metal-free phthalocyanine (η-type metal-free phthalocyanine) having major peaks at 1 °, 17.4 °, 21.5 °, and 27.5 °, 7.5 °, 9.1 °, 16.8 °, 17. Three
°, 20.3 °, 20.8 °, 21.4 °, 27.4 °
Or 7.5 °, 9.1 °, 16.8 °, 17.3
°, 20.3 °, 20.8 °, 21.4 °, 22.1
Metal-free phthalocyanine (η'-type metal-free phthalocyanine) showing major peaks at °, 27.4 °, and 28.5 °,
7.7 °, 9.3 °, 16.9 °, 22.4 °, 28.
Metal-free phthalocyanine showing a major peak at 8 °, 6.
Metal-free phthalocyanine showing a major peak at 7 °, 6.
7 °, 8.7 °, 15.1 °, 17.7 °, 23.8
Metal-free phthalocyanine showing major peaks at °, 26.1 °, 27.4 °, 30.0 °, 6.7 °, 7.2 °,
13.4 °, 14.5 °, 15.2 °, 16.0 °, 2
0.2 °, 21.7 °, 24.0 °, 24.8 °, 2
Metal-free phthalocyanine showing major peaks at 6.6 ° and 27.3 °, 6.6 °, 13.4 °, 14.5 °, 2
Metal-free phthalocyanine showing major peaks at 0.2 °, 24.8 °, 26.6 °, 27.2 °, 6.7 °, 7.
3 °, 13.5 °, 14.9 °, 15.9 °, 16.7
Metal-free phthalocyanine showing major peaks at °, 24.7 °, 26.1 °, 7.4 °, 9.0 °, 16.5 °,
17.2 °, 22.1 °, 23.8 °, 27.0 °, 2
Metal-free phthalocyanine showing a major peak at 8.4 °,
Metal-free phthalocyanine showing a shoulder at 13.5 ° around 15.2 °, and 24.8 around 26.8 °
Mention may be made of metal-free phthalocyanines having shoulders at °.

Among the phthalocyanines containing a titanium atom as a central metal atom, a particularly preferable example in the present invention is CuKα1.54 in X-ray diffraction spectrum.
Bragg angle (2θ ± 0.2 for 1 angstrom X-ray
°) 7.5 °, 12.3 °, 16.3 °, 25.3 °,
8. Titanyloxyphthalocyanine (α-type titanyloxyphthalocyanine) showing a major peak at 28.7 °,
3 °, 10.6 °, 13.2 °, 15.1 °, 15.7
°, 16.1 °, 20.8 °, 23.3 °, 26.3
Titanyloxyphthalocyanine (β-type titanyloxyphthalocyanine) showing a major peak at 2 °, 27.1 °,
Titanyloxyphthalocyanine (C-type titanyloxyphthalocyanine) showing major peaks at 7.0 °, 15.6 °, 23.4 °, and 25.5 °, 6.9 °, 15.5.
, Titanyloxyphthalocyanine (m-type titanyloxyphthalocyanine) showing a major peak at 23.4 °,
9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.
Titanyloxyphthalocyanine (Y-type titanyloxyphthalocyanine) showing major peaks at 5 °, 24.1 °, and 27.3 °, 7.3 °, 17.7 °, 24.0 °, 2
Titanyloxyphthalocyanine (γ-type titanyloxyphthalocyanine) showing major peaks at 7.2 ° and 28.6 °, 9.0 °, 14.2 °, 23.9 °, 27.1 °.
Titanyloxyphthalocyanine (type I titanyloxyphthalocyanine) showing a major peak at 7.4 °, 1
1.0 °, 17.9 °, 20.1 °, 26.5 °, 2
Titanyloxyphthalocyanine (E-type titanyloxyphthalocyanine) showing a major peak at 9.0 °, 7.4
°, 10.1 °, 12.4 °, 24.1 °, 25.2
Titanyloxyphthalocyanine (ω-type titanyloxyphthalocyanine) showing major peaks at 2 ° and 28.5 °,
7.5 °, 22.4 °, 24.4 °, 25.4 °, 2
Titanyloxyphthalocyanine showing major peaks at 6.2 °, 27.2 °, 28.6 °, 9.2 °, 13.1
Titanyloxyphthalocyanine showing major peaks at 20.7 °, 26.2 °, 27.1 °, 7.3 °, 2
Titanyloxyphthalocyanine showing major peaks at 2.9 ° and 27.4 °, 7.6 °, 10.5 °, 12.5
°, 15.6 °, 16.4 °, 17.7 °, 26.3
Titanyloxyphthalocyanine showing a major peak at 2 °, 28.9 °, 30.5 ° and 32.0 °, Titanyloxyphthalocyanine showing a major peak at 27.3 °,
7.4 °, 11.0 °, 17.9 °, 20.1 °, 2
Titanyloxyphthalocyanine showing major peaks at 6.4 ° and 29.0 °, 6.8 °, 9.7 °, 15.4 °
Titanyloxyphthalocyanine showing a major peak in
9.2 °, 11.6 °, 13.0 °, 24.1 °, 2
Titanyloxyphthalocyanine showing major peaks at 6.2 ° and 27.2 °, 9.1 °, 12.2 °, 16.3
Titanyloxyphthalocyanine showing major peaks at °, 26.9 °, 7.4 °, 9.2 °, 10.4 °, 1
1.6 °, 13.0 °, 14.3 °, 15.0 °, 1
5.5 °, 23.4 °, 24.1 °, 26.2 °, 2
Titanyloxyphthalocyanine showing a major peak at 7.2 °, 4.8 °, 9.6 °, titanyloxyphthalocyanine showing a major peak at 26.2 °, 6.5 °, 1
Titanyloxyphthalocyanine showing major peaks at 4.5 ° and 23.8 °, 7.0 °, 9.1 °, 14.1
Titanyloxyphthalocyanine showing major peaks at °, 18.1 °, 26.2 °, 6.8 °, 14.9 °, 2
Titanyloxyphthalocyanine showing major peaks at 4.8 ° and 26.2 °, titanyloxyphthalocyanine showing major peaks at 7.5 ° and 27.3 °, 7.3 °,
Titanyloxyphthalocyanine showing major peaks at 19.4 °, 21.5 °, 23.8 °, 10.5 °, 1
Titanyloxyphthalocyanine showing major peaks at 2.6 °, 15.0 °, 26.6 °, 8.5 °, 13.6
°, 17.1 °, 18.0 °, 23.9 °, 27.4 °
Titanyloxyphthalocyanine showing a major peak in
Titanyloxyphthalocyanine showing major peaks at 8.9 °, 11.4 °, 27.2 °, 6.8 °, 26.1
, Titanyloxyphthalocyanine showing a major peak at 27.1 °, titanyloxyphthalocyanine showing a major peak at 26.2 °, 7.3 °, 15.2 °, 2
Titanyloxyphthalocyanine showing a major peak at 6.2 °, 13.1 °, 20.6 °, 26.1 °, 27.
Titanyloxyphthalocyanine showing a major peak at 0 °, 6.7 °, 7.4 °, 10.2 °, 12.6 °, 1
5.2 °, 16.0 °, 17.1 °, 18.2 °, 2
2.4 °, 23.2 °, 24.2 °, 25.2 °, 2
Titanyloxyphthalocyanine showing a major peak at 8.5 °, 6.8 °, titanyloxyphthalocyanine showing a major peak at 27.3 °, 9.5 °, 24.1 °,
Titanyloxyphthalocyanine showing a major peak at 27.2 °, 7.2 °, 14.2 °, 24.0 °, 27.
Titanyloxyphthalocyanine showing a major peak at 2 °, 21.6 °, titanyloxyphthalocyanine showing a major peak at 28.0 °, titanyloxyphthalocyanine showing a major peak at 9.6 °, 27.2 °, 7.
Titanyloxyphthalocyanine showing major peaks at 5 °, 22.5 ° and 28.6 °, titanyloxyphthalocyanine showing major peaks at 8.4 °, 7.6 °, 1
0.3 °, 12.7 °, 16.3 °, 22.7 °, 2
Titanyloxyphthalocyanine showing major peaks at 4.3 °, 25.5 °, 28.6 °, 6.8 °, 7.4
°, 15.0 °, 24.7 °, 26.2 °, 27.2 °
Titanyloxyphthalocyanine showing a major peak in
And amorphous titanyloxyphthalocyanine which does not show a clear peak.

Among the phthalocyanines containing an aluminum atom as the central metal atom, a particularly preferable example in the present invention is CuKα in the X-ray diffraction spectrum.
Bragg angle (2θ of 1.541 angstrom X-ray)
± 0.2 °) 6.7 °, 11.2 °, 16.7 °, 2
Chloroaluminum phthalocyanine showing a major peak at 5.6 °, chloroaluminum phthalocyanine showing a major peak at 7.0 °, chloroaluminum phthalocyanine showing a major peak at 25.5 °, and 6.5.
°, 11.1 °, 13.7 °, 17.0 °, 22.0
Examples thereof include chloroaluminum phthalocyanine showing major peaks at 2 °, 23.0 °, 24.1 °, and 25.7 °.

Among the phthalocyanines containing an indium atom as a central metal atom, particularly preferable examples in the present invention are CuKα1.
Bragg angle (2θ ± 2) for X-ray of 541 Å
0.2 °) 7.4 °, 16.7 °, 25.3 °, 27.
Bromoindium phthalocyanine showing major peaks at 5 ° and 28.4, and 7.4 °, 16.7 °, and 27.
An example is chloroindium phthalocyanine, which shows a major peak at 8 °.

Among the phthalocyanines containing a vanadium atom as the central metal atom, particularly preferable examples in the present invention are CuKα1.
Bragg angle (2θ ± 2) for X-ray of 541 Å
0.2 °) 9.3 °, 10.7 °, 13.1 °, 15.
1 °, 15.7 °, 16.1 °, 20.7 °, 23.3
Vanadyloxyphthalocyanine showing major peaks at °, 26.2 °, 27.1 °, 7.5 °, 24.2 °, 2
Vanadyloxyphthalocyanine showing major peaks at 7.2 ° and 28.6 °, 14.3 °, 18.0 °, 24.
Vanadyloxyphthalocyanine showing major peaks at 1 ° and 27.3 °, 7.4 °, 10.3 °, 12.6 °,
16.3 °, 17.8 °, 18.5 °, 22.4 °, 2
Mention may be made of vanadyloxyphthalocyanine showing major peaks at 4.2 °, 25.4 °, 27.2 °, and 28.6 °, and amorphous vanadyloxyphthalocyanine showing no distinct peaks.

Among the phthalocyanines containing a gallium atom as the central metal atom, a particularly preferable example in the present invention is CuKα1.5 in the X-ray diffraction spectrum.
Bragg angle (2θ ± 0.
2 °) 7.4 °, 16.6 °, 25.5 °, 28.3 °
Chlorogallium phthalocyanine showing a major peak in
Chlorogallium phthalocyanine showing major peaks at 6.7 °, 15.2 °, 20.5 °, 27.0 °, 6.7
°, 13.7 °, 16.3 °, 20.9 °, 26.3 °
Chlorogallium phthalocyanine showing a major peak in
7.5 °, 9.5 °, 11.0 °, 13.5 °, 19.
1 °, 20.3 °, 21.8 °, 25.8 °, 27.1
, Chlorogallium phthalocyanine showing a major peak at 33.0 °, 11.0 °, 13.5 °, and chlorogallium phthalocyanine showing a major peak at 27.1 °,
Chlorogallium phthalocyanine showing major peaks at 6.8 °, 17.3 °, 23.6 °, 26.9 °, 8.7
Chlorogallium phthalocyanine showing major peaks at ˜9.2 °, 17.6 °, 27.4 °, 28.8 °, 2
The main peak appears at 7.1 ° and the other peaks are 2
Chlorogallium phthalocyanine having a strength of 10% or less of 7.1 °, 7.5 °, 9.9 °, 12.5 °, 16.
Hydroxygallium phthalocyanine showing major peaks at 3 °, 18.6 °, 25.1 °, and 28.3 °, 7.7
Hydroxygallium phthalocyanine showing major peaks at °, 16.5 °, 25.1 ° and 26.6 °, 7.9
Hydroxygallium phthalocyanine showing major peaks at °, 16.5 °, 24.4 °, 27.6 °, 7.0
°, 7.5 °, 10.5 °, 11.7 °, 12.7 °,
17.3 °, 18.1 °, 24.5 °, 26.2 °, 2
Hydroxygallium phthalocyanine showing a major peak at 7.1 °, 6.8 °, 12.8 °, 15.8 °, 2
Hydroxygallium phthalocyanine showing a major peak at 6.0 °, and 7.4 °, 9.9 °, 25.0 °,
Examples thereof include hydroxygallium phthalocyanine showing major peaks at 26.2 ° and 28.2 °.

Among the phthalocyanines containing a copper atom as a central metal atom, a particularly preferable example in the present invention is CuKα1.541 in X-ray diffraction spectrum.
Bragg angle (2θ ± 0.2 for angstrom X-ray
°) 7.0 °, 9.2 °, 12.5 °, 16.8 °, 1
8.6 °, 21.3 °, 23.8 °, 26.2 °, 2
Copper phthalocyanine (β-type copper phthalocyanine) showing major peaks at 8.0 °, 30.5 °, 7.6 °, 9.1
°, 14.2 °, 17.4 °, 20.4 °, 21.2
°, 23.0 °, 26.5 °, 27.2 °, 29.5 °
Copper phthalocyanine (ε-type copper phthalocyanine) showing a major peak at 7.0 °, 9.8 °, 15.8 °, 24.
7. Copper phthalocyanine (α-type copper phthalocyanine) showing major peaks at 9 °, 26.7 °, and 27.3 °, and 7.
Copper phthalocyanine which shows a main peak at 0 degree, 7.7 degree, and 9.2 degree can be mentioned.

Among the phthalocyanines containing a germanium atom as the central metal atom, a particularly preferable example in the present invention is CuKα in the X-ray diffraction spectrum.
Bragg angle (2θ of 1.541 angstrom X-ray)
± 0.2 °) 9.0 °, 11.2 °, 17.1 °, 1
8.1 °, 20.9 °, 22.7 °, 25.8 °, 2
An example is diphenoxygermanium phthalocyanine, which shows a major peak at 9.3 °.

In the present invention, the phthalocyanine composition described in JP-A-2000-313819 may be used as the phthalocyanine. Among the phthalocyanine compositions, a phthalocyanine composition containing titanyloxy phthalocyanine and a metal-free phthalocyanine is preferable, and a particularly preferable example thereof is a Bragg angle (2θ ± 0.2 °) 7.0
°, 9.0 °, 14.1 °, 18.0 °, 23.7 °,
A phthalocyanine composition showing a major peak at 27.3 ° can be mentioned. It is preferable to use this phthalocyanine composition because a photoreceptor having particularly good sensitivity and durability can be obtained.

The method for producing the phthalocyanine compound used in the present invention includes phthalodinitrile and a metal chloride,
Alternatively, a phthalodinitrile method in which an alkoxy metal is heated and melted or heated in the presence of an organic solvent, a Weyler method in which phthalic anhydride is heated and melted or heated in the presence of an organic solvent, cyanobenzamide and a metal salt are used. There is a method of reacting at a high temperature, a method of reacting dilithium phthalocyanine with a metal salt, and the like, but the method is not limited thereto. As the solvent used in the reaction, various organic solvents can be used, but α-chloronaphthalene, β-chloronaphthalene, α-methylnaphthalene, methoxynaphthalene, diphenylnaphthalene, ethylene glycol, dialkyl ether, quinoline, sulfolane, A reaction-inert high boiling point solvent such as dichlorobenzene, N-methyl-2-pyrrolidone, or dichlorotoluene is preferable.

The phthalocyanine compound obtained by the above-mentioned method is treated with acid, alkali, acetone, methanol, ethanol, methyl ethyl ketone, tetrahydrofuran, pyridine, quinoline, sulfolane, α-chloronaphthalene,
A highly pure phthalocyanine compound that can be used for electrophotography can be obtained by purification with toluene, xylene, dioxane, chloroform, dichloroethane, N, N-dimethylformamide, N-methyl-2-pyrrolidone or the like. As a purification method, various methods such as a washing method, a recrystallization method, an extraction method such as Soxhlet, a heat suspension method, and a sublimation method are known, and any of these methods can be used. The purification method is not limited to these, and any known method for removing unreacted substances and reaction byproducts may be used.

Further, as a method for converting the phthalocyanine compound into a required crystal form, a method by acid treatment such as an acid pasting method, an acid slurry method, a paint conditioner or a ball mill such as a salt milling method or a solvent milling method, A method of applying mechanical shearing force with a sand mill, a mortar or the like, a method of heating, a method of treating with an organic solvent and the like are known, but for the crystal form conversion of the phthalocyanine compound of the present invention, any method is required. Can be used alone or in combination of two or more methods.

Next, synthesis examples and X-ray diffraction spectra of the phthalocyanines used in the present invention are already proposed in JP-A-10-69107 and JP-A-10-142819.
It is described in Japanese Patent Publication No. Further, the phthalocyanine composition used in the present invention has been proposed in JP-A 2000-
It can be manufactured by the method described in Japanese Patent No. 313819. An example of the X-ray diffraction spectrum of the phthalocyanine composition is shown in FIG.

There are various types of photoreceptors, and any of them can be used. For example, a single-layer type photoreceptor in which a charge generating substance, a charge transporting substance, and a photosensitive layer made of a film-forming binder resin are provided on a conductive support,
An example is a laminated type photoreceptor in which a charge generating layer composed of a charge generating substance and a binder resin and a charge transporting layer composed of a charge transporting substance and a binder resin are provided on a conductive support. Either the charge generation layer or the charge transport layer may be the upper layer. If necessary, an undercoat layer may be provided between the conductive support and the photosensitive layer, an overcoat layer may be provided on the surface of the photoreceptor, and an intermediate layer may be provided between the charge generation layer and the charge transport layer in the case of a laminated type photoreceptor. Can be provided. As a support for producing a photoconductor using the compound of the present invention, a metal drum, a metal plate, a conductive paper, a sheet of plastic film, a drum-shaped or belt-shaped support and the like are used. .

As the film-forming binder resin used for forming the photosensitive layer on those supports, various resins can be mentioned depending on the field of use. For example, in the application of photoconductor for copying, polystyrene resin, polyvinyl acetal resin, polyvinyl butyral resin, polysulfone resin, polycarbonate resin, vinyl acetate / crotonic acid copolymer resin,
Examples thereof include polyester resins, polyphenylene oxide resins, polyarylate resins, alkyd resins, acrylic resins, methacrylic resins, and phenoxy resins. Among these, polystyrene resin, polyvinyl acetal resin, polyvinyl butyral resin, polycarbonate resin, polyester resin, polyarylate resin and the like are excellent in potential characteristics as a photoreceptor. Further, these resins may be used alone or as a copolymer by mixing one kind or two or more kinds. The amount of these binder resins added to the photoconductive compound is 20 to 1000% by mass.
Is preferable, and 50-500 mass% is more preferable.

In the case of a laminated type photoreceptor, these resins contained in the charge generating layer are contained in an amount of 10 to 50 relative to the charge generating substance.
0 mass% is preferable, and 50-150 mass% is more preferable. If the ratio of the resin is too high, the charge generation efficiency is lowered, and if the ratio of the resin is too low, the film formability becomes a problem. The content of these resins contained in the charge transport layer is preferably 20 to 1000% by mass, more preferably 50 to 500% by mass, based on the charge transport substance. If the ratio of the resin is too high, the sensitivity is lowered, and if the ratio of the resin is too low, the repeating characteristics may be deteriorated or the coating film may be damaged.

Some of these resins include pulling, bending,
Some have weak mechanical strength such as compression. To improve this property, plasticizing agents can be added. Specifically, phthalate ester (for example, DOP, D
BP, etc., phosphoric acid ester (eg TCP, TOP
Etc.), sebacic acid ester, adipic acid ester, nitrile rubber, chlorinated hydrocarbon and the like. If these substances are added more than necessary, the electrophotographic characteristics are adversely affected, so the proportion thereof is preferably 20% or less relative to the binder resin.

Other additives such as an antioxidant and an anti-curl agent added to the photoreceptor may be added, if necessary, for improving the coating property.

The compound represented by the general formula (1) can be used in combination with other charge transport materials. The charge transport material includes a hole transport material and an electron transport material. Examples of the former include oxadiazoles disclosed in JP-B-34-5466 and JP-B-45-555.
Such as triphenylmethanes disclosed in Japanese Patent Publication No. 52-4188, etc.,
Examples thereof include the hydrazones disclosed in JP-B-55-42380 and the oxadiazoles disclosed in JP-A-56-123544. On the other hand, examples of the electron transport material include chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,
7-trinitro-9-fluorenone, 2,4,5,7-
Tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 1,3,7-trinitrodibenzothiophene, 1,3,7-trinitrodibenzothiophene- 5,
5-dioxide and the like. These charge transport materials may be used alone or in combination of two or more.

It is also possible to add a certain electron-withdrawing compound as a sensitizer which forms a charge transfer complex with the compound represented by the general formula (1) and further enhances the sensitizing effect. Examples of the electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, phenanthrenequinone, and 4-nitro. Aldehydes such as benzaldehyde, 9
-Benzoylanthracene, indandione, 3,5-
Ketones such as dinitrobenzophenone, 3,3 ′, 5,5′-tetranitrobenzophenone, phthalic anhydride, 4
Acid anhydrides such as chloronaphthalic anhydride, terephthalalmalononitrile, 9-anthrylmethylidene malononitrile, 4-nitrobenzalmalononitrile, 4- (p-
Cyano compounds such as (nitrobenzoyloxy) benzalmalononitrile, 3-benzalphthalide, 3- (α-cyano-p-nitrobenzal) phthalide, 3- (α-cyano-p-nitrobenzal) -4,5,6,7- Examples thereof include phthalides such as tetrachlorophthalide.

The phthalocyanines and the compound represented by the general formula (1) are dissolved or dispersed in a suitable solvent together with various additives according to the form of the photoreceptor, and the coating solution is added to the electroconductive support described above. The photoconductor can be produced by coating on the body and drying.

As the coating solvent, chloroform, 1,2-
Dichloroethane, dichloromethane, trichloroethane,
Halogenated hydrocarbons such as trichloroethylene, chlorobenzene and dichlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, 1,3-dioxolane, 1,
4-dioxane, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, ether solvents such as ethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone and cyclohexanone, esters such as ethyl acetate, methyl formate, methyl cellosolve acetate System solvent,
N, N-dimethylformamide, acetonitrile, N-
Examples include aprotic polar solvents such as methylpyrrolidone and dimethyl sulfoxide, alcoholic solvents and the like. These solvents can be used alone or as a mixed solvent of two or more kinds.

[0056]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 Polyvinyl butyral resin (manufactured by Sekisui Chemical; BM-1)
1.0 g was dissolved in 100 g of 1,3-dioxolane,
1.5 g of a phthalocyanine composition having an X-ray diffraction spectrum using CuKα-ray as shown in FIG. 1 as a charge generating substance was mixed, and a low alkali glass bead having a diameter of 1 mm was applied by a paint conditioner device manufactured by Red Devil. And dispersed for 4 hours. The dispersion liquid thus obtained was coated with a metal aluminum thin plate (JIS
Standard # 1050) and dried to a film thickness of 0.2
A charge generation layer of μm was formed. Next, the exemplified compound (3
1) 10 g, 10 g of polycarbonate (manufactured by Teijin Chemicals; Panlite K-1300) and 200 g of tetrahydrofuran
And the solution was applied onto the charge generation layer with an applicator and dried to form a charge transport layer having a thickness of about 20 μm.

An electrostatic recording tester (Kawaguchi Electric Co .; EPA-820) was used for the laminated photoconductor thus manufactured.
0) was used to evaluate electrophotographic characteristics. Measurement conditions: applied voltage -6 kV, static No. Three
(Turntable rotation speed mode: 10 m / mi
n). As a result, the charging potential (Vo) is -800 V, the residual potential (Vr) is -5 V, and the half-exposure amount (E1 / 2) is 0.7.
The value of looks seconds and high sensitivity was shown.

Further, the same apparatus was used to evaluate the characteristics for repeated use in which one cycle of charging-discharging (eliminating light: irradiation with white light of 400 lux × 1 second) was set as one cycle. 500
When the changes in the charging potential and the residual potential due to the repetition of 0 times were obtained, the charging potential (Vo) of the first time was -800 V,
With respect to the residual potential (Vr) of -5V, the charging potential (Vo) at the 5000th time was -795V, and the residual potential (Vr) was -5V, which showed stable characteristics with no change in potential due to repetition. In addition, the first half exposure amount (E1 / 2) of 0.7 lux · second is compared with the 5000th half exposure amount (E1 /
2) showed excellent characteristics with no change of 0.7 lux · sec.

Examples 2 to 31 Phthalocyanine composition of Example 1, exemplified compound (31)
Instead of using the phthalocyanines and exemplified compounds shown in Tables 1 to 3, a photoreceptor was prepared in the same manner as in Example 1 and its characteristics were evaluated. The results are shown in Tables 4-6.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

[Table 6]

Example 32 1 g of a phthalocyanine composition having a crystal form whose X-ray diffraction spectrum using CuKα rays is shown in FIG. 1 and 40 g of tetrahydrofuran were used together with low-alkali glass beads having a diameter of 1 mm by a paint conditioner apparatus manufactured by Red Devil. It was dispersed for 4 hours. To the dispersion thus obtained, 2.5 g of Exemplified Compound (31), 10 g of a polycarbonate resin (PCZ-200; manufactured by Mitsubishi Gas Chemical Co., Inc.), and 60 g of tetrahydrofuran were added, and further subjected to a dispersion treatment for 30 minutes by a paint conditioner device, It was coated on aluminum vapor-deposited polyester with an applicator and dried to form a photoreceptor having a film thickness of about 15 μm. The electrophotographic characteristics of this photoreceptor were evaluated in the same manner as in Example 1. However, only the applied voltage was changed to +5 kV. As a result, the first charge potential (Vo) + 400V, the residual potential (Vr) + 5V,
Half-exposure amount (E1 / 2) 1.0 lux · second, charging potential (Vo) + 395V after repeating 5000 times, residual potential (Vr) + 5V, half-exposure amount (E1 / 2) 1.0 lux · second, It showed excellent characteristics with high sensitivity and little change.

Examples 33 to 62 The phthalocyanine composition of Example 32 and the exemplified compound (3
A photoreceptor was prepared in the same manner as in Example 32 except that phthalocyanines and exemplified compounds shown in Tables 1 to 3 were used instead of 1), and the characteristics thereof were evaluated. The results are shown in Table 7-
9 shows.

[0069]

[Table 7]

[0070]

[Table 8]

[0071]

[Table 9]

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1 except that the comparative compound (54) shown below was used as the charge transporting material in place of the exemplified compound (31), and its characteristics were evaluated. as a result,
The first charging potential (Vo) is -760V, the residual potential (V
r) is -70 V, the half-exposure amount (E1 / 2) is 3.5 lux · sec, which is low in sensitivity, and the 5000th charging potential (V
o) was -485 V, the residual potential (Vr) was -115 V, and the half-dose exposure amount (E1 / 2) was 3.8 lux · sec, and a large change in potential was observed with repetition.

[0073]

[Chemical 16]

Comparative Example 2 A photoconductor was prepared in the same manner as in Example 1 except that the comparative compound (55) shown below was used as the charge transporting material in place of the exemplified compound (31), and its characteristics were evaluated. as a result,
The charging potential (Vo) for the first time is -730V, and the residual potential (V
r) was -45 V, and the half-dose exposure amount (E1 / 2) was 2.0 lux · sec, which was a relatively good result, but the 5000th charging potential (Vo) was -250 V, and the residual potential (Vr) was −
At 70 V, the half-dose exposure (E1 / 2) was 1.9 lux · sec, and a large change in the potential was observed with repetition.

[0075]

[Chemical 17]

Comparative Example 3 A photoconductor was prepared in the same manner as in Example 1 except that the comparative compound (56) shown below was used as the charge generating substance instead of the phthalocyanine composition, and the characteristics thereof were evaluated. As a result, the charging potential (Vo) is -750V and the residual potential (Vr).
Is -95V, and half exposure (E1 / 2) is 3.8 lux.
Seconds and lack of sensitivity.

[0077]

[Chemical 18]

Comparative Example 4 A photoconductor was prepared in the same manner as in Example 1 except that the following compound (57) was used as the charge generating substance instead of the phthalocyanine composition, and the characteristics were evaluated. As a result, the charge potential (Vo) at the first time was -780 V, the residual potential (Vr) was -50 V, and the half-exposure amount (E1 / 2) was 1.9 lux · sec, which were relatively good results. The 5000th charging potential (Vo) is -290V, residual potential (Vr)
Is -85V, and the half exposure (E1 / 2) is 1.8 lux.
Seconds, a large change in the electric potential was observed with repetition.

[0079]

[Chemical 19]

Comparative Example 5 A photoconductor was prepared in the same manner as in Example 32 except that the comparative compound (54) was used as the charge transporting material instead of the exemplified compound (31), and its characteristics were evaluated. As a result, the first charging potential (Vo) is +295 V and the residual potential (Vr) is +.
100V, half-exposure amount (E1 / 2) is low at 3.6 lux.sec., 5000th charging potential (Vo) is + 220V, residual potential (Vr) is + 115V, half-exposure amount (E1 / 2) It was 4.0 lux · sec, and a large change in potential was observed with repetition.

Comparative Example 6 A photoconductor was prepared in the same manner as in Example 32 except that the comparative compound (55) was used as the charge transporting material instead of the exemplified compound (31), and the characteristics thereof were evaluated. As a result, the first charging potential (Vo) is + 355V and the residual potential (Vr) is +.
75V, half exposure (E1 / 2) was 2.2 lux · sec, which was a relatively good result, but the 5000th charging potential (Vo) was + 240V and the residual potential (Vr) was +130.
V, half-exposure amount (E1 / 2) was 3.1 lux · sec, and a large change in potential due to repetition and a decrease in sensitivity were observed.

Comparative Example 7 A photoconductor was prepared in the same manner as in Example 32 except that the comparative compound (56) was used as the charge generating material instead of the phthalocyanine composition, and the characteristics were evaluated. As a result, the charging potential (Vo) is + 315V and the residual potential (Vr) is +16.
The sensitivity was insufficient at 5 V and the half-exposure amount (E1 / 2) being 4.7 lux · sec.

Comparative Example 8 A photoconductor was prepared in the same manner as in Example 32 except that the comparative compound (57) was used as the charge generating substance instead of the phthalocyanine composition, and the characteristics were evaluated. As a result, the charging potential (Vo) is + 270V and the residual potential (Vr) is +18.
The sensitivity was 0 V and the half exposure (E1 / 2) was 5.2 lux.sec.

From these results, it was found that when a phthalocyanine compound is used as the charge generating substance and a compound represented by the general formula (1) is used as the charge transporting substance, a highly sensitive and highly durable electrophotographic photoreceptor can be obtained. .

[0085]

As is apparent from the above, according to the present invention, it is possible to provide an electrophotographic photosensitive member having high sensitivity and high durability.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction spectrum diagram of a phthalocyanine composition.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/083 G03G 9/08 331 9/087 325 101 F term (reference) 2H005 AA01 AA02 AA06 AA08 CA04 CA08 CA16 CB13 DA02 EA03 EA05 EA06 EA07

Claims (14)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer containing a charge generating substance and a charge transporting substance as constituents on a conductive support, wherein at least one phthalocyanine compound is used as the charge generating substance and the following general formula is used as the charge transporting substance. (1)
An electrophotographic photoreceptor comprising at least one compound represented by: [Chemical 1] (In the general formula (1), R ¹ represents an alkyl group, R ²
Represents a hydrogen atom, an alkyl group or a halogen atom.
Ar ¹ and Ar ² each represent an aryl group or a heterocyclic group which may have a substituent. ) 2. An electrophotographic photosensitive member characterized in that the phthalocyanines according to claim 1 are metal-free phthalocyanines. 3. The central metal atom of the phthalocyanines according to claim 1 is titanium atom, aluminum atom, gallium atom, germanium atom, indium atom, magnesium atom, tin atom, vanadium atom, zinc atom, cobalt atom, nickel atom or copper. An electrophotographic photoreceptor characterized by being an atom. 4. The metal-free phthalocyanines according to claim 2 are CuKα1.54 in X-ray diffraction spectrum.
Bragg angle (2θ ± 0.2 for 1 angstrom X-ray
°) 7.6 °, 9.2 °, 16.8 °, 17.4 °, 2
Metal-free phthalocyanine (τ type metal-free phthalocyanine) showing major peaks at 0.4 ° and 20.9 °, 7.5 °,
9.1 °, 16.8 °, 17.3 °, 20.3 °, 2
Metal-free phthalocyanine (τ'-type metal-free phthalocyanine) showing major peaks at 0.8 °, 21.4 °, and 27.4 °, 7.5 °, 9.1 °, 16.7 °, 17.3. °,
Metal-free phthalocyanine (X-type metal-free phthalocyanine) showing a major peak at 22.3 °, 7.6 °, 9.2 °,
16.8 °, 17.4 °, 28.5 ° or 7.6
°, 9.2 °, 16.8 °, 17.4 °, 21.5 °,
Metal-free phthalocyanine (η type metal-free phthalocyanine) showing a major peak at 27.5 °, 7.5 °, 9.1 °,
16.8 °, 17.3 °, 20.3 °, 20.8 °, 2
1.4 °, 27.4 ° or 7.5 °, 9.1 °, 1
6.8 °, 17.3 °, 20.3 °, 20.8 °, 2
Metal-free phthalocyanine (η'-type metal-free phthalocyanine) showing major peaks at 1.4 °, 22.1 °, 27.4 °, and 28.5 °, 7.7 °, 9.3 °, 16.9. ° 2
Metal-free phthalocyanine showing major peaks at 2.4 ° and 28.8 °, metal-free phthalocyanine showing major peaks at 6.7 °, 6.7 °, 8.7 °, 15.1 °, 17.
7 °, 23.8 °, 26.1 °, 27.4 °, 30.0
Metal-free phthalocyanine showing a major peak at °, 6.7
°, 7.2 °, 13.4 °, 14.5 °, 15.2 °,
16.0 °, 20.2 °, 21.7 °, 24.0 °, 2
Metal-free phthalocyanine showing major peaks at 4.8 °, 26.6 °, 27.3 °, 6.6 °, 13.4 °, 1
4.5 °, 20.2 °, 24.8 °, 26.6 °, 2
Metal-free phthalocyanine showing a major peak at 7.2 °,
6.7 °, 7.3 °, 13.5 °, 14.9 °, 15.
Metal-free phthalocyanine showing major peaks at 9 °, 16.7 °, 24.7 °, 26.1 °, 7.4 °, 9.0
°, 16.5 °, 17.2 °, 22.1 °, 23.8
Metal-free phthalocyanine showing major peaks at 2 °, 27.0 ° and 28.4 °, metal-free phthalocyanine showing a shoulder at 13.5 ° around 15.2 °, or 26.8
An electrophotographic photosensitive member characterized by being a metal-free phthalocyanine showing a shoulder at 24.8 ° centering on °. 5. The central metal atom of the phthalocyanines according to claim 1 is a titanium atom, and the phthalocyanines have a Bragg angle (2θ ± 0.2 °) to an X-ray of CuKα1.541 angstrom in the X-ray diffraction spectrum.
7.5 °, 12.3 °, 16.3 °, 25.3 °, 2
Titanyloxyphthalocyanine (α-type titanyloxyphthalocyanine) showing a major peak at 8.7 °, 9.3
°, 10.6 °, 13.2 °, 15.1 °, 15.7
°, 16.1 °, 20.8 °, 23.3 °, 26.3
Titanyloxyphthalocyanine (β-type titanyloxyphthalocyanine) showing a major peak at 2 °, 27.1 °,
Titanyloxyphthalocyanine (C-type titanyloxyphthalocyanine) showing major peaks at 7.0 °, 15.6 °, 23.4 °, and 25.5 °, 6.9 °, 15.5.
, Titanyloxyphthalocyanine (m-type titanyloxyphthalocyanine) showing a major peak at 23.4 °,
9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.
Titanyloxyphthalocyanine (Y-type titanyloxyphthalocyanine) showing major peaks at 5 °, 24.1 °, and 27.3 °, 7.3 °, 17.7 °, 24.0 °, 2
Titanyloxyphthalocyanine (γ-type titanyloxyphthalocyanine) showing major peaks at 7.2 ° and 28.6 °, 9.0 °, 14.2 °, 23.9 °, 27.1 °.
Titanyloxyphthalocyanine (type I titanyloxyphthalocyanine) showing a major peak at 7.4 °, 1
1.0 °, 17.9 °, 20.1 °, 26.5 °, 2
Titanyloxyphthalocyanine (E-type titanyloxyphthalocyanine) showing a major peak at 9.0 °, 7.4
°, 10.1 °, 12.4 °, 24.1 °, 25.2
Titanyloxyphthalocyanine (ω-type titanyloxyphthalocyanine) showing major peaks at 2 ° and 28.5 °,
7.5 °, 22.4 °, 24.4 °, 25.4 °, 2
Titanyloxyphthalocyanine showing major peaks at 6.2 °, 27.2 °, 28.6 °, 9.2 °, 13.1
Titanyloxyphthalocyanine showing major peaks at 20.7 °, 26.2 °, 27.1 °, 7.3 °, 2
Titanyloxyphthalocyanine showing major peaks at 2.9 ° and 27.4 °, 7.6 °, 10.5 °, 12.5
°, 15.6 °, 16.4 °, 17.7 °, 26.3
Titanyloxyphthalocyanine showing a major peak at 2 °, 28.9 °, 30.5 ° and 32.0 °, Titanyloxyphthalocyanine showing a major peak at 27.3 °,
7.4 °, 11.0 °, 17.9 °, 20.1 °, 2
Titanyloxyphthalocyanine showing major peaks at 6.4 ° and 29.0 °, 6.8 °, 9.7 °, 15.4 °
Titanyloxyphthalocyanine showing a major peak in
9.2 °, 11.6 °, 13.0 °, 24.1 °, 2
Titanyloxyphthalocyanine showing major peaks at 6.2 ° and 27.2 °, 9.1 °, 12.2 °, 16.3
Titanyloxyphthalocyanine showing major peaks at °, 26.9 °, 7.4 °, 9.2 °, 10.4 °, 1
1.6 °, 13.0 °, 14.3 °, 15.0 °, 1
5.5 °, 23.4 °, 24.1 °, 26.2 °, 2
Titanyloxyphthalocyanine showing a major peak at 7.2 °, 4.8 °, 9.6 °, titanyloxyphthalocyanine showing a major peak at 26.2 °, 6.5 °, 1
Titanyloxyphthalocyanine showing major peaks at 4.5 ° and 23.8 °, 7.0 °, 9.1 °, 14.1
Titanyloxyphthalocyanine showing major peaks at °, 18.1 °, 26.2 °, 6.8 °, 14.9 °, 2
Titanyloxyphthalocyanine showing major peaks at 4.8 ° and 26.2 °, titanyloxyphthalocyanine showing major peaks at 7.5 ° and 27.3 °, 7.3 °,
Titanyloxyphthalocyanine showing major peaks at 19.4 °, 21.5 °, 23.8 °, 10.5 °, 1
Titanyloxyphthalocyanine showing major peaks at 2.6 °, 15.0 °, 26.6 °, 8.5 °, 13.6
°, 17.1 °, 18.0 °, 23.9 °, 27.4 °
Titanyloxyphthalocyanine showing a major peak in
Titanyloxyphthalocyanine showing major peaks at 8.9 °, 11.4 °, 27.2 °, 6.8 °, 26.1
, Titanyloxyphthalocyanine showing a major peak at 27.1 °, titanyloxyphthalocyanine showing a major peak at 26.2 °, 7.3 °, 15.2 °, 2
Titanyloxyphthalocyanine showing a major peak at 6.2 °, 13.1 °, 20.6 °, 26.1 °, 27.
Titanyloxyphthalocyanine showing a major peak at 0 °, 6.7 °, 7.4 °, 10.2 °, 12.6 °, 1
5.2 °, 16.0 °, 17.1 °, 18.2 °, 2
2.4 °, 23.2 °, 24.2 °, 25.2 °, 2
Titanyloxyphthalocyanine showing a major peak at 8.5 °, 6.8 °, titanyloxyphthalocyanine showing a major peak at 27.3 °, 9.5 °, 24.1 °,
Titanyloxyphthalocyanine showing a major peak at 27.2 °, 7.2 °, 14.2 °, 24.0 °, 27.
Titanyloxyphthalocyanine showing a major peak at 2 °, 21.6 °, titanyloxyphthalocyanine showing a major peak at 28.0 °, titanyloxyphthalocyanine showing a major peak at 9.6 °, 27.2 °, 7.
Titanyloxyphthalocyanine showing major peaks at 5 °, 22.5 ° and 28.6 °, titanyloxyphthalocyanine showing major peaks at 8.4 °, 7.6 °, 1
0.3 °, 12.7 °, 16.3 °, 22.7 °, 2
Titanyloxyphthalocyanine showing major peaks at 4.3 °, 25.5 °, 28.6 °, 6.8 °, 7.4
°, 15.0 °, 24.7 °, 26.2 °, 27.2 °
Titanyloxyphthalocyanine showing a major peak in
An electrophotographic photosensitive member characterized by being an amorphous titanyloxyphthalocyanine which does not show a clear peak. 6. The central metal atom of the phthalocyanines according to claim 1 is an aluminum atom, and the phthalocyanines have a CuKα1.54 in an X-ray diffraction spectrum.
Bragg angle (2θ ± 0.2 for 1 angstrom X-ray
) Chloro aluminum phthalocyanine showing a major peak at 6.7 °, 11.2 °, 16.7 °, 25.6 °, chloroaluminum phthalocyanine showing a major peak at 7.0 °, at 25.5 ° Chloroaluminum phthalocyanine showing a major peak, or 6.5 °, 1
1.1 °, 13.7 °, 17.0 °, 22.0 °, 2
An electrophotographic photoreceptor, which is chloroaluminum phthalocyanine showing major peaks at 3.0 °, 24.1 °, and 25.7 °. 7. The central metal atom of the phthalocyanines according to claim 1 is an indium atom, and the phthalocyanines have a CuKα1.541 in an X-ray diffraction spectrum.
Bragg angle (2θ ± 0.2 for angstrom X-ray
°) 7.4 °, 16.7 °, 25.3 °, 27.5 °,
An electrophotographic photosensitive member characterized by being bromoindium phthalocyanine showing a main peak at 28.4 or chloroindium phthalocyanine showing a main peak at 7.4 °, 16.7 °, and 27.8 °. 8. The central metal atom of the phthalocyanines according to claim 1 is a vanadium atom, and the phthalocyanines have an X-ray diffraction spectrum of CuKα1.541.
Bragg angle (2θ ± 0.2 for angstrom X-ray
°) 9.3 °, 10.7 °, 13.1 °, 15.1 °,
15.7 °, 16.1 °, 20.7 °, 23.3 °, 2
Vanadyloxyphthalocyanine showing major peaks at 6.2 ° and 27.1 °, 7.5 °, 24.2 °, 27.2
, Vanadyloxyphthalocyanine showing a major peak at 28.6 °, 14.3 °, 18.0 °, 24.1 °,
15. vanadyloxyphthalocyanine showing a major peak at 27.3 °, 7.4 °, 10.3 °, 12.6 °, 16.
3 °, 17.8 °, 18.5 °, 22.4 °, 24.2
An electrophotographic photosensitive member characterized by being vanadyloxyphthalocyanine showing major peaks at °, 25.4 °, 27.2 ° and 28.6 °, or amorphous vanadyloxyphthalocyanine showing no clear peak. 9. The central metal atom of the phthalocyanines according to claim 1 is a gallium atom, and the phthalocyanines have a Bragg angle (2θ ± 0.2 °) with respect to an X-ray of CuKα1.541 angstrom in an X-ray diffraction spectrum.
Chlorogallium phthalocyanine showing major peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 °, 6.7
Chlorogallium phthalocyanine showing major peaks at °, 15.2 °, 20.5 °, 27.0 °, 6.7 °, 1
Chlorogallium phthalocyanine showing major peaks at 3.7 °, 16.3 °, 20.9 ° and 26.3 °, 7.5
°, 9.5 °, 11.0 °, 13.5 °, 19.1 °,
20.3 °, 21.8 °, 25.8 °, 27.1 °, 3
Chlorogallium phthalocyanine showing a major peak at 3.0 °, 11.0 °, 13.5 °, chlorogallium phthalocyanine showing a major peak at 27.1 °, 6.8
Chlorogallium phthalocyanine showing major peaks at 1 °, 17.3 °, 23.6 ° and 26.9 °, 8.7-9.
Chlorogallium phthalocyanine showing major peaks at 2 °, 17.6 °, 27.4 °, 28.8 °, or 2
The main peak appears at 7.1 ° and the other peaks are 2
An electrophotographic photosensitive member characterized by being chlorogallium phthalocyanine having a strength of 10% or less at 7.1 °. 10. The central metal atom of the phthalocyanines according to claim 1 is a gallium atom, and the phthalocyanines have a CuKα1.541 in an X-ray diffraction spectrum.
Bragg angle (2θ ± 0.2 for angstrom X-ray
°) 7.5 °, 9.9 °, 12.5 °, 16.3 °, 1
Hydroxygallium phthalocyanine showing major peaks at 8.6 °, 25.1 °, and 28.3 °, 7.7 °, 1
Hydroxygallium phthalocyanine showing major peaks at 6.5 °, 25.1 ° and 26.6 °, 7.9 °, 1
Hydroxygallium phthalocyanine showing major peaks at 6.5 °, 24.4 ° and 27.6 °, 7.0 °, 7.
5 °, 10.5 °, 11.7 °, 12.7 °, 17.3
°, 18.1 °, 24.5 °, 26.2 °, 27.1 °
Hydroxygallium phthalocyanine showing a major peak at, 6.8 °, 12.8 °, 15.8 °, hydroxygallium phthalocyanine showing a major peak at 26.0 °, or 7.4 °, 9.9 °, 25.0 °, 26.2
An electrophotographic photosensitive member, which is hydroxygallium phthalocyanine showing a major peak at 2 ° and 28.2 °. 11. The central metal atom of the phthalocyanines according to claim 1 is a copper atom, and the phthalocyanines are X.
In the line diffraction spectrum, the Bragg angle (2θ ± 0.2 °) with respect to the X-ray of CuKα1.541 Å 7.
0 °, 9.2 °, 12.5 °, 16.8 °, 18.6
°, 21.3 °, 23.8 °, 26.2 °, 28.0
Copper phthalocyanine (β-type copper phthalocyanine) showing major peaks at 3 °, 3 °, 7.6 °, 9.1 °, 1
4.2 °, 17.4 °, 20.4 °, 21.2 °, 2
Copper phthalocyanine (ε-type copper phthalocyanine) showing major peaks at 3.0 °, 26.5 °, 27.2 °, 29.5 °, 7.0 °, 9.8 °, 15.8 °, 24 .9 °,
Copper phthalocyanine (α-type copper phthalocyanine) showing major peaks at 26.7 ° and 27.3 °, or 7.0 °,
An electrophotographic photosensitive member, which is copper phthalocyanine showing major peaks at 7.7 ° and 9.2 °. 12. The central metal atom of the phthalocyanines according to claim 1 is a germanium atom, and the phthalocyanines have a CuKα1.5 in an X-ray diffraction spectrum.
Bragg angle (2θ ± 0.
2 °) 9.0 °, 11.2 °, 17.1 °, 18.1
°, 20.9 °, 22.7 °, 25.8 °, 29.3 °
An electrophotographic photosensitive member characterized by being a diphenoxygermanium phthalocyanine showing a major peak in. 13. An electrophotographic photosensitive member characterized in that the phthalocyanine according to claim 1 is a phthalocyanine composition containing titanyloxyphthalocyanine and a metal-free phthalocyanine. 14. The phthalocyanine composition according to claim 1 is a phthalocyanine composition containing titanyloxyphthalocyanine and a metal-free phthalocyanine, and the phthalocyanine has a CuKα1.5 in an X-ray diffraction spectrum.
Bragg angle (2θ ± 0.
2 °) 7.0 °, 9.0 °, 14.1 °, 18.0 °,
An electrophotographic photosensitive member, which is a phthalocyanine composition showing major peaks at 23.7 ° and 27.3 °.