JP3455690B2 - Electrophotographic photoreceptor - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member which uses oxotitanyl phthalocyanine as a charge generating substance and uses an amine-hydrazone compound as a charge transporting substance and exhibits high sensitivity in the near infrared wavelength region.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors (hereinafter, simply referred to as "photoreceptors") currently in practical use include inorganic photoreceptors and organic photoreceptors that use an inorganic photoconductive material having excellent sensitivity and durability. It is classified as an organic photoconductor using a photoconductive material of the type.
Examples of the inorganic photoconductive material include ZnO (zinc oxide) based materials, CdS (cadmium sulfide) based materials, Se based materials such as a-Se (amorphous selenium) and a-AsSe (amorphous selenium arsenic), and a-Si. (Amorphous silicon) -based materials and the like.

However, the ZnO-based material cannot form a stable image for a long period of time because the added sensitizer deteriorates its chargeability due to corona discharge or light brown due to exposure. Further, the photoconductor provided with the photoconductive layer formed by dispersing ZnO in the binder resin has low sensitivity and low durability. CdS-based materials cannot obtain stable sensitivity in a humid environment, and Se-based materials are highly toxic, and crystallization easily progresses due to external factors such as temperature and humidity, resulting in reduced chargeability and image formation. White spots may occur. In addition, since a photoreceptor having a photosensitive layer using a CdS-based material and a Se-based material has low heat resistance and storage stability and is toxic,
There is a problem in its disposal, which causes pollution. The a-Si-based material, which is attracting attention as a pollution-free material, has high sensitivity and high durability, but since the photosensitive layer is manufactured by using the plasma CVD (chemical vapor deposition) method, it is caused by the manufacturing process. Image defects occur and the productivity is low, which increases the manufacturing cost.

On the other hand, an organic photoconductive material is generally easy to form a thin film by coating, has a low manufacturing cost, and has high mass productivity. In addition, since there are various kinds of organic materials themselves, a photosensitive layer having low storage stability and low toxicity can be produced by proper selection and easy disposal.
Further, the setting of the light absorption wavelength region can be easily changed, and the electrophotographic characteristics can be easily controlled by the combination of materials. Therefore, in recent years, further improvement in sensitivity and durability has been studied, and organic materials are widely used. The photosensitive member has a function separation type in which a photosensitive layer having a laminated structure of a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance is formed on a conductive support. There is a single layer type in which a photosensitive layer containing a charge generating substance and a charge transporting substance is formed on the body, and in the photoconductor using an organic material, a function separation type is mainly researched and developed.

A large number of substances having various molecular structures have been developed as the charge-transporting substance.
JP-A-59143 discloses a hydrazone type, JP-A-58-1.
No. 98043 discloses a stilbene / styryl type charge-transporting substance, and Japanese Patent Publication No. 58-32373 discloses a triarylamine type charge-transporting substance. In addition,
Phenothiazine-based, triazole-based, quinoxaline-based,
Oxadiazole type, oxazole type, pyrazoline type,
Triphenylmethane compounds, dihydronicotinamide compounds, indoline compounds and semicarbazone compounds have been developed.

Further, in recent years, an image forming apparatus such as a laser printer, which uses a laser light source instead of a white light source to achieve high speed, high image quality and non-impact, has been widely spread. In particular, various methods using a semiconductor laser as a light source, which has made remarkable progress in recent years, have been tried, and a photosensitive member having a high sensitivity in a long wavelength region around 800 nm which is a wavelength band of laser light is strongly desired.

[0007] Examples of organic materials satisfying this requirement include methine squarate dyes, indoline dyes,
Cyanine dye, pyrrolium dye, polyazo dye,
There are phthalocyanine dyes and naphthoquinone dyes. However, although methine squalic acid dyes, indoline dyes, cyanine dyes and virium dyes can have a longer wavelength, they have low stability, particularly low repeatability,
In addition, polyazo dyes are not easily made to have a long wavelength and their productivity is low, and naphthoquinone dyes have low sensitivity.

On the other hand, the phthalocyanine dye has a high sensitivity to long-wavelength light and is more stable than the above dyes.
Phthalocyanine-based compounds not only have different sensitivity peaks and physical properties depending on the presence or type of central metal, but also have a large change in physical properties due to the difference in their crystal form. "Dyes and chemicals, Vol. 24, No. 6, p. 122, 1979, Gaku Sawada ”. Further, in the case of a photoconductor using a metal phthalocyanine compound, the sensitivity peak varies depending on the central metal, but both are 700 nm to 750 n.
m is on the relatively long wavelength side, U.S. Pat. No. 3,357.
989, JP-A-49-11136, US Pat. No. 4,214,907, and British Patent No. 1268422. Therefore, it is important to research and develop the photoconductor including the examination of the crystal type of phthalocyanine.

A technique in which a specific crystal type phthalocyanine compound is selected for an electrophotographic photoreceptor has been reported. For example, JP-A-60-86551 discloses a metal-free phthalocyanine and JP-A-63-133462 discloses. Is a phthalocyanine containing aluminum, JP-A-59-
In Japanese Patent Publication No. 49544, examples using phthalocyanine using titanium as a central metal are described. Further, in Japanese Patent Publication No. 55860/1993, a photosensitive layer formed by laminating a charge transport layer containing a hydrazone compound and a binder resin on a charge generating layer containing a specific titanium phthalocyanine compound and a binder resin. The body is disclosed. Further, Japanese Patent Laid-Open No. 10-142819 discloses a photoconductor containing phthalocyanines as a charge generating substance and a specific styryl compound as a charge transporting substance. Also, as the central metal of the phthalocyanine compound, many metals such as indium and gallium are known.

Among the phthalocyanine compounds, oxotitanyl phthalocyanine has a particularly high sensitivity, and many are reported in "Electrophotographic Society Journal, Vol. 32, No. 3, p. 282" due to the difference in the diffraction angle of the X-ray diffraction spectrum. It is stated that they are classified into crystalline forms. Further, as the crystal form of oxotitanyl phthalocyanine, α-forms are disclosed in JP-A-61-217050 and JP-A-61-239248.
JP-A-62-67094 discloses A type, JP-A-63-
No. 366 and Japanese Patent Laid-Open No. 63-198067, C type, Japanese Patent Laid-Open No. 63-20365, Japanese Patent Laid-Open No. 2-8
No. 256, JP-A-1-17066 and JP-A-7-271073 disclose a Y type, JP-A-3-542.
No. 65 discloses an M type, JP-A-3-54264 discloses an M-α type, JP-A-3-128973 discloses an I type, and JP-A-62-67094 describes an I type and a II type. Each is listed.

In the crystal of oxotitanyl phthalocyanine, the lattice ruler of which is known from the structural analysis is C type,
Phase I type and Phase II type. Pha
seII type belongs to the triclinic system, and Phase I type and C
The type belongs to the monoclinic system. When the crystal forms described in the above publications are analyzed from these known crystal lattice constants, A type and I type belong to Phase I type, and α type and B type have P type.
Hase II type, M type C type. Such an explanation can be found, for example, in “J. of Imaging Science and Techn.
ology Vol. 37, No. 6, 1993, p. 605-p. 609 ".

Specifically, in JP-A-59-49544, oxo-titaniflurocyanine is vapor-deposited on a substrate to form a charge generation layer, on which 2,6-dimethoxy-9,
A photoreceptor having a charge transport layer containing 10-dihydroxyanthracene as a main component is described. However, the photoconductor has a high residual potential, there is a limitation in the method of use, and the reproducibility of electrical characteristics is low due to the nonuniformity of the film thickness by the vapor deposition method. Further, the mass productivity of the photoconductor on an industrial scale is low. Further, JP-A-61-109056 discloses a photoreceptor in which a charge transport layer containing a hydrazone compound and a binder resin is laminated on a charge generating layer containing an oxotitanyl phthalocyanine compound and a binder resin. There is. In this publication, 800
Although it has sensitivity in the wavelength region around nm, it does not reach the sensitivity required for practical high image quality and high speed. Thus, oxotitanyl phthalocyanine still has low sensitivity,
Poor potential stability after repeated use.

Generally, in an electrophotographic photosensitive member, a charge transport substance effective for a specific charge generating substance is not always effective for another charge generating substance, and conversely, a specific charge generating substance is not effective. A charge generating substance effective for a transport substance is not always effective for other charge transport substances. In other words, it is necessary to combine the charge-generating substance and the charge-transporting substance in the photoconductor, and if the combination is not appropriate, not only the sensitivity will decrease, but also the residual potential will increase and the charge will accumulate after repeated use. As a result, toner adheres to the non-image area and scumming occurs, and a clear image cannot be obtained. As described above, the combination of the charge-generating substance and the charge-transporting substance is important, but there is not necessarily a general law selection method for this combination, and it is difficult to find a charge-transporting substance suitable for a specific charge-generating substance. Have difficulty.

[0014]

As described above, in the photoconductor using the phthalocyanine compound, which is an organic photoconductive material having sensitivity in the long wavelength region, particularly the highly sensitive oxotitanyl phthalocyanine, In terms of repetitive use characteristics and stability, none of them satisfy practical requirements sufficiently.

An object of the present invention is to provide an electrophotographic photosensitive member which is excellent in photosensitivity characteristics, repeated use characteristics and stability.

[0016]

The present invention provides an electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer contains oxotitanyl phthalocyanine as a charge generating substance, and the following as a charge transporting substance. The general formula (IV-
I) containing an amine-hydrazone compound, and the oxotitanyl phthalocyanine has a Bragg angle (2θ ± 0.2 °) of 7.3 ° in an X-ray diffraction spectrum.
9.4 °, 9.6 °, 11.6 °, 13.3 °, 17.
The major diffraction peaks are shown at 9 °, 24.1 ° and 27.2 °, the intensities in the overlapping diffraction peak bundles at the Bragg angles 9.4 ° and 9.6 ° are maximum, and the Bragg angle 27. The electrophotographic photosensitive member is characterized in that it has the second highest intensity at a diffraction peak of 2 °.

[0017]

[Chemical 2]

[In the formula (IV-I), R ^{12 to} R ¹⁵ may be the same or different and each has a lower alkyl group, an aromatic hydrocarbon residue which may have a substituent or a substituent. Represents an optionally substituted heterocyclic residue or an aralkyl group optionally having a substituent. R ¹⁶ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower dialkylamino group, a trifluoromethyl group or an aralkyl group which may have a substituent. l1 is an integer of 1 to 3. ]

According to the present invention, the above-mentioned oxotitanyl phthalocyanine is contained as a charge generating substance, and the compound of the general formula (IV
-I) is a photoreceptor having a photosensitive layer containing an amine-hydrazone compound as a charge-transporting substance formed on a conductive support, and exhibits excellent photosensitivity characteristics and repeated use characteristics. It was found that the effect of suppressing surface potential decrease, residual potential increase and sensitivity deterioration was excellent. Therefore, it can be suitably mounted in a highly sensitive image forming apparatus such as a laser printer or a digital copying machine using a semiconductor laser light source.

In the present invention, the oxotitanyl phthalocyanine is diffracted in the X-ray diffraction spectrum such that the intensity at the diffraction peak at the Bragg angle of 27.2 ° overlaps at the Bragg angles of 9.4 ° and 9.6 °. It is characterized by being 80% or less of the intensity in the peak flux.

According to the present invention, it has been found that as the oxotitanyl phthalocyanine, one having an X-ray spectrum as described above is particularly preferable.

In the present invention, the oxotitanyl phthalocyanine has a plurality of diffraction peaks having the same intensity in Bragg angles of 14.1 ° to 14.9 ° in the X-ray diffraction spectrum, The plurality of the diffraction peaks are characterized by exhibiting a trapezoidal peak aggregate that is difficult to separate.

According to the present invention, it has also been found that as the oxotitanyl phthalocyanine, those having an X-ray spectrum as described above are particularly preferable.

Further, in the present invention, the oxotitanyl phthalocyanine has a diffraction peak flux in which the intensities of the oxotitanyl phthalocyanine and the Bragg angles of 9.4 ° and 9.6 ° are superposed at positions of Bragg angles of 9.0 ° in the X-ray diffraction spectrum. Of the diffraction peak, and the diffraction peak exists as a shoulder peak of the diffraction peak bundle.

According to the present invention, it has further been found that the oxotitanyl phthalocyanine particularly preferably has an X-ray spectrum as described above.

The present invention is also characterized in that the photosensitive layer has a laminated structure of a charge generating layer containing the charge generating substance and a charge transporting layer containing the charge transporting substance.

According to the present invention, the so-called function-separated type photosensitive member composed of the above-mentioned materials exhibits excellent photosensitivity characteristics and repeated use characteristics as described above, and particularly, the surface potential lowering and residual The photoconductor is excellent in the effect of suppressing potential rise and sensitivity deterioration, and the photoconductor can be suitably mounted in a high-sensitivity image forming apparatus.

The present invention is also characterized in that the photosensitive layer has a single layer structure containing the charge generating substance and the charge transporting substance.

According to the present invention, a so-called single-layer type photoreceptor composed of the above-mentioned materials exhibits excellent photosensitivity characteristics and repeated use characteristics, and in particular, a decrease in surface potential,
It is excellent in the effect of suppressing the increase in residual potential and the deterioration of sensitivity, and the photoreceptor can be suitably mounted in a highly sensitive image forming apparatus.

The present invention is also characterized by including an intermediate layer arranged between the conductive support and the photosensitive layer.

According to the present invention, the intermediate layer provided between the conductive support and the photosensitive layer has a protective function and an adhesive function,
The coatability is improved, and the charge injection from the conductive support to the photosensitive layer is improved.

[0032]

1 is a sectional view showing electrophotographic photosensitive members 8a to 8d according to an embodiment of the present invention. The photosensitive member 8a in FIG. 1A is configured by forming a photosensitive layer 4a on the conductive support 1. The photoconductor 8a is a photosensitive layer 4a.
Is a so-called function-separated type photoreceptor having a laminated structure of a charge generation layer 5 containing the charge generation substance 2 and a charge transport layer 6 containing the charge transport substance 3. In the present embodiment, the charge generation layer 5 is arranged on the conductive support 1 side,
Although the charge transport layer 6 is disposed on the above, the charge generation layer 5 and the charge transport layer 6 may be disposed in reverse. Figure 1 (B)
The photoconductor 8b has a structure similar to that of the photoconductor 8a, but is characterized in that it includes an intermediate layer 7 disposed between the conductive support 1 and the photoconductive layer 4a.

The photosensitive member 8c shown in FIG. 1C is constructed by forming a photosensitive layer 4b on the conductive support 1. Photoconductor 8c
Is a so-called single-layer type photoreceptor in which the photosensitive layer 4b contains the charge generating substance 2 and the charge transporting substance 3. Figure 1
The photoconductor 8d of (D) has a structure similar to that of the photoconductor 8c, but is characterized in that it includes an intermediate layer 7 disposed between the conductive support 1 and the photoconductive layer 4b.

The photoconductors 8a to 8d (hereinafter, collectively referred to as "photoconductor 8") are composed of the photosensitive layers 4a and 4b (hereinafter, referred to as "photoconductor 8").
When collectively referred to, it may be configured by disposing an overcoat layer (not shown) on the "photosensitive layer 4". The overcoat layer has a protective function of the photosensitive layer 4.

The conductive support 1 is aluminum,
It is realized by a conductive metallic material such as stainless steel, copper and nickel. The conductive support 1 may be realized by providing a conductive layer of aluminum, copper, palladium, tin oxide, indium oxide or the like on the surface of an insulating support such as a polyester film or paper.

The photosensitive layer 4 of the present invention contains oxotitanyl phthalocyanine as described below as the charge generating substance 2 and an amine-hydrazone compound as described below as the charge transporting substance 3.

The basic structure of oxotitanyl phthalocyanine is represented by the following general formula (VIII).

[0038]

[Chemical 3]

In the general formula (VIII), X represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, j
Represents an integer of 0 to 4.

The oxotitanyl phthalocyanine used in the present invention has a Bragg angle of 7.3 °, 9.4 °, 9.6 °, 11.6 °, 13.3 in X-ray diffraction spectrum.
Major diffraction peaks are shown at .degree., 17.9.degree., 24.1.degree. And 27.2.degree., And the Bragg angles are 9.4.degree.
It is characterized in that the intensity at the overlapping diffraction peak bundle of 6 ° is the maximum and the intensity at the diffraction peak of the Bragg angle 27.2 ° is the second.

In particular, the intensity at the diffraction peak at the Bragg angle of 27.2 ° is 80% of the intensity at the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 °.
The following is preferable, and particularly, the Bragg angle is 14.
It is preferable that a plurality of diffraction peaks having intensities substantially the same as each other be provided between 1 ° and 14.9 °, and the plurality of diffraction peaks represent trapezoidal peak-separable peak aggregates,
In particular, at the position of Bragg angle 9.0 °, there is a diffraction peak whose intensity is almost half of the overlapping diffraction peak bundles of the Bragg angles 9.4 ° and 9.6 °, and the diffraction peak is the diffraction peak bundle. It is preferably present as a shoulder peak of.

The method of synthesizing oxotitanyl phthalocyanine is described in Mosa and Thomas's "Phthalocyanine Compounds".
(MOSER and Thomas. “Phthalocianine Compound
The method described in s ″) and other known methods can be used.

For example, dichlorotitanium phthalocyanine can be obtained in good yield by heating and melting o-phthalonitrile and titanium tetrachloride or heating in the presence of an organic solvent such as α-chloronaphthalene. Furthermore, oxo titanyl phthalocyanine is obtained by hydrolyzing dichlorotitanium phthalocyanine with a base or water. Further, oxotitanyl phthalocyanine can be obtained by heating 1,3-diiminoisoindoline and tetrabutoxytitanium with an organic solvent such as N-methylpyrrolidone. The obtained oxotitanyl phthalocyanine may contain a phthalocyanine derivative in which the hydrogen atom of the benzene ring is substituted with any substituent such as chlorine, fluorine, nitro group, cyano group and sulfone group. . The crystalline form of the present invention for oxotitanyl phthalocyanine is obtained by treating oxo titanyl phthalocyanine with a water immiscible organic solvent such as dichloroethane in the presence of water.

As a method for treating oxotitanyl phthalocyanine with an organic solvent immiscible with water in the presence of water,
Examples include a method of swelling oxotitanyl phthalocyanine with water and treating it with an organic solvent, and a method of adding water to the organic solvent without performing the swelling treatment and adding an oxotitanyl phthalocyanine powder therein. It is not limited.

As a method of swelling oxotitanyl phthalocyanine with water, a method of dissolving oxo titanyl phthalocyanine in sulfuric acid and precipitating it in water to form a wet paste, and stirring / dispersing with a homomixer, a paint mixer, a ball mill, a sand mill or the like are used. Examples include a method of swelling oxotitanyl phthalocyanine with water using an apparatus to form a wet paste, but the method is not limited to these.

The oxotitanyl phthalocyanine obtained by hydrolysis is stirred in a solution or in a solution in which a binder resin is dissolved for a sufficient time, or is subjected to a milling treatment with a mechanical straining force. A crystalline form is obtained.

An apparatus used for the above-mentioned processing is
In addition to general mixers, homomixers, paint mixers, dispersers, agitators, ball mills, sand mills,
A paint shaker, a dyno mill, an attritor, an ultrasonic dispersion device, etc. can be used. After treatment, the oxotitanyl phthalocyanine is filtered, washed with methanol, ethanol, water and the like and isolated.
Also, after the treatment, a binder resin may be added and used as it is as a coating liquid. When a binder resin is added in advance during the treatment, it can be used as it is as a coating liquid.

The oxotitanyl phthalocyanine of the present invention is not limited to the one produced by the above-mentioned production method, and may be produced by any method as long as it exhibits the above-mentioned X-ray diffraction spectrum peculiar to the present invention. But it doesn't matter.

The oxotitanyl phthalocyanine thus obtained exhibits excellent characteristics as the charge generating substance 2 of the photoconductor 8.

The charge generating layer 5 or the photosensitive layer 4b may contain as the charge generating substance 2 other than the above-mentioned oxotitanyl phthalocyanine. For example, α-type, β-type, which has a different crystal form from the oxotitanyl phthalocyanine of the present invention,
Y-type and amorphous oxotitanyl phthalocyanine may be contained. Further, other phthalocyanines, azo pigments, anthraquinone pigments, perylene pigments, polycyclic quinone pigments, squarylium pigments and the like may be contained.

As described above, oxotitanyl phthalocyanine having a crystal form peculiar to the present invention is produced, and a photosensitive layer containing the oxo titanyl phthalocyanine is prepared. Since the oxotitanyl phthalocyanine exhibits a high sensitivity even in a long wavelength region, a photoreceptor having an optimum photosensitive wavelength region for an image forming apparatus using a long wavelength light source such as a semiconductor laser or an LED (light emitting diode) is used. can get. The oxotitanyl phthalocyanine has a stable crystal form and is excellent in crystal stability against a solvent and heat. Therefore, a photoreceptor using this material exhibits excellent photosensitivity characteristics and repeated use characteristics. Also, the excellent crystal stability is a great advantage not only in the production and properties of oxotitanyl phthalocyanine, but also in the production and use of the photoreceptor.

In the function-separated type photosensitive layer 4a, the charge generation layer 5 preferably contains a binder resin in addition to the charge generation substance 2. As the binder resin, polyester, polyvinyl acetate, polyacrylic acid ester,
Polymethacrylic acid ester polyester, polycarbonate, polyvinyl chloride, polyvinyl acetate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin, cellulose ester, cellulose ether and copolymers thereof alone or It may be used as a mixture of two or more kinds.

The coating liquid for forming the charge generating layer 5 by the coating method contains a solvent in addition to the charge generating substance 2 and the binder resin. As the solvent, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylene, N An aprotic polar solvent such as N, N-dimethylformamide and dimethylsulfoxide may be used alone or in combination of two or more kinds.

The charge generation layer 5 is formed by a vapor deposition method such as vacuum vapor deposition, sputtering and CVD. Further, the charge generating substance 2 and the binder resin are added to a solvent, which is pulverized and dispersed using a ball mill, a sand grinder, a paint shaker, an ultrasonic disperser or the like to obtain a coating liquid. Using the coating solution thus obtained, in the case of a sheet shape, by a coating method such as a baker applicator, bar coater, casting and spin coating, and in the case of a drum shape, a spray method, a vertical ring method and a dipping method. The charge generation layer 5 may be formed by a coating method or the like. The thickness of the charge generation layer 5 is, for example, 0.05 μm.
m to 5 μm, preferably 0.08 μm to
It is selected in the range of 1 μm.

As the amine-hydrazone compound, the amine-hydrazone compound represented by the above general formula (IV-I) is used. Among them, particularly, the following general formula (IV-I
The amine-hydrazone compound represented by I) or (IV-III) is preferable from the viewpoint of synthetic cost.

[0056]

[Chemical 4]

[In the general formula (IV-II), R ²⁵ and R ²⁶ may be the same or different and each has a lower alkyl group, an aromatic hydrocarbon residue which may have a substituent or a substituent. Represents an optionally substituted heterocyclic residue or an aralkyl group optionally having a substituent. R ²⁷ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower dialkylamino group, a trifluoromethyl group or an aralkyl group which may have a substituent. R ²⁸ and R ²⁹ may be the same or different and each has a lower alkyl group, an aromatic hydrocarbon residue which may have a substituent, a heterocyclic residue which may have a substituent, or a substituent. Represents an optionally substituted aralkyl group. l2 is 1 to 3
Is an integer. ]

[0058]

[Chemical 5]

[In general formula (IV-III), Ar ¹¹ and Ar ¹² may be the same or different, and may have an aromatic hydrocarbon residue which may have a substituent or a heterocyclic group which may have a substituent. Represents a ring residue. R ³⁰ is a hydrogen atom, a halogen atom,
It represents a lower alkyl group, a lower alkoxy group, a lower dialkylamino group, a trifluoromethyl group or an aralkyl group which may have a substituent. R ³¹ and R ³² may be the same or different and each has a lower alkyl group, an aromatic hydrocarbon residue which may have a substituent, a heterocyclic residue which may have a substituent, or a substituent. Represents an optionally substituted aralkyl group. t, u
And l3 are integers of 1 to 3. ]

In the general formulas (IV-I), (IV-II) and (IV-III), R ¹² , R ¹³ , R ¹⁴ and
R ¹⁵ , R ²⁵ , R ²⁶ , R ²⁸ , R ²⁹ , R ³¹ and R ³² may be the same or different, and may be a lower alkyl group, an aromatic hydrocarbon residue which may have a substituent, a substituent Represents a heterocyclic residue which may have or an aralkyl group which may have a substituent. Examples of the lower alkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl. Can be mentioned. Examples of the aromatic hydrocarbon residue which may have a substituent include a phenyl group and a 1-naphthyl group. Examples of the heterocyclic residue which may have a substituent include a 1-pyridyl group. The aralkyl group which may have a substituent has 1 carbon atom with a phenyl group at the terminal.
~ 3 alkyl groups can be mentioned, such as benzyl and phenethyl.

Examples of the substituents on the aromatic hydrocarbon residue, heterocyclic residue and aralkyl group include lower alkyl groups such as methyl and ethyl, lower alkoxy groups such as methoxy and ethoxy, methylamino, dimethylamino and ethyl. Examples thereof include amino groups such as amino, ethylmethylamino and diethylamino, and halogen atoms such as fluorine atom, chlorine atom and bromine atom, and it is preferable to have one or two of these substituents.

R ¹⁶ , R ²⁷ and R ³⁰ represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower dialkylamino group, a trifluoromethyl group and an aralkyl group which may have a substituent. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the lower alkyl group include R ¹² and R ²⁵ described above.
And the same lower alkyl group as described above. Examples of the lower alkoxy group include a linear or branched alkoxy group having 1 to 4 carbon atoms, and specific examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy and sec-.
Examples include butoxy and tert-butoxy.
As the lower dialkylamino group, an amino group substituted by a linear or branched alkyl group having 1 to 4 carbon atoms can be mentioned, and specific examples thereof include dimethylamino, diethylamino, diisopropylamino and dibutylamino. To be Examples of the aralkyl group include the above R ¹² ,
The same lower aralkyl group as R ²⁵ can be mentioned.

Ar ¹¹ and Ar ^{12, which} may be the same or different, each represents an aromatic hydrocarbon residue which may have a substituent and a heterocyclic residue which may have a substituent. The aromatic hydrocarbon residue which may have a substituent includes a phenyl group and a 1-naphthyl group, and the heterocyclic residue which may have a substituent includes a 1-pyridyl group. Can be mentioned.

Specific examples of amine-hydrazone compounds are shown in Table 1.
However, this does not limit the compounds of the present invention.

[0065]

[Table 1]

One or more of the above amine-hydrazone compounds may be contained as the charge transport material. Further, other charge transport material may be contained.

In the function-separated type photosensitive layer 4a, the charge transport layer 6 preferably contains a binder resin in addition to the charge transport substance 3. Examples of the binder resin include polymethylmethacrylate, polymers of vinyl compounds such as polystyrene and polyvinyl chloride, and copolymers thereof,
Examples thereof include polycarbonate, polyester, polyarylate, polyester carbonate, polysulfone, polyvinyl butyral, phenoxy resin, cellulosic resin, urethane resin, epoxy resin, and silicone resin. These may be used alone or in combination of two or more. Absent. Also, a partially crosslinked thermosetting resin may be used.

The above-mentioned amine-hydrazone compound is used in the range of 0.2 parts by weight or more and 1.5 parts by weight or less, preferably 0.3 parts by weight or more and 1.2 parts by weight or less, based on the binder resin. It is preferable to use in the range of.

In the function-separated type photosensitive layer 4a, the charge transport layer 6 may optionally contain various additives such as a leveling agent, an antioxidant and a sensitizer. As the antioxidant, α-tocopherol, hydroquinone,
Hindered amines, hindered phenols, paraphenylenediamines, aryl alkanes and their derivatives, organic sulfur compounds, organic phosphorus compounds and the like may be used. In particular, the charge transport material 3 is N, N'-
When a bisenamine compound and a benzofuran-bishydrazone compound are used, it is preferable to include α-tocopherol as an antioxidant. Note that α-tocopherol is 0.1 wt% or more and 5 wt% with respect to the charge transport substance 3.
It is preferably contained in the range of not more than%. Further, it is preferable to contain 2,6-di-t-butyl-4-methylphenol as an antioxidant. In this case, it is preferable that the 2,6-di-t-butyl-4-methylphenol is contained in the range of 0.1 wt% or more and 10 wt% or less with respect to the charge transport substance 3.

Further, the charge transport layer 6 is the charge transport layer 6 concerned.
It can be formed by a known method such as a method of dissolving or dispersing the substance to be contained in a solvent in a solvent and applying the obtained coating liquid. For example, by dissolving the charge transport substance 3 in a solvent,
Adjust the coating solution by adding the binder resin. With this coating liquid,
In the case of sheet-shaped photoreceptor, it is formed by coating method such as baker applicator, bar coater, casting and spin coating, and in the case of drum-shaped photoreceptor, it is formed by spray method, vertical ring type and dip coating method. can do.

Examples of the solvent used for the coating liquid for the charge transport layer include halogen solvents such as dichloromethane and 1,2-dichloroethane, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate. , Ethers such as tetrahydrofuran, dioxane, benzene,
Aromatic hydrocarbons such as toluene and xylene, N,
Aprotic polar solvents such as N-dimethylformamide and dimethylsulfoxide can be used.

The thickness of the charge transport layer 6 is, for example, 5 μm to
It is selected in the range of 60 μm, preferably 10 μm to 40 μm
It is selected in the range of m.

The single-layer type photosensitive layer 4b is composed of the charge transport layer 6 and the charge generating substance 2 dispersed therein. In this case, it is preferable that the particle size of oxotitanyl phthalocyanine, which is the charge generating substance 2, is sufficiently small.
A particle size of less than μm is preferred. If the amount of the charge generating substance 2 dispersed in the photosensitive layer 4b is too small, the sensitivity will be insufficient, and if it is too large, the charging property and the sensitivity will be lowered. Therefore, it is used in the range of 0.5% to 50% by weight, preferably in the range of 1% to 20% by weight, based on the total weight of the photosensitive layer 4b.

The film thickness of the photosensitive layer 4b is, for example, 5 μm to 5 μm.
It is selected in the range of 0 μm, preferably 10 μm to 40 μm
Is selected in the range.

Further, with respect to the photosensitive layer 4b, known plasticizers for improving film-forming properties, flexibility, mechanical strength, etc., additives for suppressing residual potential, and improving dispersion stability. Dispersion aid, leveling agent for improving coating properties, surfactant, silicone oil, fluorine-based oil,
Antioxidants and other additives may be added. As the antioxidant, the same one as in the case of the function separation type can be used.

The intermediate layer 7 is an anodized aluminum film,
It is realized with an inorganic layer such as aluminum oxide, aluminum hydroxide and titanium oxide. In addition, polyvinyl alcohol, polyvinyl butyral, casein, polyvinyl pyrrolidone, polyacrylic acid, celluloses, gelatin,
It may be realized by an organic layer such as starch, polyurethane, polyimide, polyamide and N-methoxymethylated nylon. Further, particles of titanium oxide, tin oxide, aluminum oxide or the like may be dispersed therein.

The overcoat layer which may be provided on the photosensitive layers 4a and 4b can be realized by a conventionally known layer mainly composed of a thermoplastic resin or a thermosetting resin.

The present invention will be specifically described below with reference to production examples and examples, but the present invention is not limited to the following production examples and examples as long as the gist thereof is not exceeded.

(Production Example 1) o-Phthalodinitrile 40
g, titanium tetrachloride 18 g and α-chloronaphthalene 5
00 ml was heated and stirred at 200 ° C. to 250 ° C. for 3 hours under a nitrogen atmosphere to react, allowed to cool to 100 ° C. to 130 ° C., filtered while hot, and washed with 200 ml of α-chloronaphthalene heated to 100 ° C. A crude product of dichlorotitanium phthalocyanine was obtained. The crude product is washed with 200 ml of α-chloronaphthalene at room temperature, further washed with 200 ml of methanol, and then subjected to hot suspension washing in 500 ml of methanol for 1 hour. The crude product obtained by filtration was repeatedly subjected to hot suspension washing in 500 ml of water until the pH became 6 to 7, and then dried to obtain an oxotitanyl phthalocyanine intermediate crystal.

FIG. 2 is an X-ray diffraction spectrum of the oxotitanyl phthalocyanine intermediate crystal obtained as described above. The maximum diffraction peak is shown at a Bragg angle (2θ ± 0.2 °) of 27.3 °, and Bragg angles of 7.4 ° and 9.
Japanese Unexamined Patent Publication (Kokai) No. 2- having diffraction peaks at 6 and 27.3.
It can be seen that it is an oxotitanyl phthalocyanine called Y type described in JP-A-8256 and JP-A-7-271073.

The oxotitanyl phthalocyanine intermediate crystal was mixed with methyl ethyl ketone, and the diameter of 2 m was measured by the paint conditioner device (manufactured by Red Level Co.).
Milled with glass beads of m, washed with methanol, and dried to obtain a crystalline oxotitanyl phthalocyanine peculiar to the present invention.

FIG. 3 is an X-ray diffraction spectrum of the oxotitanyl phthalocyanine obtained as described above. Bragg angle (2θ ± 0.2 °) 7.3 °, 9.4
°, 9.6 °, 11.6 °, 13.3 °, 17.9 °,
A crystalline type oxotitanyl phthalocyanine unique to the present invention, which has diffraction peaks at 24.1 ° and 27.2 ° and has a maximum diffraction peak in the overlapping peak bundles at Bragg angles of 9.4 ° and 9.6 °. I know there is.

The measurement conditions of the X-ray diffraction spectrum are as follows. X-ray source CuKα = 1.54050Å Voltage 30 kV-40 kV Current 50 mA Start angle 5.0 deg. Stop angle 30.0 deg. Step angle 0.01deg.-0.02deg. Measurement time 0.5deg. / Min to 2.0 deg. / Min measurement method θ / 2θ scan method

(Production Example 2) The oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was mixed with polybutyral (Sekisui Chemical Co., Ltd .: Eslec BL-1) and methyl ethyl ketone, and glass beads having a diameter of 2 mm were mixed with a bead mill. Then, a milling treatment was carried out together with the above to obtain oxotitanyl phthalocyanine in a crystalline form peculiar to the present invention.

FIG. 4 is an X-ray diffraction spectrum of the oxotitanyl phthalocyanine obtained as described above. Bragg angle (2θ ± 0.2 °) 7.3 °, 9.4
°, 9.6 °, 11.6 °, 13.3 °, 17.9 °,
It has diffraction peaks at 24.1 ° and 27.2 °, and shows a maximum diffraction peak in the overlapping peak bundles at Bragg angles 9.4 ° and 9.6 °, and further, Bragg angles 14.1 ° to 14. It can be seen that the crystalline oxotitanyl phthalocyanine peculiar to the present invention shows an aggregate of trapezoidally difficult peaks having a plurality of diffraction peaks having the same intensity at 9 °.

(Production Example 3) The oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1, polybutyral (Sekisui Chemical Co., Ltd .: S-REC BL-1), and vinyl chloride vinyl acetate copolymer resin (Sekisui Chemical Co., Ltd .: S-REC M-
1) and methyl ethyl ketone were mixed and milled together with glass beads having a diameter of 2 mm by a paint conditioner to obtain a crystalline oxotitanyl phthalocyanine unique to the present invention.

FIG. 5 is an X-ray diffraction spectrum of the oxotitanyl phthalocyanine obtained as described above. Bragg angle (2θ ± 0.2 °) 7.3 °, 9.4
°, 9.6 °, 11.6 °, 13.3 °, 17.9 °,
It has diffraction peaks at 24.1 ° and 27.2 °, and shows a maximum diffraction peak in the overlapping peak bundles at Bragg angles 9.4 ° and 9.6 °, and further, Bragg angles 14.1 ° to 14. At 9 °, a plurality of diffraction peaks having the same intensity are provided to form a trapezoidal peak-difficult peak separation, and at the Bragg angle of 9.0 °, Bragg angles of 9.4 ° and 9 It can be seen that the crystal form of oxotitanyl phthalocyanine peculiar to the present invention has an intensity peak of about half of the overlapping peak bundle of 6 ° as a shoulder peak of the peak bundle.

Examples 1 to 8 and Comparative Examples 1 and 2 using the oxotitanyl phthalocyanine and the amine-hydrazone compound will be described.

Example 1 Titanium oxide and copolymerized nylon (CM8000 made by Toray Industries, Inc.) were mixed with a mixed solvent of methyl alcohol and dichloroethane on a conductive support 1 made of a polyester film on which aluminum was vapor-deposited. The dissolved intermediate layer coating liquid was applied and dried to form an intermediate layer 7 having a film thickness of 1 μm. Next, 1 part by weight of oxotitaniflurocyanine obtained in Production Example 1 (charge-generating substance 2) and 1 part by weight of polybutyral (binder resin) (Sekisui Chemical Co., Ltd .; S-REC BL-1) were used. 70 parts by weight of methyl ethyl ketone is mixed and dispersed with glass beads having a diameter of 2 mm by a paint conditioner device (manufactured by Red Level), and the obtained charge generation layer coating liquid is applied onto the intermediate layer 7 and dried. Then, the charge generation layer 5 having a film thickness of 0.4 μm was formed. Furthermore, exemplary compound AH1 (charge transport substance 3) and polycarbonate (binder resin) (PCZ-200 manufactured by Mitsubishi Gas Chemical Co., Inc.) were mixed at a weight ratio of 1: 1.
A 15 wt% coating liquid for a charge transport layer was prepared using dichloromethane as a solvent, and the coating liquid was applied onto the charge generation layer 5 and dried to form a charge transport layer 6 having a film thickness of 20 μm. As described above, the intermediate layer 7, the charge generation layer 5, and the charge transport layer 6
A function-separated type photoreceptor 8b having a photosensitive layer 4a having a laminated structure was obtained.

(Examples 2 to 5) As the charge transport substance 3, instead of the exemplified compound AH1, the exemplified compounds AH3, AH5 and
A function-separated photoreceptor 8b was obtained in the same manner as in Example 1, except that AH10 and AH16 were used.

(Example 6) The oxo-titanyl phthalocyanine obtained in Production Example 2 was used in place of the charge generating substance 2 in Example 1, and the function-separated photoreceptor 8b was obtained in the same manner as in Example 1 except for the above. It was

(Example 7) The oxo-titanyl phthalocyanine obtained in Production Example 3 was used in place of the charge generating substance 2 in Example 1, and the function-separated photoreceptor 8b was obtained in the same manner as in Example 1 except for the above. It was

Example 8 An intermediate layer 7 was formed on the conductive support 1 in the same manner as in Example 1. Next, 1 part by weight of oxotitaniflurocyanine obtained in Production Example 1 (charge-generating substance 2), 10 parts by weight of exemplary compound AH2 (charge-transporting substance 3), and 10 parts by weight of polycarbonate (binder resin). (Mitsubishi Gas Chemical Co., Ltd .: PCZ-200) was mixed, and a coating liquid of 18 wt% was prepared using dichloromethane as a solvent, and the diameter was adjusted to 2 by the paint conditioner device.
Dispersion treatment was performed together with mm glass beads. The photosensitive layer coating liquid thus obtained is applied onto the intermediate layer 7 and dried to give a film thickness of 20.
A photosensitive layer 4b having a thickness of μm was formed. As described above, a single layer type photoreceptor 8d including the intermediate layer 7 and the photosensitive layer 4b containing the charge generating substance 2 and the charge transporting substance 3 was obtained.

(Comparative Example 1) The oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was used in place of the oxotitanyl phthalocyanine used in Example 1, and the function-separated type was prepared in the same manner as in Example 1 except for the above. A photoconductor was obtained.

(Comparative Example 2) In place of the charge transporting material used in Example 1, a charge transporting material represented by the following structural formula (XIII) was used, and the other functions were separated in the same manner as in Example 1. A mold type photoreceptor was obtained.

[0096]

[Chemical 6]

The photoreceptors prepared in Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated as follows. The function-separated type photoconductor is an electrostatic recording paper testing device (made by Kawaguchi Electric Co., Ltd .: EP
A-8200) was used to evaluate the electrophotographic characteristics.
The measurement conditions were: applied voltage: -6 kV, static: No.
3, and the potential is -500 V with monochromatic light of 780 nm (irradiation light: ² μW / cm ² ) that is separated by the interference filter.
Exposure dose E _1/2 required to attenuate from -1 to -250V
(ΜJ / cm ² ) and initial potential V ₀ (−V) were measured. The electrophotographic characteristics of the single-layer type photoconductor were evaluated using the above electrostatic recording paper test apparatus. The measurement conditions are: applied voltage: +6 kV, static: No. 3 and the monochromatic light of 780 nm (irradiation light: 10 μm) that is separated by the interference filter.
W / cm ² ) to change the potential from + 500V to + 250V
Half exposure E _1/2 (μJ / cm
² ) and the initial potential V ₀ (+ V) were measured. Further, a commercially available digital copying machine (manufactured by Sharp Corporation: AR5130) was modified to mount the photoconductors of Examples 1 to 8 and Comparative Examples 1 and 2 on the photoconductor drum portion, and durability was obtained by continuous blank copy of 30,000 times. A test is conducted and the charging potential is measured before and after the test, and the half-exposure amount E is measured by using the electrostatic recording paper testing device.
_1/2 was measured. Furthermore, in an environment of high temperature and high humidity (35 ° C
(85%), a durability test by continuous blank copy was performed 30,000 times, and the residual potential Vr was measured before and after that. The results are shown in Table 2.

[0098]

[Table 2]

As shown in Table 2, it can be seen that in Examples 1 to 8, the deterioration amount of the charging potential in the durability test was sufficiently smaller than that in Comparative Examples 1 and 2. Further, it can be seen that the initial sensitivity (half exposure amount) is sufficiently higher than that of Comparative Examples 1 and 2. Further, it can be seen that the sensitivity deterioration after the durability test is small.
Furthermore, it can be seen that the increase in residual potential after the durability test in a high temperature and high humidity environment is sufficiently smaller than in Comparative Examples 1 and 2.

[0100]

As described above, according to the present invention, the photosensitive layer provided on the conductive support contains X as a charge generating substance.
In the line diffraction spectrum, Bragg angles of 7.3 °, 9.
4 °, 9.6 °, 11.6 °, 13.3 °, 17.9
Major diffraction peaks are shown at °, 24.1 °, and 27.2 °, and the intensities in the overlapping diffraction peak bundles at the Bragg angles 9.4 ° and 9.6 ° are maximum, and the Bragg angle 27.2. It contains crystalline oxotitanyl phthalocyanine, which has the second highest intensity at the diffraction peak of °, and contains an amine-hydrazone compound represented by the general formula (IV-I) as a charge transport material. A photoreceptor having such a photosensitive layer has excellent photosensitivity characteristics and repeated use characteristics, and is particularly excellent in suppressing surface potential decrease, residual potential increase and sensitivity deterioration. Therefore,
It can be suitably used for a highly sensitive image forming apparatus.

Further, according to the present invention, the intensity of the oxotitanyl phthalocyanine at the diffraction peak at the Bragg angle of 27.2 ° in the X-ray diffraction spectrum overlaps at the Bragg angles of 9.4 ° and 9.6 °. It is preferably 80% or less of the intensity in the diffraction peak flux.

Further, according to the present invention, the oxotitanyl phthalocyanine has a plurality of diffraction peaks having intensities substantially equal to each other between the Bragg angles of 14.1 ° and 14.9 ° in the X-ray diffraction spectrum, It is preferable that the plurality of diffraction peaks exhibit a trapezoidal peak separation that is difficult to separate.

According to the present invention, the oxotitanyl phthalocyanine has an intensity at the Bragg angle of 9.0 ° in the X-ray diffraction spectrum, and the Bragg angle of 9.4 °.
And a diffraction peak that is almost half of the overlapping diffraction peak flux of 9.6 °, and the diffraction peak is preferably present as a shoulder peak of the diffraction peak flux.

Further, according to the present invention, it is possible to provide a photoreceptor having a laminated structure or a single layer structure which can obtain the effects as described above.

Further, according to the present invention, the coatability can be improved by the intermediate layer having a protective function and an adhesive function provided between the conductive support and the photosensitive layer, and the conductive support is exposed to light. The charge injection into the layer can be improved.

[Brief description of drawings]

FIG. 1 is an electrophotographic photoreceptor 8 according to an embodiment of the present invention.
It is sectional drawing which shows a-8d.

FIG. 2 is an X-ray diffraction spectrum of an oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1.

3 is an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained in Production Example 1. FIG.

FIG. 4 is an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained in Production Example 2.

FIG. 5 is an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained in Production Example 3.

[Explanation of symbols]

1 Conductive support 2 Charge generation material 3 Charge transport material 4,4a, 4b Photosensitive layer 5 Charge generation layer 6 Charge transport layer 7 Middle class 8,8a, 8b Electrophotographic photoreceptor

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Akihiro Kondo 22-22 Nagaike-cho, Abeno-ku, Osaka-shi, Osaka Sharp Corporation (56) References JP-A-64-17066 (JP, A) JP-A-10- 239871 (JP, A) JP 10-237347 (JP, A) JP 10-221871 (JP, A) JP 10-171137 (JP, A) JP 10-148953 (JP, A) JP-A-10-73936 (JP, A) JP-A-10-72412 (JP, A) JP-A-10-20516 (JP, A) JP-A-8-278646 (JP, A) JP-A-8-113636 (JP, A) JP-A-8-6270 (JP, A) JP-A-6-89038 (JP, A) JP-A-3-75660 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) G03G 5/00

Claims (7)

(57) [Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer contains oxotitanyl phthalocyanine as a charge generating substance, and has the following general formula (IV-I) as a charge transporting substance. The amine-hydrazone compound represented is contained, and the oxotitanyl phthalocyanine has a Bragg angle (2θ ± 0.2 °) of 7.3 in an X-ray diffraction spectrum.
°, 9.4 °, 9.6 °, 11.6 °, 13.3 °, 1
Major diffraction peaks are shown at 7.9 °, 24.1 ° and 27.2 °, and the intensity is highest in the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 °. The intensity at the diffraction peak at 27.2 ° is the second
An electrophotographic photoreceptor characterized by being the second. [Chemical 1] [In the formula (IV-I), R ^{12 to} R ¹⁵ may be the same or different, and may have a lower alkyl group, an aromatic hydrocarbon residue which may have a substituent, or a substituent. It represents a heterocyclic residue or an aralkyl group which may have a substituent. R ¹⁶ is
It represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower dialkylamino group, a trifluoromethyl group or an aralkyl group which may have a substituent. l
1 is an integer of 1 to 3. ] 2. The oxotitanyl phthalocyanine is
In the X-ray diffraction spectrum, the Bragg angle 27.2
The intensity at the diffraction peak of ° is the Bragg angle of 9.4.
2. The electrophotographic photosensitive member according to claim 1, which has an intensity of 80% or less in the overlapping diffraction peak fluxes of 90 ° and 9.6 °. 3. The oxotitanyl phthalocyanine is
In the X-ray diffraction spectrum, between the Bragg angles 14.1 ° to 14.9 °, there are a plurality of diffraction peaks having almost the same intensities, and the plurality of diffraction peaks are trapezoidal and difficult to separate peaks. The electrophotographic photosensitive member according to claim 1, which is a body. 4. The oxotitanyl phthalocyanine is
In the X-ray diffraction spectrum, at the position of Bragg angle 9.0 °, there is a diffraction peak whose intensity is almost half of the overlapping diffraction peak bundles at the Bragg angles 9.4 ° and 9.6 °. Is present as a shoulder peak of the diffraction peak flux, and the electrophotographic photosensitive member according to claim 1. 5. The photosensitive layer has a laminated structure of a charge generating layer containing the charge generating substance and a charge transporting layer containing the charge transporting substance.
The electrophotographic photosensitive member according to any one of the above. 6. The electrophotography according to claim 1, wherein the photosensitive layer has a single-layer structure containing the charge generating substance and the charge transporting substance. Photoconductor. 7. The electrophotographic photosensitive member according to claim 1, further comprising an intermediate layer disposed between the conductive support and the photosensitive layer.