JPH0598180A - Brominated indium phthalocyanine, its production and electrophotographic photoreceptor using the same - Google Patents

Abstract

PURPOSE:To obtain a new brominated indium phthalocyanine, having high sensitivity to light at a long wavelength, useful as an organic photoconductive substance and capable of providing electrophotographic photoreceptors suitable as laser beam printers, etc., and excellent in charge producing ability. CONSTITUTION:The objective compound having diffraction peaks at 6.7 deg., 7.4 deg., 13.5 deg., 14.9 deg., 15.9 deg., 24.8 deg. and 26.2 deg. Bragg angles (2theta+ or -0.2 deg.) in an X-ray diffraction spectrum of CuKalpha. This compound is obtained by treating a brominated indium phthalocyanine in an amorphous state with an ethereal solvent such as THF and/or a ketonic solvent such as acetone. Furthermore, the raw material compound in the amorphous state is obtained by reacting, e.g. phthalonitrile with indium tribromide in distilled and deoxidized quinoline under heating and refluxed conditions, then dissolving the produced crystals of monobromoindium phthalocyanine in concentrated sulfuric acid and dropping the prepared solution into pure water while cooling the pure water and reprecipitating the crystals.

Description

Detailed Description of the Invention

[0001]

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

[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, and they are not yet sufficiently satisfactory. Absent.

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, the spectral sensitivity changes depending on the absorption spectrum depending on the crystal form, and in copper phthalocyanine, the ε-type absorption is at the longest wavelength side, and the spectral sensitivity is also extended to the long wavelength side (Kumano). Yuuo; Journal of the Electrophotographic Society 2nd
Volume 2, Issue 2, p. 111 (1984)).

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, as a crystal form of chloroindium phthalocyanine, a black 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.

JP-A-59-174845, JP-A-61-45249, JP-A-63-14154, JP-A-63-56564, and JP-A-63-26.
In JP 1267, JP 63-261266 A, and JP 1-312552 A, a vapor deposition film of chloroindium phthalocyanine is exposed to a vapor of tetrahydrofuran for 20 hours, and an absorption maximum peak of an electronic spectrum is 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, this is not preferable because the amount of capital investment is large and the mass productivity is poor, resulting in high cost.

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.
Provided are a brominated indium phthalocyanine having high sensitivity to long and short wavelengths of light, a method for producing the same, and an electrophotographic photoreceptor using the same.

[0014]

The present invention relates to CuKα X
In the line diffraction spectrum, the Bragg angle (2θ ± 0.2
Degree) is 6.7 degrees, 7.4 degrees, 13.5 degrees, 14.9 degrees,
It relates to brominated indium phthalocyanine having diffraction peaks at 15.9 degrees, 24.8 degrees and 26.2 degrees.

In the present invention, the brominated indium phthalocyanine in an amorphous state is mixed with an ether solvent and / or
Alternatively, CuKα characterized by being treated with a ketone solvent
Of the Bragg angle (2θ ± 0.
2 degrees) is 6.7 degrees, 7.4 degrees, 13.5 degrees, 14.9 degrees
The present invention relates to a method for producing brominated indium phthalocyanine having diffraction peaks at 15.9 degrees, 15.9 degrees, 24.8 degrees and 26.2 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 6.7 degrees, 7.4 degrees, 13.5 degrees, 14.9 degrees, 15.
The present invention relates to an electrophotographic photosensitive member which is a brominated indium phthalocyanine having diffraction peaks at 9 degrees, 24.8 degrees and 26.2 degrees.

The present invention will be described in detail below. The indium phthalocyanine compound (monobromoindium phthalocyanine, monobromoindium bromophthalocyanine) as a precursor used for producing a brominated indium phthalocyanine exhibiting a specific X-ray diffraction spectrum of the present invention is produced by the inorganic chemistry [In
organic Chemistry 19 , 3131
(1980)] and JP-A-59-44054.

Monobromoindium phthalocyanine can be produced, for example, as follows. 10 g of phthalonitrile and 3.5 g of indium tribromide were put into 100 ml of quinoline that had been twice distilled and deoxygenated, and the mixture was heated under reflux for 1 hour, then gradually cooled, then cooled to 0 ° C., and filtered to give dark purple crystals as methanol. After washing with toluene or acetone, it is dried at 110 ° C. (yield 6.3 g).

Monobromoindium bromophthalocyanine can be produced as follows. 20 g of phthalonitrile and 8.3 g of indium tribromide were mixed and melted at 300 ° C. and heated for 60 minutes to obtain a crude product of monobromoindium bromophthalocyanine 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 °) is 6.7 °,
7.4 degrees, 13.5 degrees, 14.9 degrees, 15.9 degrees, 2
Brominated indium phthalocyanine having a diffraction peak at 4.8 degrees and 26.2 degrees is obtained by using a crystal of an indium phthalocyanine compound having a very strong diffraction peak at a Bragg angle of 7.4 degrees in the X-ray diffraction spectrum, For example, it can be manufactured 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.
Then, the solution is added dropwise to 1 to reprecipitate brominated indium phthalocyanine. After filtration, the precipitate was thoroughly washed with a mixed solution of pure water and pure water of methanol and then dried at 110 ° C to obtain 3.9 g of brominated indium phthalocyanine powder. The X-ray diffraction spectrum of the brominated 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 thus-obtained amorphous brominated indium phthalocyanine is treated with an ether solvent and / or a ketone solvent to produce a brominated indium phthalocyanine showing a specific X-ray diffraction spectrum of the present invention. it can. For example, 1 g of amorphous brominated indium phthalocyanine powder is put in 120 ml of tetrahydrofuran as an ether solvent and stirred with heating (the powder / solvent (weight ratio) is 1/1).
~ 1/100). The heating temperature is 30 ° C to 100 ° C,
It is preferably 50 ° C to 80 ° C, and the heating time is 1 hour to
It is 12 hours, preferably 2 hours to 8 hours. After completion of heating and stirring, filtration, washing with methanol, and vacuum drying at 60 ° C. were carried out to obtain 700 mg of the brominated indium phthalocyanine crystal of the present invention.
Can be obtained. Examples of the ether-based solvent used in this treatment include tetrahydrofuran and dioxane. Examples of the ketone solvent include acetone and methyl ethyl ketone.

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 brominated 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 brominated 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 these, any organic pigment 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. It may be contained in an amount of 500% by weight or less based on the organic pigment, and the above-mentioned additive may be added to the phthalocyanine or the total amount thereof together with the organic pigment in an amount of 5
You may add by weight% or less. In addition, the charge transport layer,
The charge transporting substance described above may be contained, and the binder may be contained in an amount of 500% by weight or less based on the charge transporting substance. 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 less 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. When the thickness is less than 5 μm, the initial potential becomes low, and when it exceeds 50 μm, the sensitivity tends to be lowered.

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 brominated indium phthalocyanine of the present invention is applied by a spin coating method, a coating solution obtained by dissolving the brominated indium phthalocyanine in a halogenated solvent such as chloroform or toluene or a non-polar solvent is used to rotate at 3000 rpm. Spin coating at 7,000 rpm is preferable, and in the case of applying by a dipping method, brominated indium phthalocyanine is ball milled with an ultrasonic 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.

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 brominated indium phthalocyanine of the present invention is shown.

Production Example 1 1.0 g of monobromoindium 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 this was dissolved in ice water. Cooled pure water 1
It was added dropwise to 1 to reprecipitate monobromoindium phthalocyanine. After filtration, the precipitate was thoroughly washed with pure water and a mixed solution of methanol / pure water and dried at 110 ° C. to give amorphous monobromoindium phthalocyanine powder 0.85.
g was obtained (X-ray diffraction spectrum is shown as FIG. 2).
Then, this powder was put in 100 ml of tetrahydrofuran, heated and stirred at 80 ° C. for 5 hours, immediately filtered, washed with methanol and vacuum dried at 60 ° C. to obtain 0.59 g of crystals of monobromoindium phthalocyanine of the present invention. The X-ray diffraction spectrum of this crystal 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 monobromoindium phthalocyanine crystal of the present invention was produced according to Production Example 1 except that methyl ethyl ketone was used instead of tetrahydrofuran. The X-ray diffraction spectrum of this crystal is shown in FIG. The electron spectrum of a film prepared from this crystal and the poly (chlorotrifluoroethylene) oil is shown in FIG.

Production Example 3 Production Example 1 was repeated except that monobromoindium bromophthalocyanine synthesized according to the method described in JP-A-59-44054 was used in place of monobromoindium phthalocyanine. According to this, a crystal of monobromoindium bromophthalocyanine of the present invention was produced. 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 monobromoindium phthalocyanine compound produced in Production Example 1 and silicon resin KR-255 [trade name of Shin-Etsu Chemical Co., Ltd.] (solid content 50% by weight) 5.0 g
And 92.5 g of 1,2-dichloroethane were mixed, and this mixed solution was kneaded for 8 hours using a ball mill (3 inch pot mill manufactured by Nippon Kagaku Togaku KK). The obtained pigment dispersion is applied to an aluminum plate (conductive support 100
mm × 70 mm × 0.1 mm) and apply at 90 ° C for 1
After drying for 5 minutes, a charge generation layer having a thickness of 0.5 μm was formed.

5 g of 1-phenyl-3- (p-diethylaminostyryl) -5- (p-diethylaminophenyl) pyrazoline and polycarbonate resin Iupilon S-30
A coating solution obtained by dissolving 10 g of 00 (trade name of Mitsubishi Gas Chemical Co., Inc.) (100% by weight of solid content) in 85 g of a mixed solvent of 1: 1 (weight ratio) of methylene chloride and 1,1,1-trichloroethane was prepared. 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.

The photoreceptor was negatively charged by corona discharge of 5 KW using an electrostatic charging tester (Kawaguchi Denki 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 was used, the half-exposure amount (E _1/2 ) (the potential residual ratio was 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 9.3 V / se.
c, the surface potential after exposure 20 seconds (residual potential V _R) is -5V
Met.

Examples 2 to 3 Using the monobromoindium phthalocyanine compound produced in Production Example 2 or 3, a charge generation layer was formed in the same manner as in Example 1. 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.

[0046]

[Table 1]

Example A charge generation layer was formed in the same manner as in Example 1 using the monobromoindium phthalocyanine compound used in Examples 1 to 3, respectively. 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.

[0048]

[Table 2]

Comparative Example 1 Monobromoindium 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 deposition on an aluminum plate. 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 Instead of the monobromoindium phthalocyanine compound used in Comparative Example 1, a monobromoindium bromophthalocyanine compound synthesized according to the method described in JP-A-59-44054 was used. A charge generation layer was formed in the same manner as in. 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.

[0051]

The electrophotographic photosensitive member using the novel brominated indium phthalocyanine obtained by the manufacturing 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 monobromoindium phthalocyanine.

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

FIG. 3 is an X-ray diffraction spectrum of monobromoindium phthalocyanine treated with tetrahydrofuran.

FIG. 4 Electronic spectrum of monobromoindium phthalocyanine treated with tetrahydrofuran.

FIG. 5: X-ray diffraction spectrum of monobromoindium phthalocyanine treated with methyl ethyl ketone.

FIG. 6 is an electronic spectrum of monobromoindium phthalocyanine treated with methyl ethyl ketone.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mikio Itagaki 4-13-1, Higashi-cho, Hitachi-shi, Ibaraki Hitachi Chemical Co., Ltd. Ibaraki Laboratory

Claims (4)

[Claims] 1. An X-ray diffraction spectrum of CuKα has a Bragg angle (2θ ± 0.2 degrees) of 6.7 degrees, 7.4 degrees,
Brominated indium phthalocyanine having diffraction peaks at 13.5 degrees, 14.9 degrees, 15.9 degrees, 24.8 degrees and 26.2 degrees. 2. A Bragg angle (2θ ± 0.2 degrees) of 6 in an X-ray diffraction spectrum of CuKα, which is characterized by treating an amorphous brominated indium phthalocyanine with an ether solvent and / or a ketone solvent. ．
7 degrees, 7.4 degrees, 13.5 degrees, 14.9 degrees, 15.9 degrees
And a method for producing brominated indium phthalocyanine having diffraction peaks at 24.8 and 26.2 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 6.7 degrees, 7.4 degrees
An electrophotographic photosensitive member which is brominated indium phthalocyanine having diffraction peaks at 13.5, 14.9, 15.9, 24.8 and 26.2 degrees. 4. The electrophotographic photosensitive member according to claim 3, wherein the brominated indium phthalocyanine is monobromoindium phthalocyanine or monobromoindium bromophthalocyanine.