JP2000235273A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the photosensitivity characteristics, repetitive service characteristics and stability of photoreceptors. SOLUTION: Photosensitive layers 4a, 4b separately formed on the electrically conductive substrates 1 of photoreceptors 8a-8d contain oxo-titanyl phthalocyanine which exhibits a specified X-ray diffraction spectrum as an electric charge generating material 2 and a bisamine compound of a specified structural formula, an N,N'-bisenamine compound, a styryl compound, an amine- hydrazone compound or a benzofuran-bishydrazone compound as an electric charge transferring material 3. A middle layer 7 may be disposed between each of the substrates 1 and each of the photosensitive layers 4a, 4b. The photoreceptor 8a is a function separation type one whose photosensitive layer 4a has a laminated structure consisting of an electric charge generating layer 5 containing the electric charge generating material 2 and an electric charge transferring layer 6 containing the electric charge transferring material 3. The photoreceptor 8c is a monolayer type one whose photosensitive layer 4b contains the electric charge generating material 2 and the electric charge transferring material 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an oxotitanyl phthalocyanine as a charge-generating substance, and a bisamine compound, N, N'-bisenamine compound, styryl compound, amine-hydrazone compound or benzofuran-bishydrazone compound as a charge-transporting substance. The present invention relates to an electrophotographic photoreceptor having high sensitivity in a near infrared wavelength range used.

[0002]

2. Description of the Related Art Electrophotographic photoconductors (hereinafter, also simply referred to as "photoconductors") currently in practical use are composed of an inorganic photoconductor using an inorganic photoconductive material excellent in sensitivity and durability and an organic photoconductor. Organic photoreceptors using photoconductive materials.
Examples of inorganic photoconductive materials 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 arsenide), and a-Si. (Amorphous silicon) based materials.

However, in the case of a ZnO-based material, the added sensitizer deteriorates its charging property by corona discharge or generates light brown by exposure, so that stable image formation cannot be performed for a long time. Further, a photoreceptor provided with a photosensitive layer formed by dispersing ZnO in a binder resin has low sensitivity and low durability. CdS-based materials do not provide stable sensitivity in humid environments, Se-based materials are highly toxic, and crystallization easily progresses due to external factors such as temperature and humidity, resulting in poor chargeability and poor image quality. White spots may occur. Further, a photoreceptor provided with 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 with its disposal, causing pollution. The a-Si-based material, which has been attracting attention as being non-polluting, has high sensitivity and high durability. However, since the photosensitive layer is manufactured by using a plasma CVD (chemical vapor deposition) method, the a-Si-based material is produced due to the manufacturing process. Image defects occur and production costs increase due to low productivity.

On the other hand, an organic photoconductive material is generally easy to form a thin film by coating, has low manufacturing cost, and has high productivity. In addition, since there are many kinds of organic materials themselves, a photosensitive layer having low storage stability and low toxicity can be manufactured by appropriate selection, and can be easily discarded.
Further, the setting of the light absorption wavelength region can be easily changed, and the electrophotographic characteristics can be easily controlled by a combination of materials. Therefore, in recent years, further improvement in sensitivity and durability has been studied, and many organic materials have been used. The photoreceptor has a function-separated type in which a photosensitive layer having a laminated structure of a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport 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 a body, and a function-separated type is mainly researched and developed for a photoreceptor using an organic material.

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

In recent years, an image forming apparatus such as a laser printer, which uses a laser light source instead of a white light source and achieves high speed, high image quality, and low impact, has been widely used. In particular, various methods using a semiconductor laser as a light source, which has remarkably progressed in recent years, have been attempted, and a photoconductor having high sensitivity to a long wavelength region of about 800 nm, which is a laser light wavelength band, is strongly desired.

As organic materials satisfying this requirement, for example, methine squaric acid dyes, indoline dyes,
Cyanine dyes, bilylium dyes, polyazo dyes,
There are phthalocyanine dyes and naphthoquinone dyes. However, methine squaric acid dyes, indoline dyes, cyanine dyes and bilylium dyes can have longer wavelengths, but have low stability, especially low repeatability,
Further, it is not easy to increase the wavelength of the polyazo dye, and the productivity is low. Further, the sensitivity of the naphthoquinone dye is low.

On the other hand, phthalocyanine dyes have high sensitivity to long-wavelength light and are more stable than the above dyes.
Phthalocyanine-based compounds not only have different sensitivity peaks and physical properties depending on the presence or absence and type of central metal, but also have a large change in physical properties depending on the crystal type. "Dyes and Chemicals, Vol. 24, No. 6, p. .122, 1979, by Manabu Sawada. " In a photoreceptor using a metal phthalocyanine compound, the sensitivity peak varies depending on the central metal.
and the relatively long wavelength side of m.
No. 989, JP-A-49-11136, U.S. Pat. No. 4,214,907 and British Patent No. 1,268,422. Therefore, it is important to research and develop the photoreceptor including the examination of the crystal form of phthalocyanine.

A technique in which a phthalocyanine compound of a specific crystal type is selected for an electrophotographic photosensitive member has been reported. For example, JP-A-60-86551 discloses a metal-free phthalocyanine and JP-A-63-133462 discloses a technique. Is a phthalocyanine containing aluminum;
No. 49544 describes examples using phthalocyanine using titanium as a central metal. Japanese Patent Publication No. 55558/1993 discloses a photosensitive structure in which a charge transport layer containing a hydrazone compound and a binder resin is laminated on a charge generation layer containing a specific titanium phthalocyanine compound and a binder resin. The body is disclosed. Further, Japanese Patent Application Laid-Open No. Hei 10-142819 discloses a photoreceptor containing a phthalocyanine as a charge generating substance and a specific styryl compound as a charge transporting substance. Also, many metals such as indium and gallium are known as central metals of phthalocyanine compounds.

Of the phthalocyanine compounds, oxotitanyl phthalocyanine is particularly high in sensitivity, and is described in "Journal of the Electrographic Society of Japan, Vol. 32, No. 3, p. 282" because of differences in diffraction angles of X-ray diffraction spectra. It is stated that it is classified into a crystal type. Further, as the crystal form of oxotitanyl phthalocyanine, α-type is disclosed in JP-A-61-217050 and JP-A-61-239248.
Japanese Patent Application Laid-Open No. Sho 62-67094 discloses an A type,
No. 366 and JP-A-63-198067 disclose the C-type, JP-A-63-20365 and JP-A-2-8.
No. 256, Japanese Unexamined Patent Publication No. 1-17066 and Japanese Unexamined Patent Publication No.
Japanese Patent Application Laid-Open No. 65-65264 discloses an M type, Japanese Patent Application Laid-Open No. 3-54264 discloses an M-α type, Japanese Patent Application Laid-Open No. 3-128973 discloses an I-type, and Japanese Patent Application Laid-Open No. 62-67094 discloses an I-type and an II-type. Each is listed.

Crystals of oxotitanyl phthalocyanine whose lattice rule is known from the structural analysis include C-type,
Phase I and Phase II. Pha
The type seII belongs to the triclinic system, and the phases I and C
The type belongs to the monoclinic system. When the crystal forms described in the above publication are analyzed from these known crystal lattice constants, A-type and I-type belong to Phase I-type, and α-type and B-type
It belongs to the case II type, and the M type belongs to the C type. Such an explanation is described, for example, in “J. of Imaging Science and Techn.
ology Vol. 37, No. 6, 1993, p. 605-p. 609 ".

[0012] Specifically, Japanese Patent Application Laid-Open No. 59-49544 discloses that a charge generation layer is formed by depositing oxotitanifurocyanine on a substrate, and 2,6-dimethoxy-9,
A photoreceptor provided with a charge transport layer containing 10-dihydroxyanthracene as a main component is described. However, the photoreceptor has a high residual potential, has a limitation in the method of use, and has low reproducibility of electrical characteristics due to non-uniformity in film thickness due to a vapor deposition method. Also, the mass productivity of the photoreceptor on an industrial scale is low. 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 generation layer containing an oxotitanyl phthalocyanine compound and a binder resin. I have. In that publication, 800
Although it has sensitivity in the wavelength range around nm, it does not reach the sensitivity required for practically high image quality and high speed. As described above, oxotitanyl phthalocyanine is still low in sensitivity,
Poor potential stability against repeated use.

In general, in an electrophotographic photoreceptor, a charge transport material effective for a specific charge generating material is not always effective for other charge generating materials. A charge generating material that is effective for a transport material is not always effective for other charge transport materials. In other words, it is necessary to use a charge generating material and a charge transporting material in a good combination for use in a photoreceptor. An improper combination not only lowers the sensitivity but also increases the residual potential. As a result, the toner adheres to the non-image area, and the background becomes dirty, so that a clear image cannot be obtained. As described above, the combination of the charge generation material and the charge transport material is important, but there is not always a general law selection method for this combination, and it is difficult to find a charge transport material suitable for a specific charge generation material. Have difficulty.

[0014]

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

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

[0016]

According to the present invention, there is provided 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. General formula (II)
The oxo titanyl phthalocyanine contains a bisamine compound represented by the following,
Bragg angles (2θ ± 0.2 °) 7.3 °, 9.4 °,
9.6 °, 11.6 °, 13.3 °, 17.9 °, 2
Showing major diffraction peaks at 4.1 ° and 27.2 °,
The intensity in the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 ° is maximum, and the Bragg angle of 2
An electrophotographic photosensitive member, wherein the intensity at the diffraction peak at 7.2 ° is the second.

[0017]

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[In the general formula (II), Ar ¹ and Ar ² are
Represents an aryl group, a heterocyclic group, an aralkyl group or a heterocyclic-substituted alkyl group which may have a substituent. Z ¹ is O,
It is an S or Se atom. R ¹ and R ² each represent an alkyl group, an alkoxy group, a dialkylamino group, a halogen atom or a hydrogen atom which may have a substituent. m1 is an integer of 1 to 4, and n1 is an integer of 1 to 3. However, m1 and n1 is when 2 or more, or different in each of R ¹ and R ² are the same, and may form a ring. ]

According to the present invention, the specific X
A photosensitive layer containing oxotitanyl phthalocyanine showing a line diffraction spectrum as a charge generating substance and containing a bisamine compound represented by the general formula (II) as a charge transporting substance is formed on a conductive support. It was found that the photoreceptor exhibited excellent photosensitivity characteristics and repetitive use characteristics, and was particularly excellent in the effect of suppressing a decrease in surface potential, an increase in residual potential, and deterioration in sensitivity. Therefore, it can be suitably mounted on a high-sensitivity image forming apparatus such as a laser printer or a digital copier using a semiconductor laser light source.

The present invention also relates to an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer contains oxotitanyl phthalocyanine as a charge generating substance,
The following general formulas (II-I) and (II-
II), containing an N, N'-bisenamine compound represented by any one of (II-III) and (II-IV), wherein the oxotitanyl phthalocyanine is represented by X
In the line diffraction spectrum, the Bragg angle (2θ ± 0.2
°) 7.3 °, 9.4 °, 9.6 °, 11.6 °, 1
It shows major diffraction peaks at 3.3 °, 17.9 °, 24.1 ° and 27.2 °, and the maximum intensity in the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 ° is maximum. Wherein the intensity at the diffraction peak at the Bragg angle of 27.2 ° is the second intensity.

[0021]

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[0022]

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[0023]

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[0024]

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[Formulas (II-I), (II-II), (I
Ar ^{3 to} Ar in (I-III) and (II-IV)
⁶ represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or an aralkyl group which may have a substituent. R ³ represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent or an alkyl group having 1 to 4 carbon atoms. R ^{4 to} R ^{7 each} represent an alkyl group having 1 to 3 carbon atoms,
Represents an alkoxy group having 1 to 3, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom. k1 is 1 to 5
K2 and k3 are integers of 1 to 4, p is an integer of 2 to 4, q is an integer of 1 to 3, k4 is an integer of 1 to 8, and s is 0.整数 2. However, when k1 is 2 or more, R ⁴ may be the same or different. Further, when k2 is 2 or more, R ⁵ may be the same or different. Further, when k3 is 2 or more, R ⁶ may be the same or different. Further, when k4 is 2 or more,
R ⁷ may be the same or different. ]

According to the present invention, the oxotitanyl phthalocyanine is contained as a charge generating substance,
-I), (II-II), (II-III) and (I
I-IV), N, N'- represented by any one of
The photosensitive layer containing a bisenamine compound as a charge transporting material also exhibits excellent photosensitivity characteristics and repeated use characteristics as in the case of the above-described materials, and is particularly excellent in suppressing surface potential drop, residual potential rise and sensitivity deterioration. I understood. Therefore, it can be suitably mounted on a high-sensitivity image forming apparatus such as a laser printer or a digital copier using a semiconductor laser light source.

The present invention also relates to an electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer contains oxotitanyl phthalocyanine as a charge generating substance,
It contains a styryl compound represented by the following general formula (III) as a charge transport material, and the oxotitanyl phthalocyanine has a Bragg angle (2
θ ± 0.2 °) 7.3 °, 9.4 °, 9.6 °, 11.
6 °, 13.3 °, 17.9 °, 24.1 ° and 2
A major diffraction peak is shown at 7.2 °, the intensity at the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 ° is the highest, and the intensity at the diffraction peak at the Bragg angle of 27.2 ° is An electrophotographic photosensitive member, which is the second one.

[0028]

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[In the formula (III), R ^{8 to} R ¹¹ represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group or an aryl group. R ¹⁰ and R ¹¹ may combine with each other to form a ring. Z ² represents an atomic group necessary for forming a saturated 5- to 8-membered ring together with two carbon atoms of the indoline ring. ]

According to the present invention, the oxotitanyl phthalocyanine is contained as a charge generating substance,
The photosensitive layer containing the styryl compound represented by I) as a charge transporting substance also exhibits excellent photosensitivity and repeated use characteristics, similarly to the case of using the above-mentioned materials, and particularly shows a decrease in surface potential, an increase in residual potential and It was found that the effect of suppressing sensitivity deterioration was excellent. Therefore, it can be suitably mounted on a high-sensitivity image forming apparatus such as a laser printer or a digital copier using a semiconductor laser light source.

According to the present invention, there is provided an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer contains oxotitanyl phthalocyanine as a charge generating substance,
It contains an amine-hydrazone compound represented by the following general formula (IV-I) as a charge transporting substance, 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 °, 17.9 °, 24.1
And the major diffraction peaks at 27.2 ° and the Bragg angles of 9.4 ° and 9.6 ° where the intensity of the overlapping diffraction peak bundles is the largest, and the Bragg angle of 27.2 °.
An electrophotographic photosensitive member, characterized in that the intensity at the diffraction peak of ° is the second.

[0032]

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[In the formula (IV-I), R ^{12 to} R ¹⁵ may be the same or different and each have a lower alkyl group, an aromatic hydrocarbon residue which may have a substituent, Represents an optionally substituted heterocyclic residue or an optionally substituted aralkyl group. 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. 11 is an integer of 1 to 3. ]

According to the present invention, the oxotitanyl phthalocyanine is contained as a charge generating substance,
The photosensitive layer containing the amine-hydrazone compound represented by -I) as a charge transporting substance also exhibits excellent photosensitivity characteristics and repeated use characteristics as in the case of using the above-mentioned materials, and particularly shows a decrease in surface potential and residual It was found that the effect of suppressing the potential rise and the sensitivity deterioration was excellent. Therefore, it can be suitably mounted on a high-sensitivity image forming apparatus such as a laser printer or a digital copier using a semiconductor laser light source.

The present invention also provides an electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer contains oxotitanyl phthalocyanine as a charge generating substance,
It contains a benzofuran-bishydrazone compound represented by the following general formula (V) as a charge transport material, 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 °, 17.9 °,
It shows major diffraction peaks at 24.1 ° and 27.2 °, and the intensity of the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 ° is the highest, and the intensity at the Bragg angle of 27.2 ° is the highest. An electrophotographic photoconductor, wherein the intensity at the diffraction peak is the second.

[0036]

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[In the general formula (V), Ar ¹³ and Ar ¹⁴ represent an aryl group which may have a substituent, an aralkyl group which may have a substituent, a heterocyclic group or a group having 1 to 4 carbon atoms. Represents an alkyl group. a represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom. n5
Is an integer of 1 to 3. However, when n5 is 2 or more, each of a plurality of a may be the same or different. ]

According to the present invention, the oxotitanyl phthalocyanine is contained as a charge generating substance,
The photosensitive layer containing a benzofuran-bishydrazone compound represented by as a charge transport material also exhibits excellent photosensitivity characteristics and repeated use characteristics as in the case of using the above-described materials. It was also found to be excellent in suppressing the sensitivity deterioration. Therefore, it can be suitably mounted on a high-sensitivity image forming apparatus such as a laser printer or a digital copier using a semiconductor laser light source.

Further, according to the present invention, the oxotitanyl phthalocyanine has an X-ray diffraction spectrum in which the intensity at the diffraction peak at the Bragg angle of 27.2 ° is the same as that at the Bragg angles of 9.4 ° and 9.6 °. The intensity is not more than 80% of the intensity in the peak bundle.

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

Further, according to the present invention, the oxotitanyl phthalocyanine has a plurality of diffraction peaks whose intensities are almost the same from each other in a Bragg angle of 14.1 ° to 14.9 ° in an X-ray diffraction spectrum. The plurality of diffraction peaks indicate a trapezoidal peak aggregate that is difficult to separate.

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

Further, according to the present invention, the oxotitanyl phthalocyanine has an X-ray diffraction spectrum in which the intensity of the diffraction peak bundle having the Bragg angles of 9.4 ° and 9.6 ° overlaps at the position of the Bragg angle of 9.0 °. , And the diffraction peak is present as a shoulder peak of the diffraction peak bundle.

According to the present invention, it is further found that the oxotitanyl phthalocyanine preferably exhibits the X-ray spectrum as described above.

Further, the present invention is 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 photoreceptor composed of the above-mentioned materials exhibits excellent light sensitivity characteristics and repetitive use characteristics as described above. The photosensitive member has an excellent effect of suppressing potential rise and sensitivity deterioration, and can be suitably mounted on a high-sensitivity image forming apparatus.

Further, the present invention is 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 repetitive use characteristics.
It is excellent in the effect of suppressing the increase in the residual potential and the deterioration in sensitivity, and the photoconductor can be suitably mounted on a high-sensitivity image forming apparatus.

Further, the present invention is characterized in that it includes an intermediate layer disposed 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.

The present invention is also characterized in that the photosensitive layer contains a polycarbonate represented by the following general formula (VI) as a binder resin.

[0052]

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[In the general formula (VI), R ³³ and R ³⁴ each represent an alkyl group having 1 to 5 carbon atoms which may have a substituent or an alkyl group having 6 to 12 carbon atoms which may have a substituent. It represents an aryl group, an aralkyl group having 7 to 17 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom. X
² has an alkylene group having 1 to 10 carbon atoms which may be directly bonded or may have a substituent, a cyclic alkylidene group having 1 to 10 carbon atoms which may have a substituent, Represents an arylene group having 6 to 12 carbon atoms, a sulfonyl group or a carbonyl group. Z ³ represents an alkylene group having 1 to 5 carbon atoms, an arylene group having 6 to 12 carbon atoms, an arylene alkyl group having 7 to 17 carbon atoms, or a halogen atom which may have a substituent. W ¹ represents an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms, and a substituent. It represents an alkyl ester group having 1 to 5 carbon atoms which may have, an aryl ester group having 6 to 12 carbon atoms which may have a substituent, a carboxyl group, an aldehyde group, a hydroxyl group, a halogen atom or a hydrogen atom. e and f represent an integer of 1 to 4, and u2 represents an integer of 10 to 200. ]

According to the present invention, when the above-mentioned N, N'-bisenamine compound or benzofuran-bishydrazone compound is used as the charge transport material, the polycarbonate of the general formula (VI) is contained as a binder resin for the photosensitive layer. Showed particularly excellent photosensitivity characteristics and repeated use characteristics, and were particularly excellent in the effects of suppressing the decrease in surface potential, the increase in residual potential, and the deterioration in sensitivity.

Further, in the present invention, the photosensitive layer comprises a polyester represented by the following general formula (VII) as a binder resin:
It is characterized in that it is contained in the range of 0.05 to 0.5 parts by weight based on the total binder resin.

[0056]

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[In the general formula (VII), g, h2 and i
2 represents an integer of 1 to 10, and v, w2, x3 and y represent an integer of 10 to 1000. ]

According to the present invention, when the above-mentioned N, N'-bisenamine compound or benzofuran-bishydrazone compound is used as the charge transport material, the polyester of the general formula (VII) is fully bound as a binder resin for the photosensitive layer. It has been found that when the resin is contained in the above-mentioned range, particularly excellent photosensitivity characteristics and repeated use characteristics are exhibited, and the effect of suppressing a decrease in surface potential, a rise in residual potential and deterioration in sensitivity is particularly excellent.

The polyester of the general formula (VII) is contained in the range of 0.05 part by weight or more and 0.5 part by weight or less with respect to the whole binder resin. More preferably, it is contained in the range of not more than 3 parts by weight. Further, a mixture of the polycarbonate of the general formula (VI) and the polyester of the general formula (VII) may be used as a binder resin for the photosensitive layer.

In the present invention, the photosensitive layer may contain α-tocopherol as an antioxidant in an amount of 0.1% by weight or more and 5% by weight or less,
It is characterized by containing 6-di-t-butyl-4-methylphenol in a range of 0.1% by weight or more and 10% by weight or less based on the charge transporting substance.

According to the present invention, when the above-mentioned N, N'-bisenamine compound or benzofuran-bishydrazone compound is used as the charge transport material, α-tocopherol is used as an antioxidant in the photosensitive layer for the charge transport material. , Or 2,6-di-t-butyl-4-methylphenol as an antioxidant for the photosensitive layer in the range described above with respect to the charge transporting substance. It showed sensitivity characteristics and repeated use characteristics, and was found to be particularly excellent in the effects of suppressing surface potential drop, residual potential rise and sensitivity degradation. Further, such an antioxidant can prevent oxidative deterioration of the photosensitive layer.

[0062]

FIG. 1 is a sectional view showing electrophotographic photosensitive members 8a to 8d according to an embodiment of the present invention. 1A is formed by forming a photosensitive layer 4 a on a conductive support 1. The photoconductor 8a includes a photosensitive layer 4a.
Is a so-called function-separated type photoconductor having a laminated structure of a charge generation layer 5 containing a charge generation substance 2 and a charge transport layer 6 containing a charge transport substance 3. In the present embodiment, the charge generation layer 5 is disposed on the side of the conductive support 1, and the charge generation layer 5
The charge transport layer 6 is disposed on the substrate, but the charge generation layer 5 and the charge transport layer 6 may be disposed in reverse. FIG. 1 (B)
The photoconductor 8b is substantially the same as the photoconductor 8a, but includes an intermediate layer 7 disposed between the conductive support 1 and the photosensitive layer 4a.

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

The photoconductors 8a to 8d (hereinafter collectively referred to as "photoconductor 8") are composed of photosensitive layers 4a and 4b (hereinafter, referred to as "photoconductor 8").
An overcoat layer (not shown) may be further arranged on the “photosensitive layer 4” when collectively referred to. The overcoat layer has a function of protecting the photosensitive layer 4.

As the conductive support 1, aluminum,
It is realized by a conductive metal material such as stainless steel, copper and nickel. In addition, a conductive layer such as aluminum, copper, palladium, tin oxide, and indium oxide may be provided on the surface of an insulating support such as a polyester film or paper to realize the conductive support 1.

The photosensitive layer 4 of the present invention contains oxotitanyl phthalocyanine described below as the charge generating substance 2, and a bisamine compound described below as the charge transporting substance 3, N,
N'-bisenamine compound, styryl compound, amine-
Contains a hydrazone compound or a benzofuran-bishydrazone compound.

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

[0068]

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In the general formula (VIII), X represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group;
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 the X-ray diffraction spectrum.
°, 17.9 °, 24.1 ° and 27.2 ° showed major diffraction peaks, and the Bragg angles of 9.4 ° and 9.
The intensity at the 6 ° overlapping diffraction peak bundle is the maximum, and the intensity at the Bragg angle 27.2 ° diffraction peak is the second intensity.

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 °.
13. The Bragg angle is particularly preferable.
It is preferable to have a plurality of diffraction peaks whose intensities are substantially the same between 1 ° and 14.9 °, and that the plurality of diffraction peaks show a trapezoidally difficult-to-separate peak aggregate,
In particular, at the position of the Bragg angle of 9.0 °, there is a diffraction peak whose intensity is almost half of the overlapping diffraction peak bundle of the Bragg angles of 9.4 ° and 9.6 °, and the diffraction peak is the diffraction peak bundle. Preferably exists as a shoulder peak.

The method for synthesizing oxotitanyl phthalocyanine is described in Mosa and Thomas, "Phthalocyanine Compounds".
(MOSER and Thomas. “Phthalocianine Compound
s ") or other known methods.

For example, by heating and melting o-phthalonitrile and titanium tetrachloride or heating in the presence of an organic solvent such as α-chloronaphthalene, dichlorotitanium phthalocyanine can be obtained in good yield. Furthermore, oxotitanyl phthalocyanine is obtained by hydrolyzing dichlorotitanium phthalocyanine with a base or water. By heating 1,3-diiminoisoindoline and tetrabutoxytitanium with an organic solvent such as N-methylpyrrolidone, oxotitanyl phthalocyanine can be obtained. 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 in oxotitanyl phthalocyanine is obtained by treating oxo titanyl phthalocyanine with a water-immiscible organic solvent such as dichloroethane in the presence of water.

A method for treating oxotitanyl phthalocyanine with a water-immiscible organic solvent in the presence of water includes:
A method in which oxotitanyl phthalocyanine is swollen with water and treated with an organic solvent, and a method in which water is added to an organic solvent without performing the swelling treatment, and a method in which oxotitanyl phthalocyanine powder is charged therein, and the like. It is not limited.

As a method of swelling oxotitanyl phthalocyanine with water, a method of dissolving oxotitanyl phthalocyanine in sulfuric acid and precipitating it in water to form a wet paste, and stirring and dispersing such as a homomixer, a paint mixer, a ball mill and a sand mill There is a method of swelling oxotitanyl phthalocyanine with water using an apparatus to form a wet paste, but the method is not limited to these methods.

The oxotitanyl phthalocyanine obtained by hydrolysis is stirred for a sufficient time in a solution or a solution in which a binder resin is dissolved, or is milled with a mechanical strain to obtain the oxotitanyl phthalocyanine of the present invention. A crystalline form is obtained.

The apparatus used for the processing described above includes
In addition to general stirring equipment, homomixers, paint mixers, dispersers, agitators, ball mills, sand mills,
A paint shaker, a dyno mill, an attritor, an ultrasonic dispersion device, and the like can be used. After the treatment, the oxotitanyl phthalocyanine is filtered, washed with methanol, ethanol, water and the like, and isolated.
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 those produced by the above production method, but may be produced by any method as long as it shows the above-mentioned X-ray diffraction spectrum specific to the present invention. It can be anything.

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

The charge generating layer 5 or the photosensitive layer 4b may contain, as the charge generating substance 2, a substance other than the above-mentioned oxotitanyl phthalocyanine. For example, α-form, β-form having a different crystal form from 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, squarium pigments and the like may be contained.

As described above, oxotitanyl phthalocyanine having a crystal form specific to the present invention is produced, and a photosensitive layer containing the oxo titanyl phthalocyanine is prepared. Since oxotitanyl phthalocyanine exhibits high sensitivity even in a long wavelength range, a photoconductor having an optimum photosensitive wavelength range for an image forming apparatus using a light source in a long wavelength range, for example, a semiconductor laser or an LED (light emitting diode) as a light source, has been developed. can get. Further, 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 light sensitivity characteristics and repeated use characteristics. 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 photoreceptors.

In the function-separated type photosensitive layer 4 a, 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, polyacrylate,
Polymethacrylate 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.

The coating liquid for preparing the charge generation layer 5 by a coating method contains a solvent in addition to the charge generation substance 2 and the binder resin. Examples of the solvent include 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-dimethylformamide and dimethylsulfoxide may be used alone or in combination of two or more.

The charge generation layer 5 is formed by, for example, a vapor deposition method such as a vacuum evaporation method, a sputtering method, and a CVD method. Further, the charge generating substance 2 and the binder resin are added to a solvent, and the mixture 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 liquid obtained in this manner, in the case of a sheet shape, by a coating method such as a baker applicator, a bar coater, casting and spin coating, and in the case of a drum shape, a spray method, a vertical ring method and immersion. 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 bisamine compound, a bisamine compound represented by the aforementioned general formula (II) is used.
Among them, the following general formulas (I-II) and (II)
The bisamine compound represented by II) is suitable from the viewpoint of synthesis cost. Table 1 shows specific examples of the bisamine compound.
Table 5 shows that the compounds of the present invention are not limited thereto.

[0086]

Embedded image

[In the general formula (I-II), Ar ⁷ , Ar
⁸ represents an aryl group, a heterocyclic group, an aralkyl group or a heterocyclic-substituted alkyl group which may have a substituent. R ¹⁷ ,
R ¹⁸ represents an alkyl group, an alkoxy group, a dialkylamino group, a halogen atom or a hydrogen atom, each of which may have a substituent. m2 is an integer of 1 to 4, and n2 is 1
-3. However, m2 and n2 are when 2 or more, may be different from each R ¹⁷ and R ¹⁸ are the same, and may form a ring. ]

[0088]

Embedded image

[In the general formula (I-III), R ¹⁹ and R
²⁰ represents an alkyl group, an alkoxy group, a dialkylamino group or a hydrogen atom, each of which may have a substituent.
R ²¹ and R ²² each represent an alkyl group, an alkoxy group, a dialkylamino group, a halogen atom or a hydrogen atom which may have a substituent. m3 is an integer of 1 to 4;
3 is an integer of 1 to 3. Where m3 and n3 are 2
In the above, R ²¹ and R ²² may be the same or different, and may form a ring with each other. h and i
Is an integer of 1 to 3. ]

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

One or more of the above-mentioned bisamine compounds may be contained as a charge transporting substance. Further, another charge transporting substance may be contained.

The N, N'-bisenamine compounds include:
Formulas (II-I), (II-II), and (II-I)
Compounds represented by II) or (II-IV) are preferred. Formulas (II-I), (II-II) and (II-
In III) and (II-IV), Ar ^{3 to} Ar ⁶
For example, specifically, aryl groups such as phenyl, tolyl, methoxyphenyl, naphthyl, bienyl and biphenyl, heterocyclic groups such as benzofuryl, benzazolyl, benzoxazolyl and N-ethylcarbazolyl, and methylbenzyl and methoxy And aralkyl groups such as benzyl.

R ³ is, for example, specifically an aryl group such as phenyl, tolyl, methoxyphenyl, naphthyl, bienyl and biphenyl; a heterocyclic group such as benzofuryl, benchazolyl, benzoxazolyl and N-ethylcarbazolyl; Aralkyl groups such as methylbenzyl and methoxybenzyl, and methyl, ethyl, n-
And alkyl groups such as propyl and Iso-propyl.

R ^{4 to} R ⁷ are, for example, specifically, methyl,
Alkyl groups such as ethyl, n-propyl and iso-propyl; alkoxy groups such as methoxy group, ethoxy group and propoxy group; dialkylamino groups such as dimethylamino group and diethylamino group; halogen atoms such as fluorine and chlorine; and hydrogen atoms But
An electron donating substituent is effective.

Specific examples of the N, N'-bisenamine compound are shown in Tables 6 to 9, but the compounds of the present invention are not limited thereto.

[0100]

[Table 6]

[0101]

[Table 7]

[0102]

[Table 8]

[0103]

[Table 9]

One or more of the above-mentioned N, N'-bisenamine compounds may be contained as a charge transporting substance. Further, another charge transporting substance may be contained.

The styryl compounds include those represented by the above general formula (I)
The styryl compounds represented by II) are preferred. In the general formula (III), R ^{8 to} R ¹¹ represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group or an aryl group. Examples of the alkyl group which may have a substituent include a linear or branched alkyl group having 1 to 4 carbon atoms, and specifically, methyl, ethyl, propyl, isopropyl, butyl, sec- Butyl and te
rt-butyl and the like. Examples of the aralkyl group include an alkyl group having a terminal phenyl group and having 1 to 3 carbon atoms, such as benzyl, methylbenzyl, chlorobenzyl, β-phenylethyl, and α-naphthylmethyl. Aryl groups include phenyl, methoxyphenyl, tolyl, chlorophenyl, naphthyl and the like.

Z ² represents an atomic group required to form a saturated 5- to 8-membered ring together with two carbon atoms of the indoline ring. Specific examples include those shown in the exemplified compounds described below.

Specific examples of styryl compounds are shown in Tables 10 to 13.
However, this does not limit the compound of the present invention.

[0108]

[Table 10]

[0109]

[Table 11]

[0110]

[Table 12]

[0111]

[Table 13]

One or more styryl compounds may be contained as a charge transport material. Further, another charge transporting substance may be contained.

As the amine-hydrazone compound, an amine-hydrazone compound represented by the aforementioned general formula (IV-I) is used. Among them, the following general formula (IV-I)
The amine-hydrazone compounds represented by I) and (IV-III) are suitable from the viewpoint of synthesis cost.

[0114]

Embedded image

[In the 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, Represents an optionally substituted heterocyclic residue or an optionally substituted aralkyl group. 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 have a lower alkyl group, an aromatic hydrocarbon residue optionally having a substituent, a heterocyclic residue optionally having a substituent or a substituent. Represents an aralkyl group which may be substituted. l2 is 1-3
Is an integer. ]

[0116]

Embedded image

[In the general formula (IV-III), Ar ¹¹ and Ar ¹² may be the same or different, and may be an aromatic hydrocarbon residue optionally having a substituent or a heterocyclic group optionally having a substituent. Represents a ring residue. R ³⁰ represents 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 have a lower alkyl group, an aromatic hydrocarbon residue optionally having a substituent, a heterocyclic residue optionally having a substituent or a substituent. Represents an aralkyl group which may be substituted. t, u
And l3 are integers from 1 to 3. ]

In the general formulas (IV-I), (IV-II) and (IV-III), R ¹² , R ¹³ , R ¹⁴ ,
R ¹⁵ , R ²⁵ , R ²⁶ , R ²⁸ , R ²⁹ , R ³¹ and R ³² may be the same or different and are a lower alkyl group, an aromatic hydrocarbon residue which may have a substituent, a substituent Represents an optionally substituted heterocyclic residue or an optionally substituted aralkyl group. Examples of the lower alkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl. No. 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 includes a phenyl group-terminated phenyl group.
To 3 alkyl groups, such as benzyl and phenethyl.

Examples of the substituent in 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 include an amino group such as amino, ethylmethylamino and diethylamino, and a halogen atom such as a fluorine atom, a chlorine atom and a 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
And the same lower alkyl groups as mentioned above. Examples of the lower alkoxy group include a linear or branched alkoxy group having 1 to 4 carbon atoms, and specifically, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-
Butoxy and tert-butoxy.
Examples of the lower dialkylamino group include an amino group substituted by a linear or branched alkyl group having 1 to 4 carbon atoms, and specific examples include dimethylamino, diethylamino, diisopropylamino, and dibutylamino. Can be As the aralkyl group, R ¹² ,
It includes the same lower aralkyl group as R ^25.

Ar ¹¹ and Ar ¹² may be the same or different and represent an aromatic hydrocarbon residue which may have a substituent and a heterocyclic residue which may have a substituent. Examples of the aromatic hydrocarbon residue which may have a substituent include a phenyl group and 1-naphthyl group, and examples of the heterocyclic residue which may have a substituent include a 1-pyridyl group. No.

Table 1 shows specific examples of the amine-hydrazone compound.
4, which does not limit the compounds of the present invention.

[0123]

[Table 14]

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

As the benzofuran-bishydrazone compound, a benzofuran-bishydrazone compound represented by the above formula (V) is used. In the general formula (V), Ar ¹³ and Ar ¹⁴ are, for example, specifically phenyl,
Examples include aryl groups such as tolyl, methoxyphenyl, naphthyl, pyrenyl and biphenyl, heterocyclic groups such as benzofuryl, benchazolyl, benzoxazolyl and N-ethylcarbazolyl, and aralkyl groups such as methylbenzyl and methoxybenzyl.

A is, for example, an alkyl group such as methyl, ethyl, n-propyl, or iso-propyl; an alkoxy group such as methoxy group, ethoxy group and propoxy group; a dialkylamino group such as dimethylamino group and diethylamino group. Groups, halogen atoms such as fluorine and chlorine, or hydrogen atoms. In general, electron-donating substituents are effective.

The benzofuran-bishydrazone compound of the general formula (V) can be synthesized by various methods.
It is easily prepared in the following synthesis process. That is, 1.0 equivalent of a bisformylbenzofuran compound represented by the following general formula (IX) and 2.0 to 2.4 equivalents of a hydrazine reagent represented by the following general formula (X) are mixed with ethanol, methanol, tetrahydrofuran. , In an organic solvent such as 1,4-dioxane and acetonitrile, 0.001 to 0.01 equivalents of a catalyst such as acetic acid, potassium acetate, calcium acetate and sodium acetate are added.
It is produced by heating and stirring for 10 hours.

[0128]

Embedded image

[In the general formula (IX), a has 1 to 1 carbon atoms.
3 represents an alkyl group, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom. n5 is an integer of 1 to 3. However, when n5 is 2 or more, each of a plurality of a may be the same or different. ]

[0130]

Embedded image

[In the general formula (X), Ar ¹³ and Ar ¹⁴ represent an aryl group which may have a substituent, an aralkyl group which may have a substituent, a heterocyclic group or a group having 1 to 4 carbon atoms. Represents an alkyl group. ]

Specific examples of the benzofuran-bishydrazone compound are shown in Tables 15 to 18, but the compounds of the present invention are not limited thereto.

[0133]

[Table 15]

[0134]

[Table 16]

[0135]

[Table 17]

[0136]

[Table 18]

One or more of the above-mentioned benzofuran-bishydrazone compounds may be contained as a charge transporting substance. Further, another charge transport material may be contained.

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

In particular, when an N, N'-bisenamine compound and a benzofuran-bishydrazone compound are used as the charge transporting substance 3, a polycarbonate represented by the following formula (VI) is preferable.

[0140]

Embedded image

In formula (VI), R ³³ and R ³⁴ each represent an alkyl group having 1 to 5 carbon atoms which may have a substituent or an aryl group having 6 to 12 carbon atoms which may have a substituent. And represents an aralkyl group having 7 to 17 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom, which may have a substituent. X
² has an alkylene group having 1 to 10 carbon atoms which may be directly bonded or may have a substituent, a cyclic alkylidene group having 1 to 10 carbon atoms which may have a substituent, Represents an arylene group having 6 to 12 carbon atoms, a sulfonyl group or a carbonyl group. Z ³ represents an alkylene group having 1 to 5 carbon atoms, an arylene group having 6 to 12 carbon atoms, an arylene alkyl group having 7 to 17 carbon atoms, or a halogen atom which may have a substituent. W ¹ represents an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms, and a substituent. It represents an alkyl ester group having 1 to 5 carbon atoms which may have, an aryl ester group having 6 to 12 carbon atoms which may have a substituent, a carboxyl group, an aldehyde group, a hydroxyl group, a halogen atom or a hydrogen atom. e and f represent an integer of 1 to 4, and u2 represents an integer of 10 to 200.

Further, a polyester represented by the following general formula (VII) is particularly preferable.

[0143]

Embedded image

In the general formula (VII), g, h2 and i2
Represents an integer of 1 to 10, and v, w2, x3 and y are 1
Represents an integer of 0 to 1000.

In particular, a mixture of a polycarbonate represented by the general formula (VI) and a polyester represented by the general formula (VII) is preferable.

Specific examples of the polycarbonate represented by the general formula (VI) are shown in Table 19, but the polycarbonate of the present invention is not limited thereto.

[0147]

[Table 19]

The polyester of the general formula (VII) is used in an amount of 0.05 to 0.5 parts by weight, preferably 0.2 to 0.3 parts by weight, based on the whole binder resin. It is preferable to use within the range.

The bisamine compound described above, N,
N'-bisenamine compound, styryl compound, amine-
The hydrazone compound and the benzofuran-bishydrazone compound are used in an amount of not less than 0.2 parts by weight and not more than 1.5 parts by weight based on the binder resin.
Parts by weight or less, preferably 0.3 parts by weight or more.
It is preferable to use it in a range of 2 parts by weight or less.

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

The charge transport layer 6 is
Can be formed by a known method such as a method of dissolving or dispersing a substance to be contained in a solvent and applying the obtained coating liquid. For example, the charge transport material 3 is dissolved in a solvent,
A coating liquid is prepared by adding a binder resin. Using this coating liquid,
In the case of a sheet-shaped photoconductor, it is formed by a coating method such as a baker applicator, a bar coater, casting and spin coating, and in the case of a drum-shaped photoconductor, it is formed by a spray method, a vertical ring type, and a dip coating method. can do.

Examples of the solvent used in the coating solution 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 and dioxane, benzene,
Aromatic hydrocarbons such as toluene and xylene, N,
Aprotic polar solvents such as N-dimethylformamide and dimethyl sulfoxide can be used.

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

The single-layer type photosensitive layer 4b is formed by dispersing the charge generating substance 2 in the charge transport layer 6 described above. In this case, it is preferable that the particle size of oxotitanyl phthalocyanine, which is the charge generating substance 2, is sufficiently small.
Particle sizes below μm are preferred. If the amount of the charge generating substance 2 dispersed in the photosensitive layer 4b is too small, the sensitivity becomes insufficient. If the amount is too large, the chargeability and the sensitivity are reduced. Therefore, it is used in the range of 0.5% by weight to 50% by weight, preferably in the range of 1% by weight to 20% by weight, based on the total weight of the photosensitive layer 4b.

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

A known plasticizer for improving the film forming property, flexibility, mechanical strength, etc., an additive for suppressing the residual potential, and an additive for improving the dispersion stability of the photosensitive layer 4b. Dispersing aids, leveling agents to improve coatability, surfactants, silicone oils, fluorinated oils,
Antioxidants and other additives may be added. As the antioxidant, the same antioxidant as in the case of the function separation type can be used.

The intermediate layer 7 is made of an aluminum anodic oxide film,
Implemented with inorganic layers such as aluminum oxide, aluminum hydroxide and titanium oxide. Also, polyvinyl alcohol, polyvinyl butyral, casein, polyvinylpyrrolidone, polyacrylic acid, celluloses, gelatin,
It may be realized by an organic layer such as starch, polyurethane, polyimide, polyamide and N-methoxymethylated nylon. Further, particles such as titanium oxide, tin oxide, and aluminum oxide 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, for example, a thermoplastic resin or a thermosetting resin.

Hereinafter, the present invention will be described specifically 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 is not exceeded.

(Production Example 1) o-phthalodinitrile 40
g, titanium tetrachloride 18 g and α-chloronaphthalene 5
The reaction was carried out by heating and stirring 00 ml at 200 ° C. to 250 ° C. for 3 hours in a nitrogen atmosphere. After cooling to 100 ° C. to 130 ° C., the mixture was filtered while hot and washed with 200 ml of α-chloronaphthalene heated to 100 ° C. A crude dichlorotitanium phthalocyanine product was obtained. This crude product is washed with 200 ml of α-chloronaphthalene at room temperature, further washed with 200 ml of methanol, and further washed with 500 ml of methanol for 1 hour while hot. The crude product obtained by filtration was repeatedly hot-washed in 500 ml of water until the pH reached 6 to 7, and then dried to obtain oxotitanyl phthalocyanine intermediate crystals.

FIG. 2 is an X-ray diffraction spectrum of the oxotitanyl phthalocyanine intermediate crystal obtained as described above. It shows the maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 27.3 °, and has a Bragg angle of 7.4 ° and 9.
Japanese Unexamined Patent Publication No. Hei 2-
It is found to be an oxotitanyl phthalocyanine called a Y-type described in Japanese Patent Application Laid-Open No. 8256 and Japanese Patent Application Laid-Open No. 7-27073.

The above-mentioned oxotitanyl phthalocyanine intermediate crystal and methyl ethyl ketone were mixed, and a diameter of 2 m was measured using the paint conditioner (manufactured by Red Level Co., Ltd.).
After milling with glass beads of m, washing with methanol, and drying, a crystalline oxotitanyl phthalocyanine unique to the present invention was obtained.

FIG. 3 is an X-ray diffraction spectrum of oxotitanyl phthalocyanine obtained as described above. Bragg angle (2θ ± 0.2 °) 7.3 °, 9.4
°, 9.6 °, 11.6 °, 13.3 °, 17.9 °,
An oxotitanyl phthalocyanine of a crystalline form unique to the present invention having diffraction peaks at 24.1 ° and 27.2 ° and a maximum diffraction peak in an overlapping peak bundle having Bragg angles of 9.4 ° and 9.6 °. It turns out there is.

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

(Production Example 2) The oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1, polybutyral (manufactured by Sekisui Chemical Co., Ltd .: Eslec BL-1) and methyl ethyl ketone were mixed, and glass beads having a diameter of 2 mm were mixed using a bead mill. And a milling treatment to obtain a crystalline form of oxotitanyl phthalocyanine unique to the present invention.

FIG. 4 is an X-ray diffraction spectrum of 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 a bundle of overlapping peaks at Bragg angles of 9.4 ° and 9.6 °, and further has a Bragg angle of 14.1 ° to 14.1 °. It can be seen that the oxotitanyl phthalocyanine is a crystalline form unique to the present invention, which has a plurality of diffraction peaks having the same intensity at 9 ° and an aggregate of difficult-to-separate peaks having a trapezoidal shape.

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

FIG. 5 is an X-ray diffraction spectrum of 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 a bundle of overlapping peaks at Bragg angles of 9.4 ° and 9.6 °, and further has a Bragg angle of 14.1 ° to 14.1 °. A plurality of diffraction peaks having the same intensity at 9 ° indicate a trapezoidal aggregate of difficult-to-separate peaks, and a Bragg angle of 9.4 ° and 9 ° at a position of 9.0 °. It can be seen that the crystalline form of oxotitanyl phthalocyanine which is characteristic of the present invention and has an intensity peak of about half of the peak bundle of 0.6 ° is present as a shoulder peak of the peak bundle.

First, Examples 1 to 8 and Comparative Examples 1 and 2 using the oxotitanyl phthalocyanine and the bisamine compound will be described.

Example 1 On a conductive support 1 made of a polyester film on which aluminum was deposited, titanium oxide and copolymerized nylon (CM8000, manufactured by Toray Industries, Inc.) were mixed in a mixed solvent of methyl alcohol and dichloroethane. The dissolved coating liquid for an intermediate layer was applied and dried to form an intermediate layer 7 having a thickness of 1 μm.

Next, 1 part by weight of oxotitanifurocyanine (charge generating substance 2) obtained in Production Example 1 and 1 part by weight of polybutyral (binder resin) (manufactured by Sekisui Chemical Co., Ltd .; Eslec BL- 1) and 70 parts by weight of methyl ethyl ketone were mixed and dispersed together with glass beads having a diameter of 2 mm by a paint conditioner (manufactured by Red Level Co.), and the obtained coating solution for a charge generation layer was placed on the intermediate layer 7. The resultant was applied and dried to form a charge generation layer 5 having a thickness of 0.4 μm.

Further, the exemplified compound BA1 (charge transporting substance 3) and polycarbonate (binder resin) (PCZ-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) were mixed at a weight ratio of 1: 1 and dichloromethane was used as a solvent at 15 wt%. Was prepared, and the coating liquid was applied on the charge generation layer 5 and dried to form a charge transport layer 6 having a thickness of 20 μm. As described above, the intermediate layer 7, the charge generation layer 5, and the charge transport layer 6
The function-separated type photoconductor 8b provided with the photoconductive layer 4a having the laminated structure was obtained.

(Examples 2 to 5) As the charge transporting substance 3,
Exemplified Compounds BA10 and BA in place of Exemplified Compound BA1
13, BA24 and BA40 were used, respectively, except that the function-separated type photoconductor 8b was obtained in the same manner as in Example 1.

Example 6 The same as Example 1 except that the oxotitanyl phthalocyanine obtained in Production Example 2 was replaced with the oxotitanyl phthalocyanine obtained in Production Example 2 as the charge generating substance 2, Thus, a function-separated type photoconductor 8b was obtained.

(Example 7) As the charge generating substance 2, the oxotitanyl phthalocyanine obtained in Production Example 3 was used instead of the oxotitanyl phthalocyanine obtained in Production Example 1, and the other conditions were the same as in Example 1. Thus, a function-separated type photoconductor 8b was obtained.

Example 8 An intermediate layer 7 was formed on a conductive support 1 in the same manner as in Example 1. Next, 1 part by weight of oxotitanylfurocyanine (charge generating substance 2) obtained in Production Example 1 and 10 parts by weight of Exemplified Compound BA4
(Charge transporting substance 3) and 10 parts by weight of a polycarbonate (binder resin) (PCZ-200, manufactured by Mitsubishi Gas Chemical Company) were mixed, and a 18 wt% coating solution was prepared using dichloromethane as a solvent to prepare the paint conditioner. Dispersion treatment was performed together with glass beads having a diameter of 2 mm by an apparatus. The obtained coating liquid for a photosensitive layer was applied on the intermediate layer 7 and dried to form a photosensitive layer 4b having a thickness of 20 μm. As described above, a single-layer type photoconductor 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 photosensitive material was the same as in Example 1 except for the above. I got a body.

Comparative Example 2 In place of the charge transporting substance used in Example 1, a charge transporting substance represented by the following structural formula (XI) was used. A photoreceptor was obtained.

[0179]

Embedded image

The photoreceptors prepared in Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated as follows. The function-separated type photoreceptor is an electrostatic recording paper test device (Kawaguchi Electric Co .: EP
A-8200) to evaluate its electrophotographic properties.
The measurement conditions were as follows: applied voltage: -6 kV, static: No.
3, and the potential was -500 V by monochromatic light of 780 nm (irradiation light: ² μW / cm ² ) dispersed by an interference filter.
Exposure E _1/2 required to attenuate from-to -250V
(ΜJ / cm ² ) and initial potential V ₀ (−V) were measured. The electrophotographic characteristics of the single-layer type photoreceptor were evaluated using the above-described electrostatic recording paper test apparatus. The measurement conditions were as follows: applied voltage: +6 kV, static: No. 3 and monochromatic light of 780 nm (irradiation light: 10 μm) dispersed by an interference filter.
W / cm ² ) to increase the potential from +500 V to +250 V
Exposure E1 / ₂ (μJ / cm
² ) and the initial potential V ₀ (+ V) were measured.

A commercially available digital copying machine (AR5130, manufactured by Sharp Corporation) was modified to mount the photoconductors of Examples 1 to 8 and Comparative Examples 1 and 2 on the photoconductor drum, and 30,000 continuous emptying operations were performed. A durability test by copying was performed, and before and after the measurement, a charged potential was measured, and a half-life exposure amount E1 _{/ 2} was measured using the electrostatic recording paper test apparatus. Further, a durability test was performed by 30,000 continuous blank copies in a high-temperature, high-humidity environment (35 ° C., 85%), and the residual potential Vr was measured before and after that. Table 20 shows the results.

[0182]

[Table 20]

As shown in Table 20, it can be seen that in all of Examples 1 to 8, the amount of deterioration of the charging potential in the durability test was sufficiently smaller than Comparative Examples 1 and 2. Also, it can be seen that the initial sensitivity (half-exposure amount) is sufficiently higher than Comparative Examples 1 and 2. Further, it can be seen that the sensitivity deterioration after the durability test is small.
Further, it can be seen that the rise in the residual potential after the durability test in a high-temperature and high-humidity environment is sufficiently smaller than in Comparative Examples 1 and 2.

Next, Examples 9 to 10 using the oxotitanyl phthalocyanine and the N, N'-bisenamine compound were described.
16 and Comparative Examples 3 to 13 will be described.

(Example 9) In the same manner as in Example 1, the intermediate layer 7 was formed on the conductive support 1, and the charge generation layer 5 was further formed. Further, 10 parts by weight of the exemplary compound BE1
N, N'-bisenamine represented by (Charge transporting substance 3), 8 parts by weight of polycarbonate (binder resin) represented by Exemplified compound V1 in Table 15, and 2 parts by weight of the above general formula (VII) Polyester (binder resin) represented by
0.2 parts by weight of α-tocopherol (an antioxidant);
0.0002 parts by weight of polydimethylsiloxane (leveling agent) was mixed to prepare a 15 wt% coating liquid for a charge transport layer using tetrahydrofuran as a solvent. The coating liquid was applied on the charge generation layer 5 and dried. Thus, a charge transport layer 6 having a thickness of 20 μm was formed. As described above, a function-separated type photoconductor 8b including the intermediate layer 7, the photosensitive layer 4a having the laminated structure of the charge generation layer 5 and the charge transport layer 6, was obtained.

(Example 10) The conductive support 1 of Example 1
In the same manner as in Example 1, the charge generation layer 5 was formed directly. Further, an N, N'-bisenamine compound represented by Exemplified Compound BE3 was used as the charge transporting substance 3, and 0.5 parts by weight of 2,6-di-t-butyl-4 was used as an antioxidant.
A charge transport layer 6 was prepared in the same manner as in Example 9 except that -methyl-phenol was used. As described above,
A function-separated type photoconductor 8b was obtained.

(Example 11) A vinyl chloride vinyl acetate copolymer resin (manufactured by Sekisui Chemical Co., Ltd .: S-LEC M-1) was used as the binder resin of the charge generation layer 5, and the charge transport material 3 is represented by Exemplified Compound BE14. A function-separated photoconductor 8b was obtained in the same manner as in Example 9, except that the N, N'-bisenamine compound was used.

Example 12 An intermediate layer 7 was formed on a conductive support 1 in the same manner as in Example 1. Next, the charge generation layer 5 was formed in the same manner as in Example 1 except that the oxotitanyl phthalocyanine obtained in Production Example 2 was used. Further, 10 parts by weight of N, N'-bisenamine represented by the exemplified compound BE1 (charge transporting substance 3), 8 parts by weight of the polycarbonate (binder resin) represented by the exemplified compound V1, and 2 parts by weight of Polyester (binder resin) represented by the general formula (VII) and 0.5 parts by weight of 2,6-di-
t-butyl-4-methyl-phenol (antioxidant)
And 0.0002 parts by weight of a polydimethylsiloxane (leveling agent), and a 15 wt% coating liquid for a charge transport layer was prepared using dichloromethane as a solvent, and the coating liquid was applied on the charge generation layer 5. After drying, the charge transport layer 6 having a thickness of 25 μm was formed. As described above, a function-separated type photoconductor 8b including the intermediate layer 7, the photosensitive layer 4a having the laminated structure of the charge generation layer 5 and the charge transport layer 6, was obtained.

Example 13 As the charge transporting substance 3, an N, N'-bisenamine-styrylated compound represented by Exemplified Compound BE27 was used instead of Exemplified Compound BE1.
Except for this, the function-separated type photoconductor 8b was obtained in the same manner as in Example 12.

(Example 14) An intermediate layer 7 was formed on a conductive support 1 in the same manner as in Example 1. Next, the charge generation layer 5 was formed in the same manner as in Example 1 except that the oxotitanyl phthalocyanine obtained in Production Example 3 was used. Further, the charge transport layer 6 was formed in the same manner as in Example 12. As described above, a function-separated type photoconductor 8b including the intermediate layer 7, the photosensitive layer 4a having the laminated structure of the charge generation layer 5 and the charge transport layer 6, was obtained.

(Example 15) As the charge transporting substance 3, an N, N'-bisenamine-styrylated compound represented by Exemplified Compound BE40 was used instead of Exemplified Compound BE1.
Other than that, the function-separated type photoconductor 8b was obtained in the same manner as in Example 14.

(Example 16) An intermediate layer 7 was formed on a conductive support 1 in the same manner as in Example 1. Next, 1 part by weight of the oxotitanyl furocyanine (charge generating substance 2) obtained in Production Example 1 and 10 parts by weight of the exemplary compound BE6
N, N'-Bisenamine compound (charge transporting substance 3), 8 parts by weight of the polycarbonate (binder resin) represented by Exemplified Compound V1, and 2 parts by weight of the general formula (VI
A polyester represented by I) and 0.5 parts by weight of 2,6
-Di-t-butyl-4-methyl-phenol (antioxidant), and 15 wt.
% Of the coating solution was prepared and dispersed together with the glass beads having a diameter of 2 mm by the paint conditioner. The obtained coating solution for a photosensitive layer was applied on the intermediate layer 7 and dried to form a photosensitive layer 4b having a thickness of 25 μm. As described above, a single-layer type photoconductor 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 3) An oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was used instead of the oxotitanyl phthalocyanine of Example 9, and a function-separated type photoconductor was prepared in the same manner as in Example 9 except for that. Obtained.

Comparative Example 4 The oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was used in place of the oxo titanyl phthalocyanine of Example 10, and a function-separated type photoreceptor was prepared in the same manner as in Example 10 except for that. Obtained.

(Comparative Example 5) A known 4- (diethylamino) -benzaldehyde-N, N, -diphenylhydrazone compound was used in place of the charge transport material of Example 9, and the other functions were the same as in Example 9. A separated photoconductor was obtained.

Comparative Example 6 A function-separated photosensitive member was prepared in the same manner as in Example 9 except that a polycarbonate containing bisphenol A as a monomer component was used instead of the binder resin of the charge generation layer in Example 9. Obtained.

(Comparative Example 7) α was added to the charge generation layer of Example 10.
-A function-separated type photoreceptor was obtained in the same manner as in Example 10 except that no tocopherol was added.

(Comparative Example 8) The charge generation layer of Example 9
A function-separated type photoconductor was obtained in the same manner as in Example 9, except that 6-di-t-butyl-4-methyl-phenol was not added.

Comparative Example 9 A function-separated type photoconductor was prepared in the same manner as in Example 9, except that polydimethylsiloxane was not added to the charge generation layer of Example 9. In Comparative Example 9, unevenness occurred on the surface of the photoconductor, and a uniform coating film was not obtained.

Comparative Example 10 A single-layer type photoreceptor was prepared in the same manner as in Example 16 except that the oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was used instead of the charge generating material of Example 16. Obtained.

(Comparative Example 11) A known 4- (diethylamino) -benzaldehyde-N, N, -diphenylhydrazone compound was used in place of the charge transporting substance of Example 16, and the other conditions were the same as in Example 16. A one-layer type photoreceptor was obtained.

(Comparative Example 12) A single-layer type photoreceptor was obtained in the same manner as in Example 16 except that polycarbonate containing bisphenol A as a monomer component was used instead of the binder resin of Example 16.

(Comparative Example 13) In Example 16, 2,6-di-
A single-layer type photoreceptor was obtained in the same manner as in Example 16 except that t-butyl-4-methyl-phenol was not added.
Table 21 shows each sample of Examples 9 to 16 and Comparative Examples 3 to 13.
Are shown together.

[0204]

[Table 21]

The photoreceptors prepared in Examples 9 to 16 and Comparative Examples 3 to 13 were evaluated for electrophotographic characteristics in the same manner as described above, and were subjected to a durability test. further,
The degree of reduction in the thickness of the photoreceptor was measured using a wear tester (manufactured by Suga Test Instruments Co., Ltd.). The measurement conditions were as follows: abrasive: aluminum oxide # 2000, load: 200 g · f, number of friction: 10,000 times. Table 22 shows the results.

[0206]

[Table 22]

As shown in Table 22, in each of Examples 9 to 16, the amount of deterioration of the charging potential in the durability test was determined in Comparative Examples 3-1.
It turns out that it is sufficiently smaller than 3. Also, it can be seen that the initial sensitivity (half-exposure amount) is sufficiently higher than Comparative Examples 3 to 13.
Further, it can be seen that the sensitivity deterioration after the durability test is small. Further, it can be seen that the increase in the residual potential after the durability test in a high-temperature and high-humidity environment is sufficiently smaller than in Comparative Examples 3 to 13.

Next, Examples 17 to 24 and Comparative Examples 14 and 15 using the oxotitanyl phthalocyanine and styryl compound will be described.

(Example 17) In the same manner as in Example 1, the intermediate layer 7 was formed on the conductive support 1, and the charge generation layer 5 was further formed. Further, the exemplified compound ST1 (charge transport material 3) and polycarbonate (binder resin) (PCZ-200, manufactured by Mitsubishi Gas Chemical Company) were mixed at a weight ratio of 1: 1, and 15% by weight of charge transport was performed using dichloromethane as a solvent. A coating liquid for a layer was prepared, and the coating liquid was applied on the charge generation layer 5 and dried to form a charge transport layer 6 having a thickness of 20 μm. As described above, a function-separated type photoconductor 8b including the intermediate layer 7, the photosensitive layer 4a having the laminated structure of the charge generation layer 5 and the charge transport layer 6, was obtained.

(Examples 18 to 21) As the charge transporting substance 3, the exemplified compounds ST9, S
T17, ST23, and ST28 were used, respectively, and the rest was the same as in Example 17 except for the function-separated type photoconductor 8b.
I got

(Example 22) A function-separated type photoreceptor was obtained in the same manner as in Example 17 except that the oxotitanyl phthalocyanine obtained in Production Example 2 was used instead of the charge generating substance 2 of Example 17. Was.

(Example 23) The oxotitanyl phthalocyanine obtained in Production Example 3 was used in place of the charge generating substance 2 of Example 17, and the function-separated type photoconductor 8b was used in the same manner as in Example 17 except for the above. Obtained.

Example 24 An intermediate layer 7 was formed on a conductive support 1 in the same manner as in Example 1. Next, 1 part by weight of the oxotitanifurocyanine (charge generating substance 2) obtained in Production Example 1 and 10 parts by weight of the exemplary compound ST2
(Charge transporting substance 3) and 10 parts by weight of a polycarbonate (binder resin) (PCZ-200, manufactured by Mitsubishi Gas Chemical Company) were mixed, and a 18 wt% coating solution was prepared using dichloromethane as a solvent to prepare the paint conditioner. Dispersion treatment was performed together with glass beads having a diameter of 2 mm by an apparatus. The obtained coating liquid for a photosensitive layer was applied on the intermediate layer 7 and dried to form a photosensitive layer 4b having a thickness of 20 μm. As described above, a single-layer type photoconductor 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 14) The oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was used in place of the oxotitanyl phthalocyanine used in Example 17, and the function-separated type was obtained in the same manner as in Example 17 except for that. A photoreceptor was obtained.

(Comparative Example 15) In place of the charge transporting substance used in Example 17, a charge transporting substance represented by the following structural formula (XII) was used. A photoreceptor of the mold was obtained.

[0216]

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Examples 17 to 24 and Comparative Examples 14 and 15
The electrophotographic characteristics of the photoreceptor prepared in the above were evaluated in the same manner as described above, and a durability test was performed. Table 23 shows the results.

[0218]

[Table 23]

As shown in Table 23, in each of Examples 17 to 24, the amount of deterioration of the charging potential by the durability test was determined in Comparative Example 1.
It turns out that it is sufficiently smaller than 4,15. Further, it can be seen that the initial sensitivity (half-exposure amount) is sufficiently higher than Comparative Examples 14 and 15. Further, it can be seen that the sensitivity deterioration after the durability test is small. Further, it can be seen that the rise in the residual potential after the durability test in a high-temperature, high-humidity environment is sufficiently smaller than in Comparative Examples 14 and 15.

Next, Examples 25 to 3 using the oxotitanyl phthalocyanine and the amine-hydrazone compound were described.
2 and Comparative Examples 16 and 17 will be described.

Example 25 An intermediate layer 7 was formed on a conductive support 1 and a charge generation layer 5 was formed in the same manner as in Example 1. Further, Exemplified Compound AH1 (charge transporting substance 3) and polycarbonate (binder resin) (PCZ-200 manufactured by Mitsubishi Gas Chemical Company) 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 on the charge generation layer 5 and dried to form a charge transport layer 6 having a thickness of 20 μm. As described above, the intermediate layer 7, the charge generation layer 5, and the charge transport layer 6
The function-separated type photoconductor 8b provided with the photoconductive layer 4a having the laminated structure was obtained.

(Examples 26 to 29) Exemplified compounds AH3 and AH in place of Exemplified compound AH1 as charge transporting substance 3
5, AH10 and AH16 were used, and otherwise the procedure of Example 25 was carried out to obtain a function-separated type photoconductor 8b.

(Example 30) In place of the charge transporting substance 2 of Example 25, the oxotitanyl phthalocyanine obtained in Production Example 2 was used, and in the same manner as in Example 25, a function-separated type photoconductor 8b was obtained. Was.

(Example 31) In place of the charge generating substance 2 of Example 25, the oxotitanyl phthalocyanine obtained in Production Example 3 was used, and in the same manner as in Example 25, a function-separated type photoconductor 8b was obtained. Was.

(Example 32) An intermediate layer 7 was formed on a conductive support 1 in the same manner as in Example 1. Next, 1 part by weight of oxotitanifurocyanine (charge generating substance 2) obtained in Production Example 1 and 10 parts by weight of Exemplified Compound AH2
(Charge transporting substance 3) and 10 parts by weight of a polycarbonate (binder resin) (PCZ-200, manufactured by Mitsubishi Gas Chemical Company) were mixed, and a 18 wt% coating solution was prepared using dichloromethane as a solvent to prepare the paint conditioner. Dispersion treatment was performed together with glass beads having a diameter of 2 mm by an apparatus. The obtained coating liquid for a photosensitive layer was applied on the intermediate layer 7 and dried to form a photosensitive layer 4b having a thickness of 20 μm. As described above, a single-layer type photoconductor 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 16) In place of the oxotitanyl phthalocyanine used in Example 25, the oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was used. A photoreceptor was obtained.

(Comparative Example 17) In place of the charge transporting substance used in Example 25, a charge transporting substance represented by the following structural formula (XIII) was used. A photoreceptor of the mold was obtained.

[0228]

Embedded image

Examples 25 to 32 and Comparative Examples 16 and 17
The electrophotographic characteristics of the photoreceptor prepared in the above were evaluated in the same manner as described above, and a durability test was performed. Table 24 shows the results.

[0230]

[Table 24]

As shown in Table 24, in each of Examples 25 to 32, the amount of deterioration of the charging potential by the durability test was the same as in Comparative Example 1.
It turns out that it is sufficiently smaller than 6,17. Further, it can be seen that the initial sensitivity (half-exposure amount) is sufficiently higher than Comparative Examples 16 and 17. Further, it can be seen that the sensitivity deterioration after the durability test is small. Further, it can be seen that the increase in the residual potential after the durability test in a high-temperature and high-humidity environment is sufficiently smaller than in Comparative Examples 16 and 17.

Next, Examples 33 to 40 and Comparative Examples 18 to 28 using the oxotitanyl phthalocyanine and the benzofuran-bishydrazone compound will be described.

(Example 33) In the same manner as in Example 1, an intermediate layer 7 was formed on a conductive support 1, and a charge generation layer 5 was further formed. Further, 10 parts by weight of the exemplified compound BB
A benzofuran-bishydrazone compound represented by 1 (charge transporting substance 3), 8 parts by weight of a polycarbonate (binder resin) represented by Exemplified Compound V1, and 2 parts by weight of a general formula (VII) Polyester (binder resin) and
0.2 parts by weight of α-tocopherol (an antioxidant);
0.0002 parts by weight of polydimethylsiloxane (leveling agent) was mixed to prepare a 15 wt% coating liquid for a charge transport layer using tetrahydrofuran as a solvent. The coating liquid was applied on the charge generation layer 5 and dried. Thus, a charge transport layer 6 having a thickness of 20 μm was formed. As described above, a function-separated type photoconductor 8b including the intermediate layer 7, the photosensitive layer 4a having the laminated structure of the charge generation layer 5 and the charge transport layer 6, was obtained.

(Example 34) The charge generation layer 5 was directly formed on the conductive support 1 of Example 33 in the same manner as in Example 33. Further, as the charge transporting substance 3, the exemplified compound BB
Using a benzofuran-bishydrazone compound represented by 12 as an antioxidant, 0.5 part by weight of 2,6-di-t
A charge transport layer 6 was prepared in the same manner as in Example 33 except that -butyl-4-methyl-phenol was used. Thus, a function-separated type photoconductor 8b was obtained.

(Example 35) A vinyl chloride vinyl acetate copolymer resin (manufactured by Sekisui Chemical Co., Ltd .: Eslec M-1) was used as the binder resin of the charge generation layer 5, and the charge transport material 3 is represented by Exemplified Compound BB24. A function-separated photoconductor 8b was obtained in the same manner as in Example 33, except that a benzofuran-bishydrazone compound was used.

(Example 36) As in Example 33,
The intermediate layer 7 was formed on the conductive support 1. Next, using the oxotitanyl phthalocyanine obtained in Production Example 2,
Otherwise, the charge generation layer 5 was formed in the same manner as in Example 33. Further, 10 parts by weight of a benzofuran-bishydrazone compound represented by Exemplified Compound BB1 (charge transport material 3), 8 parts by weight of a polycarbonate (binder resin) represented by Exemplified Compound V1, and 2 parts by weight of a general resin Formula (VII)
A polyester (binder resin), 0.5 parts by weight of 2,6-di-t-butyl-4-methyl-phenol (antioxidant), and 0.0002 parts by weight of polydimethylsiloxane ( Leveling agent) to prepare a 15 wt% coating solution for the charge transport layer using dichloromethane as a solvent. The coating solution is applied on the charge generation layer 5 and dried to form a charge transport layer 6 having a thickness of 25 μm. It was created. As described above, the function-separated type photoconductor 8 including the intermediate layer 7 and the photoconductive layer 4 a having the stacked structure of the charge generation layer 5 and the charge transport layer 6.
b was obtained.

(Example 37) As the charge transporting substance 3, a benzofuran-bishydrazone compound represented by Exemplified Compound BB36 was used instead of Exemplified Compound BB1, and otherwise a function-separated type photosensitive material was obtained in the same manner as in Example 36. A body 8b was obtained.

(Example 38) As in Example 33,
The intermediate layer 7 was formed on the conductive support 1. Next, using the oxotitanyl phthalocyanine obtained in Production Example 3,
Otherwise, the charge generation layer 5 was formed in the same manner as in Example 33. Further, the charge transport layer 6 was formed in the same manner as in Example 36. As described above, a function-separated type photoconductor 8b including the intermediate layer 7 and the photosensitive layer 4a having the laminated structure of the charge generation layer 5 and the charge transport layer 6 was obtained.

(Example 39) As the charge transporting substance 3, a benzofuran-bishydrazone compound represented by Exemplified Compound BB40 was used in place of Exemplified Compound BB1. A body 8b was obtained.

(Example 40) In the same manner as in Example 33,
The intermediate layer 7 was formed on the conductive support 1. Next, 1 part by weight of the oxotitanyl furocyanine (charge generating substance 2) obtained in Production Example 1 and 10 parts by weight of the exemplified compound BB
7, a benzofuran-bishydrazone compound (charge-transporting substance 3), 8 parts by weight of a polycarbonate (binder resin) represented by Exemplified Compound V1, and 2 parts by weight of a general formula (VII) Polyester and 0.5 part by weight of 2,6-di-t-butyl-4-methyl-phenol (antioxidant) were mixed, and dichloromethane was used as a solvent to prepare 1 part.
A coating solution of 5 wt% was prepared and subjected to a dispersion treatment together with glass beads having a diameter of 2 mm by the paint conditioner. The obtained coating solution for a photosensitive layer was applied on the intermediate layer 7 and dried to form a photosensitive layer 4b having a thickness of 25 μm. As described above, a single-layer type photoconductor 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 18 A function-separated type photoconductor was prepared in the same manner as in Example 33 except that the oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was used instead of the oxotitanyl phthalocyanine of Example 33. Obtained.

Comparative Example 19 An oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was used in place of the oxotitanyl phthalocyanine of Example 33, and a function-separated type photoconductor was prepared in the same manner as in Example 34 except for that. Obtained.

(Comparative Example 20) A known 4- (diethylamino) -benzaldehyde-N, N, -diphenylhydrazone compound was used in place of the charge transporting substance of Example 33, and the other functions were the same as in Example 33. A separated photoconductor was obtained.

(Comparative Example 21) A function-separated photosensitive member was prepared in the same manner as in Example 33 except that a polycarbonate containing bisphenol A as a monomer component was used instead of the binder resin of the charge generation layer of Example 33. Obtained.

Comparative Example 22 A function-separated photosensitive member was obtained in the same manner as in Example 34 except that α-tocopherol was not added to the charge generation layer of Example 34.

(Comparative Example 23) A function-separated type photosensitive material was prepared in the same manner as in Example 33 except that 2,6-di-tert-butyl-4-methyl-phenol was not added to the charge generating layer of Example 33. I got a body.

Comparative Example 24 Example 3 was repeated except that no polydimethylsiloxane was added to the charge generation layer of Example 33.
In the same manner as in Example 3, a function-separated type photoconductor was prepared. In Comparative Example 24, unevenness occurred on the surface of the photoreceptor, and a uniform coating film was not obtained.

(Comparative Example 25) A single-layer type photoreceptor was prepared in the same manner as in Example 40 except that the oxotitanyl phthalocyanine intermediate crystal obtained in Production Example 1 was used instead of the charge generating material of Example 40. Obtained.

(Comparative Example 26) A known 4- (diethylamino) -benzaldehyde-N, N, -diphenylhydrazone compound was used in place of the charge transport material of Example 40. A one-layer type photoreceptor was obtained.

(Comparative Example 27) A single-layer type photoreceptor was obtained in the same manner as in Example 40 except that a polycarbonate containing bisphenol A as a monomer component was used instead of the binder resin of Example 40.

(Comparative Example 28) In Example 40, 2,6-di-
A single-layer type photoreceptor was obtained in the same manner as in Example 40 except that t-butyl-4-methyl-phenol was not added.
Table 25 summarizes the samples of Examples 33 to 40 and Comparative Examples 18 to 28.

[0252]

[Table 25]

Examples 33 to 40 and Comparative Examples 18 to 28
The electrophotographic characteristics of the photoreceptor prepared in the above were evaluated in the same manner as described above, a durability test was performed, and the degree of reduction in the thickness of the photoreceptor was measured. The results are shown in Table 26.

[0254]

[Table 26]

As shown in Table 26, in each of Examples 33 to 40, the amount of deterioration of the charging potential by the durability test was measured in Comparative Example 18.
It turns out that it is sufficiently smaller than ~ 28. Also, it can be seen that the initial sensitivity (half-exposure amount) is sufficiently high. Further, it can be seen that the sensitivity deterioration after the durability test is small. Further, it can be seen that the rise in the residual potential after the durability test in a high temperature and high humidity environment is sufficiently small.

[0256]

As described above, according to the present invention, the photosensitive layer provided on the conductive support comprises X as a charge generating substance.
In the line diffraction spectrum, a Bragg angle of 7.3 °, 9.
4 °, 9.6 °, 11.6 °, 13.3 °, 17.9
, 24.1 °, and 27.2 °, the intensity of the overlapping diffraction peak bundles having the Bragg angles of 9.4 ° and 9.6 ° was the largest, and the Bragg angle of 27.2 °. A bisamine compound represented by the general formula (II) containing a crystalline oxotitanyl phthalocyanine having a second intensity at the diffraction peak of ° and represented by the general formula (II) as a charge transport material; ), (II-
N), N'-bisenamine compounds represented by the formula (II), (II-III) or (II-IV);
And any one of an amine-hydrazone compound represented by the general formula (IV-I) and a benzofuran-bishydrazone compound represented by the general formula (V). In a photoreceptor having such a photosensitive layer, excellent photosensitivity characteristics and repeated use characteristics are obtained,
In particular, the effect of suppressing a decrease in surface potential, an increase in residual potential, and deterioration in sensitivity is excellent. Therefore, it can be suitably used for a highly sensitive image forming apparatus.

Further, according to the present invention, the oxotitanyl phthalocyanine particularly exhibits an intensity at the diffraction peak at the Bragg angle of 27.2 ° in the X-ray diffraction spectrum, which overlaps with the Bragg angles of 9.4 ° and 9.6 °. The intensity is preferably 80% or less of the intensity in the diffraction peak bundle.

According to the present invention, the oxotitanyl phthalocyanine has a plurality of diffraction peaks whose intensities are substantially the same between Bragg angles of 14.1 ° to 14.9 °, particularly in the X-ray diffraction spectrum, Preferably, the plurality of diffraction peaks indicate a trapezoidal peak aggregate that is difficult to separate.

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

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

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

According to the present invention, when the N, N'-bisenamine compound or the benzofuran-bishydrazone compound is used as the charge transport material, the photosensitive layer contains a polycarbonate represented by the general formula (VI) as a binder resin. According to the present invention, the compound represented by the general formula (VII)
By containing the polyester in a predetermined range with respect to the entire binder resin, excellent photosensitivity characteristics and repeated use characteristics can be obtained, and excellent effects of suppressing a decrease in surface potential, an increase in residual potential, and a deterioration in sensitivity can be obtained. According to the present invention,
Even if the photosensitive layer contains α-tocopherol or 2,6-di-t-butyl-4-methylphenol as an antioxidant in a predetermined range with respect to the charge transport material, excellent photosensitivity characteristics and repeated use characteristics are obtained. Is obtained, the surface potential decreases,
An excellent effect of suppressing the increase in the residual potential and the deterioration in sensitivity can be obtained, and the oxidative deterioration of the photosensitive layer can be prevented.

[Brief description of the drawings]

FIG. 1 shows an electrophotographic photosensitive member 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.

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

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]

 REFERENCE SIGNS LIST 1 conductive support 2 charge generating substance 3 charge transporting substance 4,4a, 4b photosensitive layer 5 charge generating layer 6 charge transporting layer 7 intermediate layer 8,8a, 8b electrophotographic photoreceptor

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03G 5/06 372 G03G 5/06 372 373 373 5/05 101 5/05 101 104 104B (72) Inventor Takashi Obata Osaka (22) Inventor Akihiro Kondo, 22-22 Nagaike-cho, Abeno-ku, Osaka City, Osaka F-term (reference) 2H068 AA13 AA19 AA35 AA41 BA12 BA13 BA14 BA16 BA23 BA24 BA25 BA39 BB26 BB53 BB54

Claims (14)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer contains oxotitanyl phthalocyanine as a charge generating substance and a charge transporting substance represented by the following general formula (II). The oxotitanyl phthalocyanine contains a bisamine compound represented by the following formula: oxo-titanyl phthalocyanine has a Bragg angle (2θ ± 0.2 °) of 7.3 in the X-ray diffraction spectrum
°, 9.4 °, 9.6 °, 11.6 °, 13.3 °, 1
It shows major diffraction peaks at 7.9 °, 24.1 ° and 27.2 °, and the intensity at the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 ° is maximum, and the Bragg angle is The intensity at the 27.2 ° diffraction peak is the second
An electrophotographic photosensitive member, characterized in that: Embedded image [In the general formula (II), Ar ¹ and Ar ² represent an optionally substituted aryl group, heterocyclic group, aralkyl group or heterocyclic-substituted alkyl group. Z ¹ is O, S or Se
Is an atom. R ¹ and R ² each represent an alkyl group, an alkoxy group, a dialkylamino group, a halogen atom or a hydrogen atom which may have a substituent. m1 is an integer of 1 to 4, and n1 is an integer of 1 to 3. However, m1 and n1 is when 2 or more, or different in each of R ¹ and R ² are the same, and may form a ring. ] 2. 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 (II-I) as a charge transporting substance. N represented by any one of (II-II), (II-III) and (II-IV),
It contains an N'-bisenamine 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 °, 1
It shows major diffraction peaks at 7.9 °, 24.1 ° and 27.2 °, and the intensity at the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 ° is maximum, and the Bragg angle is The intensity at the 27.2 ° diffraction peak is the second
An electrophotographic photosensitive member, characterized in that: Embedded image Embedded image Embedded image Embedded image [Formulas (II-I), (II-II), (II-III)
And in (II-IV), Ar ^{3 to} Ar ⁶ represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or an aralkyl group which may have a substituent. . R ³
Represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, or an alkyl group having 1 to 4 carbon atoms. R ^{4 to} R ⁷ represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom. k1 is an integer of 1 to 5, and k
2, k3 is an integer of 1 to 4, p is an integer of 2 to 4, q is an integer of 1 to 3, k4 is an integer of 1 to 8, s is an integer of 0 to 2 is there. However, when k1 is 2 or more, R ⁴ may be the same or different. Also, k2 is 2
In the above, R ⁵ may be the same or different. further,
When k3 is 2 or more, R ⁶ may be the same or different.
Further, when k4 is 2 or more, R ⁷ may be the same or different. ] 3. 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 is represented by the following general formula (III) as a charge transporting substance. The oxotitanyl phthalocyanine contains a styryl compound, and the oxotitanyl phthalocyanine has a Bragg angle (2θ ± 0.2 °) of 7.3 ° and 9.3 ° in the X-ray diffraction spectrum.
4 °, 9.6 °, 11.6 °, 13.3 °, 17.9
, 24.1 ° and 27.2 °, and the intensity of the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 ° is the highest, and the Bragg angle of 27.2 °. An electrophotographic photosensitive member having a second intensity at a diffraction peak of °. Embedded image [In the formula (III), R ^{8 to} R ¹¹ represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group or an aryl group. R ¹⁰ and R ¹¹ may combine with each other to form a ring. Z ² represents an atomic group necessary for forming a saturated 5- to 8-membered ring together with two carbon atoms of the indoline ring. ] 4. An electrophotographic photoreceptor 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 oxotitanyl phthalocyanine contains an amine-hydrazone compound represented by the formula: 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
It shows major diffraction peaks at 7.9 °, 24.1 ° and 27.2 °, and the intensity at the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 ° is maximum, and the Bragg angle is The intensity at the 27.2 ° diffraction peak is the second
An electrophotographic photosensitive member, characterized in that: Embedded image [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
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. ] 5. 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 is represented by the following general formula (V) as a charge transporting substance. Oxofuran-bishydrazone compound, wherein the oxotitanyl phthalocyanine has a Bragg angle (2θ ± 0.2 °) of 7.3 in the X-ray diffraction spectrum.
°, 9.4 °, 9.6 °, 11.6 °, 13.3 °, 1
It shows major diffraction peaks at 7.9 °, 24.1 ° and 27.2 °, and the intensity at the overlapping diffraction peak bundles at the Bragg angles of 9.4 ° and 9.6 ° is maximum, and the Bragg angle is The intensity at the 27.2 ° diffraction peak is the second
An electrophotographic photosensitive member, characterized in that: Embedded image [In the general formula (V), Ar ¹³ and Ar ¹⁴ represent an aryl group which may have a substituent, an aralkyl group which may have a substituent, a heterocyclic group or an alkyl group having 1 to 4 carbon atoms. Represents a is an alkyl group having 1 to 3 carbon atoms,
3 represents an alkoxy group, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom. n5 is 1 to
It is an integer of 3. However, when n5 is 2 or more, each of a plurality of a may be the same or different. ] 6. The oxotitanyl phthalocyanine,
In the X-ray diffraction spectrum, the Bragg angle was 27.2.
The intensity at the diffraction peak of ° is the Bragg angle of 9.4.
The electrophotographic photoreceptor according to any one of claims 1 to 5, wherein the intensity is 80% or less of the intensity of the overlapping diffraction peak bundles at an angle of 9.6 ° and 9.6 °. 7. The oxotitanyl phthalocyanine,
In the X-ray diffraction spectrum, a plurality of diffraction peaks having substantially the same intensity are formed between Bragg angles 14.1 ° to 14.9 °, and the plurality of diffraction peaks are trapezoidal and difficult to separate peak sets. The electrophotographic photoreceptor according to any one of claims 1 to 5, wherein the electrophotographic photoreceptor shows a body. 8. The oxotitanyl phthalocyanine,
In the X-ray diffraction spectrum, at the position of the Bragg angle of 9.0 °, there is a diffraction peak whose intensity is almost half of the overlapping diffraction peak bundles of the Bragg angles of 9.4 ° and 9.6 °. 6. The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor exists as a shoulder peak of the diffraction peak bundle. 9. The photosensitive layer according to claim 1, wherein 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. 10. The electrophotograph according to claim 1, wherein the photosensitive layer has a single-layer structure containing the charge generating material and the charge transporting material. Photoconductor. 11. The method according to claim 1, further comprising an intermediate layer disposed between said conductive support and said photosensitive layer.
The electrophotographic photosensitive member according to any one of the above. 12. The electrophotographic photoreceptor according to claim 2, wherein the photosensitive layer contains a polycarbonate represented by the following general formula (VI) as a binder resin. Embedded image [In the general formula (VI), R ³³ and R ³⁴ are an alkyl group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, An aralkyl group having 7 to 17 carbon atoms which may have a substituent,
5 represents an alkenyl group, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom. X ² has an alkylene group having 1 to 10 carbon atoms which may be directly bonded or may have a substituent, a cyclic alkylidene group having 1 to 10 carbon atoms which may have a substituent, May have 6 or more carbon atoms
12 represents an arylene group, a sulfonyl group or a carbonyl group. Z ³ represents an alkylene group having 1 to 5 carbon atoms, an arylene group having 6 to 12 carbon atoms, an arylene alkyl group having 7 to 17 carbon atoms, or a halogen atom which may have a substituent. W ¹ represents an alkyl group having 1 to 5 carbon atoms which may have a substituent, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, an alkoxy group having 1 to 5 carbon atoms, and a substituent. It represents an alkyl ester group having 1 to 5 carbon atoms which may have, an aryl ester group having 6 to 12 carbon atoms which may have a substituent, a carboxyl group, an aldehyde group, a hydroxyl group, a halogen atom or a hydrogen atom. e and f represent an integer of 1 to 4,
u2 represents an integer of 10 to 200. ] 13. The photosensitive layer contains, as a binder resin, a polyester represented by the following general formula (VII) in a range of 0.05 part by weight or more and 0.5 part by weight or less based on the whole binder resin. The electrophotographic photosensitive member according to claim 2, wherein Embedded image [In the general formula (VII), g, h2 and i2 are 1 to 10
And v, w2, x3 and y are 10 to 100
Represents an integer of 0. ] 14. The photosensitive layer comprises α as an antioxidant.
0.1% by weight of tocopherol, based on the charge transport material
In the range of not less than 5% by weight or less, or 2,6-di-t-
6. The electrophotographic photoreceptor according to claim 2, wherein butyl-4-methylphenol is contained in a range of 0.1% by weight or more and 10% by weight or less based on the charge transporting substance.