JPH06348051A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To provide a low-cost electrophotographic photoreceptor with a single layer type photosensitive layer excellent in positive electrification ability and light stability and having high sensitivity, high surface potential and low residual potential. CONSTITUTION:This electrophotographic photoreceptor has a single layer type photosensitive layer contg. an electric charge generating material, an electric charge transferring material and a bonding resin. The photosensitive layer contains dichloro-tin phthalocyanine crystals as the electric charge generating material and a benzidine compd. represented by formula I and/or triarylamine compd. represented by foumula II as the electric charge transferring material. In the formula I, R1 is H, alkyl, alkoxy or halogen, each of R2 and R3 is alkyl, alkoxy, halogen or substd. amino and each of (m) and (n) is 0-2. In the formula II, each of Ar1 and Ar2 is an arom. mono- or polycyclic carbocyclic group which may have alkyl, alkoxy, substd, amino or halogen as a substituent or a heterocylic group.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member having a single-layer type photosensitive layer on a conductive support. More specifically, it relates to an electrophotographic photoreceptor containing a specific compound in a charge generating material and a charge transporting material.

[0002]

2. Description of the Related Art Conventionally, as electrophotographic photoreceptors, there are a photoconductive layer of a single layer type and a photoconductive layer of a laminated type. In particular, recently, as a photoconductive layer, an organic photoconductive substance such as resin is used. Various proposals have been made regarding an organic electrophotographic photoreceptor having a layer structure in which the charge transport layer and the charge generating layer are bound to each other and are functionally separated. As these materials, various materials have been proposed for charge generation materials and charge transport materials. For example, as the charge generating material, a polycyclic quinone pigment, a perylene pigment, an indigo pigment, a bisimidazole pigment, a quinacridone pigment, a phthalocyanine pigment, a monoazo pigment, a bisazo pigment, a trisazo pigment, a polyazo pigment, etc. are known. Known examples include amino compounds, hydrazone compounds, pyrazoline compounds, oxazole compounds, oxadiazole compounds, stilbene compounds, and carbazole compounds. Also, various proposals have been made to use these charge generating materials and charge transporting materials in combination. (For example, as to a combination with a phthalocyanine pigment, JP-A-57-5
No. 4942, No. 60-59355, No. 61-2034.
No. 61, No. 62-47054, No. 62-67094, etc.) Since the above-mentioned laminated type photoreceptor separates various functions by the charge generation layer and the charge transport layer, it is generally a high-sensitivity electrophotographic photoreceptor. And the wide selection range of the photosensitive material. Many of the above charge transport materials are hole transport type, and in order to impart durability to the surface, a charge generation layer is provided on a conductive support, and a charge transport layer is further provided on the charge transport layer to provide a negative photosensitive laminated photoconductor. It is generally a body structure. However, in such a negative charging laminated photoreceptor, ozone is generated in the atmosphere during negative charging to cause deterioration of the photoreceptor and contamination of the copying environment, and to develop a latent electrostatic image formed on the photoreceptor. Since it is difficult to obtain charged toner, the selection range of toner materials is narrowed. Further, since the charge transport layer has to be formed on the charge generation layer, there are problems that the number of steps for manufacturing the photoconductor is increased, the workability is lowered, the yield is lowered, and the cost is increased.

On the other hand, a single-layer type organic photoconductor containing a charge generating material, a charge transporting material, and a binder resin is also known. This photoconductor can be positively charged, prevents generation of ozone, and has a toner. It has the advantages of a wide selection of materials and good workability in manufacturing (for example, JP-A-63-271461)
No. 1-118147, No. 3-1149, etc.). However, since electrons and holes are moved in one layer, either one becomes a trap, and the residual potential tends to increase. In addition, there is a problem that the combination of the charge generating material and the charge transporting material greatly affects the electrophotographic characteristics such as charging characteristics, sensitivity and residual potential.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its object is to have excellent positive charging property and light stability, high sensitivity and surface potential, and residual potential. To provide an inexpensive electrophotographic photoreceptor having a single-layer type photosensitive layer.

[0005]

DISCLOSURE OF THE INVENTION As a result of studying various materials, the present inventors have found that in a photoreceptor having a single-layer type photosensitive layer containing a charge generating material, a charge transporting material and a binder resin, By using a dichlorotin phthalocyanine crystal as the charge generating material and using a benzidine compound represented by the following general formula (I) and / or a triarylamine compound represented by the following general formula (II) as the charge transporting material, It was found that an electrophotographic photosensitive member having high sensitivity and excellent in repeated stability was obtained, and the present invention was completed.

The electrophotographic photoreceptor of the present invention has a single-layer type photosensitive layer containing a charge generating material, a charge transporting material and a binder resin, and the photosensitive layer is a dichlorotin phthalocyanine crystal as the charge generating material. And a benzidine compound represented by the following general formula (I) or a triarylamine compound represented by the following general formula (II) as a charge transport material.

[Chemical 5] (In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkoxy group or halogen, R ₂ and R ₃ may be the same or different and each represents an alkyl group, an alkoxy group, a halogen or a substituted amino group, m And n is 0-2
Represents the integer. )

[Chemical 6] (In the formula, Ar ₁ and Ar ₂ may be the same or different and each is substituted with an alkyl group, an alkoxy group, a substituted amino group or a phenyl group which may have a halogen atom, or an alkyl group as a substituent. Optionally represents a polycyclic aromatic group or an aromatic heterocyclic group.)

The present invention will be described in more detail below. In the present invention, a compound represented by the following general formula (III) or the following general formula (IV) is preferably used as the benzidine compound represented by the above general formula (I) which is a charge transport material. These benzidine compounds are
As shown in JP-A-62-247374, the solubility in a solvent and the compatibility with a resin are high, a uniform coating film can be obtained, and a uniform interface can be formed.
In addition, an electrophotographic photoreceptor having excellent repetitive stability can be obtained, which is preferable.

[Chemical 7] (In the formula, R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a methyl group.)

[Chemical 8] (In the formula, one of R ₆ and R ₇ represents an alkyl group having 2 or more carbon atoms, and the other represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino group.)

Specific examples of the benzidine compound represented by the general formula (I) include those shown in Tables 1 and 2 below. These may be used alone or in combination of two or more. The triarylamine compound represented by the general formula (II) can be produced by condensing an amine with an aryl halide compound in the presence of a copper catalyst. Specific examples of the triarylamine compound include those shown in Tables 3 to 6 below. You may use these individually or in mixture of 2 or more types. In the table below, Me, Et, Pr and Bu
Each represents a methyl group, an ethyl group, a propyl group or a butyl group.

[0009]

[Table 1]

[0010]

[Table 2]

[0011]

[Table 3]

[0012]

[Table 4]

[0013]

[Table 5]

[0014]

[Table 6]

On the other hand, as the charge generating material, dichlorotin phthalocyanine crystal is used. Specifically, Cu
In an X-ray diffraction spectrum using Kα as a radiation source, a dichlorotin phthalocyanine crystal having a strongest diffraction peak at 28.2 ° in the Bragg angle (2θ ± 0.2 °) range of 25 ° to 30 °, Bragg angle (2θ ±
0.2 °) is 8.3 °, 12.2 °, 13.7 °, 2
Dichlorotin phthalocyanine crystal having a strong diffraction peak at 8.2 °, Bragg angle (2θ ± 0.2 °) of 8.
7 °, 9.9 °, 10.9 °, 13.1 °, 15.2
°, 16.3 °, 17.4 °, 21.9 °, 25.5 °
Dichlorotin phthalocyanine crystal having a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) of 9.2 °, 1
2.2 °, 13.4 °, 14.6 °, 17.0 °, 2
Dichlorotin phthalocyanine crystal having a strong diffraction peak at 5.3 °, and Bragg angle (2θ ± 0.2 °)
A dichlorotin phthalocyanine crystal having a strong diffraction peak at 8.5 °, 11.2 °, 14.5 ° and 27.2 ° is preferably used. When these are used, an electrophotographic photosensitive member having high sensitivity and excellent repeated stability can be obtained. The above dichlorotin phthalocyanine crystal is 1
You may use it, or in mixture of 2 or more types. These phthalocyanine crystals are obtained by, for example, grinding dichlorotin phthalocyanine obtained by reacting phthalonitrile with anhydrous stannic chloride in the presence or absence of salt, or by grinding in chlorobenzene or tetrahydrofuran. Obtainable.

The binder resin for binding the charge transport material and charge generating material can be selected from a wide range of insulating resins. In addition, poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene,
It can also be selected from organic photoconductive polymers such as polysilanes. Preferred binder resins include polyvinyl butyral resin and polyarylate resin (bisphenol A
And polyphthalic acid), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin , Casein, polyvinyl alcohol resin, polyvinylpyrrolidone resin, methacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-
Acrylonitrile copolymer, vinyl chloride-vinyl acetate-
Known resins such as maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin and styrene-alkyd resin can be used, but are not limited thereto. These binder resins may be used alone or in combination of two or more.

The ratio of the dichlorotin phthalocyanine crystal, the benzidine compound represented by the general formula (1) and the triarylamine compound represented by the general formula (II) to the binder resin is not particularly limited. Can be appropriately selected depending on the desired characteristics of the electrophotographic photosensitive member and the like, but preferably 100 parts by weight of the binder resin,
1 to 500 parts by weight of dichlorotin phthalocyanine crystals,
The total amount of the benzidine compound and the triarylamine compound is more preferably 10 to 500 parts by weight, more preferably 50 to 200 parts by weight.

As a method for dispersing these, a usual method such as a ball mill dispersion method, an attritor dispersion method or a sand mill dispersion method can be used. At this time, the crystal form of the dichlorotin phthalocyanine is changed by the dispersion. No conditions are required. By the way, it has been confirmed that in any of the above-mentioned dispersion methods carried out in the present invention, the crystal form does not change from that before dispersion. Further, as the solvent used for dispersing these, methanol, ethanol,
n-propanol, n-butanol, benzyl alcohol, n-hexane, octane, cyclohexane, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, acetic acid Methyl, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride,
Ordinary organic solvents such as chloroform may be used alone or in admixture of two or more.

In the single-layer type photosensitive layer having the above composition, other charge generating material and charge transporting material may be used as long as the photosensitive characteristics are not impaired. The thickness of the single-layer type photosensitive layer is generally 5 to 50 μm, preferably 10 to 30 μm. As a coating method, a blade coating method, a Meyer bar coating method,
Conventional methods such as a spray coating method, a dip coating method, a bead coating method, an air knife coating method and a curtain coating method can be used.

Further, for the purpose of preventing the deterioration of the photoreceptor due to ozone or oxidizing gas generated in the copying machine, or light or heat, an antioxidant, a light stabilizer, a heat stabilizer, etc. are added to the photosensitive layer. Agents can be added. For example, as the antioxidant, hindered phenol, hindered amine, p
-Phenylenediamine, arylalkanes, hydroquinones, spirochromans, spiroindanones and their derivatives, organic sulfur compounds, organic phosphorus compounds and the like. Examples of the light stabilizer include benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine derivatives. Further, at least one electron-accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use. Examples of the electron acceptor usable in the photoconductor of the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, and o. -Dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-
Examples thereof include nitrobenzoic acid and phthalic acid. Of these, fluorenone-based, quinone-based, Cl, CN,
A benzene derivative having an electron-withdrawing substituent such as NO ₂ is particularly preferable.

The photoconductor of the present invention can be obtained by preparing a coating solution containing the above-mentioned components, coating the coating solution on a conductive support, and drying. Examples of the conductive support include metals such as aluminum, nickel, chromium, and stainless steel, and aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide,
Examples thereof include a plastic film provided with a thin film of indium oxide or ITO, paper coated with or impregnated with a conductivity-imparting agent, and a plastic film. These conductive supports are used in a suitable shape such as a drum shape, a sheet shape, and a plate shape, but are not limited thereto. Further, if necessary, the surface of the conductive support can be subjected to various treatments within a range that does not affect the image quality. For example, surface oxidation treatment, chemical treatment, coloring treatment, or irregular reflection treatment such as graining can be performed.

An undercoat layer may be further provided between the conductive support and the single-layer type photosensitive layer. This subbing layer prevents the injection of charges from the conductive support to the photosensitive layer during charging of the photosensitive layer, and also acts as an adhesive layer for integrally bonding and holding the photosensitive layer to the conductive support, Alternatively, depending on the case, it exhibits the function of preventing the reflected light of light from the conductive support. Materials used for the undercoat layer include polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, vinylidene chloride resin, polyvinyl. Acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound, Known materials such as a titanyl chelate compound, a titanyl alkoxide compound, an organic titanyl compound and a silane coupling agent can be used. The thickness of the undercoat layer is 0.01 to 10 μm, preferably 0.05 to
2 μm is suitable. Further, as the coating method used for providing the undercoat layer, those described for the photosensitive layer can be similarly used.

If desired, a protective layer may be provided on the photosensitive layer. This protective layer is used to prevent chemical deterioration of the photosensitive layer during charging and to improve the mechanical strength of the photosensitive layer. This protective layer is formed by containing a conductive material in a suitable binder. As the conductive material, a metallocene compound such as N, N'-dimethylferrocene, N, N'-diphenyl-N, N '
Aromatic amine compounds such as -bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine, antimony oxide, tin oxide, titanium oxide, indium oxide, tin oxide-antimony oxide Materials such as metal oxides can be used, but are not limited to these. As the binder resin used for this protective layer, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin,
Known resins such as polyvinyl ketone resin, polystyrene resin and polyacrylamide resin can be used.
Also, this protective layer has an electric resistance of 10 ⁹ to 10 ¹⁴ Ω.
It is preferable to configure it to be cm. When the electric resistance is 10 ¹⁴ Ω · cm or more, the residual potential rises to give a copy with a lot of fog, and when it is 10 ⁹ Ω · cm or less, the image becomes blurred and the resolution is lowered. Also, the protective layer should be constructed so as not to substantially interfere with the transmission of light used for imagewise exposure. The thickness of the protective layer used in the present invention is 0.5 to 20 μm, preferably 1 to 10
μm is suitable. As the coating method, those described for the photosensitive layer can be similarly used.

[0024]

EXAMPLES The present invention will be described below with reference to examples. Synthesis Example 1 (Synthesis of dichlorotin phthalocyanine) 50 g of phthalonitrile and 27 g of anhydrous stannic chloride,
1-Chlornaphthalene was added to 350 ml and reacted at 195 ° C. for 5 hours, then the product was filtered off, washed with 1-chlornaphthalene, acetone, methanol and then with water, and dried under reduced pressure to give dichlorotin phthalocyanine. 18.3 g (27%) of crystals were obtained. The powder X-ray diffraction diagram of the obtained dichlorotin phthalocyanine crystal using CuKα as a radiation source is shown in FIG.

Production Example 1 Dichlorotin phthalocyanine crystal 5 obtained in Synthesis Example 1
g with 500 g of agate ball (20 mmφ),
The mixture was placed in an agate pot (500 ml) and pulverized with a planetary ball mill (F-5 type, P-5 type) at 400 rpm for 10 hours. The powder X-ray diffraction spectrum of the obtained dichlorotin phthalocyanine crystal using CuKα as a radiation source has a Bragg angle (2θ ± 0.2 °) of 8.3 °, 1
It had strong diffraction peaks at 2.2 °, 13.7 °, and 28.2 °. The powder X-ray diffraction pattern is shown in FIG. Production Example 2 Dichlorotin phthalocyanine crystal 5 obtained in Synthesis Example 1
g together with 10 g of salt agate ball (20 mmφ) 5
Put it in an agate pot (500 ml) together with 00 g, and use a planetary ball mill (Fritsch P-5 type) to
Grinding was carried out at 00 rpm for 10 hours. The powder X-ray diffraction spectrum of the obtained dichlorotin phthalocyanine crystal using CuKα as a radiation source has a Bragg angle (2θ ± 0.2 °) of 8.5 °, 11.2 °, 14.5 °, 27.2. It had a strong diffraction peak at °. The powder X-ray diffraction pattern is shown in FIG. Production Example 3 Dichlorotin phthalocyanine crystal 1 obtained in Synthesis Example 1
g was crushed with 100 g of glass beads (1 mmφ) in 30 ml of chlorobenzene at room temperature for 72 hours using a ball mill, the obtained slurry was filtered, repeatedly washed with methanol, and then dried under reduced pressure to obtain dichlorotin phthalocyanine. 0.97 g of crystals were obtained. The powder X-ray diffraction spectrum of the obtained dichlorotin phthalocyanine crystal using CuKα as a radiation source shows a Bragg angle (2θ ± 0.2).
°) is 8.7 °, 9.9 °, 10.9 °, 13.1 °,
15.2 °, 16.3 °, 17.4 °, 21.9 °, 2
It had a strong diffraction peak at 5.5 °. The powder X-ray diffraction pattern is shown in FIG. Production Example 4 Dichlorotin phthalocyanine crystals (0.93 g) were obtained in the same manner as in Production Example 3 except that tetrahydrofuran was used as the solvent during pulverization. The powder X-ray diffraction spectrum of the obtained dichlorotin phthalocyanine crystal using CuKα as a radiation source shows Bragg angles (2θ ± 0.2 °) of 9.2 °, 12.2 °, 13.4 °, 14.6. ° 1
It had strong diffraction peaks at 7.0 ° and 25.3 °.
The powder X-ray diffraction pattern is shown in FIG.

Synthesis Example 2 (Synthesis of 3,4,4 ', 4 "-tetramethyltriphenylamine (II-3)) 3,4,4'-trimethyldiphenylamine 50 g, p
-62 g of iodotoluene, 33 g of anhydrous potassium carbonate, 2 g of copper sulfate pentahydrate, and 10 ml of n-tridecane were placed in a 1-liter three-necked flask, reacted at 200 ° C for 120 hours under a nitrogen stream, and then cooled to room temperature. did. The reaction mixture was column purified with activated alumina (solvent: n-hexane /
Toluene = 10/1) and the solvent was distilled off under reduced pressure. The residue was recrystallized with a mixed solvent of ethyl acetate / ethanol,
4,4 ', 4 "-tetramethyltriphenylamine 52
g was obtained. (Melting point 107-109 ° C., colorless crystal) Synthesis Examples 3 and 4 In the same manner as in Synthesis Example 2, 3,3 ′, 4,4 ′, 4 ″ -pentamethyltriphenylamine (II-13, melting point 115-115).
117.5 ° C., colorless crystals), and 3,3 ′, 3 ″,
4,4 ', 4 "-hexamethyltriphenylamine (II
-25, melting point 137-139 ° C., colorless crystals) was synthesized.

Example 1 First, a zirconium compound (trade name: Organix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) on an aluminum substrate 1
A solution consisting of 0 part and 1 part of a silane compound (trade name: A1110, manufactured by Junker Japan Ltd.), 40 parts of i-propanol and 20 parts of butanol was applied by a dip coating method, and dried by heating at 150 ° C. for 10 minutes to form a film thickness. 0.5
An undercoat layer of μm was formed. Next, 1 part of dichlorotin phthalocyanine crystal obtained in Production Example 1, polyvinyl butyral resin (trade name: S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.)
After 2 parts, 2 parts of the exemplified compound (I-53) and a predetermined amount of n-butyl acetate were treated with a glass bead for 2 hours on a paint shaker to disperse them, the obtained coating liquid was applied onto the undercoat layer. It was applied to form a photosensitive layer having a film thickness of about 20 μm. The electrophotographic characteristics of the electrophotographic photoreceptor thus obtained were measured at room temperature and normal humidity (20 ° C., 40% RH) using an electrostatic copying paper tester (Kawaguchi Electric: Electrostatic Analyzer EPA-8100). Environment of + 6k
After performing V corona discharge and charging, the tungsten lamp light was converted into monochromatic light of 800 nm using a monochromator, adjusted to 1 μW / cm ² on the surface of the photoreceptor, and irradiated. And the surface potential V0 (V), to measure the half decay exposure ^{E1 / 2 (erg / cm 2} ), then the white light 10lux irradiated for 1 second, to measure the residual potential VR (V). Further, V0, E1 / 2 and VR were measured after the above charging and exposure were repeated 1000 times, and the fluctuation amounts were represented by .DELTA.V0, .DELTA.E1 / 2 and .DELTA.VR, and the results are shown in Table 7.

Example 2 A photoconductor was prepared in the same manner as in Example 1 except that the dichlorotin phthalocyanine crystal obtained in Production Example 2 was used instead of the dichlorotin phthalocyanine crystal in Example 1. The measurement was performed. The results are shown in Table 7. Example 3 A photoreceptor was prepared in the same manner as in Example 1 except that the dichlorotin phthalocyanine crystal obtained in Production Example 3 was used instead of the dichlorotin phthalocyanine crystal in Example 1, and the same measurement was performed. It was The results are shown in Table 7. Example 4 A photoconductor was prepared in the same manner as in Example 1 except that the dichlorotin phthalocyanine crystal obtained in Production Example 4 was used instead of the dichlorotin phthalocyanine crystal in Example 1, and the same measurement was performed. It was The results are shown in Table 7.

Examples 5 to 17 Photosensitive members were prepared in the same manner as in Example 2 except that the charge transporting materials shown in Table 7 were used instead of the charge transporting materials in Example 2, and the same measurements were carried out. went. The results are shown in Table 7. Example 18 Furthermore, a photoreceptor was prepared in the same manner as in Example 2 except that 0.5 part of the exemplified compound (II-25) was added, and the same measurement was performed. The results are shown in Table 8. Example 19 Furthermore, a photoreceptor was prepared in the same manner as in Example 6 except that 0.5 part of the exemplified compound (II-14) was added, and the same measurement was performed. The results are shown in Table 8. Example 20 A photoconductor was prepared in the same manner as in Example 18 except that the dichlorotin phthalocyanine crystal obtained in Production Example 1 was used instead of the dichlorotin phthalocyanine crystal in Example 18, and the same measurement was performed. It was The results are shown in Table 8. Example 21 A photoconductor was prepared in the same manner as in Example 19 except that the dichlorotin phthalocyanine crystal obtained in Production Example 1 was used instead of the dichlorotin phthalocyanine crystal in Example 19, and the same measurement was performed. It was The results are shown in Table 8. Example 22 A photoconductor was prepared in the same manner as in Example 18 except that the dichlorotin phthalocyanine crystal obtained in Production Example 4 was used instead of the dichlorotin phthalocyanine crystal in Example 18, and the same measurement was performed. It was The results are shown in Table 8. Example 23 A photoconductor was prepared in the same manner as in Example 19 except that the dichlorotin phthalocyanine crystal obtained in Production Example 4 was used instead of the dichlorotin phthalocyanine crystal in Example 19, and the same measurement was performed. It was The results are shown in Table 8.

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1 except that the compound represented by the following structural formula (V) was used as the charge transport material. It was The results are shown in Table 8. Comparative Example 2 A photoconductor was prepared in the same manner as in Example 1 except that the compound represented by the following structural formula (VI) was used as the charge transport material, and the same measurement was performed. The results are shown in Table 8. Comparative Example 3 A photoconductor was prepared in the same manner as in Example 1 except that the compound represented by the following structural formula (VII) was used as the charge transport material, and the same measurement was performed. The results are shown in Table 8.

[0031]

[Chemical 9] Comparative Example 4 As Example 1 except that the charge-generating material in Example 1 was replaced by the above-mentioned dichlorotin phthalocyanine crystal, and a metal-free phthalocyanine crystal whose powder X-ray diffraction diagram using CuKα as a radiation source is shown in FIG. 6 was used. A similar photoconductor was prepared and the same measurement was performed. The results are shown in Table 8.

[0032]

[Table 7]

[0033]

[Table 8]

[0034]

The electrophotographic photosensitive member of the present invention has high photosensitivity and excellent repeated stability. Further, since it is a single-layer type photoconductor, it is excellent in use by positive charging, can prevent generation of ozone, is excellent in light stability, has a high surface potential, and has a low residual potential. Further, it can be manufactured with high yield.

[Brief description of drawings]

FIG. 1 shows a powder X-ray diffraction diagram of a dichlorotin phthalocyanine crystal obtained in Synthesis Example using CuKα as a radiation source.

FIG. 2 shows a powder X-ray diffraction pattern of the dichlorotin phthalocyanine crystal obtained in Production Example 1 using CuKα as a radiation source.

FIG. 3 shows a powder X-ray diffraction pattern of the dichlorotin phthalocyanine crystal obtained in Production Example 2 using CuKα as a radiation source.

FIG. 4 shows a powder X-ray diffraction diagram of the dichlorotin phthalocyanine crystal obtained in Production Example 3 using CuKα as a radiation source.

FIG. 5 shows a powder X-ray diffraction pattern of the dichlorotin phthalocyanine crystal obtained in Production Example 4 using CuKα as a radiation source.

FIG. 6 Cu of X-type metal-free phthalocyanine crystal
The powder X ray diffraction pattern which makes K (alpha) a radiation source is shown.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Katsumi Nukata 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Xerox Co., Ltd. (72) Inventor Akira Imai 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Xerox Co., Ltd.

Claims (12)

[Claims] 1. An electrophotographic photoreceptor having a single-layer type photosensitive layer containing a charge generating material, a charge transporting material and a binder resin, wherein the photosensitive layer contains dichlorotin phthalocyanine crystals as the charge generating material, An electrophotographic photoreceptor comprising at least one compound selected from a benzidine compound represented by the following general formula (I) or a triarylamine compound represented by the following general formula (II) as a transport material. [Chemical 1] (In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkoxy group or halogen, R ₂ and R ₃ may be the same or different and each represents an alkyl group, an alkoxy group, a halogen or a substituted amino group, m And n is 0-2
Represents the integer. ) [Chemical 2] (In the formula, Ar ₁ and Ar ₂ may be the same or different and each is substituted with an alkyl group, an alkoxy group, a substituted amino group or a phenyl group which may have a halogen atom, or an alkyl group as a substituent. May represent a polycyclic aromatic group or an aromatic heterocyclic group.) 2. An electrophotographic photoreceptor having a single-layer type photosensitive layer containing a charge generating material, a charge transporting material and a binder resin, wherein the photosensitive layer contains dichlorotin phthalocyanine crystals as the charge generating material, An electrophotographic photoreceptor comprising at least one benzidine compound represented by the general formula (I) and at least one triarylamine compound represented by the general formula (II) as transport materials. 3. A benzidine compound represented by the following general formula (III
3. The electrophotographic photosensitive member according to claim 1, which is represented by the formula (1). [Chemical 3] (In the formula, R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a methyl group.) 4. A benzidine compound is represented by the following general formula (IV):
The electrophotographic photosensitive member according to claim 1 or 2, wherein: [Chemical 4] (In the formula, one of R ₆ and R ₇ represents an alkyl group having 2 or more carbon atoms, and the other represents a hydrogen atom, an alkyl group, an alkoxy group or a substituted amino group.) 5. Ar _{1 of the} general formula (II) is 3,4,-
The electrophotographic photoreceptor according to claim 1 or 2, further comprising a triarylamine compound which is dimethylphenyl. 6. Ar ₁ and Ar ₂ of the general formula (II)
Contains a triarylamine compound, both of which are 3,4-dimethylphenyl groups.
Alternatively, the electrophotographic photosensitive member according to claim 2. 7. The dichlorotin phthalocyanine crystal is Cu
In the X-ray diffraction spectrum with Kα as the radiation source, a dichlorotin phthalocyanine crystal having the strongest diffraction peak at 28.2 ° in the Bragg angle (2θ ± 0.2 °) range of 25 ° to 30 °. The electrophotographic photosensitive member according to claim 1 or 2, wherein 8. The dichlorotin phthalocyanine crystal is Cu.
In the X-ray diffraction spectrum with Kα as the radiation source, the Bragg angles (2θ ± 0.2 °) were 8.3 °, 12.2 °, 1
The electrophotographic photosensitive member according to claim 1 or 2, which is a dichlorotin phthalocyanine crystal having strong diffraction peaks at 3.7 ° and 28.2 °. 9. The dichlorotin phthalocyanine crystal is Cu.
In the X-ray diffraction spectrum using Kα as the radiation source, the Bragg angle (2θ ± 0.2 °) was 8.5 °, 11.2 °, 1
The electrophotographic photosensitive member according to claim 1 or 2, which is a dichlorotin phthalocyanine crystal having strong diffraction peaks at 4.5 ° and 27.2 °. 10. The dichlorotin phthalocyanine crystal is C
In the X-ray diffraction spectrum using uKα as the radiation source, the Bragg angles (2θ ± 0.2 °) were 8.7 °, 9.9 °, and 1
0.9 °, 13.1 °, 15.2 °, 16.3 °, 1
The electrophotographic photosensitive member according to claim 1 or 2, which is a dichlorotin phthalocyanine crystal having strong diffraction peaks at 7.4 °, 21.9 °, and 25.5 °. 11. The dichlorotin phthalocyanine crystal is C
In an X-ray diffraction spectrum using uKα as a radiation source, Bragg angles (2θ ± 0.2 °) were 9.2 °, 12.2 °,
The electrophotographic photosensitive member according to claim 1 or 2, which is a dichlorotin phthalocyanine crystal having strong diffraction peaks at 13.4 °, 14.6 °, 17.0 °, and 25.3 °. 12. The electrophotographic photosensitive member according to claim 1 or 2, wherein the photosensitive layer contains an antioxidant. [0001]