JPH05297617A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide good electrification property and high sensitivity by using a phthalocyanine compsn. having a specified spin density as an org. photoconductive material. CONSTITUTION:A photoconductive layer containing an org. photoconductive material is formed on a conductive substrate. This org. photoconductive material is a phthalocyanine compsn. having <=.0X10<18> spins/g spin density. If the spin density exceeds 7.0X10<18> spins/g or too small, the electrification property, dark decay, and sensitivity decrease. The phthalocyanine compsn. having <=7.0X10<18> spins/g spin density is preferably such a compsn. containing titanylphthalocyanine and metal halide phthalocyanine with tervalent center metal, considering the availability, electrification property, dark decay, sensitivity, etc., of the material. It is preferable that the phthalocyanine compsn. has main diffraction peaks at 7.5 deg. 22.5 deg., 24.3 deg., 25.3 deg. and 28.6 deg. Bragg angle in the CmuKalpha X-ray diffraction spectrum.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor.

[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 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 with phthalocyanines of the same central metal, there are specific crystal types. Several examples have been reported that have been selected for electrophotographic photoreceptors.

[0006] For example, various crystal forms of titanyl phthalocyanine exist, and due to the difference in the crystal forms, chargeability,
It has been reported that there are large differences in dark decay, sensitivity, etc.

Japanese Patent Application Laid-Open No. 59-49544 discloses that the crystal form of titanyl phthalocyanine is Bragg angle (2
θ ± 0.2 degrees) is 9.2 degrees, 13.1 degrees, 20.7 degrees,
Those which give a strong diffraction peak at 26.2 degrees and 27.1 degrees are described as being suitable, and an X-ray diffraction spectrum diagram is shown.

Further, in JP-A-59-166959, a vapor-deposited film of titanyl phthalocyanine is allowed to stand in saturated steam of tetrahydrofuran for 1 to 24 hours to change its crystal form to form a charge generation layer. The X-ray diffraction spectrum has a small number of peaks and a wide width, and the Bragg angle (2θ) is 7.5 degrees, 12.6 degrees, 13.0 degrees, 25.
It has been shown to give strong diffraction peaks at 4 degrees, 26.2 degrees and 28.6 degrees.

Further, in Japanese Patent Application Laid-Open No. 64-17066, the Bragg angle (2
at least 9.5 degrees,
9.7 degrees, 11.7 degrees, 15.0 degrees, 23.5 degrees, 2
Those with 4.1 degrees and 27.3 degrees are said to be preferred.

In JP-A-2-131243 and JP-A-2-214867, it is described that the crystal form of titanyl phthalocyanine is preferably one having a main diffraction peak at a Bragg angle of 27.3 degrees. There is.

As described above, titanyl phthalocyanine has extremely high sensitivity depending on the crystal form and exhibits excellent electrophotographic characteristics. However, in applications such as laser printers, high image quality and high definition have been advanced, and electrophotographic photoreceptors having higher sensitivity characteristics are required.

[0012]

SUMMARY OF THE INVENTION The present invention provides an electrophotographic photosensitive member having good chargeability and high sensitivity.

[0013]

The present invention provides an electrophotographic photoreceptor having a photoconductive layer containing an organic photoconductive substance on a conductive substrate, wherein the organic photoconductive substance has a spin concentration of 7. The present invention relates to an electrophotographic photosensitive member which is a phthalocyanine composition having a spin rate of 0 × 10 ¹⁸ spins / g or less.

The present invention will be described in detail below. The conductive base material used in the present invention is not particularly limited as long as it has conductivity, for example, conductive treated paper or plastic film, plastic film laminated metal foil such as aluminum, a metal plate, etc. Can be mentioned. The shape of the conductive substrate is not particularly limited, for example, a sheet shape,
Examples thereof include a belt shape and a cylindrical shape.

The organic photoconductive substance in the present invention needs to be a phthalocyanine composition having a spin concentration of 7.0 × 10 ¹⁸ spins / g or less. The lower limit of spin concentration is usually 1.0 × 10 ¹⁴ spins / g. The spin concentration is preferably 5.0 × 10 ^{14 to} 7.0 × 10 ¹⁸ spins / g, and 1.0 × 10 ^{15 to} 1.0 × 10 ¹⁷
Spins / g is more preferable, 5.0 × 10
It is particularly preferable that the spin rate is ^{15 to} 1.0 × 10 ¹⁶ spins / g. If the spin concentration exceeds 7.0 × 10 ¹⁸ spins / g or is too small, the charging property, dark decay, sensitivity, etc. are poor. The spin concentration can be known by measuring the ESR spectrum of the sample. For example, the ESR spectrum can be measured using an electron spin resonance spectrometer (JES-RE2X type manufactured by JEOL Ltd.) and calculated by an automatic analysis system (ES-PRIT330 manufactured by JEOL Ltd.). To obtain a phthalocyanine composition having a desired spin concentration, adjustment conditions of the phthalocyanine composition (raw material, amorphization, washing,
It can be easily performed by changing the solvent treatment, etc.).

The above-mentioned phthalocyanine composition having a spin concentration of 7.0 × 10 ¹⁸ spins / g or less is a trivalent titanyl phthalocyanine and a central metal in view of availability, chargeability, dark decay, sensitivity and the like. It is preferable that the composition contains the halogenated metal phthalocyanine.

The above-mentioned phthalocyanine composition having a spin concentration of 7.0 × 10 ¹⁸ spins / g or less is used in the X-ray diffraction spectrum of CuKα in terms of availability, chargeability, dark decay and sensitivity. Angle (2θ ± 0.2 degrees)
Is preferably a phthalocyanine composition having major diffraction peaks at 7.5 degrees, 22.5 degrees, 24.3 degrees, 25.3 degrees and 28.6 degrees.

The titanyl phthalocyanine used in the present invention can be obtained, for example, according to the description in JP-A-3-71144, and can be produced as follows. Phthalonitrile 18.4 g (0.144 mol)
Was added to 120 ml of α-chloronaphthalene, and then 4 ml of titanium tetrachloride (0.0364 mol) was added dropwise under a nitrogen atmosphere. After dropping, the temperature is raised and the mixture is stirred at 200 to 220.
After reacting at ℃ for 3 hours, hot filtration at 100 to 130 ℃, washed with α-chloronaphthalene, methanol.
Hydrolysis (90 ° C., 1 hour) is performed with 140 ml of ion-exchanged water, and this operation is repeated until the solution becomes neutral, followed by washing with methanol. Next, 200 ml of N-
A hot suspension washing treatment (100 ° C., 1 hour) is performed three times with methyl-2-pyrrolidone, and washing is performed with methanol. The compound thus obtained is dried by heating under vacuum at 60 ° C. to obtain titanyl phthalocyanine (yield 46%).

In the halogenated metal phthalocyanine compound having a trivalent central metal used in the present invention, examples of the trivalent metal as a central metal include In, Ga and Al.
Examples of halogen include Cl and Br, and the phthalocyanine ring may have a substituent such as halogen. Although the compound is a known compound, among these,
For example, monohalogenated metal phthalocyanines and methods for synthesizing monohalogenated metal phthalocyanines are described in Inorganic Chemistry [Inorganic Chemistry].
Chemistry, 19 , 3131 (1980)],
It is described in JP-A-59-44054.

The monohalogen metal phthalocyanine can be produced, for example, as follows. 78.2 mmol phthalonitrile and 15.8 metal trihalides
The millimole was added twice to 100 ml of deoxygenated quinoline, heated under reflux for 0.5 to 3 hours, then slowly cooled, and then cooled to 0.
After cooling to ℃, filtered, the crystals were methanol, toluene,
Then, after washing with acetone, it is dried at 110 ° C.

The monohalogen metal halogen phthalocyanine can be manufactured as follows. 156 mmol of phthalonitrile and metal trihalide 3
7.5 mmol was mixed and melted at 300 ° C. and heated for 0.5 to 3 hours to obtain a monohalogen metal halogen phthalocyanine composition, which was washed with α-chloronaphthalene using a Soxhlet extractor. To do.

In the present invention, when the phthalocyanine composition contains titanyl phthalocyanine and the central metal is a trivalent metal halide phthalocyanine, the composition ratio of both is titanyl from the viewpoint of electrophotographic characteristics such as chargeability, dark decay and sensitivity. The phthalocyanine content is preferably 20 to 95% by weight, more preferably 50 to 90% by weight, particularly preferably 65 to 90% by weight, and 75 to 90% by weight. The range is most preferable.

A phthalocyanine mixture composed of titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent can be made amorphous by the acid paste method. For example, 1 g of the phthalocyanine mixture is dissolved in 50 ml of concentrated sulfuric acid, and this is dropped into 1 liter of ion-exchanged water cooled with ice water and reprecipitated. After filtration, the precipitate is thoroughly washed with pure water and then with a mixed solution of methanol / pure water, and then dried at 110 ° C. to obtain a powder of a phthalocyanine composition. The X-ray diffraction spectrum of the phthalocyanine composition thus obtained has no clear sharp peak and becomes a spectrum showing a wide amorphous state.
As a method for forming an amorphous state, there is a method by dry milling other than the acid paste method using concentrated sulfuric acid.

The phthalocyanine composition thus obtained can be crystal-transformed by treating it with an organic solvent to obtain a phthalocyanine composition having a specific spin concentration according to the present invention. For example, 1 g of the powder of the phthalocyanine composition obtained by the above method is used as an organic solvent for N-methyl-2-pyrrolidone, toluene or xylene 10 m.
and heat and stir (the above powder / solvent (weight ratio) is
1/1 to 1/100). Heating temperature is 50 ℃ ~ 20
The temperature is 0 ° C., preferably 80 ° C. to 150 ° C., and the heating time is 1 hour to 10 hours, preferably 1 hour to 6 hours.
After completion of heating and stirring, filtration, washing with methanol, vacuum heating and drying at 60 ° C., and crystal 700 of the phthalocyanine composition of the present invention
mg can be obtained. Examples of the organic solvent used in this treatment include alcohols such as methanol, ethanol, isopropanol and butanol, alicyclic hydrocarbons such as n-hexane, octane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. , Ethers such as tetrahydrofuran, dioxane, diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, acetate cellosolve, acetone, methyl ethyl ketone, cyclohexanone, ketones such as isophorone, methyl acetate, esters such as ethyl acetate, dimethyl sulfoxide, dimethyl Formamide, phenol, cresol, anisole, nitrobenzene, acetophenone, benzyl alcohol, pyridine, N-methyl-2-pyrrolidone, quinoline Chlorine-free organic solvent picoline, dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, carbon tetrachloride, chloroform, chloromethyl oxirane, chlorobenzene, such as chlorine-based organic solvents such as dichlorobenzene and the like. Of these, ketones and non-chlorine organic solvents are preferable, and among them, N-methyl-2-pyrrolidone, pyridine, methyl ethyl ketone and diethyl ketone are preferable.

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 composed of a film of an organic photoconductive substance, 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 phthalocyanine composition is used as an essential component, and known substances can be used in combination. From the viewpoints of charging property, sensitivity, etc., it is preferable to use an organic pigment and / or a charge-transporting substance which generate an electric charge in the phthalocyanine composition as an organic photoconductive substance. The charge generating layer contains the phthalocyanine composition and / or an organic pigment that generates a charge, and the charge transporting layer contains a charge transporting substance.

The organic pigments which generate the above-mentioned charges include azoxybenzene type, disazo type, trisazo type, benzimidazole type, polycyclic quinone type, indigoid type, quinacridone type, perylene type, methine type, α type and β type. , Γ
It is possible to use pigments known to generate electric charges, such as metal-free or metal-type phthalocyanine-based pigments having various crystal structures such as γ-type, δ-type, ε-type, and χ-type. 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-
It is disclosed in JP-A-44028, JP-A-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, etc., and low molecular compounds include fluorenone, fluorene, 2,7-dinitro-9-fluorenone, 4H-indeno (1,2,6).
Thiofen-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) pyrazolin, 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)
Examples include -1,3-oxazole, imidazole, chrysene, tetraphene, aclidene, triphenylamine, benzidine, and their derivatives. As the charge-transporting substance, a benzidine derivative represented by the following general formula [I] is particularly preferable.

[Chemical 1] (R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, and two R ₃ are each independently a hydrogen atom. Or an alkyl group, Ar ₁ and Ar ₂ each independently represent an aryl group, and k, l, m and n are each independently 0.
~ Represents an integer of 5)

In the general formula [I], examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group and a tert-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group and an iso-propoxy group. As the aryl group, a phenyl group, a tolyl group,
Biphenyl group, terphenyl group, naphthyl group and the like can be mentioned. Examples of the fluoroalkyl group include a trifluoromethyl group, a trifluoroethyl group, a heptafluoropropyl group and the like. As the fluoroorcoxy group, trifluoromethoxy group, 2,3-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 1H, 1H
-Pentafluoropropoxy group, hexafluoro-is
Examples thereof include fluoroalkoxy groups such as o-propoxy group, 1H, 1H-pentafluorobutoxy group, 2,2,3,4,4,4-hexafluorobutoxy group and 4,4,4-trifluorobutoxy group. Specific examples of the benzidine derivative represented by the general formula [I] are shown below. 1 to N
o. Compound 6 is shown.

[0030]

[Chemical 2]

The above-mentioned phthalocyanine composition and an organic pigment which generates an electric charge used as necessary (both are the former)
And a charge-transporting substance (the latter) are used as a mixture (when forming a single-layer photoconductive layer), the latter / the former is in a weight ratio of 10/1 to 2/1. It is preferable to mix them. At this time, the binder is 0 to 500% by weight, particularly 30 to 500% by weight based on the total amount of these compounds (the former + the latter).
It is preferably used in the range of wt%. 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 type photoconductive layer comprising a charge generating layer and a charge transporting layer is formed, the charge generating layer contains the above-mentioned phthalocyanine composition and, if necessary, an organic pigment which generates a charge, The agent may be contained in an amount of 500% by weight or less based on the total amount of the phthalocyanine composition and the organic pigment, and the above-mentioned additive is contained in an amount of 5% by weight or less based on the total amount of the phthalocyanine composition and the organic pigment. May be added in. Further, the charge transport layer may contain the above-mentioned charge transport material, and further may contain a binder 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.

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 or a photocurable resin which is 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 film in a normal state and a resin which is cured by heat and / or light to form a coating film.

Examples of the plasticizer as the above additive include halogenated paraffin, dimethylnaphthalene, dibutyl phthalate, and the like, and as the fluidity-imparting agent, Modaflow (manufactured by Monsanto Chemical Co., Ltd.), Acronal 4F (manufactured by Basuf Co.), etc. As the pinhole inhibitor,
Examples thereof include benzoin and dimethyl phthalate. These may be appropriately selected and used, and the amount thereof may be appropriately determined.

The electrophotographic photoreceptor of the present invention comprises a photoconductive layer formed on a conductive substrate. The thickness of the photoconductive layer is preferably 5 to 50 μm. 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
The thickness is 5 μm. 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 characteristics tend to deteriorate. The thickness of the charge transport layer is preferably 5 to 50 μm, particularly preferably 8 to
It is 25 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 substrate on a conductive substrate, a method of depositing an organic photoconductive substance on the conductive substrate,
Homogeneous organic photoconductive substance and other components as necessary in aromatic solvents such as toluene and xylene, halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, alcohol solvents such as methanol, ethanol and propanol. There is a method in which it is dissolved or dispersed in, and applied on a conductive substrate, and then dried. 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 phthalocyanine composition of the present invention is applied by the spin coating method, a coating solution obtained by dissolving the phthalocyanine composition in a halogenated solvent such as chloroform or toluene or a non-polar solvent is used and the number of revolutions is 500 to 4
Spin coating at 000 rpm is preferable, and in the case of applying by a dipping method, the phthalocyanine composition is subjected to a ball solvent, an ultrasonic wave or the like 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 that has been dispersed.

The electrophotographic photosensitive member according to the present invention may further have a thin adhesive layer or a barrier layer directly on the conductive base material, or may have a protective layer on the surface.

[0040]

EXAMPLES The present invention will be described in detail below with reference to examples.

Production Example 1 1 g of a phthalocyanine mixture consisting of 0.75 g of titanyl phthalocyanine and 0.25 g of indium phthalocyanine chloride was dissolved in 50 ml of sulfuric acid and stirred at room temperature for 30 minutes,
About 1 liter of deionized water cooled with ice water
It was dripped at 0 minutes and reprecipitated. After stirring for 1 hour under cooling, the mixture was left standing overnight. After removing the supernatant liquid by decantation, a precipitate was obtained by centrifugation. This precipitate was washed 6 times with ion-exchanged water. The pH and conductivity of the wash water after washing 6 times were measured. Model PH51 manufactured by Yokogawa Electric Corporation was used for the measurement of pH. Further, the conductivity was measured using a model SC-17A manufactured by Shibata Scientific Instruments Co., Ltd. The pH of the wash water is 3.3 and the conductivity is 65.1 μS /
It was cm. Then, after washing 3 times with methanol, 6
It was vacuum dried at 0 ° C. for 4 hours. Then 1g of this product
Was placed in 10 ml of N-methyl-2-pyrrolidone, heated and stirred (150 ° C., 1 hour), filtered, washed with methanol, and vacuum-dried at 60 ° C. for 4 hours to obtain crystals of the phthalocyanine composition of the present invention. It was The X-ray diffraction spectrum of this crystal is shown in FIG.

Evaluation 0.6 mg of the phthalocyanine composition produced in Production Example 1 was placed in a quartz ESR measuring tube and the ESR spectrum was measured using an electron spin resonance spectrometer (JES-RE2X type, manufactured by JEOL Ltd.). The microwave frequency was 9.21 GHz, the intensity was 4 mW, and the magnetic field was 3281 ± 50 G. The magnetic field calibration was performed with a standard sample of Mn (II). For the spin concentration, a temporum (1 × 10 ⁻⁶ M) was used as a standard sample, and an automatic analysis system (ES-PRIT330) manufactured by JEOL Ltd.
I asked. The results are shown in Table 1.

Production Example 2, 3 Heating time in N-methyl-2-pyrrolidone was 3 hours,
A phthalocyanine composition was produced in exactly the same manner as in Production Example 1 except that the time was changed to 6 hours. The spin concentration of the phthalocyanine composition was determined by the same method as described in the evaluation, and the results are shown in Table 1.

Comparative Production Examples 1-3 A phthalocyanine composition was produced in exactly the same manner as in Production Example 1 except that the heating time in N-methyl-2-pyrrolidone was changed to 12 hours, 18 hours and 24 hours, respectively. did. The spin concentration of the phthalocyanine composition was determined by the same method as described in the evaluation, and the results are shown in Table 1. After heating in N-methyl-2-pyrrolidone for 24 hours, the X-ray diffraction spectrum of the obtained crystal is shown as FIG.

[0045]

[Table 1]

Production Examples 4 to 6 In Production Examples 1 to 3, indium phthalocyanine bromide was used instead of indium phthalocyanine chloride, and toluene (110 ° C., 1 ° C. was used instead of N-methyl-2-pyrrolidone).
Crystals of the phthalocyanine composition were obtained according to Production Examples 1 to 3 except that the time was 3 hours, 6 hours). The spin concentration of the phthalocyanine composition was determined by the same method as described in the evaluation, and the results are shown in Table 2.

Comparative Production Examples 4 to 6 In Comparative Production Examples 1 to 3, indium phthalocyanine bromide and N- were used instead of indium phthalocyanine chloride.
Instead of methyl-2-pyrrolidone, toluene (110
Crystals of the phthalocyanine composition were obtained according to Comparative Production Examples 1 to 3 except that (C, 12 hours, 18 hours, 24 hours) was used. The spin concentration of the phthalocyanine composition was determined by the same method as described in the evaluation, and the results are shown in Table 2.

[0048]

[Table 2]

Production Examples 7 to 9 In Production Examples 1 to 3, gallium phthalocyanine chloride was used instead of indium phthalocyanine chloride, and xylene (120 ° C., 1 hour, 3 hours, 6 hours) was used instead of N-methyl-2-pyrrolidone. Crystals of a phthalocyanine composition were obtained according to Production Examples 1 to 3 except that the phthalocyanine composition was used. The spin concentration of the phthalocyanine composition was obtained by the same method as described in the evaluation, and the results are shown in Table 3.

Comparative Production Examples 7 to 9 In Comparative Production Examples 1 to 3, gallium phthalocyanine chloride was used instead of indium phthalocyanine chloride, and xylene (120 ° C., instead of N-methyl-2-pyrrolidone).
Crystals of a phthalocyanine composition were obtained according to Comparative Production Examples 1 to 3 except that 12 hours, 18 hours, and 24 hours) were used. The spin concentration of the phthalocyanine composition was obtained by the same method as described in the evaluation, and the results are shown in Table 3.

[0051]

[Table 3]

Production Examples 10 to 12 In Production Examples 1 to 3, aluminum chloride phthalocyanine was used instead of indium phthalocyanine chloride, and tetralin (150) was used instead of N-methyl-2-pyrrolidone.
C., 1 hour, 3 hours, 6 hours)
Crystals of the phthalocyanine composition were obtained in accordance with The spin concentration of the phthalocyanine composition was obtained by the same method as described in the evaluation, and the results are shown in Table 4.

Comparative Production Examples 10 to 12 In Comparative Production Examples 1 to 3, aluminum chloride phthalocyanine and N were substituted for indium phthalocyanine chloride.
-Tetralin (15 instead of methyl-2-pyrrolidone
Crystals of a phthalocyanine composition were obtained according to Comparative Production Examples 1 to 3 except that 0 ° C., 12 hours, 18 hours, and 24 hours) were used. The spin concentration of the phthalocyanine composition was obtained by the same method as described in the evaluation, and the results are shown in Table 4.

[0054]

[Table 4]

Example 1 1.5 g of the phthalocyanine composition produced in Production Example 1, 1 g of silicon resin KR-255 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 98 g of 1,2-dichloroethane were mixed and dispersed by a ball mill. An aluminum plate (conductive substrate 100 mm x 100 mm x 0.1 mm) was obtained by dipping the obtained dispersion liquid.
Coated on top and dried at 140 ° C for 1 hour to a thickness of 0.5 μm
The charge generation layer of was formed. The above No. No. 4 charge-transporting substance 1.5 g, polycarbonate resin Iupilon S-3
5,000 (manufactured by Mitsubishi Gas Chemical Co., Inc.) and 15.5 g of methylene chloride were mixed to obtain a coating liquid, which was coated on the substrate by a dipping method and dried at 120 ° C. for 1 hour to give a thickness of 20.
A μm charge transport layer was formed. The electrophotographic characteristics of this electrophotographic photosensitive member were measured by an electrostatic copying paper test apparatus (Kawaguchi Electric Co., model SP-428). Initial charging Vo (-) 10 seconds after charging by corona discharge of -5 kV in the dark
V), dark decay DDR (%) after 30 seconds, and sensitivity E1 / 2 (lux · sec) when exposed to white light with an illuminance of 2lux
I asked. As a result, V ₀ = 640 (−V), DDR = 6
It was 8.5 (%) and E1 / 2 = 0.7 (lux · sec).

Examples 2 and 3 An electrophotographic photosensitive member was produced and evaluated according to Example 1 except that the titanyl phthalocyanine composition obtained in Production Examples 2 and 3 was used. The results are shown in Table 1.

Comparative Examples 1 to 3 Electrophotographic photosensitive members were produced and evaluated according to Example 1 except that the titanyl phthalocyanine composition obtained in Comparative Production Examples 1 to 3 was used. The results are shown in Table 1.

Examples 4 to 6 The titanyl phthalocyanine compositions obtained in Production Examples 4 to 6 in Example 1 were used, and N was used as the charge transport material.
o. Instead of the compound of No. 4, Electrophotographic photoreceptors were manufactured and evaluated according to Examples 1 to 3 except that 2 was used. The results are shown in Table 2.

Comparative Examples 4 to 6 The titanyl phthalocyanine compositions obtained in Comparative Production Examples 4 to 6 in Example 1 were used, and No. 1 was used as the charge transport material. Instead of the compound of No. 4, An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that 2 was used. The results are shown in Table 2.

Examples 7 to 9 The titanyl phthalocyanine compositions obtained in Production Examples 7 to 9 in Example 1 were used, and N was used as the charge transport material.
o. Instead of the compound of No. 4, Electrophotographic photoreceptors were manufactured and evaluated according to Examples 1 to 3 except that 1 was used. The results are shown in Table 3.

Comparative Examples 7 to 9 The titanyl phthalocyanine compositions obtained in Comparative Production Examples 7 to 9 in Example 1 were used, and No. 1 was used as the charge transport material. Instead of the compound of No. 4, An electrophotographic photosensitive member was produced and evaluated according to Example 1 except that 1 was used. The results are shown in Table 3.

Examples 10 to 12 The titanyl phthalocyanine compositions obtained in Production Examples 10 to 12 in Example 1 were used, and No. 1 was used as the charge transport material. Instead of the compound of No. 4, Electrophotographic photoreceptors were produced and evaluated according to Examples 1 to 3 except that 5 was used. The results are shown in Table 4.

Comparative Examples 10 to 12 The titanyl phthalocyanine compositions obtained in Comparative Production Examples 10 to 12 in Example 1 were used, and No. 1 was used as the charge transport material. Instead of the compound of No. 4, An electrophotographic photosensitive member was produced and evaluated according to Example 1 except that No. 5 was used. The results are shown in Table 4.

[0064]

The electrophotographic photosensitive member according to the present invention has excellent electrophotographic characteristics such as chargeability, dark decay and sensitivity, and is suitable for electrophotographic processes requiring higher density and higher image quality than ever before. Can be applied to.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction spectrum of a phthalocyanine composition treated with N-methyl-2-pyrrolidone for 1 hour.

FIG. 2 is an X-ray diffraction spectrum of a phthalocyanine composition treated with N-methyl-2-pyrrolidone for 24 hours.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Megumi Matsui, 4-13-1, Higashimachi, Hitachi, Ibaraki Prefecture, Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Takayuki Akimoto, 4-13, Higashimachi, Hitachi, Ibaraki No. 1 Hitachi Chemical Co., Ltd. Ibaraki Research Center

Claims (3)

[Claims] 1. An electrophotographic photosensitive member having a photoconductive layer containing an organic photoconductive substance on a conductive substrate, wherein the organic photoconductive substance has a spin concentration of 7.0 × 10 ¹⁸ spins /
An electrophotographic photosensitive member which is a phthalocyanine composition having an amount of g or less. 2. The electrophotographic photoreceptor according to claim 1, wherein the phthalocyanine composition is a composition containing titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent. 3. The Bragg angle (2θ ± 0.2) in the X-ray diffraction spectrum of CuKα, wherein the phthalocyanine composition is
The electrophotographic photosensitive member according to claim 1, which is a phthalocyanine composition having major diffraction peaks at 7.5 degrees, 22.5 degrees, 24.3 degrees, 25.3 degrees, and 28.6 degrees.