JP2000075521A - Electrophotographic photoreceptor, process cartridge having the electrophotographic photoreceptor, and electrophotographic apparatus - Google Patents

Abstract

(57) [Problem] Reversal development that has sufficiently high sensitivity in a long wavelength region, maintains a stable electric potential during repeated use, and exhibits stable image characteristics regardless of the use environment of temperature and humidity. An object of the present invention is to provide an electrophotographic photoreceptor which is hard to generate a transfer memory, has light resistance, and hardly generates a photo memory even in a system. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a chlorogallium phthalocyanine compound or a hydroxygallium phthalocyanine compound as a charge generating substance, and has the following structure as a charge transporting substance: An electrophotographic photosensitive member comprising a compound of the formula:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

[0002]

2. Description of the Related Art Electrophotography is disclosed in U.S. Pat. No. 2,297,691.
As shown in the specification, a photoconductive material comprising a support coated with an insulating material is used in which the electric resistance changes according to the amount of irradiation received during image exposure, and in a dark place.
The basic characteristics required of an electrophotographic photoreceptor using this photoconductive material are (1) that it can be charged to an appropriate potential in a dark place, (2) that there is little charge dissipation in a dark place,
(3) Charges can be quickly dissipated by light irradiation.

Conventionally, as an electrophotographic photoreceptor, an inorganic photoreceptor having a photosensitive layer containing an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide or the like as a main component has been widely used. However, they satisfy the above conditions (1) to (3), but do not always satisfy thermal stability, moisture resistance, durability, productivity, and the like. For example, when selenium is crystallized, the characteristics of the photoconductor deteriorate.
Cadmium sulfide has problems in moisture resistance and durability, and zinc oxide has problems in smoothness, hardness and abrasion resistance. Furthermore, the photosensitive wavelength of many inorganic photosensitive members is limited. Have been. For example,
The photosensitive wavelength region of selenium is a blue region, and has little sensitivity in a red region.

Therefore, various methods have been devised to extend the photosensitivity to the long wavelength region, but there are many restrictions on the selection of the photosensitive wavelength region. Even when zinc oxide or cadmium sulfide is used as a photoreceptor, the photosensitive wavelength range of the photoreceptor itself is narrow, and it is necessary to add various sensitizers. In order to overcome these drawbacks of the inorganic photoreceptor, electrophotographic photoreceptors containing various organic photoconductive compounds as main components have been actively developed in recent years. For example, U.S. Pat.
Discloses a photoreceptor having a charge transport layer containing triallyl pyrazoline, and U.S. Pat. No. 3,871,882 discloses a charge generation layer comprising a derivative of perylene pigment and a charge comprising a condensate of 3-propylene and formaldehyde. A photoreceptor comprising a transport layer is already known.

An electrophotographic photosensitive member using an organic compound can be a function-separated type electrophotographic photosensitive member classified into a charge-generating substance that generates electric charges and a charge-transporting substance that transports the same. The type photoreceptor has an advantage that a material selection range of each of a charge generation material and a charge transport material is wide, and an electrophotographic photoreceptor having arbitrary characteristics can be relatively easily prepared. A photoreceptor using a bisazo pigment or a trisazo pigment as a charge generating substance is disclosed in
JP-A-33445, JP-A-56-46237 and JP-A-60-111249 are already known.

Further, the photoreceptor using an organic photoconductive compound can freely select the photosensitive wavelength of the electrophotographic photoreceptor depending on the compound. For example, with respect to azo organic pigments, those disclosed in JP-A-61-272754 and JP-A-56-167759 have been disclosed which exhibit high sensitivity in the visible light region. JP-A-57-195767 and JP-A-61-228
Some of the substances disclosed in Japanese Patent No. 453 have sensitivity up to the infrared region.

Among these materials, those having sensitivity in the infrared region are laser beam printers, which have been remarkably advanced in recent years.
(Hereinafter abbreviated as LBP) and the like, and its demand frequency is increasing.

Apart from azo pigments, phthalocyanine compounds such as copper phthalocyanine as disclosed in JP-A-50-38543 have been attracting attention as those having sensitivity in the infrared region. JP-A-61-2705, JP-A-61-239248, and JP-A-64-17066 as materials having high sensitivity in the region.
Oxytitanium phthalocyanine compounds and the like disclosed in Japanese Patent Application Laid-Open No. Hei.

Further, as the prior art of the chlorogallium phthalocyanine compound used in the electrophotographic photoreceptor of the present invention, Japanese Patent Application Laid-Open Nos.
No. 181, JP-A-5-194523, JP-A-5-247361, JP-A-6-73303, JP-A-7-53891 and JP-A-7-207
171 and the like.

The prior art of the hydroxygallium phthalocyanine compound used for the electrophotographic photoreceptor of the present invention is disclosed in JP-A-5-236007 and JP-A-5-252.
Japanese Patent Application Laid-Open Nos. 795991, 6-93203, 6-279698, and 7-53892 disclose.

Regarding the charge transport material which is the other component of the function-separated type photoreceptor, for example, Japanese Patent Publication No.
No. 4188, pyrazoline compound, JP-B-55-4
2380, hydrazone compounds disclosed in JP-A-54-150128 and JP-A-57-101844,
JP-B-58-32372 and JP-A-61-123
No. 955, a triphenylamine compound disclosed in
Stilbene compounds and the like disclosed in JP-A-151955 and JP-A-58-198043 are known.

Examples of the combination of the charge generating substance and the charge transporting substance include a combination of oxytitanium phthalocyanine and a hydrazone compound having a specific structure described in JP-A-5-55860.
No. 4502 discloses a combination of hydroxygallium phthalocyanine and a triarylamine-based compound having a specific structure.

As described above, a photoreceptor having improved characteristics by combining a charge generating material having a specific structure and a charge transporting material having a specific structure is also provided, but a high sensitivity in the infrared region is not always required. It cannot be said that it has, but the potential stability during repeated use is poor, the charging ability is poor, and image deterioration due to a change in the use environment is observed.

In the case of an apparatus employing a reversal development system corresponding to digitization for applications such as LBP, primary charge and transfer have opposite polarities, and the chargeability differs depending on the presence or absence of transfer. Is generated, and it is very easy to appear as density unevenness on an image.

Further, in the electrophotographic photosensitive member having a high sensitivity, a so-called photo memory, in which the chargeability of a bright portion and a dark portion is different due to external leakage light or the like, occurs, and this also causes uneven density on an image. It is very easy to appear.

As described above, there are some problems in actual use, and it is hard to say that a photoconductor having achieved these characteristics at a high level has been supplied. Electrophotographic photoreceptors satisfying all of the above at a higher level are being studied.

In general, in an electrophotographic photoreceptor, a charge transport material that is very effective for a specific charge generating material is not always as effective as another charge generating material. Conversely, a charge generating material that is very effective for one particular charge transport material is not always as effective as another. That is, there is always a more preferable combination between these charge generating materials that transfer charges and the charge transporting materials.

When a more preferable combination of the charge generating substance and the charge transporting substance is used, it is possible to obtain an electrophotographic photoreceptor having more excellent properties in terms of residual potential and potential stability upon repeated use. Further, by using a more preferable combination of the charge generating substance and the charge transporting substance, the above-described transfer memory and photo memory can be efficiently improved.

However, no general rule has been found for the compatibility between the charge generating substance and the charge transporting substance.
It is very difficult at present to predict the optimal charge transport material for a particular charge generating material.

The present inventors have conducted a number of experimental studies on various combinations of a charge generating substance and a charge transporting substance. As a result, at least one selected from a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound as the charge generating substance has been obtained. When used in combination with a hydrazone compound having a specific structure as a charge transport material, it has high sensitivity and durability in the infrared region, and can provide a stable image even in various environments. The present inventors have found that a photoreceptor capable of improving a transfer memory and a photo memory can be formed, and have reached the present invention.

The reason why the combination of the chlorogallium phthalocyanine compound and the hydroxygallium phthalocyanine compound of the present invention and the hydrazone compound having the specific structure of the present invention is not clear is not clear, but the ionization potential or the charge generating material and the charge transporting material are suitable. The charge injection from the charge generating substance to the charge transporting substance is performed well because of the good steric overlap when and are mixed, and the sensitivity is good, the residual potential is small, and the potential stability when repeatedly used. It is presumed that the transfer memory and the photo memory also exhibit small characteristics.

[0022]

SUMMARY OF THE INVENTION The object of the present invention is to
(1) having a sufficiently high sensitivity in a long wavelength region;
(2) the potential during repeated use is stably maintained,
(3) Stable image characteristics irrespective of the use environment of temperature and humidity; (4) Transfer memory is less likely to occur even in a reversal development system; (5) Light resistance and electrophotographic sensitivity which is less likely to cause photo memory. Is to provide the body. Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus using the electrophotographic photosensitive member.

[0023]

According to the present invention, there is provided an electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the photosensitive layer is selected from a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound as a charge generating substance. And an electrophotographic photoreceptor containing at least one compound represented by the following general formula (1) as a charge transport material. General formula (1)

Embedded image In the formula, X and Y represent a group represented by the general formula (2) or the general formula (3), and represented by the general formula (2) -Z-Ar n represents an integer of 0 or 1. R ₁ , R ₂ and R ₃ are a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent or a substituted amino group And p and r are 0 to
Represents an integer of 4. q represents an integer of 0 to 5 when n = 0, and represents an integer of 0 to 4 when n = 1. R ₄ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and R ₅ and R ₆ are An alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent; ₅ and R ₆ may be the same or different, and may form a ring directly or via a bonding group. Z represents an alkylene group which may have a substituent;
r represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent. R ₇ is an alkyl group which may have a substituent, an aralkyl group which may have a substituent,
It represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

According to the present invention, the electrophotographic photosensitive member of the present invention, and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported, and are detachably mounted on an electrophotographic apparatus main body. It is composed of a process cartridge characterized by being flexible.

Further, the present invention comprises an electrophotographic apparatus comprising the electrophotographic photosensitive member of the present invention, a charging unit, an image exposing unit, a developing unit and a transferring unit.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The electrophotographic photoreceptor of the present invention contains at least one selected from a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound as a charge generating substance in a photosensitive layer. Among these gallium phthalocyanine-based compounds, those having several crystal types as shown below exhibit more preferable characteristics of the present invention.

The chlorogallium phthalocyanine compound is
Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα
Is composed of a crystalline pigment having strong peaks at 7.4 °, 16.6 °, 25.5 ° and 28.2 °.

The chlorogallium phthalocyanine compound is
Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα
8.7 ° to 9.2 °, 17.5 °, 24.0 °, 2
It is composed of a crystalline pigment having a strong peak at 7.4 ° and 28.7 °.

The hydroxygallium phthalocyanine compound has a Bragg angle of 2 ± 0.1 in X-ray diffraction of CuKα.
2 ° is composed of a pigment of a crystalline type having strong peaks at 6.8 ° and 26.2 °.

The hydroxygallium phthalocyanine compound has a Bragg angle of 2 ± 0.1 in X-ray diffraction of CuKα.
2 ° is composed of a pigment of the crystalline type having strong peaks at 7.4 ° and 28.2 °.

The hydroxygallium phthalocyanine compound has a Bragg angle of 2 ± 0.1 in X-ray diffraction of CuKα.
2 ° is 7.5 °, 16.3 °, 24.9 ° and 26.4
It is composed of a crystalline pigment having a peak at a high degree.

The hydroxygallium phthalocyanine compound has a Bragg angle of 2 ± 0.1 in X-ray diffraction of CuKα.
2 ° is 6.9 °, 13.3 °, 16.5 ° and 26.7
It is composed of a crystalline pigment having a peak at a high degree.

The electrophotographic photoreceptor of the present invention contains a specific arylamine hydrazone compound represented by the general formula (1) as a charge transporting substance. In the general formula (1), X and Y are groups represented by the general formula (2) or (3), and particularly preferably a group represented by the general formula (2).

In the general formula (1), n is an integer of 0 or 1, and it is more preferable that n = 0.
Further, in the general formula (1), n = 0 and X
It is further preferred that the -O- substitution position is at the 4-position (para position as viewed from the n-atom substitution position).

In the general formula (1), R ₁ , R ₂ and R ₃ are
Halogen atoms such as chlorine atom, bromine atom and iodine atom, alkyl groups such as methyl group, ethyl group and propyl group, alkoxy groups such as methoxy group, ethoxy group and propoxy group, aryl groups such as phenyl group and naphthyl group. Group, dialkylamino group such as dimethylamino group, diarylamino group such as diphenylamino group, diaralkylamino group such as dibenzylamino group, diheterocyclic amino group such as dipyridylamino group, diallylamino group, and the above. A substituted amino group such as a disubstituted amino group obtained by combining amino group substituents, which may be the same or different from each other,
Particularly, a hydrogen atom, a chlorine atom, a methyl group and a methoxy group are preferred.

The alkyl group, alkoxy group and aryl group may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a methyl group and an ethyl group. , Propyl group, butyl group, alkyl group such as hexyl group, methoxy group, ethoxy group, propoxy group, alkoxy group such as butoxy group, phenyl group,
Aryl groups such as naphthyl groups, benzyl groups, naphthylmethyl groups, aralkyl groups such as phenethyl groups, phenoxy groups,
Aryloxy group such as toloxy group, benzyloxy group, arylalkoxy group such as phenethyloxy group, styryl group, arylvinyl group such as naphthylvinyl group, dialkylamino group such as dimethylamino group and diethylamino group, diphenyl Amino group, diarylamino group such as dinaphthylamino group, dibenzylamino group, diaralkylamino group such as diphenethylamino group, dipyridylamino group, diheterocyclic amino group such as dithienylamino group, diallylamino group, Further, a disubstituted amino group obtained by combining the above-mentioned amino group substituents and the like can be mentioned.

P and r are integers from 0 to 4, and q is n
When n = 0, it is an integer from 0 to 5, and when n = 1, it is an integer from 0 to 4.

R ₄ represents a hydrogen atom, a methyl group, an ethyl group,
Alkyl group such as propyl group, phenyl group, naphthyl group,
It is an aryl group such as an anthracenyl group, a heterocyclic group such as a pyrrolyl group, a thienyl group, a furyl group, a caribazolyl group.
These alkyl group, aryl group and heterocyclic group may have a substituent, and examples of the substituent include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a methyl group, an ethyl group and a propyl group. Groups, butyl, hexyl and other alkyl groups, methoxy, ethoxy, propoxy, butoxy and other alkoxy groups, phenyl and naphthyl and other aryl groups, benzyl, naphthylmethyl, phenethyl and the like Aryloxy groups such as aralkyl groups, phenoxy groups and toloxy groups, arylalkoxy groups such as benzyloxy groups and phenethyloxy groups, arylvinyl groups such as styryl groups and naphthylvinyl groups, dimethylamino groups and diethylamino groups Dialkylamino group, diphenylamino group, dinaphthylamino group, etc. Enechiruamino diaralkylamino group such as, dipyridyl amino group, di heterocyclic amino groups such as Jichieniruamino group, diallylamino group, more like disubstituted amino group which combines substituents of the amino groups mentioned above.

R ₅ and R ₆ each represent an alkyl group such as a methyl group, an ethyl group or a propyl group, an aralkyl group such as a benzyl group or a phenethyl group, a phenyl group, a naphthyl group;
It is an aryl group such as an anthracenyl group, a heterocyclic group such as a pyrrolyl group, a thienyl group, a furyl group, a caribazolyl group.
These alkyl group, aralkyl group, aryl group, and heterocyclic group may have a substituent, and examples of the substituent include a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methyl group, and an ethyl group. Groups, propyl group, butyl group, alkyl group such as hexyl group, methoxy group, ethoxy group, propoxy group, alkoxy group such as butoxy group, phenyl group, aryl group such as naphthyl group, benzyl group, naphthylmethyl group,
Aryl groups such as phenethyl group, aryloxy groups such as phenoxy group and toloxy group, benzyloxy group, aryloxy groups such as phenethyloxy group, arylalkoxy groups such as benzyloxy group and phenethyloxy group, styryl groups. Arylalkyl groups such as naphthylvinyl group, dialkylamino groups such as dimethylamino group and diethylamino group; diarylamino groups such as diphenylamino group and dinaphthylamino group; dibenzylamino groups such as dibenzylamino group and diphenethylamino group. Examples thereof include a diheterocyclic amino group such as an aralkylamino group, a dipyridylamino group, and a dithienylamino group, a diallylamino group, and a disubstituted amino group obtained by combining the above-described amino group substituents. In particular, at least one of R ₅ and R ₆ is preferably an aryl group which may have a substituent. Further, R ₅ and R ₆ may be linked directly or via a bonding group. The bonding group, a methylene group, an ethylene group, alkylene groups such as trimethylene group, -S -, - O -, - include heteroatom N- such, in particular -S -, - O -, - CH 2 - Is more preferable, and -S- is more preferable.

Z is an alkylene group such as a methylene group, an ethylene group and a propylene group, and particularly preferably a methylene group. These alkylene groups may have a substituent, such as a methyl group, a lower alkyl group such as an ethyl group, a methoxy group, a lower alkoxy group such as an ethoxy group, a chlorine atom, a bromine atom and the like. And an aryl group such as a halogen atom, a phenyl group and a naphthyl group.

Ar is a phenyl group or a naphthyl group. Aryl groups such as anthracenyl group, pyrrolyl group, thienyl group,
It is a heterocyclic group such as a furyl group and a carbazolyl group, and a phenyl group is particularly preferable. These aryl groups and heterocyclic groups may have a substituent. Examples of the substituent include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, a methyl group, an ethyl group, a propyl group and a butyl group. Group, alkyl group such as hexyl group, methoxy group, ethoxy group, propoxy group,
Aryl groups such as alkoxy groups such as butoxy group, phenyl group and naphthyl group, aralkyl groups such as benzyl group, naphthylmethyl group and phenethyl group, aryloxy groups such as phenoxy group and toloxy group, benzyloxy group and phenethyl group Aryloxy group such as oxy group, benzyloxy group,
Aryloxy groups such as phenethyloxy group, styryl group, arylvinyl groups such as naphthylvinyl group, dialkylamino groups such as dimethylamino group and diethylamino group, and diarylamino groups such as diphenylamino group and dinaphthylamino group. A diaralkylamino group such as dibenzylamino group or diphenethylamino group, a diheterocyclic amino group such as dipyridylamino group or dithienylamino group, a diallylamino group, or a combination of the above amino group substituents. And a substituted amino group.

R ₇ is an alkyl group such as a methyl group, an ethyl group or a propyl group; an aralkyl group such as a benzyl group or a phenethyl group; an aryl group such as a phenyl group, a naphthyl group or an anthracenyl group; a pyrrolyl group; It is a heterocyclic group such as a thienyl group, a furyl group, and a caribazolyl group, and an alkyl group is particularly preferable. These alkyl group, aralkyl group, aryl group, and heterocyclic group may have a substituent, and examples of the substituent include a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methyl group, and an ethyl group. Group, propyl group,
Alkyl groups such as butyl group and hexyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; aryl groups such as phenyl group and naphthyl group; aralkyl groups such as benzyl group, naphthylmethyl group and phenethyl group. Aryloxy groups such as benzyl, phenoxy and phenoxy groups
Aryloxy groups such as a ruoxy group, a benzyloxy group, and a phenethyloxy group; aryl vinyl groups such as a styryl group and a naphthylvinyl group; dialkylamino groups such as a dimethylamino group and a diethylamino group; diphenylamino groups; and dinaphthylamino. Diarylamino group such as group, dibenzylamino group, diaralkylamino group such as diphenethylamino group, diheterocyclic amino group such as dipyridylamino group, dithienylamino group, diallylamino group, and the above amino group And a disubstituted amino group obtained by combining the above substituents.

The effect of the present invention is such that an excellent effect is selectively exhibited only when the above-mentioned charge generating material and charge transporting material are used in combination.

Next, specific examples of the compound represented by the general formula (1) are shown in Tables 1 to 11. However, it is not limited to these specific examples.

[0045]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

The structure of chlorogallium phthalocyanine used in the present invention is shown by the following general formula (4).

Embedded image In the formula, X ₁ , X ₂ , X ₃ and X ₄ represent Cl or Br, and n, m, l and k are integers of 0-4.

The structure of hydroxygallium phthalocyanine used in the present invention is represented by the following general formula (5).

Embedded image In the formula, X ₁ , X ₂ , X ₃ and X ₄ represent Cl or Br, and n, m, l and k are integers of 0-4.

Next, production examples of the charge generation material and the charge transport material used in the present invention will be described. However, it is not limited to these examples.

Production of chlorogallium phthalocyanine Production Example 1 72.6 g of o-phthalonitrile, 25 gallium trichloride
g, 375 ml of α-chloronaphthalene in a nitrogen atmosphere 2
The reaction was performed at 00 ° C. for 4 hours. After the reaction, the precipitated product was cooled to 130 ° C. and filtered. The product obtained is N,
The mixture is dispersed and washed with N-dimethylformamide at 130 ° C. for 1 hour, and filtered. After washing on a filter with methanol, it was dried under reduced pressure to obtain chlorogallium phthalocyanine 3
9.8 g were obtained. Yield 45%. The result of elemental analysis of the obtained chlorogallium phthalocyanine is shown. FIG. 1 shows an infrared absorption spectrum (KBr tablet method) of this crystal, and FIG. 2 shows a powder X-ray diffraction pattern.

Production Example 2 Next, 30 g of the chlorogallium phthalocyanine obtained in Production Example 1 was added to 100 g of an agate ball having a diameter of 10 mm and 20 m
Dry milling was performed for 24 hours in a ball mill together with 200 g of agate ball having a diameter of mφ. Next, 7 g of the crystal after the dry milling treatment and 280 g of benzyl alcohol were added to 1 mmφ.
Was milled with a sand mill together with 420 g of the above glass beads at room temperature (22 ° C.) for 20 hours. The pigment was separated from this dispersion by filtration, washed with methanol and dried under reduced pressure, whereby the Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα was 7.4 °, 16.6 °, 6.3 g of crystalline chlorogallium phthalocyanine having a strong peak at 25.5 ° and 28.2 ° was obtained. Powder X of this crystal
The line diffraction diagram is shown in FIG.

Production Example 3 7 g of chlorogallium phthalocyanine crystals and 280 g of methanol, which had been subjected to dry milling in the same manner as in Production Example 2, were placed in 1 m.
Milling treatment was performed at room temperature (22 ° C.) for 20 hours with a sand mill together with 420 parts of mφ glass beads. The pigment is filtered from the dispersion and dried under reduced pressure, whereby C
Bragg angle 2θ ± 0.2 ° in X-ray diffraction of uKα is 8.7 ° to 9.2 °, 17.5 °, 24.0 °, 27.
6.8 g of crystalline chlorogallium phthalocyanine having a strong peak at 4 ° and 28.7 ° was obtained. FIG. 4 shows a powder X-ray diffraction pattern of this crystal.

Production of hydroxygallium phthalocyanine Production Example 4 Chlorogallium phthalocyanine 35 obtained in Production Example 1
g was gradually added to and dissolved in 1050 g of concentrated sulfuric acid cooled to 0 ° C., followed by stirring at 0 ° C. for 30 minutes. Then 525 ice water
The solution was slowly dropped into 0 g with stirring to reprecipitate. After reprecipitation, filtration is performed, and the obtained powder is dispersed and washed in 2500 g of ion-exchanged water, and filtered again. Furthermore, 2% of the obtained powder
The solid obtained by dispersing and washing in 2500 g of aqueous ammonia and further sufficiently washing with ion-exchanged water is dried under reduced pressure. Hydroxygallium phthalocyanine with low crystallinity
3.9 g were obtained. 97% yield. The elemental analysis value of the obtained hydroxygallium phthalocyanine is shown. FIG. 5 shows an infrared absorption spectrum (KBr tablet method) of the crystal, and FIG. 6 shows a powder X-ray diffraction pattern.

Production Example 5 Next, 7 g of the hydroxygallium phthalocyanine obtained in Production Example 4 and N, N-dimethylformamide 21
0 g was milled by a sand mill together with 300 g of a 1 mmφ glass bead at room temperature (22 ° C.) for 5 hours.
The pigment was separated from this dispersion by filtration, washed with methanol and dried under reduced pressure, whereby the Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα was 7.4 ° and 28.2 °.
Thus, 6.4 g of crystalline hydroxygallium phthalocyanine having a strong peak was obtained. FIG. 7 shows a powder X-ray diffraction pattern of this crystal.

Production Example 6 Next, 7 g of hydroxygallium phthalocyanine and 210 g of methanol obtained in Production Example 4 were milled with a glass bead having a diameter of 1 mm by a sand mill at room temperature (22 ° C.) for 5 hours. By filtering the pigment from this dispersion and drying it under reduced pressure, the Bragg angle 2θ ± 0.2 ° in X-ray diffraction of CuKα is 7.5 °, 1 °
Crystalline hydroxygallium phthalocyanine 6.1 with strong peaks at 6.3 °, 24.9 ° and 26.4 °
g was obtained. FIG. 8 shows a powder X-ray diffraction pattern of this crystal.

Production Example 7 Next, 7 g of the hydroxygallium phthalocyanine obtained in Production Example 4 and 210 g of chloroform were milled by a sand mill together with 300 g of a 1 mmφ glass bead at room temperature (22 ° C.) for 5 hours. The pigment was filtered off from this dispersion and dried under reduced pressure, whereby the Bragg angle 2θ ± 0.2 ° in CuKα X-ray diffraction was 6.9 °, 1 °
Crystalline hydroxygallium phthalocyanine 6.6 with strong peaks at 3.3 °, 16.5 ° and 26.7 °
g was obtained. FIG. 9 shows a powder X-ray diffraction pattern of this crystal.

The chlorogallium phthalocyanine compound and the hydroxygallium phthalocyanine compound used in the present invention can be produced as described above.
It is not limited to these production examples.

Production of Illustrative Hydrazone Compound 3 Production Example 8 A hydrazone compound represented by the general formula (1) is a hydrazine derivative represented by the following general formula (6):

Embedded image In the formula, R ₅ and R ₆ have the same meaning as described above, and a triphenylamine derivative represented by the general formula (7);

Embedded image In the formula, R ₁ , R ₂ R ₃ , R ₄ , X, Y, n, p, q and r can be synthesized using the same meaning as described above.

Ethanol 5 was added to a 300 ml three-necked flask.
0 ml, 50 ml of acetic acid, 3.21 g (0.0174 mol) of 1,1-diphenylhydrazine (a compound in which R ₅ and R ₆ are represented by a phenyl group in the general formula (6)) and 6.85 g of a compound of the following structural formula (0 0.0174 mol)

Embedded image Was added and reacted at room temperature for 1 hour and poured into water. Next, the obtained solid was filtered and washed with water repeatedly, and the solid was filtered off and dried. Next, recrystallization from methyl ethyl ketone / ethanol gave 3.21 g of yellow crystals. Yield 33%.

Other hydrazone compounds used in the present invention can be produced in the same manner. However,
It is not limited to these production examples.

A typical layer structure of the electrophotographic photoreceptor of the present invention includes a form in which a charge generating substance and a charge transporting substance are contained in the same layer, a form in which a charge generating layer containing a charge generating substance and a charge transporting substance are contained. There is a form in which a charge transport layer is laminated.
Further, there is a form in which a conductive support, a charge generation layer and a charge transport layer are laminated in this order, and a form in which a conductive support, a charge transport layer and a charge generation layer are laminated in this order.

In the electrophotographic photoreceptor of the present invention, the charge generation layer contains as much charge generation material as possible to obtain a sufficient absorbance and shortens the range of generated charge carriers. It is desirable that the thin film layer has a thickness of 5 μm or less, preferably 0.01 to 1 μm.

The charge generation layer can be formed by dispersing a charge generation substance in a suitable binder and applying the dispersion to a conductive support.

The binder used when forming by coating can be selected from a wide range of insulating resins, and can be selected from organic photoconductive polymers such as poly-N-vinyl carbazole, polyvinyl anthracene and polyvinyl pyrene. it can. Preferably, polyvinyl butyral, polyarylate (polycondensate of bisphenol and aromatic dicarboxylic acid), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, Examples include polyvinyl pyridine, cellulose resin, polyurethane, epoxy resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, and the like.
The amount of the resin contained in the charge generation layer is suitably 80% by weight or less, preferably 40% by weight or less.

The solvent for dissolving these resins differs depending on the type of the resin, and is preferably selected from those which do not dissolve the charge transport layer or the undercoat layer. Specifically, alcohols such as methanol, ethanol and isopropanol are used.
, Acetone, methyl ethyl ketone, ketones such as cyclohexane, N, N-dimethylformamide, N, N
Amides such as dimethylacetamide, sulfoxides such as dimethylsulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, methylene chloride, and dichloroethylene. And aliphatic halogenated hydrocarbons such as carbon tetrachloride and trichloroethylene, or aromatic compounds such as benzene, toluene, xylene, ligroin, chlorobenzene and dichlorobenzene.

As a coating method, a dipping coating method,
Spray coating method, spinner coating method,
Bead coating method, myr bar coating method,
A method such as a blade coating method, a roller coating method, and a curtain coating method can be employed. Drying is
A method of drying by heating after touch drying at room temperature is preferable. The heating and drying is performed at a temperature of 30 to 200 ° C. for 5 minutes to 2 hours in a still or blowing condition.

The charge transport layer is electrically connected to the charge generation layer, receives charge carriers injected from the charge generation layer in the presence of an electric field, and transports these charge carriers to the surface. Has a function. At this time, the charge transport layer may be stacked on the charge generation layer, or may be stacked thereunder. The charge transport layer dissolves an arylamine hydrazone compound having a specific structure represented by the general formula (1) together with a suitable binder,
This can be formed by coating.

Examples of the binder include acrylic resin, polyarylate, polyester, polycarbonate and the like.
Insulating resin such as polystyrene, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber, or poly-N-vinyl carbazole And organic photoconductive polymers such as polyvinyl anthracene and polyvinyl pyrene. Since the charge transport layer has a limit for transporting charge carriers, it cannot be made thicker than necessary, but it has a thickness of 3 to 50 μm, preferably 8 to 50 μm.
30 μm. When forming the charge transport layer by coating, the same appropriate coating method as used for forming the charge generation layer can be employed.

A photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer is provided on a conductive support. As the conductive support, a support having conductivity itself, for example, a metal or alloy such as aluminum or an aluminum alloy is used. In addition, aluminum, aluminum alloy, indium oxide, tin oxide, indium oxide-tin oxide alloy, or the like is used. Having a layer formed by vacuum deposition on a plastic or conductive support (e.g., carbon black, silver particles, etc.) together with a suitable binder on a plastic or the metal support. A conductive support or a conductive polymer in which conductive particles are impregnated in plastic or paper.
And the like.

A barrier is provided between the conductive support and the photosensitive layer.
An undercoat layer having a function and an adhesive function can be provided. The undercoat layer is made of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylate copolymer, polyamide (nylon 6, nylon 66, nylon 610,
Nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide and the like. The thickness of the undercoat layer is 0.1 to 5 μm, preferably 0.5 to 3 μm.

Further, the electrophotographic photosensitive member of the present invention may be provided with a surface protective layer as required.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer, C
RT printer, LED printer, LCD printer,
It can be widely used in electrophotographic applications such as laser plate making and facsimile.

Next, the process cartridge and the electrophotographic apparatus of the present invention will be described. FIG. 10 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. In the figure, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around a shaft 2 at a predetermined peripheral speed in a direction indicated by an arrow. In the rotation process, the photosensitive member 1 is uniformly charged at a predetermined positive or negative potential on the peripheral surface thereof by the primary charging means 3, and then the image exposure means (such as a slit exposure or a laser beam scanning exposure) is used. Shown)
Receives image exposure light 4 from. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then transferred to developing means 5
Is transferred to the transfer material 6 from the paper supply unit (not shown) and fed between the photosensitive member 1 and the transfer means 6 in synchronization with the rotation of the photosensitive member 1. Are sequentially transferred by the transfer means 6. The transfer material 7 having undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing, thereby being printed out as a copy (copy) outside the apparatus. The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the transfer residual toner by the cleaning means 9, and further subjected to a static elimination process by the pre-exposure light 10 from the pre-exposure means (not shown). After that, it is repeatedly used for image formation. When the primary charging means 3 is a contact charging means using a charging roller or the like, pre-exposure is not necessarily required.

In the present invention, of the above-mentioned components such as the photoreceptor 1, the primary charging means 3, the developing means 5 and the cleaning means 9, a plurality of components are integrally connected as a process cartridge. Alternatively, the process cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging means 3, the developing means 5 and the cleaning means 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and the apparatus main body is guided by a guide means such as the rail 12 of the apparatus main body. The process cartridge 11 can be detachably mounted on the cartridge. When the electrophotographic apparatus is a copier or a printer, the image exposure light 4 uses reflected light or transmitted light from the original, or reads the original with a sensor and converts it into a signal. This is light emitted by scanning of the laser beam, driving of the LED array, driving of the liquid crystal shutter array, and the like.

Next, the charge generating substances used in the examples and comparative examples will be described.

Crystal Form of Charge Generating Substance Used in Examples

[Table 12]

Crystal Form of Charge Generating Material Used in Comparative Example

[Table 13]

Example 1 An undercoat layer of 0.42 μm of a vinyl chloride / maleic anhydride / vinyl acetate copolymer was formed on an aluminum support. Next, 4 parts of a hydroxygallium phthalocyanine compound having a crystal form of pigment number P-4 shown in Table 12 and 2 parts of polyvinyl butyral (butyralization degree: 65 mol%, average molecular weight: 35,000) were converted to 80 parts of cyclohexanone. , And dispersed with a glass bead in a sand mill for 4 hours.
A dispersion obtained by adding 80 parts of ethyl acetate and diluting the mixture was applied on a subbing layer with a myrbar so that the film thickness after drying was 0.24 μm to form a charge generation layer.

Next, 4.5 parts of Exemplified Compound 1 and 5 parts of bisphenol Z-type polycarbonate (viscosity average molecular weight 20,000) as monochlorobenzene 38 were used as charge transporting substances.
Part of the solution, and the solution is dried on the charge generation layer to a thickness of 2
Coating with a Myrbar so as to have a thickness of 3 μm, and drying to form a charge transport layer, thereby preparing an electrophotographic photoreceptor (photoreceptor 1)
did.

Electrophotography was performed in the same manner as in Example 1, except that chlorogallium phthalocyanine having a crystal form of pigment number P-1 was used instead of pigment number P-4 used in Example 1 as the charge generating substance. A photoreceptor (photoreceptor 2) was prepared.

Comparative Example 1 An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the pigment number P-4 in Example 1 was used instead of the pigment number P-4 in Example 1 as the charge generating substance. A body was prepared (Comparative Photoconductor 1).

Comparative Example 2 An electrophotographic photosensitive member was prepared in the same manner as in Example 1, except that the pigment number P-2 in Example 13 was used instead of the pigment number P-4 in Example 1 as the charge generating substance. A body was prepared (Comparative Photoconductor 2).

Comparative Example 3 An electrophotographic photosensitive member was prepared in the same manner as in Example 1, except that the pigment number P-3 in Example 13 was used instead of the pigment number P-4 in Example 1 as the charge generating substance. A body was prepared (Comparative Photoconductor 3).

Comparative Example 4 The procedure of Example 1 was repeated, except that the pigment of Comparative pigment number Q-4 shown in Table 13 was used instead of the pigment number P-4 of Example 1 as the charge generating material. A photoreceptor was prepared (Comparative Photoreceptor 4).

The photoconductors 1 and 2 and the electrophotographic photoconductors of the comparative photoconductors 1 to 4 were respectively mounted on a cylinder of a remodeled laser beam printer (trade name: LBP-SX, manufactured by Canon Inc.). And set the charging so that the dark area potential becomes -700 V, irradiate it with laser light having a wavelength of 780 nm, and measure the amount of light required to reduce the -700 V potential to -200 V. Sensitivity. 20 μJ / cm ²
Was measured as the residual potential Vr. Table 14 shows the results.

[0086]

[Table 14]

Next, these six types of electrophotographic photosensitive members were mounted on a cylinder of a modified laser beam printer (described above).
Attached and attached to, humidity 10% / air temperature 5 ℃, humidity 50
The image test was performed in three environments of% / temperature 18 ° C. and humidity 80% / temperature 35 ° C. The conditions are as follows. Dark area potential: -700 V, light area potential: -200 V, transfer potential: +700 V, development polarity: negative polarity, process speed
Scan: image scanning, exposure before primary charging: 6.50 lux · sec red overall exposure, image formation with laser beam and character signal and Line scanning was performed according to the image signal. In addition, the continuous paper passing durability of 3,000 sheets was performed, and the fluctuation amounts ΔVd and ΔVl of the absolute values of the dark part potential and the light part potential after the durability were measured.

Next, the transfer memory was measured under the following conditions. Transfer current OFF using the same device as above
The primary charge potential at the time of transfer is Vd1, and the primary charge potential at the time of the transfer current ON is Vd2, and the transfer memory is (Vd1-Vd2).
Was measured.

Further, as a measurement of a photo memory with respect to white light, the initial potential (Vd) when the electrophotographic photosensitive member prepared as described above was charged to -700 V by the same printer as above before irradiation with light was measured. The potential (Vl) after the entire surface exposure was measured, and then the electrophotographic photosensitive member was masked so that a dark portion and a bright portion were formed.
After irradiating with light for 0 minutes, it was left for 5 minutes, and the absolute values (ΔVd and ΔVl) of the amount of change from the initial potential were measured.

Table 15 shows the values of the variation amounts ΔVd and ΔV1 of the absolute values of the dark portion potential and the bright portion potential, the value of the transfer memory, and the value of the photo memory after the continuous running of 3,000 sheets.

In the photoreceptors 1 and 2, the same good image as in the initial stage was obtained even after the durability in any environment, but in the comparative photoreceptors 1, 2, 3 and 4, a white background was obtained in any environment. Causes fogging in the ground, especially 80% humidity
At 35 ° C./temperature, comparatively poor images were obtained for Comparative Photoconductor 4. Further, comparative photoreceptor 1,
With respect to 2, 3 and 4, when the density was adjusted by a density adjusting lever to remove background fog, the density in the black portion became insufficient.

[0092]

[Table 15]

Examples 3 to 25 Electrophotographic photoreceptors were prepared in the same manner as in Example 1 using gallium phthalocyanine compounds of various crystal types shown in Table 12 and the above-mentioned charge transporting material represented by the general formula (1). Preparation (photoreceptors 3 to 25).

These photoreceptors were used in the same manner as in the first embodiment, and the cylinders of the remodeled laser beam printer (described above) were used.
And set the charging so that the dark portion potential becomes -700 V, and irradiate this with laser light having a wavelength of 780 nm.
The light amount EΔ500 required for lowering the potential of 700 V to −200 V was measured and defined as sensitivity. Furthermore, 20 μJ / cm
The potential when the light amount of No. ² was irradiated was measured as the residual potential Vr.

Further, these photosensitive members are set to a dark potential of -700.
V, the light-part potential was set to -200 V, and then continuous 3,000 sheets were passed, and the variations ΔVd and ΔVl of the absolute values of the dark part potential and the light-part potential at the initial stage and after 3,000 sheets were measured. . Table 16 shows the results.

[0096]

[Table 16]

Further, the photo memory and the transfer memory were measured in the same manner as in Example 1. Table 17 shows the results.

[0098]

[Table 17]

Comparative Examples 5 to 20 In place of the charge-generating substances used in Example 3, various phthalocyanine compounds shown in Table 13 were used, and in combination with a charge-transporting substance as shown in Table 18 below. An electrophotographic photosensitive member was prepared in the same manner as in Example 3 (comparative photosensitive members 5-2).
0) and evaluated similarly. The results are shown in Table 18.

[0100]

[Table 18]

Further, with respect to these comparative photoconductors, the measurement of the photo memory and the transfer memory was performed in the same manner as in Example 1. The results are shown in Table 19.

[0102]

[Table 19]

Comparative Examples 21 to 26 Comparative photoreceptors 21 to 26 were prepared in the same manner as in Example 1 except that the charge transporting substances were replaced by compounds H-1 to H-6 of the following structural formulas. Was prepared and evaluated in the same manner.
The results are shown in Table 20.

H-1

Embedded image H-2

Embedded image H-3

Embedded image H-4

Embedded image H-5

Embedded image H-6

Embedded image

[0105]

[Table 20]

Further, with respect to these comparative photoreceptors, the photo memory and the transfer memory were measured in the same manner as in Example 1. The results are shown in Table 21.

[0107]

[Table 21]

As is clear from the results of Tables 14 to 21,
The electrophotographic photoreceptor of the present invention comprising a combination of a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound as the charge generating substance and an arylamine hydrazone compound having a specific structure represented by the general formula (1) as the charge transporting substance in the present invention. Has high sensitivity, low residual potential, extremely small decrease in charging ability and sensitivity during repeated use, has stable characteristics, and has extremely small transfer memory and photo memory. It can be seen that

Example 26 Example 1 on a 50 μm thick aluminum sheet support
An undercoat layer was formed by bar coating in the same manner as in Example 1, and the same charge transport layer as in Example 1 was formed thereon with a thickness of 18 μm.

Next, bisphenol Z-type polycarbonate
Was dissolved in 66 parts of cyclohexane, and 3.8 parts of hydroxygallium phthalocyanine of Pigment No. P-4 shown in Table 12 was mixed with the solution, and dispersed in a sand mill for 1 hour. 5 parts and 9.5 parts of the charge transport material used in Example 1 were dissolved, and further diluted with 40 parts of tetrahydrofuran and 40 parts of dichloromethane to obtain a dispersion paint. This coating material was applied on the charge transport layer by spray coating and dried to form a charge generating layer having a thickness of 8 μm, whereby a photoreceptor 26 was prepared.

Example 27 Pigment No. P-4 in Example 26 as a charge generating substance
Instead of using chlorogallium phthalocyanine having a crystal form of pigment number P-1 shown in Table 12, an electrophotographic photosensitive member was prepared in the same manner as in Example 26 (photosensitive member 2).
7)

Comparative Example 27 Pigment No. P-4 in Example 26 as a charge generating substance
An electrophotographic photoreceptor was prepared in the same manner as in Example 26 except that Comparative Pigment No. Q-1 shown in Table 13 was used (Comparative Photoreceptor 27).

Comparative Example 28 Pigment No. P-4 in Example 26 as a charge generating substance
An electrophotographic photoreceptor was prepared in the same manner as in Example 26 except that Comparative Pigment No. Q-2 shown in Table 13 was used (Comparative Photoreceptor 28).

Comparative Example 29 Pigment No. P-4 in Example 26 as a charge generating substance
Comparative pigment No. Q-3 shown in Table 13 in place of
An electrophotographic photoreceptor was prepared in the same manner as in Example 26 except that the above pigment was used (Comparative photoreceptor 29).

Comparative Example 30 Pigment No. P-4 in Example 26 as a charge generating substance
In place of the pigment of Comparative pigment No. Q-4 shown in Table 13.
An electrophotographic photoreceptor was prepared (Comparative Photoreceptor 30) in the same manner as in Example 26, except for using the pigment No.

The electrophotographic photoreceptors 26 and 27 and the comparative photoreceptors 27 to 30 thus prepared were evaluated using an electrostatic tester (trade name: EPA-8100, manufactured by Kawaguchi Electric Co., Ltd.). The evaluation was first set so that the surface potential was 700 V by positive corona charging.
The light intensity when the surface potential was lowered to 200 V after exposure to 800 nm monochromatic light separated by a light source was measured and defined as sensitivity. The results are shown in Table 22.

[0117]

[Table 22]

Example 28 On an aluminum support, 4.2 parts of N-methoxymethylated 6 nylon resin (weight average molecular weight: 45,000) and an alcohol-soluble copolymerized nylon resin (weight average molecular weight: 5000)
0) A solution prepared by dissolving 8.8 parts in 90 parts of methanol was applied with a Myer bar to form an undercoat layer having a thickness of 0.5 μm after drying.

Next, 12 parts of Pigment No. P-4 shown in Table 12 as charge generating substances, 10 parts of polyvinyl butyral (butyralization ratio: 65%, weight average molecular weight: 45,000) and 200 parts of cyclohexanone were used. Dispersion for 24 hours. The dispersion was applied on the undercoating layer by blade coating to form a charge generation layer having a thickness of 0.22 μm after drying.

Next, 6 parts of Exemplified Compound 3, 3.5 parts of Exemplified Compound 30 and 10 parts of bisphenol Z-type polycarbonate (weight average molecular weight of 40,000) were converted to 70 parts of monochlorobenzene as charge transport materials. The solution was dissolved, and this solution was coated on the charge generation layer by blade coating to form a charge transport layer having a thickness of 20 μm after drying, thereby producing an electrophotographic photosensitive member (photosensitive member 28).

The photosensitive member 28 was subjected to a corona discharge of -5 KV. At this time, the surface potential (initial potential V0) was measured.
Further, the surface potential of this photoreceptor when left in a dark place for 1 second was measured. The sensitivity is the exposure amount (E1 / 6: μJ / cm ² ) required to attenuate the potential V1 after dark attenuation to 1/6.
Was evaluated by measuring. At this time, a quaternary semiconductor laser of indium / gallium / aluminum / phosphorus (output: 5 mW, oscillation wavelength: 680 nm) was used as a light source. The results are shown. V0: -700V, V1: -695V, E1 / 6: 0.
34 μJ / cm ²

Next, the photosensitive member 28 was attached to a laser beam printer of the reversal development type provided with a semiconductor laser as described above (described above), and an actual image forming test was performed. The conditions were as follows. Surface potential of primary charging: -700
V, surface potential of image exposure: -150 V transfer potential +700
V, development polarity: negative polarity, process speed: 50 mm /
sec, development condition (development bias): -450 V, image exposure scan method: image scan, exposure before primary charging:
The 50 lux / sec red whole surface exposure and image formation were performed by line scanning the laser beam in accordance with the character signal and the image signal, and good prints were obtained for both the character and the image. Further, 5000 images were continuously output, and stable prints were obtained from the initial to 5000 sheets.

[0123]

The electrophotographic photoreceptor of the present invention exhibits high sensitivity and a low residual potential in a long wavelength region such as a laser diode oscillation wavelength, and is free from repeated use and environmental fluctuations.
It exhibits a stable and excellent potential characteristic, and has a remarkable effect that a transfer memory and a photo memory are extremely small and a good image quality free from image defects such as fog is provided. In addition, a remarkable effect is similarly obtained in a process cartridge and an electrophotographic apparatus.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum (KBr tablet method) of chlorogallium phthalocyanine obtained in Production Example 1.

FIG. 2 is a powder X-ray diffraction diagram of chlorogallium phthalocyanine obtained in Production Example 1.

FIG. 3 shows that the Bragg angles 2θ ± 0.2 ° in the X-ray diffraction of CuKα obtained in Production Example 2 were 7.4 ° and 16.6 °.
FIG. 2 is an X-ray diffraction pattern of chlorogallium phthalocyanine having a crystalline form having strong peaks at, 25.5 ° and 28.2 °.

FIG. 4 shows a Bragg angle 2θ ± 0.2 ° in the X-ray diffraction of CuKα obtained in Production Example 3 of 8.7 to 9.2 °, 1
FIG. 3 is an X-ray diffraction pattern of chlorogallium phthalocyanine having a crystal form having strong peaks at 7.5 °, 24.0 °, 27.4 ° and 28.7 °.

FIG. 5 is an infrared absorption spectrum (KBr tablet method) of hydroxygallium phthalocyanine obtained in Production Example 4.

FIG. 6 shows that the Bragg angles 2θ ± 0.2 ° in the X-ray diffraction of CuKα obtained in Production Example 4 were 6.8 ° and 26.2 °.
FIG. 2 is an X-ray diffraction diagram of hydroxygallium phthalocyanine having a crystal form having a strong peak.

FIG. 7 shows that the Bragg angle 2θ ± 0.2 ° in the X-ray diffraction of CuKα obtained in Production Example 5 was 7.4 ° and 28.2 °.
FIG. 2 is an X-ray diffraction diagram of hydroxygallium phthalocyanine having a crystal form having a strong peak.

FIG. 8 shows that the Bragg angle 2θ ± 0.2 ° in the X-ray diffraction of CuKα obtained in Production Example 6 is 7.5 °, 16.3 °,
FIG. 2 is an X-ray diffraction pattern of hydroxygallium phthalocyanine having a crystal form having strong peaks at 24.9 ° and 26.4 °.

FIG. 9 shows Bragg angles 2θ ± 0.2 ° in X-ray diffraction of CuKα obtained in Production Example 7 being 6.9 °, 13.3 °,
FIG. 3 is an X-ray diffraction pattern of hydroxygallium phthalocyanine having a crystal form having strong peaks at 16.5 ° and 26.7 °.

FIG. 10 is a view showing a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor of this invention 2 axis 3 Primary charging means 4 Image exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Image fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Rail

Claims (11)

[Claims] 1. An electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains at least one selected from a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound as a charge generating substance. And an electrophotographic photosensitive member containing at least one compound represented by the following general formula (1) as a charge transporting substance. General formula (1) In the formula, X and Y represent a group represented by the general formula (2) or the general formula (3), and represented by the general formula (2) -Z-Ar n represents an integer of 0 or 1. R ₁ , R ₂ and R ₃ are a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent or a substituted amino group And p and r are 0 to
Represents an integer of 4. q represents an integer of 0 to 5 when n = 0, and represents an integer of 0 to 4 when n = 1. R ₄ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent, and R ₅ and R ₆ are An alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent; ₅ and R ₆ may be the same or different, and may form a ring directly or via a bonding group. Z represents an alkylene group which may have a substituent;
r represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent. R ₇ is an alkyl group which may have a substituent, an aralkyl group which may have a substituent,
It represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent. 2. The electrophotographic photosensitive member according to claim 1, wherein in the compound represented by the general formula (1), n in the general formula is 0. 3. In the compound represented by the general formula (1), n in the general formula is 0, and X—O— is at the 4-position (para-position as viewed from the bonding position of the n atom). The electrophotographic photosensitive member according to claim 1. 4. The chlorogallium phthalocyanine compound has a Bragg angle of 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 7.4 °, 16.6 °, 25.5 ° and 2
2. The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor is of a crystal type having a strong peak at 8.2 [deg.]. 5. The chlorogallium phthalocyanine compound has a Bragg angle of 2θ ± in X-ray diffraction of CuKα.
0.2 ° is 8.7 ° to 9.2 °, 17.5 °, 24.0
2. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is of a crystal type having strong peaks at .degree., 27.4.degree. And 28.7.degree .. 6. The method according to claim 1, wherein the hydroxygallium phthalocyanine compound has a Bragg angle 2θ in X-ray diffraction of CuKα.
2. The electrophotographic photoreceptor according to claim 1, wherein ± 0.2 ° is a crystal type having a strong peak at 6.8 ° and 26.2 °. 7. The method according to claim 1, wherein the hydroxygallium phthalocyanine compound has a Bragg angle 2θ in X-ray diffraction of CuKα.
2. The electrophotographic photoreceptor according to claim 1, wherein ± 0.2 ° is a crystal type having strong peaks at 7.4 ° and 28.2 °. 8. The method according to claim 1, wherein the hydroxygallium phthalocyanine compound has a Bragg angle 2θ in X-ray diffraction of CuKα.
± 0.2 ° is 7.5 °, 16.3 °, 24.9 ° and 2
2. The electrophotographic photoreceptor according to claim 1, wherein the electrophotographic photoreceptor is of a crystal type having a strong peak at 6.4 [deg.]. 9. The method according to claim 8, wherein the hydroxygallium phthalocyanine compound has a Bragg angle 2θ in X-ray diffraction of CuKα.
± 0.2 ° is 6.9 °, 13.3 °, 16.5 ° and 2
2. The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor is of a crystal type having a strong peak at 6.7 [deg.]. 10. An electrophotographic photoreceptor according to claim 1, and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means, integrally supported and detachably attached to an electrophotographic apparatus main body. A process cartridge characterized by the following. 11. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an image exposing unit, a developing unit, and a transfer unit.