JPH05249716A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide an electrophotographic sensitive body for near IR. CONSTITUTION:This electrophotographic sensitive body has a photosensitive layer contg. hydroxygallium phthalocyanine crystals as an electric charge generating material and a compd. represented by formula I, II, III or IV as an electric charge transferring material. In the formulae I-IV, each of R1-R13 is H, alkyl, aryl, etc., X is -C(CH3)2-, -(CH2)m-[(m) is an integer of 1-5],-(OCH2CH2)m-[(m) is an integer of 1-5], -CH=CH-, -COCH2)2-, -COCH2)3-, cyclobenzylidene or cyclohexylidene and (n) is 0 or 1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor having a photosensitive layer on a conductive support. More specifically, it relates to an electrophotographic photoreceptor containing a specific compound as a charge generating material and a charge transporting material.

[0002]

BACKGROUND OF THE INVENTION Phthalocyanine is used for paints, printing inks,
It is a material useful as a catalyst or an electronic material, and in recent years, it has been widely studied as an electrophotographic photosensitive material, an optical recording material and a photoelectric conversion material. In general, phthalocyanine compounds are known to show a large number of crystal types depending on the difference in production method and treatment method, and it is known that this difference in crystal type has a great influence on photoelectric conversion characteristics of phthalocyanine. There is. Regarding the crystal form of the phthalocyanine compound, for example, regarding copper phthalocyanine, α, π, x, ρ, γ, δ and other crystal forms are known in addition to the stable β form. Other than copper phthalocyanine, metal-free phthalocyanine, hydroxygallium phthalocyanine, chloroaluminum phthalocyanine,
It has been proposed to use various crystal types of chloroindium phthalocyanine and the like for electrophotographic photoreceptors. Further, the present inventors have examined the relationship between various phthalocyanine crystal forms and electrophotographic characteristics, and found five types of hydroxygallium phthalocyanine crystals, and in JP-A-3-122814, these are referred to as electron It has been disclosed that it is excellent as a photographic light-sensitive material. In addition, regarding hydroxygallium phthalocyanine, those obtained by the acid pasting method are disclosed in JP-A-1-221459.

On the other hand, various kinds of charge transport materials have been proposed in the past for electrophotographic photoreceptors.
For example, JP-A-51-93224 and JP-A-3-158.
862, 3-192262, 3-200750
No. 3,203,739 and No. 3-208057, there are described triarylamine compounds represented by the following general formula (I), which are disclosed in JP-A-55-59483 and JP-A-5-59483.
7-195254, JP-A-2-178668 and 2
-190862, 3-101739, 3-12
Japanese Patent No. 7765 discloses a triarylamine compound represented by the general formula (II) described below.
98425, 59-216853, and 60-984.
No. 37, No. 61-32062, No. 63-225660
JP-A No. 63-31455 discloses a stilbene compound represented by the general formula (III) described later.
No. 4, JP-A-1-279253, describes ethylene derivatives represented by the general formula (IV) described below, and methods for synthesizing these compounds are also known.

[0004]

By the way, in order to obtain electrophotographic characteristics with high sensitivity and excellent repetitive stability in an electrophotographic photosensitive member, 1) the charge generation material is efficiently charged with respect to the light absorbed. 2) that the generated charge is smoothly injected from the charge generating material into the charge transporting material, 3) that it is chemically and photochemically stable,
4) It is necessary that the charges injected into the charge transport material can move at high speed in the charge transport layer. That is, 1),
Even if there are charge generation materials that efficiently generate charges that satisfy the conditions 3) and 4) and charge transport materials that can move charges at high speed, the charge generation materials that satisfy the condition 2). It is not possible to obtain electrophotographic photosensitivity having high sensitivity and excellent repeated stability unless a combination of the charge transport material and the charge transport material is used. Further, in order to put the electrophotographic photoreceptor into practical use, it is necessary to satisfy the above conditions,
Electrophotographic characteristics such as receptive potential, potential holding ability, potential stability, residual potential, spectral characteristics, mechanical durability such as abrasion resistance, heat,
A material that is satisfactory in all respects, such as chemical stability with respect to light and discharge products, must be selected. However, it is extremely difficult to select a combination of materials that satisfies all of these points, and a combination of the charge generation material and the charge transport material that has been conventionally proposed should satisfy the above conditions sufficiently. Has not been obtained. The present invention has been made in view of the circumstances as described above, and an object thereof is to use a specific charge generation material and a specific charge transport material for near infrared light for a semiconductor laser, An object of the present invention is to provide an electrophotographic photosensitive member having extremely high sensitivity, excellent image quality, and excellent repeated stability.

[0005]

The present invention relates to an electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer uses a hydroxygallium phthalocyanine crystal as a charge generating material, and the following charge transporting material is used. It is characterized by using a compound represented by the general formula (I), (II), (III) or (IV).

[Chemical 5] (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or an aryl group, and X represents — (C (CH ₃ )).
_{2 -, - (CH 2)} m - ( provided that, m is an integer of from 1 to _{5), - (OCH 2 CH 2} ) m ( where m is an integer of 1 to 5), - CH = CH -, - CO _{(CH 2) 2 -, -} C
O (CH _{2) 3} -, represent cycloalkyl benzylidene group or cyclohexylidene group. )

[Chemical 6] (In the formula, R ₃ , R ₄ and R ₅ are each a hydrogen atom,
It represents an alkyl group, a substituted or unsubstituted aryl group or an aralkyl group. )

[Chemical 7] (In the formula, R ₆ and R ₇ each represent a hydrogen atom, a halogen atom, an alkyl group, a substituted or unsubstituted aryl group, and R ₈ and R ₉ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, respectively. Represents an aryl group, or represents an atomic group in which R ₈ and R ₉ are combined to form a condensed carbocycle.)

[Chemical 8] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom,
Represents an alkyl group, a substituted amino group or an aryl group,
n is 0 or 1. )

The hydroxygallium phthalocyanine crystal according to the present invention has 1) Bragg angle (2θ ± 0.2 °) of 7.7 °, 1 in X-ray diffraction spectrum.
Crystal form having strong diffraction peaks at 6.5 °, 25.1 ° and 26.6 °, 2) Bragg angle (2θ ± 0.2 °) of 7.9 °, 1
Crystal form having strong diffraction peaks at 6.5 °, 24.4 ° and 27.6 °, 3) Bragg angle (2θ ± 0.2 °) of 7.0 °, 7.
5 °, 10.5 °, 11.7 °, 12.7 °, 17.3
°, 18.1 °, 24.5 °, 26.2 ° and 27.
Crystal type having a strong diffraction peak at 1 °, 4) Bragg angle (2θ ± 0.2 °) of 7.5 °, 9.
9 °, 12.5 °, 16.3 °, 18.6 °, 25.1
Crystal form having strong diffraction peaks at 90 ° and 28.3 °,
And 5) Bragg angle (2θ ± 0.2 °) of 6.8 °, 1
The crystalline forms with strong diffraction peaks at 2.8 °, 15.8 ° and 26.0 ° are used as preferred.

Each layer constituting the electrophotographic photosensitive member of the present invention will be described in detail below. 9 to 14 are schematic cross-sectional views of the electrophotographic photosensitive member of the present invention. 9 to 12 show the case where the photosensitive layer has a laminated structure.
The charge generation layer 1 is provided on the conductive support 3, and the charge transport layer 2 is provided thereon. In FIG. 10, an undercoat layer 4 is further provided on the conductive support 3,
Further, in FIG. 11, a protective layer 5 is provided on the surface. Further, in FIG. 12, both the undercoat layer 4 and the protective layer 5 are provided. 13 and 14 show the case where the photosensitive layer has a single layer structure, and the conductive support 3
The photoconductive layer 6 is provided on the upper side, and in FIG.
Further, an undercoat layer 4 is provided.

In the following, the case where the photosensitive layer has a laminated structure will be mainly described. As the conductive support, metals such as aluminum, nickel, chromium and stainless steel, and plastics provided with thin films of aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, ITO, etc. Examples thereof include a film or the like, paper coated 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 charge generation layer. This undercoat layer is an adhesive layer that prevents the injection of charges from the conductive support to the photosensitive layer during charging of the photosensitive layer, and also integrally holds the photosensitive layer to the conductive support. Or, depending on the case, the function of preventing light reflection of the conductive support. The binder resin used for this undercoat layer is 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 Well-known materials such as a titanyl chelate compound, a titanyl alkoxide compound, an organic titanium compound, and a silane coupling agent can be used. The thickness of the undercoat layer is 0.01 to 10 μm, preferably 0.
The range of 05 to 2 μm is suitable.

The charge generation layer comprises a charge generation material dispersed in a binder resin, and hydroxygallium phthalocyanine crystal is used as the charge generation material.
In the above-mentioned crystal form, that is, in the X-ray diffraction spectrum, 1) Bragg angle (2θ ± 0.2 °) of 7.7 °,
Those having strong diffraction peaks at 16.5 °, 25.1 ° and 26.6 °, 2) Bragg angle (2θ ± 0.2
7.9 °, 16.5 °, 24.4 ° and 27.
Those having a strong diffraction peak at 6 °, 3) Bragg angles (2θ ± 0.2 °) of 7.0 °, 7.5 °, 10.5
°, 11.7 °, 12.7 °, 17.3 °, 18.1
Having strong diffraction peaks at 2 °, 24.5 °, 26.2 ° and 27.1 °, 4) Bragg angle (2θ ± 0.
2 °) is 7.5 °, 9.9 °, 12.5 °, 16.3
With strong diffraction peaks at °, 18.6 °, 25.1 ° and 28.3 °, and 5) Bragg angle (2θ
Those having strong diffraction peaks at 6.8 °, 12.8 °, 15.8 ° and 26.0 ° (± 0.2 °) are preferably used.

These products are prepared by hydrolyzing a chlorogallium phthalocyanine crystal produced by a known method in an acid or alkaline solution, or by acid pasting to synthesize a hydroxygallium phthalocyanine crystal, which is directly solvent-treated. Or a hydroxygallium phthalocyanine crystal obtained by the synthesis with a solvent, a ball mill, a mortar, a sand mill, a wet mill using a kneader or the like, or after performing a dry milling process without using a solvent It can be produced by solvent treatment. When a solvent is used in the above treatment, examples of the solvent include amides (dimethylformamide, N-methylpyrrolidone, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), and Examples include mixed systems of several kinds, mixed systems of water and these organic solvents, and the like. These solvents are 1 to 200 for 1 part of hydroxygallium phthalocyanine.
Parts, preferably 10 to 100 parts. The treatment temperature is in the range of 0 to 150 ° C, preferably room temperature to 100 ° C. In addition, at the time of crushing, a grinding aid such as salt or sodium sulfate may be used. The grinding aid is used in an amount of 0.5 to 20 times, preferably 1 to 10 times the amount of hydroxygallium phthalocyanine.

The binder resin can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene and the like. As a preferable binder resin, polyvinyl butyral resin,
Polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin, polyacrylamide resin, polyvinylpyridine resin, cellulose resin Insulating resins such as urethane resin, epoxy resin, casein, polyvinyl alcohol resin, and polyvinylpyrrolidone resin can be used, but not limited thereto. These binder resins may be used alone or in combination of two or more. In the present invention, the compounding ratio (weight ratio) of hydroxygallium phthalocyanine and the binder resin
Is preferably in the range of 10: 1 to 1:10. Further, as a method of dispersing using the above components, a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like, which is commonly used, can be adopted. At the time of dispersion, the crystalline form of the hydroxygallium phthalocyanine crystal is used. It is necessary to use the condition that does not change. Further, during this dispersion, the particles are 0.5 μm or less, preferably 0.3 μm.
It is effective to make the particle size not more than μm, and more preferably not more than 0.15 μm. As the solvent used for these dispersions, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofutane. Organic solvents such as methylene chloride, methylene chloride, chloroform, chlorobenzene, and toluene can be used, and these can be used alone or in admixture of two or more. A well-known acceptor can be further added to the charge generation layer, whereby sensitivity,
Stability can be increased. As the acceptor, for example, TNF, TeNF, TCNE, benzoquinone, chloranil and the like can be used. The thickness of the charge generation layer is generally 0.1 to 5 μm, preferably 0.2 to
2.0 μm is suitable. Further, as a coating method used when providing the charge generation layer, a blade coating method,
Usual methods such as a Mayer bar coating method, 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.

The charge transport layer is formed by containing the charge transport material in a suitable binder resin. As the charge transport material, the compounds represented by the above general formulas (I) to (IV) are used. Specific examples thereof are shown in Tables 1 to 11 below.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

[Table 4]

[0017]

[Table 5]

[0018]

[Table 6]

[0019]

[Table 7]

[0020]

[Table 8]

[0021]

[Table 9]

[0022]

[Table 10]

[0023]

[Table 11]

Examples of the binder resin used in the charge transport layer include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, Vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly- Known resins such as N-vinylcarbazole can be used, but the present invention is not limited thereto. Among these binder resins, a polycarbonate resin composed of monomer units represented by the following structural formulas (V) to (IX), and a monomer forming the monomer units are obtained by copolymerization. Polycarbonate resin is preferable, in which case a uniform coating film having good compatibility is obtained, and particularly good properties are exhibited.

[0025]

[Chemical 9]

The above binder resins may be used alone or in admixture of two or more. The compounding ratio (weight ratio) of the charge transport material and the binder resin is preferably in the range of 10: 1 to 1: 5. As the solvent used when forming the charge transport layer,
Aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and ethylene chloride, cyclics such as tetrahydrofuran and ethyl ether Ordinarily used organic solvents such as linear ethers may be mentioned, and these may be used alone or
A mixture of two or more species can be used. The thickness of the charge transport layer is generally 5 to 50 μm, preferably 10 to 30 μm.
It is set to the range of. As a coating method for forming the charge transport layer, a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like, which is usually used for coating, is used. Can be used. Above the charge transport layer is
You may provide a protective layer as needed. The protective layer has the functions of preventing chemical deterioration of the charge transport layer during charging of the photosensitive layer and improving the mechanical strength of the photosensitive layer.

The protective layer is formed by containing a conductive material in a suitable binder resin. As the conductive material, N,
Metallocene compounds such as N'-dimethylferrocene, N,
Aromatic amine compounds such as N′-diphenyl-N, N′-bis (3-methylphenyl)-[1.1′-biphenyl] -4,4′-diamine, antimony oxide, tin oxide, titanium oxide, oxidation Materials such as indium and metal oxides such as tin oxide-antimony oxide can be used, but are not limited to these. Examples of the binder resin used for this protective layer include known resins such as polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinylketone resin, polystyrene resin and polyacrylamide resin. The protective layer has an electric resistance of 10 ⁹ to 10
^It is preferable to configure it to be ¹⁴ Ω · cm. When the electric resistance is higher than 10 ¹⁴ Ω · cm, the residual potential is increased and a copy with a lot of fog is formed, and when it is lower than 10 ⁹ Ω · cm, the image is blurred and the resolution is lowered. Will occur. Further, the protective layer should be configured so as not to substantially interfere with transmission of light used for image exposure. The thickness of the protective layer is 0.5 to 20 μm, preferably 1 to 10 μm.

[0028]

EXAMPLES The present invention will be described below with reference to examples. Synthesis Example 1 (Synthesis of hydroxygallium phthalocyanine) 30 parts of 1,3-diiminoisoindoline and 9.1 parts of gallium trichloride were placed in 230 parts of quinoline and reacted at 200 ° C. for 3 hours. After filtering off, washing with acetone and methanol, and then drying the wet cake, 28 parts of chlorogallium phthalocyanine crystals were obtained.
After dissolving 3 parts of the obtained chlorogallium phthalocyanine crystal in 60 parts of concentrated sulfuric acid at 0 ° C., the obtained solution was added dropwise to 450 parts of distilled water at 5 ° C. to reprecipitate the crystal. After washing with distilled water, diluted ammonia water, etc., it was dried to obtain 2.5 parts of hydroxygallium phthalocyanine crystal. The powder X-ray diffraction pattern is shown in FIG. The crystals were crushed for 5.5 hours in an automatic mortar to obtain amorphous hydroxygallium phthalocyanine. The powder X-ray diffraction pattern is shown in FIG.

Synthesis Examples 2 to 5 Hydroxyl gallium phthalocyanine crystals obtained in Synthesis Example 1 showing the powder X-ray diffraction pattern of FIG. 1 or hydroxygallium phthalocyanine showing the powder X-ray diffraction diagram of FIG.
5 parts and 15 parts of the solvent shown in Table 12 below, diameter 1 mm
After milling for 24 hours with 30 parts of glass beads, the crystals were separated. After washing with methanol and drying, hydroxygallium phthalocyanine crystals were obtained. The powder X-ray diffraction patterns are shown in FIGS. As reference data, FIG. 7 shows an infrared absorption spectrum of the hydroxygallium phthalocyanine crystal obtained in Synthesis Example 5. The elemental analysis values are shown in Table 13.

[0030]

[Table 12]

[0031]

[Table 13]

Synthesis Example 6 0.5 part of a hydroxygallium phthalocyanine crystal showing the powder X-ray diffraction pattern of FIG. 1 obtained in Synthesis Example 1 was added to 5 parts of ethylene glycol, and the mixture was stirred at 100 ° C. for 7 hours, and then the crystal was formed. separated. After washing with methanol and drying, hydroxygallium phthalocyanine crystals were obtained. The powder X-ray diffraction pattern is shown in FIG.

Example 1 A zirconium compound (trade name:
Organix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd. 10 parts and a silane compound (trade name: A1110, manufactured by Nippon Unicar Co., Ltd.) 1 part, and a solution consisting of 40 parts of i-propanol and 20 parts of butanol are applied by a dip coating method. Then, it was heated and dried at 150 ° C. for 10 minutes to form an undercoat layer having a film thickness of 0.5 μm. Next, 1 part of the hydroxygallium phthalocyanine crystal obtained in Synthesis Example 5 was added to
Polyvinyl butyral resin (Product name: S-REC BM-
S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate, and treated with a glass bead for 1 hour on a paint shaker to disperse, and the obtained coating liquid is applied to the above-mentioned undercoat layer by a dip coating method. It was applied and heated and dried at 100 ° C. for 10 minutes to form a charge generation layer having a film thickness of 0.15 μm. Further, it was confirmed by X-ray diffraction that the crystal form of the hydroxygallium phthalocyanine crystal after dispersion was not changed as compared with the crystal form before dispersion. Next, 2 parts of the exemplified compound I-3 and 3 parts of a polycarbonate resin composed of the monomer unit represented by the exemplified structural formula (VII) are dissolved in 29 parts of monochlorobenzene, and the obtained coating solution is It was applied on an aluminum substrate having a charge generation layer formed thereon by a dip coating method, and dried by heating at 120 ° C. for 1 hour to form a charge transport layer having a film thickness of 20 μm. The electrophotographic characteristics of the electrophotographic photoreceptor thus obtained were evaluated using an electrostatic copying tester (Electrostatic Analyzer EPA-8100, manufactured by Kawaguchi Electric Co., Ltd.). That is, normal temperature and humidity (20 ° C, 40% R
In the environment of H), after corona discharge of -6 KV and charging, the light of the tungsten lamp is converted into monochromatic light of 800 nm using a monochromator, and 1 μW /
Irradiation was carried out after adjusting to cm ² . And the surface potential V0 (V), to measure the half decay exposure ^{E1 / 2 (erg / cm 2} ), a white light of 10 lux was irradiated for 1 second, to measure the residual potential VR (V). Furthermore, the above charging,
V0, E1 / 2 and V after exposure was repeated 1000 times
R was measured. Then, the fluctuation amounts thereof are ΔV0, ΔE1 /
2 and ΔVR. The results are shown in Table 14.

Examples 2 to 21 Exemplified Compound I-3 which is the charge transport material in Example 1
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the charge transporting materials shown in Tables 14 to 15 were used instead of, and the same measurement was performed. The results are shown in Table 14.
And shown in Table 15.

Comparative Example 1 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that the compound represented by the following structural formula (X) was used in place of the charge transport material in Example 1. Was measured. The results are shown in Table 15.

[Chemical 10]

Comparative Example 2 An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the compound represented by the following structural formula (XI) was used instead of the charge transport material in Example 1. Was measured. The results are shown in Table 15.

[Chemical 11]

Comparative Example 3 An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that polyvinylcarbazole was used alone as the charge transport material, and the same measurements were performed. The results are shown in Table 15.

Comparative Example 4 Instead of the hydroxygallium phthalocyanine crystal in Example 1, an x-type metal-free phthalocyanine (x-
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that H ₂ Pc) was used, and the same measurement was performed. The results are shown in Table 15. Comparative Example 5 Instead of the hydroxygallium phthalocyanine crystal in Example 10, x-type metal-free phthalocyanine (x
An electrophotographic photosensitive member was produced in the same manner as in Example 10 except that —H ₂ Pc) was used, and the same measurement was performed. The results are shown in Table 15. Comparative Example 6 Instead of the hydroxygallium phthalocyanine crystal in Example 14, x-type metal-free phthalocyanine (x
An electrophotographic photosensitive member was prepared in the same manner as in Example 14 except that —H ₂ Pc) was used, and the same measurement was performed. The results are shown in Table 15. Comparative Example 7 Instead of the hydroxygallium phthalocyanine crystal in Example 19, x-type metal-free phthalocyanine (x
An electrophotographic photosensitive member was produced in the same manner as in Example 19 except that —H ₂ Pc) was used, and the same measurement was performed. The results are shown in Table 15.

[0039]

[Table 14]

[0040]

[Table 15]

[0041]

EFFECT OF THE INVENTION The electrophotographic photoreceptor of the present invention uses the above-mentioned specific combination as the charge-generating material and the charge-transporting material. It has very high sensitivity to near-infrared light for use, excellent image quality, and excellent repeatability.

[Brief description of drawings]

FIG. 1 shows a powder X-ray diffraction diagram of a hydroxygallium phthalocyanine crystal obtained in Synthesis Example 1.

FIG. 2 shows a powder X-ray diffraction pattern of amorphous hydroxygallium phthalocyanine obtained in Synthesis Example 1.

FIG. 3 shows a powder X-ray diffraction pattern of the hydroxygallium phthalocyanine crystal obtained in Synthesis Example 2.

FIG. 4 shows a powder X-ray diffraction pattern of the hydroxygallium phthalocyanine crystal obtained in Synthesis Example 3.

FIG. 5 shows a powder X-ray diffraction pattern of the hydroxygallium phthalocyanine crystal obtained in Synthesis Example 4.

FIG. 6 shows a powder X-ray diffraction pattern of the hydroxygallium phthalocyanine crystal obtained in Synthesis Example 5.

FIG. 7 shows an infrared absorption spectrum diagram of the hydroxygallium phthalocyanine crystal obtained in Synthesis Example 5.

FIG. 8 shows a powder X-ray diffraction pattern of the hydroxygallium phthalocyanine crystal obtained in Synthesis Example 6.

FIG. 9 shows a schematic sectional view of an example of the electrophotographic photosensitive member of the present invention.

FIG. 10 shows a schematic sectional view of an example of the electrophotographic photosensitive member of the present invention.

FIG. 11 shows a schematic sectional view of an example of the electrophotographic photosensitive member of the present invention.

FIG. 12 shows a schematic sectional view of an example of the electrophotographic photosensitive member of the present invention.

FIG. 13 shows a schematic sectional view of an example of the electrophotographic photosensitive member of the present invention.

FIG. 14 is a schematic sectional view of an example of the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

1 ... Charge generating layer, 2 ... Charge transporting layer, 3 ... Conductive support,
4 ... Undercoat layer, 5 ... Protective layer, 6 ... Photoconductive layer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Yamazaki 1600 Takematsu, Ashigara, Kanagawa Prefecture, Fuji Xerox Co., Ltd. Takematsu Plant (72) Fumio Kojima 1600 Takematsu, Ashigara, Kanagawa Fuji Xerox Co., Ltd. Takematsu Business In-house (72) Masayuki Nishikawa 1600 Takematsu, Ashigara, Kanagawa Prefecture Fuji Xerox Co., Ltd., Takematsu Works (72) Inventor Ryosaku Igarashi 1600 Takematsu, Ashigara, Kanagawa Fuji Xerox Co., Ltd., Takematsu Office (72) Inventor Kiyokazu Mashita 1600 Takematsu, Ashigara, Kanagawa Fuji Xerox Co., Ltd. Takematsu Plant

Claims (6)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer uses a hydroxygallium phthalocyanine crystal as a charge generating material, and a charge transporting material represented by the following general formula (I), ( II), (III) or (IV) is used as an electrophotographic photoreceptor. [Chemical 1] (In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or an aryl group, and X represents — (C (CH ₃ )).
_{2 -, - (CH 2)} m - ( provided that, m is an integer of from 1 to _{5), - (OCH 2 CH 2} ) m ( where m is an integer of 1 to 5), - CH = CH -, - CO _{(CH 2) 2 -, -} C
O (CH _{2) 3} -, represent cycloalkyl benzylidene group or cyclohexylidene group. ) [Chemical 2] (In the formula, R ₃ , R ₄ and R ₅ are each a hydrogen atom,
It represents an alkyl group, a substituted or unsubstituted aryl group, or an aralkyl group. ) [Chemical 3] (In the formula, R ₆ and R ₇ each represent a hydrogen atom, a halogen atom, an alkyl group, a substituted or unsubstituted aryl group, and R ₈ and R ₉ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, respectively. Represents an aryl group or represents an atomic group in which R ₈ and R ₉ are combined to form a condensed carbocycle. (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom,
Represents an alkyl group, a substituted amino group or an aryl group,
n is 0 or 1. ) 2. A hydroxygallium phthalocyanine crystal has a Bragg angle (2θ) in an X-ray diffraction spectrum.
2. The electrophotographic photosensitive member according to claim 1, which is a crystal type having strong diffraction peaks at 7.7 °, 16.5 °, 25.1 ° and 26.6 ° of ± 0.2 °). .. 3. A hydroxygallium phthalocyanine crystal has a Bragg angle (2θ) in an X-ray diffraction spectrum.
2. The electrophotographic photosensitive member according to claim 1, which is a crystal type having strong diffraction peaks at 7.9 °, 16.5 °, 24.4 ° and 27.6 ° of ± 0.2 °). .. 4. A hydroxygallium phthalocyanine crystal has a Bragg angle (2θ) in an X-ray diffraction spectrum.
± 0.2 °) 7.0 °, 7.5 °, 10.5 °, 1
1.7 °, 12.7 °, 17.3 °, 18.1 °, 2
The electrophotographic photosensitive member according to claim 1, which is of a crystal type having strong diffraction peaks at 4.5 °, 26.2 ° and 27.1 °. 5. A hydroxygallium phthalocyanine crystal has a Bragg angle (2θ) in an X-ray diffraction spectrum.
± 0.2 °) 7.5 °, 9.9 °, 12.5 °, 1
The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is of a crystal type having strong diffraction peaks at 6.3 °, 18.6 °, 25.1 ° and 28.3 °. 6. A hydroxygallium phthalocyanine crystal has a Bragg angle (2θ) in an X-ray diffraction spectrum.
2. The electrophotographic photosensitive member according to claim 1, which is a crystal type having strong diffraction peaks at 6.8 °, 12.8 °, 15.8 ° and 26.0 ° of ± 0.2 °). ..