JPS62103652A - Electrophotographic sensitive material - Google Patents

Abstract

PURPOSE:To form an electrophotographic sensitive body capable of stably maintaining hysteresis condition of potential without causing increase in the residual potential even if the photosensitive body is used repeatedly by incorporating a phthalocyanine compd. in the carrier material and a specified hydrazone compd. in the carrier transporting material. CONSTITUTION:The carrier generating material contains a metal phthalocyanine compd. and/or a nonmetal phthalocyanine compd., and the carrier transporting material contains at least one hydrazone compd. expressed by the formulas [I] and [II]. In the formula [I], R<1> is a substituted or unsubstituted aryl group, etc.; R<2> is H atom, etc.; X<1> is H atom, etc.; p is an integer 0 or 1. In the formula [II], R<3> is a substituted or unsubstituted aryl, etc.; R<4> is H atom, etc.: X<2> is H atom, etc.; q is an integer 0 or 1. Specific examples for the carrier transporting material expressed by the formulas [I] and [II] are given by the formulas (I-1), and (II-1).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an electrophotographic photoreceptor, which exhibits high sensitivity to light with wavelengths longer than visible light and semiconductor laser light used in printers, copiers, etc. This relates to photoreceptors.

BACKGROUND OF THE INVENTION Conventionally, electrophotographic photoreceptors having high sensitivity to visible light have been widely used in copying machines, printers, and the like.

As such electrophotographic photoreceptors, inorganic photoreceptors provided with a photosensitive layer mainly composed of an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium sulfide are widely used. However, such inorganic photoreceptors do not necessarily satisfy the characteristics such as photosensitivity, thermal stability, moisture resistance, and durability required of electrophotographic photoreceptors for copying machines and the like.

For example, since selenium crystallizes due to heat or fingerprint stains when touched, the above-mentioned characteristics as an electrophotographic photoreceptor tend to deteriorate. Further, electrophotographic photoreceptors using cadmium sulfide have poor moisture resistance and durability, and electrophotographic photoreceptors using zinc oxide have problems in durability. Further, electrophotographic photoreceptors made of selenium or cadmium sulfide have the disadvantage that there are significant restrictions in manufacturing and handling.

In order to improve these problems with inorganic photoconductive materials, attempts have been made to use various organic photoconductive materials in the photosensitive layer of electrophotographic photoreceptors, and active research and development has been conducted in recent years. For example, in Japanese Patent Publication No. 50-10496, poly-N-vinylcarbazole and 2.4.7-)
An organic photoreceptor is described having a photosensitive layer containing limtro-9-fluorenone. However, this photoreceptor also lacks sufficient sensitivity and durability. Therefore, the photosensitive layer was divided into two layers, a carrier generation layer and a carrier transport layer were constructed separately, and each contained a carrier generation substance and a carrier transport substance. A functionally separated electrophotographic photoreceptor has been developed. This is because the carrier generation function and the carrier transport function can be assigned to different substances, and the substances that exhibit each function can be selected from a wide range of materials. It is expected that organic photoreceptors with high sensitivity and durability can be obtained relatively easily.

Many substances have been proposed as carrier-generating substances effective for the carrier-generating layer of such functionally separated electrophotographic photoreceptors. An example of using an inorganic substance is amorphous selenium, as described in Japanese Patent Publication No. 43-16198. This carrier generation layer containing amorphous selenium is used in combination with a carrier transport layer containing an organic carrier transport material. However, as described above, this carrier generation layer made of amorphous selenium has the problem that it is crystallized by heat or the like and its properties deteriorate. Furthermore, examples of using an organic substance as the carrier generating substance include organic dyes and organic pigments. For example, as having a photosensitive layer containing a bisazo compound, JP-A No. 47-37543,
JP-A-55-22834, JP-A-54-7963
This method is already known from Publication No. 2, Japanese Unexamined Patent Publication No. 116040/1980, and the like.

However, although these known bisazo compounds exhibit relatively good sensitivity in the short or medium wavelength range, their sensitivity in the long wavelength range is low, making them difficult to use in laser printers that use semiconductor laser light sources, which are expected to be highly reliable. That was difficult.

Gallium-aluminum-arsenic (Ga-Aj2.As) light-emitting elements, which are currently widely used as semiconductor lasers, have an oscillation wavelength of about 750 nm or more. Many studies have been made in the past in order to obtain electrophotographic photoreceptors that are highly sensitive to such long wavelength light. For example, it has been considered to add an exacerbating agent to photosensitive materials such as Se and CdS, which have high sensitivity in the visible light region, to extend the wavelength to longer wavelengths, but Se and CdS are sensitive to temperature, humidity, etc. environmental resistance is insufficient. Furthermore, as mentioned above, the sensitivity of many known organic photoconductive materials is usually 70.
The sensitivity is limited to the visible light region of 0 nm or less, and there are few materials that have sufficient sensitivity to wavelengths longer than this.

Among these, phthalocyanine compounds, which are one of the organic photoconductive materials, are known to have a photosensitive range extended to longer wavelength regions than other compounds. Various crystalline forms of phthalocyanine compounds have been discovered in the process of converting α-type phthalocyanine compounds into stable crystalline β-type phthalocyanine compounds. Examples of these phthalocyanine compounds exhibiting photoconductivity include those described in Japanese Patent Publication No. 49-433
X-type metal-free phthalocyanine compound described in Publication No. 8 and JP-A-58-182639, JP-A-60-1915
Examples include τ, τ′, η, η” type metal-free phthalocyanine compounds described in Publication No. 1.

By the way, in general, in photoreceptors, a carrier transporting substance that is effective against a certain carrier-generating substance is not necessarily effective against other carrier-generating substances; It cannot be said that an effective carrier-generating substance is also effective against other carrier-transporting substances. After all, in order to be used in an electrophotographic photoreceptor, a suitable combination of carrier-generating and carrier-transporting substances is required, and if this combination is inappropriate, the sensitivity of the electrophotographic photoreceptor will be affected. Not only does this reduce the discharge efficiency, especially at low electric fields, the so-called residual potential increases, and in the worst case, if this electrophotographic photoreceptor is used in a copying machine, for example, it may be used repeatedly. Charges accumulate each time the toner is used, and as a result, toner may also adhere to non-image areas, causing background smudges on the copy or making it impossible to obtain a clear copy image.

Although there are some rules regarding suitable combinations of carrier-generating substances and carrier-transporting substances, they do not apply to all substances, and in fact, there are currently no rules that apply to suitable combinations of carrier-generating substances and carrier-transporting substances. Experimental selection of suitable combinations has been carried out, and it is unclear which combination should be selected as the most suitable carrier transport substance when using the above phthalocyanine compounds or other phthalocyanine compounds as carrier generating substances. It wasn't known.

Problems to be Solved by the Invention As mentioned above, it has been known that phthalocyanine compounds have high sensitivity to light in the long wavelength range.
In order to use this as an electrophotographic photoreceptor, it is not known what to use as a carrier transporting substance, and it has been desired to improve this problem.

Therefore, the first object of the present invention is to prevent the residual potential from increasing even during repeated use by using a carrier transporting material that is optimal for using a phthalocyanine compound as a carrier generating material. An object of the present invention is to provide an electrophotographic photoreceptor whose potential history state is stably maintained.

A second object of the present invention is to be stable to heat and light;
The present invention provides an electrophotographic photoreceptor having high sensitivity to long wavelength light and semiconductor laser light.

Means for Solving the Problems In order to solve the above problems, the present invention provides an electrophotographic photoreceptor having a photoreceptor layer containing a carrier-generating substance and a carrier-transporting substance, in which the carrier-generating substance is a metal phthalocyanine compound and a metal phthalocyanine compound. / or contains a metal-free phthalocyanine compound, and the carrier transport substance has the following general formula [7]
The present invention provides an electrophotographic photoreceptor comprising at least one hydrazone compound represented by (U).

General formula CI) (However, in this general formula, R1 is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, R2 is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted (xl is a hydrogen atom, a halogen atom, an alkyl group, a substituted amino group, an alkoxy group, or a cyano group, p is an integer of 0 or l) General formula (n) (However, this In the general formula, R3 is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, R" is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, Xt represents a hydrogen atom, a halogen atom, an alkyl group, a substituted amino group, an alkoxy group, or a cyano group, and q represents an integer of 0 or 1.) Next, the present invention will be explained in detail.

The phthalocyanine compound used in the present invention can be a metal-free phthalocyanine compound or a metal phthalocyanine compound, or both can be used in combination, and in each of these, one or more phthalocyanines belonging to each of metal and metal-free phthalocyanines can be used. These phthalocyanines include, for example, α, β, T1 τ, τ′,
Examples include η, η', X-type metal-free phthalocyanine compounds, and ε-type phthalocyanine compounds. Among these, metal-free phthalocyanine compounds are characterized by excellent sensitivity and charging stability. Table 1 shows some characteristic values of the 7 talocyanine compounds in focus.

(Hereinafter, the margin of this page) These metal-free phthalocyanine compounds were
Publication No. 9-4338, Japanese Unexamined Patent Publication No. 1988-19154,
It is described in detail in Japanese Unexamined Patent Publication No. 182639/1983.

Also, as shown in Figure 1, the Bragg angle (error 2θ±0.2 degrees) for CuK α 1.541 person's X-rays is 7.7.9.3.16.9.17, 6.22, 4 .28
．． It has an Xb% diffraction spectrum having a main peak at 8, and the intensity ratio of the peak at Bragg angle 16.9 to the peak at Bragg angle 9.3 is 0.8 to 1.0, and the intensity ratio of the peak at Bragg angle 16.9 is 0.8 to 1.0. The intensity ratio of the peaks at Bragg angles of 22.4 and 28.8 to the peak at Bragg angles of .3 is 0.4 or more, and as shown in Figure 2, the infrared absorption spectrum is between 700 and 760 cm to 72
0 ±2cIn fence is the strongest four absorption bands, 1320±
Those having characteristic absorption at 2CI+1-' and 3288±3 cm-' and having maximum visible and near-infrared absorption spectra in the range of 770 nm or more to 790 nm, as shown in FIG. 3, can be preferably used. This metal-free phthalocyanine compound is stable in its crystal form and can be immersed in organic solvents such as acetone, tetrahydrofuran, toluene, ethyl acetate, 1,2-dichloroethane, left at 200°C for 50 hours, or even milled. It is preferable because it is difficult to undergo transformation of its crystalline form even when a mechanical strain force such as the like is applied thereto, and it also has excellent potential stability etc. for repeated use of the photoreceptor. This is described in detail in the specification of the patent application dated August 26, 1985.

Metal phthalocyanine compound and/or used in the present invention
Alternatively, carrier generating substances that can be used in combination with metal-free phthalocyanine compounds include azo pigments, anthraquinone pigments,
Examples include perylene pigments, polycyclic quinone pigments, and methine squaric acid pigments.

Specific examples of these will be described later.

In the present invention, at least one of the carrier transport substances represented by the general formulas CI) and (II) is used in combination with the metal phthalocyanine compound and/or metal-free phthalocyanine compound, and specific examples include the following: Things can be mentioned.

(Margin below this page) (I-6) CJ UU
UCH.

(I-21) (r-22) (r-23) (l-24) CH5 (I-28) 〇Sui OCR.

U
0(I-38) CH(T-43) (T-44) Furthermore, as specific examples of the hydrazone compound represented by the above general formula [E], those having the following structural formula may be mentioned. Yes, but not limited to these.

(I[-2) CH.

(I[-4) OCH.

(■-5) C revision 5 (n-6) ([-7) (■-8) (n-9) (IF, -10) (II-11) (I-19) (II-20) (■-21) (I[-22) (n-23) (n-24) ■ CH.

++/
-ノ (■-28) (n-29) tJuMwou (JOO (II-33) (II-35) (■-37) CU-38) (IF -39) (II-40) (n-41 ) (n-42) "C!Hr The above-mentioned metal phthalocyanine compounds and/or are mentioned.

(I R'It"R'R"-NgoN-
A [However, in this formula, Ar I, Arz and Ar uni are each substituted or contributed 1 negative carbocyclic aromatic ring group, R', R', R and R3: respectively, at least one of R5-R8 is an electron-withdrawing group such as a cyano group, X X A' (X is a hydroxy group, -NHSO□-R), R10 and R'' are each a hydrogen atom, substituted or unsubstituted alkyl, or unsubstituted alkyl group, or !IA or next summer IA's Ryoryl group>, Y is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, IA's alkyl group, alkoxy group, carboxyl group, sulfo group, substituted or unsubstituted carbamoyl group, or substituted or next summer IA's sulfamoyl group (however, when m is 2 or more, the groups are different from each other) ), Z is an atomic group necessary to constitute gLIA or an unsubstituted carbocyclic aromatic ring or a heterocyclic aromatic ring of IIA or Next Summer IA, R9 is a hydrogen atom, or an unsubstituted amino group, a substituted or unsubstituted carbamo group, a carboxyl group, or an ester group thereof, 8' is a substituted or unsubstituted 7 aryl group, and Xl is an integer of 1 or 2. , Ill is an integer from 0 to 4.)] (Page ヱ>-A lower odor removal) (III-4-1) (Tff-5-1) (III-6-1) In addition, polycyclic Examples of quinone pigments include compounds represented by the following general formula (tV).

General formula (rv) (In this general formula, X'' represents a halogen atom, a nitro group, a cyano group, an acyl group, or a carboxyl group, and n is 0 to 4
represents an integer. ) Specific examples are as follows.

(■-1) (■-2) (rV -3) ○ (IV -4) (rV-5) C) (IV -6) (I'/ -7) (IV--8) (IV-g ) In order to constitute the photosensitive layer of the electrophotographic photoreceptor of the present invention, a carrier-generating substance and a carrier-transporting substance are combined to form a functionally separated photosensitive layer of a laminated type or a dispersed type. In this case, it is usually as shown in FIGS. 4 to 9.

That is, in the layer structure shown in FIG. 4, a carrier generation layer 2 containing a metal phthalocyanine compound and/or a metal-free phthalocyanine compound is formed on a conductive support 1, and a carrier transport layer containing the above-mentioned carrier transport substance is formed on this carrier generation layer 2. 3 is laminated to form a photosensitive layer 4. In FIG. 5, a photosensitive layer 4'' is formed by reversing these carrier generation layer 2 and carrier transport layer 3, and the layer structure shown in FIG. is the fifth
Intermediate layer 5 between photosensitive N4 and conductive support 1 in the layer configuration shown in the figure.
In FIG. 7, an intermediate layer 5 is provided between the photosensitive layer 4' having the layer structure shown in FIG. 6 and the conductive support 1 to prevent injection of free electrons into the conductive support 1. This is what I did. The layer structure shown in FIGS. 5 and 7 is suitably used as a positively charged light body, and in this case, the carrier generation layer 2 may contain a carrier transport substance together with a carrier generation substance. The layer structure shown in FIG. 8 is one in which a photosensitive layer 4' containing a carrier generating substance 6 containing a metal phthalocyanine compound and/or a metal-free phthalocyanine compound and a carrier transporting substance 7 combined therewith is formed. In the layer structure shown in the figure, the above-mentioned intermediate layer 5 is provided between the photosensitive layer 4''' and the conductive support 1.

In the case of forming a photosensitive layer having a two-layer structure, the carrier generation layer 2 can be provided by the following method.

(a) A method of applying a solution in which a carrier-generating substance is dissolved in a suitable solvent, or a solution in which a binder is added and mixed and dissolved.

(b) A method in which a carrier-generating substance is made into fine particles in a dispersion medium using a ball mill, a homomixer, etc., and a binder is added as necessary to mix and disperse the obtained dispersion, and the resulting dispersion is applied.

Dispersing the particles under the action of ultrasound in these methods allows for homogeneous dispersion.

Solvents or dispersion media used to form the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methylethylketone, cyclohexanone, and benzene. , toluene, xylene, chloroform, 1,2-dichloromethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, and the like.

When a binder is used to form a carrier generation layer or a carrier transport layer, any binder can be used, but in particular, a polymer that is hydrophobic, has a high dielectric constant, and has the ability to form an electrically insulating film. Polymers are preferred. Examples of such polymers include, but are not limited to, the following:

a) Polycarbonate b) Polyester C) Methacrylic resin d) Acrylic resin e) Polyvinyl chloride f) Polyvinylidene chloride g) Polystyrene h) Polyvinyl acetate i) Styrene-butadiene copolymer j) Vinylidene chloride-acrylonitrile copolymer k ) Vinyl chloride-vinyl acetate copolymer 2) Vinyl chloride-vinyl acetate-maleic anhydride copolymer m) Silicone resin n) Silicone-alkyd resin 0) Phenol-formaldehyde resin p) Styrene-
Alkyd resin q) Poly-N-vinylcarbazole r) Polyvinyl butyral These binders can be used alone or in a mixture of two or more. The ratio of the carrier generating substance to the binder is 10 to 600% by weight, preferably 50 to 400% by weight, and the proportion of the carrier transporting substance is 10 to 50% by weight.
It is preferable to set it to 0% by weight.

The thickness of the carrier generation layer 2 formed in this way is 0.
It is preferably 401 to 20 μm, more preferably 0.05 to 5 μm. The thickness of the carrier transport layer is 2 to 100 μm, preferably 5 to 30 μm.

When the photosensitive layer is formed by dispersing the carrier-generating substance, the carrier-generating substance has a thickness of 2 μm or less,
It is preferable that the powder or granules have an average particle size of 1 μm or less. In other words, if the particle size is too large, dispersion in the layer will be poor, and some of the particles will protrude from the surface, resulting in poor surface smoothness. In some cases, electrical discharge may occur at the protruding parts of the particles, or Toner particles tend to adhere and a toner filming phenomenon occurs easily. For carrier generating substances that are sensitive to long wavelength light (~70Qnm), the surface charge is neutralized by the generation of thermally excited carriers in the carrier generating substance, and if the particle size of the carrier generating substance is large, this It seems to have a large neutralizing effect.

Further, the photosensitive layer may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use. Examples of electron-accepting substances that can be used here include succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromo phthalic anhydride, 3-nitro phthalic anhydride, 4- Nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, 0-dinitrobenzene, todinitrobenzene, 1.3.5-
) dinitrobenzene, varanitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, brumanil, dichlorodicyanobarabenzoquinone, anthraquinone, dinitroanthraquinone, 9-fluorenylidene [dicyanomethylenemalonodinitrile], polynitro-9-fluorenylidene [dicyanomethylene malonodinitrile], picric acid, 0-nitrobenzoic acid, p-
Examples include nitrobenzoic acid, 3,5-dinicylobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds with high electron affinity. Further, the addition ratio of the electron-accepting substance is carrier-generating substance:electron-accepting substance in a weight ratio of 100:0.01 to 200, preferably 100:0.1 to 100.

Note that the support 1 on which the above-mentioned angry light layer is to be provided is a metal plate, a metal drum, or a conductive thin layer coated with a conductive polymer, a conductive compound such as indium oxide, or a metal such as aluminum, palladium, or gold. Those provided on a substrate such as paper or plastic film by means of thin coating, lamination, etc. are used. The intermediate layer that functions as an adhesive layer or a barrier layer may be made of a polymer material such as a polymer such as the binder resin described above, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminum oxide. The one that consists is used.

Effects of the Invention As explained above, in the present invention, when a metal phthalocyanine compound and/or a metal-free phthalocyanine compound is used as a carrier generating substance, the above-mentioned human tedene compound is used as a carrier transport substance, so that it has high sensitivity as a photoreceptor. In addition, even during repeated use, the potential history is small and the photoreceptor characteristics are maintained stably. Further, it is possible to provide an electrophotographic photoreceptor that takes advantage of the heat and light stability characteristics of the phthalocyanine compound. Due to these, it is possible to provide an electrophotographic photoreceptor that is unprecedentedly superior to long-wavelength light and laser light.

EXAMPLES Examples will be described below, but first, 6A example of metal-free phthalocyanine compound A having the properties shown in FIGS. 1 to 3 and a synthesis example of a τ-type metal-free phthalocyanine compound will be shown.

Synthesis Example 1 50 g of lithium phthalocyanine is added to 600 ml of concentrated sulfuric acid with thorough stirring at 0°C. The mixture is then stirred at this temperature for 2 hours. The resulting solution is then filtered through a coarse sintered glass funnel and
Pour slowly into 4 liters of ice and water with stirring. After standing for several hours, the mixture is filtered and the resulting mass is washed with water until neutral. The mass is then finally washed several times with methanol and dried in air. This dried powder is extracted with acetone in a 24 hour continuous extractor and dried in air to give a blue powder.

In the above the precipitation is repeated to ensure a salt residue for lithium. 30.5 g of blue powder was thus obtained. The X-ray diffraction pattern of the obtained product was consistent with the X-ray diffraction pattern of an α-type phthalocyanine compound described in previously published materials.

30 g of the metal-free α-phthalocyanine compound thus obtained was charged into a 900 ml porcelain ball mill half-grooved with a 13/16 inch diameter pole and milled at about 8 Orpm for 164 hours. Thereafter, 200 ml of an organic solvent such as tetrahydrofuran or 1,2-dichloroethane was added to the ball mill, and the mixture was milled again for 24 hours. The organic solvent was removed from the dispersion after milling and the dispersion was dried to obtain 28.2 g of metal-free phthalocyanine compound A.

Synthesis Example 2 An α-type metal-free phthalocyanine compound (Monolite Fast Pull GS manufactured by ICI) was extracted and purified three times with heated dimethyl formaldehyde. Through this operation, the purified product was transferred to the β form. Next, a portion of this β-type metal-free phthalocyanine compound was dissolved in concentrated sulfuric acid, and this solution was poured into ice water to cause reprecipitation, thereby transforming it into the α-type.

After washing this reprecipitate with aqueous ammonia, methanol, etc.
It was dried at 0°C. Next, the α-type metal-free phthalocyanine compound purified as described above was placed in a sand mill together with a grinding aid and a dispersant, and kneaded at a temperature of 100±20° C. for 15 to 25 hours. This operation transformed the crystal form to τ type.
After confirming if, the product was taken out from the container, the grinding aid and dispersant were thoroughly removed with water, methanol, etc., and then dried to obtain blue crystals of clear blue-tinted metal-free phthalocyanine.

Example 1 1.0 g of the metal-free phthalocyanine compound obtained in Synthesis Example 1 and polymethyl methacrylate (
Elvacite-2010 (manufactured by DuPont) 2.0g to 100m of 1,2-dichloroethane I! In addition, it is dispersed by ultrasonic dispersion. This dispersion was coated and dried so that the film thickness after drying was 0.5 μm to form a carrier generation layer.

Furthermore, 12.4 g of the carrier transport material of Example 1-14 shown in Table 2 and 16.5 g of polycarbonate (Panlite L-12°50, manufactured by Kijin Kasei Co., Ltd.) were added on top of this.
A carrier transport layer was formed by coating and drying a solution dissolved in 2-dichloroethane Loom 1 so that the film thickness after drying was 12 μm, and an electrophotographic photoreceptor was obtained.

Examples 2 to 6 Examples 2 to 6 were used instead of the substances in Table 2 in Example 1.
Electrophotographic photoreceptors of Examples 2 to 6 were obtained in the same manner except that the substances listed in the columns corresponding to each of Examples 2 to 6 were used.

Comparative Examples 1 and 2 Comparative Examples 1 and 2 were used as carrier transport substances in Example 1.
Electrophotographic photoreceptors of Comparative Examples 1 and 2 were obtained in the same manner except that the substances listed in the columns corresponding to were used.

Comparative Examples 3 to 4 Comparative Examples 3 to 4 were carried out in the same manner except that the τ-type phthalocyanine compound of Synthesis Example 2 was used in Example 1, and the carrier transport substance described in each column of Comparative Example 3.4 was used. An electrophotographic photoreceptor was obtained.

Evaluation Test The electrophotographic characteristics of each of the electrophotographic photoreceptors obtained as described above were investigated using an electrometer 5P428 model J (Kawaguchi Electric Manufacturing Co., Ltd.). The amount of exposure E1/2 (Lux・sec ) (using a tungsten light source) and dark decay rate (V^L)/L X100
% and 10 (Lux-see) Residual potential VR after exposure (
v) was measured.

Next, in a similar measurement system, a tungsten light source is used as the light source, and the wavelength 78 in particular is measured using a monochromator.
Half-decreased exposure amount El/2 (λ=
780) (erg/crl) was measured. Further, the acceptance potential VA (v) and residual potential were also measured after 10,000 copies.

Table 3 shows these results. ΔvA, ΔvR in the table
is the value obtained by subtracting the characteristic value after 10,000 copies from each initial characteristic value.

(Leave space below this tribute)

[Brief explanation of drawings]

Figure 1 is an X-ray diffraction diagram of metal-free phthalocyanine compound A used in the present invention, Figure 2 is its infrared absorption spectrum, Figure 3 is its near-infrared absorption spectrum, Figures 4 and 5. , FIG. 6, FIG. 7, FIG. 8, and FIG. 9 show specific examples of the layer structure of the electrophotographic photoreceptor of the present invention. In the figure, 1 is a conductive support, 2 is a carrier generation layer, 3 is a carrier transport layer, 4.4°, 4° is a photosensitive layer, 5 is an intermediate layer, 6 is a carrier generation material, 7 is a carrier transport material It is. October 31, 1985, Figure 1, Figure 3, rare absorption sumactor map ML+CWavelengtn+nnu), Figure 4, Figure 7, Figure 8, Figure 9, Procedure Amendment (December 2, 1985, Patent Office) Director Uga Michibu 1, Indication of the case Patent Application No. 242884 of 1985 2, Name of the invention Electrophotographic photoreceptor 3, Relationship with the M-correction case Patent applicant 1-chome Nishi-Shinjuku, Shinjuku-ku, Tokyo 26 No. 2 (127) Roku Konishi Photo Industry Co., Ltd. Representative Keizumi Ide 4, Agent ■105 5. Date of amendment order Voluntary 6. Number of inventions increased by amendment None 7. Subject of amendment

Claims (1)

[Claims] (1) In an electrophotographic photoreceptor having a photosensitive layer containing a carrier-generating substance and a carrier-transporting substance, the carrier-generating substance contains a metal phthalocyanine compound and/or a metal-free phthalocyanine compound, and the carrier-transporting substance has the following general formula [ An electrophotographic photoreceptor comprising at least one of the hydrazone compounds represented by [I] and [II]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (However, in this general formula, R^1 is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and R^2 is hydrogen atom, substituted or unsubstituted alkyl group, or substituted or unsubstituted aryl group, X^1 is a hydrogen atom, a halogen atom, an alkyl group, a substituted amino group, an alkoxy group, or a cyano group, p is 0 or 1 ) General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc.▼ (However, in this general formula, R^3 is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, R^4 is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, X^2 is a hydrogen atom, a halogen atom, an alkyl group, a substituted amino group, an alkoxy group, or a cyano group, q represents an integer of 0 or 1.)