JPH0570709A - Chlorinated indium phthalocyanine, its production, and electrophotographic photoreceptor containing the same - Google Patents

Abstract

PURPOSE:To provide a novel chlorinated indium phthalocyanine and an electrophotographic photoreceptor containing the phthalocyanine and having high sensitivity to long-wavelength light of around 800nm. CONSTITUTION:A chlorinated indium phthalocyanine whose Cu Ka X-ray diffraction spectrum has diffraction peaks at Bragg angles (2theta+ or -0.2 deg.) of 7.0 deg., 9.4 deg., 14.1 deg., 15.4 deg., 18.0 deg., 19.4 deg., 23.8 deg., 26.1 deg., 27.9 deg., and 30.2 deg.; a process for producing the same; and an electrophotographic photoreceptor containing the same as an organic photoconductive substance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel chlorinated indium phthalocyanine excellent in charge generating ability, a method for producing the same, and a semiconductor laser oscillation region using the same, 800 nm
The present invention relates to an electrophotographic photosensitive member having high sensitivity to front and rear long wavelength light.

[0002]

2. Description of the Related Art As a conventional electrophotographic photosensitive member, selenium (S) of about 50 μm is formed on a conductive substrate such as aluminum.
e) There is a film formed by a vacuum deposition method. However, this Se photoconductor has a problem that it has sensitivity only up to a wavelength of about 500 nm. Moreover, a Se layer of about 50 μm is formed on the conductive substrate, and several μ is further formed on this.
There is a photoconductor on which a selenium-tellurium (Se-Te) alloy layer of m is formed. This photoconductor is Te of the above Se-Te alloy.
The higher the content ratio of the, the spectral sensitivity extends to a longer wavelength, but on the other hand, as the amount of Te added increases, the surface charge retention property becomes poor, and there is a serious problem that it cannot be used as a photoconductor in practice.

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

In recent years, in this composite two-layer type photoreceptor,
The above drawbacks are improved, that is, the semiconductor laser oscillation region 80.
Although many photoreceptors having a sensitivity of around 0 nm have been reported, most of them use a phthalocyanine pigment as a charge generating material, and polyvinylcarbazole, which has a thickness of about 0.5 to 1 μm, is formed on the charge generating layer. A mixture of a pyrazoline derivative or a hydrazone derivative and a polycarbonate resin or a polyester resin having a high insulation resistance is used in an amount of 10 to 2
A coating of 0 μm is formed to form a charge transport layer to form a composite two-layer type photoreceptor.

Phthalocyanines differ not only in their absorption spectra and photoconductivity depending on the type of central metal, but also in their physical properties depending on the crystal type. Even for phthalocyanines of the same central metal, there are specific crystal types. Several examples have been reported that have been selected for electrophotographic photoreceptors.
Among the metal-free phthalocyanines, it has been reported that the X-type crystal type has high photoconductivity and is sensitive to 800 nm or more. In copper phthalocyanine, ε-type is the longest among many crystal types. It is reported to have sensitivity up to the wavelength range.

However, the X-type metal-free phthalocyanine is a metastable crystal type, and its production is difficult, and it is difficult to obtain stable quality. on the other hand,
ε-type copper phthalocyanine has a spectral sensitivity extending to a longer wavelength than that of α- and β-type copper phthalocyanine, but has a wavelength of 800 nm.
The sensitivity is drastically lower than that of 780 nm, which makes it difficult to use for the current semiconductor lasers that have fluctuations in the oscillation wavelength. For this reason, many metal phthalocyanines have been investigated, and oxyvanadyl phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, oxytitanium phthalocyanine, chlorogallium phthalocyanine, magnesium phthalocyanine, etc. have high sensitivity to near infrared light such as semiconductor lasers. Phthalocyanines have been reported. However, in order to use these phthalocyanines as charge generating materials for electrophotographic photoreceptors for copying machines and printers, not only sensitivity but also many required performances must be satisfied. In this respect, I am still not fully satisfied.

The electrical characteristics are largely different depending on the kind of coordination metal of phthalocyanine, but even the same metal phthalocyanine has a large difference in characteristics depending on the crystal form. For example, copper phthalocyanine is known to have a large difference in chargeability, dark decay, sensitivity, etc. due to differences in crystal forms such as α, β, γ, and ε type (Sawada Manabu; “Dyes and chemicals”). Vol. 24, No. 6, p. 1
22 (1979)). In addition, since the absorption spectrum varies depending on the crystal form, the spectral sensitivity also changes, and in copper phthalocyanine, the ε-type absorption is at the longest wavelength side, and the spectral sensitivity is also the longest wavelength side (Yuo Kumano; Electrophotography Academic Journal Volume 22, No. 2, p. 111 (1984)).

As described above, the difference in the electrical characteristics depending on the crystal form is
There are many known metal-free phthalocyanines and many other metal phthalocyanines, and much effort has been made in how to form a crystalline form with good electrical properties. For example, there are many cases in which a vapor-deposited film of metal phthalocyanine is used as the charge generation layer, but the vapor-deposited film is immersed in an organic solvent such as dichloromethane or tetrahydrofuran, or is exposed to a solvent vapor to cause a crystal transition, thereby improving the electrical characteristics. An improved example has been reported for aluminum, indium and titanium phthalocyanines (Japanese Patent Laid-Open No. 58-1586).
49, JP-A-59-44054, JP-A-5
9-49544, JP-A-59-155851, JP-A-59-166959).

However, regarding indium phthalocyanine, Japanese Patent Laid-Open No. 60-59355 and Journal of Imaging Science [Journ.
alof Imaging Science, 29 , 1
48 (1985)], it is reported that even if the indium phthalocyanine powder and the vapor-deposited film are exposed to a solvent vapor or immersed in a solvent, the absorption wavelength shifts to a long wavelength but the crystal form does not change. In the Journal of Imaging Science, the Bragg angle (2θ ± 0.2
Degree) is 7.4 degrees, 12.6 degrees, 16.7 degrees, 21.4 degrees
The X-ray diffraction spectrum of CuKα giving strong diffraction peaks at degrees, 23.4 degrees, 25.3 degrees, and 27.9 degrees is shown.

Further, Japanese Patent Laid-Open No. 174845/1984,
JP-A-61-45249, JP-A-63-1415
4, JP-A-63-56564, JP-A-63
In JP-A-261267, JP-A-63-261266 and JP-A-1-125552, a vapor-deposited film of chloroindium phthalocyanine was exposed to tetrahydrofuran vapor for 20 hours, and an absorption maximum peak of an electronic spectrum was detected in a semiconductor laser oscillation wavelength region. , Which is about 800 nm, to form a charge generation layer.

These known indium phthalocyanines form a charge generation layer mainly by vapor deposition and are exposed to a solvent vapor after vapor deposition to obtain a charge generation layer. However, the vapor deposition method is different from the coating method. However, the amount of capital investment is large and the mass productivity is poor, so that the cost tends to be high.

In a laser beam printer or the like using a laser beam as a light source and an electrophotographic photosensitive member, various attempts have recently been made to use a semiconductor laser as a light source. In this case,
Since the wavelength of the light source is around 800 nm,
There is a strong demand for an electrophotographic photosensitive member having high sensitivity to long-wavelength light of around nm.

[0013]

DISCLOSURE OF THE INVENTION The present invention is 800 nm.
It is intended to provide an electrophotographic photosensitive member having high sensitivity to light having long and short wavelengths.

[0014]

The present invention relates to CuKα X
In the line diffraction spectrum, the Bragg angle (2θ ± 0.2
Degree) is 7.0 degrees, 9.0 degrees, 14.1 degrees, 15.4 degrees,
18.0 degrees, 19.4 degrees, 23.8 degrees, 26.1 degrees, 2
It relates to chlorinated indium phthalocyanine having diffraction peaks at 7.9 degrees and 30.2 degrees.

In the present invention, chlorinated indium phthalocyanine in an amorphous state is mixed with an aromatic solvent and / or
Or CuK characterized by being treated with a solvent containing titanium
In the X-ray diffraction spectrum of α, the Bragg angle (2θ ±
0.2 degree) is 7.0 degrees, 9.0 degrees, 14.1 degrees, 15.
4 degrees, 18.0 degrees, 19.4 degrees, 23.8 degrees, 26.1
And a method for producing chlorinated indium phthalocyanine having diffraction peaks at 27.9 degrees and 30.2 degrees.

The present invention also provides an electrophotographic photoreceptor having a photoconductive layer containing an organic photoconductive substance on a conductive support, wherein the organic photoconductive substance has a Bragg angle in an X-ray diffraction spectrum of CuKα. (2θ ± 0.2 degrees) is 7.0 degrees, 9.0 degrees, 14.1 degrees, 15.4 degrees, 18.
0 degree, 19.4 degree, 23.8 degree, 26.1 degree, 27.9 degree
And an electrophotographic photoreceptor which is a chlorinated indium phthalocyanine having a diffraction peak at 30.2 degrees.

The present invention will be described in detail below. The method for synthesizing an indium phthalocyanine compound (monochloroindium phthalocyanine, monochloroindium chlorophthalocyanine) as a precursor used for producing a chlorinated indium phthalocyanine showing a specific X-ray diffraction spectrum of the present invention is described in Inorganic Chemistry [Inorganic. Chemistry 19 , 31
31 (1980)] and JP-A-59-44054.

Monochloroindium phthalocyanine is
For example, it can be manufactured as follows. 10 g of phthalonitrile and 3.5 g of indium trichloride were placed in 100 ml of quinoline that had been distilled and deoxygenated twice, and the mixture was heated under reflux for 1 hour, then gradually cooled, then cooled to 0 ° C., and then filtered.
The dark purple crystals are washed with methanol, toluene and acetone, and then dried at 110 ° C. (yield 6.3 g).

Further, monochloroindium chlorophthalocyanine can be produced as follows. 20 g of phthalonitrile and 8.3 g of indium trichloride are mixed and melted at 300 ° C. and heated for 60 minutes to obtain a crude product of monochloroindium chlorophthalocyanine 23.
0 g is obtained, which is washed with α-chloronaphthalene using a Soxhlet extractor (yield 14.0 g).

The indium phthalocyanine compound produced in this manner has a very strong diffraction peak at a Bragg angle of 7.4 degrees in the X-ray diffraction spectrum.

In the X-ray diffraction spectrum of CuKα according to the present invention, the Bragg angle (2θ ± 0.2 degrees) is 7.0 degrees,
9.0 degrees, 14.1 degrees, 15.4 degrees, 18.0 degrees, 1
The chlorinated indium phthalocyanine having diffraction peaks at 9.4 degrees, 23.8 degrees, 26.1 degrees, 27.9 degrees and 30.2 degrees has a Bragg angle of 7.4 degrees in the X-ray diffraction spectrum. By using a crystal of an indium phthalocyanine compound having a strong diffraction peak, it can be produced, for example, as follows.

5.0 g of crystals of an indium phthalocyanine compound having a strong Bragg angle of 7.4 degrees was dissolved in 500 ml of concentrated sulfuric acid, and this was cooled with ice water to obtain pure water 5.
It is dripped at 1 l to reprecipitate chlorinated indium phthalocyanine. After filtration, the precipitate is thoroughly washed with pure water and a mixed solution of methanol and pure water, and then dried at 110 ° C. to obtain 3.9 g of chlorinated indium phthalocyanine powder. The X-ray diffraction spectrum of the chlorinated indium phthalocyanine thus obtained is a spectrum showing a wide amorphous state without a clear sharp peak. As a method for obtaining an amorphous state, there is a method by dry milling other than the acid pasting method using concentrated sulfuric acid.

The amorphous chlorinated indium phthalocyanine thus obtained is treated with an aromatic solvent and / or a nitrogen-containing solvent to give a specific X-ray diffraction spectrum of the present invention. Can be manufactured. For example, 1 g of amorphous chlorinated indium phthalocyanine powder is placed in 120 ml of tetralin as an aromatic solvent and heated and stirred (the powder / solvent (weight ratio) is 1/1 to 1/100.
Is). The heating temperature is 100 ° C to 200 ° C, preferably 110 ° C to 150 ° C, and the heating time is 1 hour to 12 hours, preferably 2 hours to 8 hours. After completion of heating and stirring, filtration, washing with methanol, and vacuum drying at 60 ° C. can give 700 mg of chlorinated indium phthalocyanine crystals of the present invention. Examples of the aromatic solvent used in this treatment include toluene, xylene, chlorobenzene, and tetralin. Examples of the nitrogen-containing solvent include N-methylpyrrolidone.

The electrophotographic photosensitive member according to the present invention has a photoconductive layer provided on a conductive support. In the present invention, the photoconductive layer is a layer containing an organic photoconductive substance, and is a composite film comprising an organic photoconductive substance film, a film containing an organic photoconductive substance and a binder, a charge generation layer and a charge transport layer. Mold coating etc.

As the organic photoconductive substance, the chlorinated indium phthalocyanine is used as an essential component, and known substances can be used in combination. Also,
As the organic photoconductive substance, it is preferable to use the chlorinated indium phthalocyanine or the phthalocyanine and the charge-generating organic pigment in combination with the charge-transporting substance. In addition,
The charge generating layer contains the phthalocyanine or an organic pigment that generates a charge with the phthalocyanine, and the charge transporting layer contains a charge transporting substance.

The charge-generating organic pigments include azoxybenzene type, disazo type, trisazo type, benzimidazole type, polycyclic quinone type, indigoid type, quinacridone type, perylene type, methine type, α type, β type , Γ
Pigments known to generate electric charges, such as metal-free or metal-type phthalocyanine-based pigments having various crystal structures such as type, δ type, ε type, and χ type can be used. These pigments are disclosed, for example, in JP-A-47-37543, JP-A-47-37544, and JP-A-47-18543.
JP-A-47-18544, JP-A-48-
No. 43942, No. 48-70538, No. 49-1231, No. 49-105536.
JP-A-50-75214, JP-A-53-
No. 44028, JP-A No. 54-17732, and the like. Further, τ, τ ′, η and η ′ type metal-free phthalocyanines disclosed in JP-A-58-182640 and European Patent Publication No. 92,255 can also be used. In addition to the above, any organic application that generates a charge carrier by light irradiation can be used.

As the charge-transporting substance, polymer compounds such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene, polyvinylindroquinoxaline, polyvinylbenzothiophene, polyvinylanthracene, polyvinylacridine are used. , Polyvinylpyrazoline and the like are low molecular weight compounds such as fluorenone, fluorene and 2,7-dinitro-9-
Fluorenone, 4H-indeno (1,2,6) thiophen-4-one, 3,7-dinitro-dibenzothiophen-5-oxide, 1-bromopyrene, 2-phenylpyrene, carbazole, N-ethylcarbazole, 3- Phenylcarbazole, 3- (N-methyl-N-phenylhydrazone) methyl-9-ethylcarbazole, 2-phenylindole, 2-phenylnaphthalene, oxadiazole, 2,5-bis (4-diethylaminophenyl) -1, 3,4-oxadiazole, 1-phenyl-
3- (4-diethylaminostyryl) -5- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline, 1-phenyl-3- (p-diethylaminophenyl) pyrazoline, p- (dimethylamino)
-Stilbene, 2- (4-dipropylaminophenyl)
-4- (4-Dimethylaminophenyl) -5- (2-chlorophenyl) -1,3-oxazole, 2- (4-dimethylaminophenyl) -4- (4-dimethylaminophenyl) -5- (2- Fluorophenyl) -1,3-oxazole, 2- (4-diethylaminophenyl) -4
-(4-Dimethylaminophenyl) -5- (2-fluorophenyl) -1,3-oxazole, 2- (4-dipropylaminophenyl) -4- (4-dimethylaminophenyl) -5- (2- Fluorophenyl) -1,3-oxazole, imidazole, chrysene, tetraphene,
There are acridene, triphenylamine, derivatives thereof and the like.

When the phthalocyanine or the phthalocyanine and the organic pigment that generates an electric charge and the charge-transporting substance are mixed and used, the latter / the former is in a weight ratio of 10/1 to
It is preferable to mix it in a ratio of 2/1. At this time, if the charge-transporting substance is a polymer compound, the binder may not be used, but even in this case or when the charge-transporting substance is a low-molecular compound, the binder may be a compound of these compounds. It is preferably used in an amount of 500% by weight or less based on the total amount.
When a low molecular weight compound is used as the charge transporting substance, it is preferable to use the binder in an amount of 30% by weight or more.
Further, the binder may be used in the same amount even when the charge transporting substance is not used. When using these binders, additives such as a plasticizer, a fluidity-imparting agent, and a pinhole suppressor can be added as required.

When a composite photoconductive layer comprising a charge generating layer and a charge transporting layer is formed, the charge generating layer contains the above-mentioned phthalocyanine or an organic pigment which generates a charge and a binder. The organic pigment may be contained in an amount of 500% by weight or less, and the above-mentioned additive may be added in an amount of 5% by weight or less based on the total amount of the phthalocyanine or the phthalocyanine and the organic pigment. The charge transport layer may contain the above-mentioned charge transport material, and the binder may be contained in an amount of 500% by weight or less based on the charge transport material. When the charge transporting substance is a low molecular weight compound, it is preferable that the binder is contained in an amount of 50% by weight or more based on the compound. The charge transport layer may contain the above-mentioned additive in an amount of 5% by weight or less based on the charge transport material.

Binders that can be used in all of the above cases include silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyacrylic resin, polystyrene resin, styrene-butadiene copolymer. , Polymethylmethacrylate resin, polyvinyl chloride, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer,
Examples thereof include polyacrylamide resin, polyvinyl carbazole, polyvinyl pyrazoline, polyvinyl pyrene and the like. Further, a thermosetting resin and a photocurable resin which are crosslinked by heat and / or light can also be used.

In any case, there is no particular limitation as long as it is an insulating resin capable of forming a coating in a normal state and a resin which is cured by heat and / or light to form a coating. Examples of the plasticizer include halogenated paraffin, dimethyl naphthalene, dibutyl phthalate and the like. Examples of the fluidity-imparting agent include Modaflow (manufactured by Monsanto Chemical Co., Ltd.) and Acronal 4F (manufactured by Basuf Co.), and the pinhole inhibitor includes benzoin, dimethyl phthalate and the like. These may be appropriately selected and used, and the amount thereof may be appropriately determined.

In the present invention, the conductive layer is a conductive material such as paper or plastic film that has been subjected to conductive treatment, a plastic film in which a metal foil such as aluminum is laminated, or a metal plate.

The electrophotographic photoreceptor of the present invention comprises a photoconductive layer formed on a conductive layer. The thickness of the photoconductive layer is 5
50μ is preferable. When the composite type of the charge generation layer and the charge transport layer is used as the photoconductive layer, the charge generation layer is preferably 0.001 to 10 μm, particularly preferably 0.2 to 5 μm.
The thickness is m. If it is less than 0.001 μm, it is difficult to uniformly form the charge generation layer, and if it exceeds 10 μm, the electrophotographic properties tend to deteriorate. The thickness of the charge transport layer is preferably 5 to 50 μm, particularly preferably 8 to 2
It is 5 μm. If the thickness is less than 5 μm, the initial potential tends to be low, and if it exceeds 50 μm, the sensitivity tends to decrease.

To form a photoconductive layer on the conductive layer, an organic photoconductive substance is vapor-deposited on the conductive layer, an organic photoconductive substance and, if necessary, other components are aromatic such as toluene and xylene. There is a method of uniformly dissolving or dispersing in a system solvent, a halogenated hydrocarbon system solvent such as methylene chloride or carbon tetrachloride, or an alcohol system solvent such as methanol, ethanol or propanol, coating on the conductive layer, and drying. As a coating method, a spin coating method, a dipping method or the like can be adopted.
When the charge generation layer and the charge transport layer are formed in the same manner, either the charge generation layer or the charge transport layer may be the upper layer, and the charge generation layer may be a two-layer charge transport layer. It may be sandwiched.

When the chlorinated indium phthalocyanine compound of the present invention is applied by a spin coating method, the chlorinated indium phthalocyanine compound is dissolved in a halogenated solvent such as chloroform or toluene or a non-polar solvent to obtain a coating solution, which is rotated. Spin coating at several 3,000 to 7,000 rpm is preferable, and when applying by a dipping method, a chlorinated indium phthalocyanine compound is ball-milled in a halogen solvent such as methanol, dimethylformamide, chloroform, methylene chloride or 1,2-dichloroethane. It is preferable to immerse the conductive substrate in the coating liquid dispersed by using ultrasonic waves or the like.

The protective layer may be formed in the same manner as the coating and drying methods in forming the photoconductive layer. The electrophotographic photosensitive member according to the present invention may further have a thin adhesive layer or a barrier layer immediately above the conductive layer, and may have a protective layer on the surface.

[0037]

EXAMPLES The present invention will be described below with reference to production examples and examples. First, a production example of the chlorinated indium phthalocyanine of the present invention will be shown.

Production Example 1 1.0 g of monochloroindium phthalocyanine synthesized according to the method described in the above Inorganic Chemistry (X-ray diffraction spectrum is shown in FIG. 1) was dissolved in 100 ml of concentrated sulfuric acid and cooled with ice water. Pure water 1
It was added dropwise to 1 to re-precipitate monochloroindium phthalocyanine. After filtration, the precipitate was thoroughly washed with pure water and a mixed solution of methanol / pure water, dried at 110 ° C., and amorphous monochloroindium phthalocyanine powder 0.8.
5 g was obtained (X-ray diffraction spectrum is shown as FIG. 2). Then, this powder was put into 100 ml of tetralin, heated and stirred at 150 ° C. for 5 hours, immediately filtered, washed with methanol and vacuum dried at 60 ° C. to obtain 0.59 g of crystals of monochloroindium phthalocyanine of the present invention. The crystal X-ray diffraction spectrum is shown in FIG. Also,
An electronic spectrum of a film prepared from this crystal and poly (chlorotrifluoroethylene) oil [trade name: Fluorolove, manufactured by Central Chemical Co.] is shown in FIG.

Production Example 2 A monochloroindium phthalocyanine crystal of the present invention was produced according to Production Example 1 except that N-methylpyrrolidone was used instead of tetralin. The X-ray diffraction spectrum of this crystal is shown in FIG. Further, the electron spectrum of a film prepared from this crystal and poly (chlorotrifluoroethylene) oil [trade name: Fluorolove, manufactured by Central Chemical Co.] is shown in FIG.

Production Example 3 A monochloroindium phthalocyanine crystal of the present invention was produced according to Production Example 1 except that toluene was used in place of tetralin and the heating temperature was 120 ° C. The X-ray diffraction spectrum and electron spectrum of this crystal were equivalent to those in FIGS. 3 and 4, respectively.

Production Example 4 This example was prepared according to Production Example 1 except that monochloroindium chlorophthalocyanine synthesized according to the method described in JP-A-59-44054 was used instead of monochloroindium phthalocyanine in Production Example 1. Crystals of the inventive monochloroindium chlorophthalocyanine were prepared. The X-ray diffraction spectrum and electron spectrum of this crystal were equivalent to those in FIGS. 3 and 4, respectively.

Example 1 2.5 g of monochloroindium phthalocyanine compound produced in Production Example 1 5.0 g of silicon resin KR-255 [trade name of Shin-Etsu Chemical Co., Ltd.] (solid content 50% by weight) and 1,2-dichloroethane 92 0.5g was blended, and this mixture was ball milled (Nippon Kagaku Sangyo Co., Ltd. 3 inch pot mill).
Was kneaded for 8 hours. The obtained pigment dispersion is applied to an aluminum plate (conductive support 100 mm by an applicator).
(× 70 mm × 0.1 mm), and dried at 90 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.5 μm.

5 g of 1-phenyl-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and polycarbonate resin Iupilon S-
3000 [trade name of Mitsubishi Gas Chemical Company] (solid content 100
(Wt%) 10 g was dissolved in 85 g of a 1: 1 (weight ratio) mixed solvent of methylene chloride and 1,1,1-trichloroethane, and a dipping coating was performed on the charge generation layer of the above substrate using a coating solution obtained. And dried for 30 minutes at 120 ℃, thickness 20μm
Was formed on the charge transport layer.

The photoreceptor was negatively charged by corona discharge of 5 KW using an electrostatic charging tester (manufactured by Kawaguchi Electric Co., Ltd.). After that, a halogen lamp was used as an external light source, and monochromatic light was irradiated with a monochromator (manufactured by Ritsu-Applied Optical Co., Ltd.) to irradiate the light, and the light attenuation of the surface potential of the photoconductor was measured.

As a result, when monochromatic light of 800 nm in the near infrared region is used, the half-exposure amount (E _1/2 ) (the potential residual ratio is 1
The product of the time for becoming 1/2 and the light intensity) was 5.0 mJ / m ² . At this time, the charged voltage (initial surface potential V ₀ ) of the photoconductor is −980 V, and the dark decay (V _D ) is 7.3 V / se.
c, the surface potential after exposure 20 seconds (residual potential V _R) is -5V
Met.

Examples 2 to 4 A charge generation layer was formed in the same manner as in Example 1 using the monochloroindium phthalocyanine compounds produced in Production Examples 2 to 4, respectively. Example 1 is formed on this charge generation layer.
A charge transport layer having a thickness of 20 μm was formed in the same manner as in.
Table 1 shows the results of electrophotographic characteristics of the thus obtained photoconductor, which were measured in the same manner as in Example 1 by using monochromatic light of 800 nm in the near infrared region.

[0047]

[Table 1]

Examples 5 to 8 Using the monochloroindium phthalocyanine compound used in Examples 1 to 4, a charge generation layer was formed in the same manner as in Example 1. Next, 5 g of p-diethylaminobenzaldehyde-diphenylhydrazone and 10 g of polycarbonate resin Iupilon S-3000 were dissolved in 85 g of a mixed solvent of 1: 1 (weight ratio) of methylene chloride and 1,1,2-trichloroethane to obtain a coating solution. By using the above, dip coating was performed on the charge generation layer of the substrate and dried at 120 ° C. for 30 minutes to form a charge transport layer having a thickness of 20 μm. Table 2 shows the results of electrophotographic characteristics of the photoreceptor thus obtained, which were measured by using monochromatic light of 800 nm in the near infrared region in the same manner as in Example 1.

[0049]

[Table 2]

Comparative Example 1 Monochloroindium phthalocyanine (X was synthesized according to the method described in Inorganic Chemistry.
2 x 10 ^-5 mmHg (line diffraction spectrum of Fig. 1)
Under vacuum, a charge generation layer was formed by vacuum vapor deposition on an aluminum vapor deposition substrate. A charge transport layer having a thickness of 20 μm was formed on this charge generation layer by the same method as in Example 1. Electrophotographic characteristics of the thus-obtained photoreceptor were measured by using monochromatic light of 800 nm in the near infrared region in the same manner as in Example 1. Initial charging V ₀ was −900 V and dark decay V _D was 27 V.
/ Sec, sensitivity E _1/2 is 31 mJ / m ² , residual potential -10
It was V.

Comparative Example 2 The same as Comparative Example 1 except that the monochloroindium chlorophthalocyanine compound synthesized according to the method described in JP-A-59-44054 was used in place of the monochloroindium phthalocyanine compound used in Comparative Example 1. The charge generation layer was formed by the above method. Example 5 is formed on this charge generation layer.
A charge transport layer having a thickness of 20 μm was formed in the same manner as in.
Electrophotographic characteristics of the thus obtained photoconductor were measured by using monochromatic light of 800 nm in the near infrared region in the same manner as in Example 1. Initial charging V ₀ was −800 V and dark decay V _D was 30 V / sec. , The sensitivity E _1/2 was 35 mJ / m ² , and the residual potential was −15 V.

[0052]

The electrophotographic photosensitive member using the novel chlorinated indium phthalocyanine obtained by the production method of the present invention has a characteristic of showing high sensitivity in a long wavelength region around 800 nm which is a semiconductor laser oscillation region. However, particularly when used in a laser beam printer, excellent effects are exhibited.
Further, the electrophotographic photosensitive member of the present invention can be suitably applied not only to the above-described laser beam printer but also to a printer using an LED as a light source, and further to other optical recording devices using a semiconductor laser as a light source.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction spectrum of monochloroindium phthalocyanine.

FIG. 2 is an X-ray diffraction spectrum of monochloroindium phthalocyanine treated with concentrated sulfuric acid.

FIG. 3 is an X-ray diffraction spectrum of monochloroindium phthalocyanine treated with tetralin.

FIG. 4 Electronic spectrum of monochloroindium phthalocyanine treated with tetralin.

FIG. 5: X-ray diffraction spectrum of monochloroindium phthalocyanine treated with N-methylpyrrolidone.

FIG. 6 Electronic spectrum of monochloroindium phthalocyanine treated with N-methylpyrrolidone.

Front Page Continuation (72) Inventor Mikio Itagaki 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Ibaraki Research Center

Claims (4)

[Claims] 1. An X-ray diffraction spectrum of CuKα having a Bragg angle (2θ ± 0.2 degrees) of 7.0 degrees, 9.0 degrees,
14.1 degrees, 15.4 degrees, 18.0 degrees, 19.4 degrees, 2
Chlorinated indium phthalocyanine having diffraction peaks at 3.8 degrees, 26.1 degrees, 27.9 degrees and 30.2 degrees. 2. A Bragg angle (2θ ± 0.2 degrees) in an X-ray diffraction spectrum of CuKα, which is characterized by treating chlorinated indium phthalocyanine in an amorphous state with an aromatic solvent and / or a nitrogen-containing solvent. Is 7.
0 degree, 9.0 degree, 14.1 degree, 15.4 degree, 18.0
A process for producing chlorinated indium phthalocyanine having diffraction peaks at 19.4 degrees, 19.4 degrees, 23.8 degrees, 26.1 degrees, 27.9 degrees and 30.2 degrees. 3. An electrophotographic photosensitive member having a photoconductive layer containing an organic photoconductive substance on a conductive support, wherein the organic photoconductive substance has a Bragg angle (2θ ± 0) in an X-ray diffraction spectrum of CuKα. .2 degrees) is 7.0 degrees and 9.0 degrees
Degrees, 14.1 degrees, 15.4 degrees, 18.0 degrees, 19.4 degrees
Degrees, 23.8 degrees, 26.1 degrees, 27.9 degrees and 30.degree.
An electrophotographic photoreceptor which is a chlorinated indium phthalocyanine having a diffraction peak at 2 degrees. 4. The electrophotographic photosensitive member according to claim 3, wherein the chlorinated indium phthalocyanine is monochloroindium phthalocyanine or monochloroindium chlorophthalocyanine.