JPH11352710A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high durability and high sensitivity to a light in near infrared region as well as excellent in other potential characteristics by using a crystalline oxotitanyl phthalocyanine having extremely high sensitivity in a long wavelength region. SOLUTION: This electrophotographic photoreceptor uses a crystalline oxotitanyl phthalocyanine, a charge transfer material such as an enamine compd. and a binder such as a polycarbonate resin. The crystalline oxotitanyl phthalocyanine is expressed by the formula and shows 9.4 or 9.7 max. diffraction peak of a Bragg angle (2θ±0.2 deg.) in an X-ray diffraction spectrum and 7.4 deg., 9.4 deg., 9.7 deg. and 27.3 deg. diffraction peaks. In the formula, X is hydrogen atom, a halogen atom, an alkyl group or an alkoxy group and m is an integer of 0 to 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor using oxotitanyl phthalocyanine of a specific crystal type as a charge generating material.

[0002]

2. Description of the Related Art Electrophotographic photoconductors that are currently in practical use are classified into inorganic photoconductors using inorganic materials and organic photoconductors using organic materials.

[0003] Since there are many kinds of organic materials themselves, an organic material itself can be produced with excellent storage stability and non-toxicity by appropriately selecting it, and it is easy to form a thin film by coating, and it can be manufactured at low cost. In recent years, sensitivity and durability have been rapidly improved, and at present, as an electrophotographic photoreceptor, organic materials are used except in special cases. It is becoming.

In recent years, laser beam printers and the like which use laser light as a light source instead of the conventional white light and have the advantages of high speed, high image quality and non-impact have become widespread. The development of the body is desired. In particular, various methods using a semiconductor laser as a light source, which has been remarkably progressing in recent years, have been attempted. In this case, the wavelength of the light source is about 800 nm, so that 8
There is a strong demand for a photoreceptor having high sensitivity to long wavelength light of about 00 nm.

Conventionally, organic materials satisfying this requirement include methine squaric acid dyes, indoline dyes,
Cyanine dyes, bilylium dyes, polyazo dyes,
Phthalocyanine dyes and naphthoquinone dyes are known. Methine squaric acid dyes, indoline dyes, cyanine dyes, and bilylium dyes can have longer wavelengths but have practical stability (repeating characteristics). In short, polyazo dyes are difficult to increase the wavelength and are disadvantageous in production, and naphthoquinone dyes have difficulty in sensitivity at present. For this reason, phthalocyanine dyes are often used.

A photosensitive member using a metal phthalocyanine compound among phthalocyanine dyes is disclosed in US Pat. No. 33579.
89, JP-A-49-11136, U.S. Pat. No. 4,214,907, British Patent No. 1,268,422, and the like, the sensitivity peak varies depending on the central metal, but in each case, it is 700 to 750 nm. Relatively longer wavelength side. However, it cannot cope with the wavelength range of 800 nm of semiconductor laser light currently used.

[0007] Among metal phthalocyanines, oxotitanyl phthalocyanine which exhibits high sensitivity particularly on the long wavelength side is being studied intensively in recent years.

[0008] Oxotitanyl phthalocyanine is represented by X as described in Journal of the Society of Electrophotography, Vol. 32, No. 3, p.
It is classified into many crystal types based on the difference in the diffraction angle of the line diffraction spectrum. Specifically, when showing a characteristic crystal form,
JP-A-61-217050, JP-A-61-239
No. 248, α-type, JP-A-62-67094, A-type, JP-A-63-366, JP-A-63-1
Japanese Patent No. 98067 discloses a C type, Japanese Patent Application Laid-Open No. 63-20365, Japanese Patent Application Laid-Open No. 2-2256, and Japanese Patent Application Laid-Open No. 1-1706.
No. 6 discloses a Y-type, and JP-A-3-54265 discloses a M-type.
JP-A-3-54264 describes an M-α type crystal, and JP-A-3-128973 describes an I-type crystal. JP-A-62-67094 describes type I and II crystals.

However, in many of the oxotitanyl phthalocyanine crystals, the lattice constants of which are known from the structural analysis are C-type, Phase-I, and Phase-I.
Type eII. Phase II type is triclinic, Pha
seI type and C type belong to the monoclinic system. When the crystal forms described in the above publication are analyzed from these known crystal lattice constants, A-type and I-type belong to Phase I type, α-type and B-type belong to Phase II-type, and M-type belongs to C-type. (Documents explaining the same thing include J. of Im
aging Science and Technology
ogy Vol. 37 No. 6 1993 p605
~ P609).

JP-A-59-49544 discloses that oxotitanyl phthalocyanines are deposited on a substrate to form a charge generating layer, and 2,6-dimethoxy-9,10-dihydroxyanthracene is further formed thereon. There is disclosed an electrophotographic photosensitive member provided with a charge transfer layer mainly composed of: However, the photoreceptor has a high residual potential and is somewhat restricted in the method of use, and is disadvantageous in terms of reproducibility of various electrical characteristics due to non-uniformity of the film thickness by a vapor deposition method. There is no choice but to restrict mass production on a scale.

On the other hand, as a problem of the photoreceptor itself, the occurrence of interference fringes, which is considered to be mainly caused by the reflection of the laser beam used for exposure on the substrate, occurs, and several techniques are known as methods for solving the problem. One known method is to increase the thickness of the charge generation layer and absorb the exposed laser light to eliminate reflection from the substrate. However, there is a limit to the thickness that can be formed by a conventional vapor deposition method. There are also difficult to control.

On the other hand, the method of forming a charge generation layer by applying a binder dispersion liquid is easy to control at an arbitrary thickness with good reproducibility, and does not require a high vacuum device at the time of vapor deposition. In addition, thermal decomposition and thermal denaturation due to heating can be avoided. Further, it is advantageous because there is no inconvenience in industrial production such as crystallization of a vapor-deposited product by various methods after vapor deposition as in a vapor deposition method.

JP-A-61-109056 discloses an electrophotographic photosensitive member in which a charge transfer layer containing a hydrazone compound and a binder polymer is laminated on a charge generation layer containing an oxotitanyl phthalocyanine compound and a binder polymer. Although it provides an electrophotographic photosensitive member having a sensitivity of about 800 nm, it does not reach the sensitivity required for high image quality and high speed at present.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide high sensitivity to near-infrared light for semiconductor lasers, excellent electrical characteristics, little decrease in sensitivity even after repeated use, and an increase in the charging potential. An object of the present invention is to provide an electrophotographic photosensitive member that is stable and has excellent wear resistance.

[0015]

The electrophotographic photoreceptor of the present invention comprises at least one of an oxotitanyl phthalocyanine compound having a specific crystal type which has not been hitherto known, and an enamine compound, a hydrazone compound, a styryl compound, a distyryl compound and a butadiene compound. Characterized by containing any one of them.

The oxotitanyl phthalocyanine compound is represented by the following general formula (1), and shows a maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 9.4 ° in an X-ray diffraction spectrum, and at least: 7.4 ゜, 9.7
It is a crystalline oxotitanyl phthalocyanine showing a diffraction peak at {, 27.3}.

[0017]

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In the formula, X represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and m represents an integer of 0 to 4.

Alternatively, the oxotitanyl phthalocyanine compound is represented by the general formula (1), and has a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum.
9.7 ° shows the maximum diffraction peak and at least
Crystalline oxotitanyl phthalocyanine which shows diffraction peaks at 7.4 °, 9.4 °, and 27.3 ° may be used.

In the above electrophotographic photosensitive member, the photosensitive layer is provided on a conductive support. As the conductive support, a metal material such as aluminum, stainless steel, copper, and nickel is used. Or, aluminum, copper, palladium, tin oxide on the surface of polyester film, paper, etc.
A surface conductive support provided with a conductive layer such as indium oxide may be used.

A known intermediate layer, which is usually used, may be provided between the conductive support and the photosensitive layer.
As the intermediate layer, an inorganic layer of aluminum anodic oxide film, aluminum oxide, aluminum hydroxide, titanium oxide, etc.,
Alternatively, an organic layer such as polyvinyl alcohol, casein, polyvinylpyrrolidone, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, and polyamide is used.

The photosensitive layer of the electrophotographic photosensitive member contains the oxotitanyl phthalocyanine compound of the present invention, at least one of an enamine compound, a hydrason compound, a styryl compound, and a butadiene compound, and a binder polymer. Are laminated in this order,
Alternatively, any of the above-described laminated type and the so-called dispersion type in which the charge generation material particles are dispersed in the charge transport medium can be used.

The charge generation layer comprises the fine particles of the oxotitanyl phthalocyanine compound of the present invention, for example, polyester resin, polyvinyl acetate, polyacrylate,
Polyester binder, various binders of polyester, polycarbonate, polyvinyl chloride, polyvinyl acetate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin, cellulose ester, cellulose ether, etc. or copolymers thereof It may be used in a dispersion layer bound by a polymer. In this case, the amount of the phthalocyanine compound used is 0.2 to the binder polymer.
Used in the range of 10 to 10 parts by weight, and the film thickness is 0.1 μm
To 20 μm. Further, the charge generation layer may contain various additives such as a leveling agent for improving coatability, an antioxidant, and a sensitizer, if necessary.

The charge transport layer is a layer containing a binder polymer and a charge transport substance. As the charge transport material, an enamine compound, a hydrazone compound, a styryl compound, a distyryl compound, and a butadiene compound are used. As the enamine compound, a compound represented by the following general formula (2) is preferable.

[0025]

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However, Ar ₁ may have an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. A heterocyclic alkyl group, and n is 2, 3 or 4.

FIGS. 8 to 12 show specific examples of the enamine compound represented by the general formula (2).

As the hydrazone compound, a compound represented by the following general formula (3) or (4) is preferable.

[0029]

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Here, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an aralkyl group or an aryl group which may be substituted, and R ₅ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. , R ₁ and R ₂ may combine to form a ring, or one of R ₁ and R ₂ and R ₅ may combine to form a ring.

[0031]

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Wherein A, B and R ₇ represent a hydrogen atom, a lower alkyl group, a dialkylamino group, a lower arakoxy group,
Represents a phenoxy group or an arylalkoxy group, R ₆ represents a hydrogen atom, a lower alkyl group, an allyl group, a phenyl group or an aralkyl group, q and r represent an integer of 1 or 2, and p represents 0 or 1. Represent.

FIG. 13 shows a specific example of the hydrazone compound represented by the general formula (3) or (4).

The styryl compound is represented by the following general formula (5)
Are preferred.

[0035]

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However, Ar ₂ and Ar ₃ are an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group or a hetero-substituted alkyl group which may have a substituent,
Alternatively, it represents a hydrogen atom. R ₈ , R ₉ and R ₁₀ represent an optionally substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group, a dialkylamino group, a halogen atom or a hydrogen atom.

FIG. 14 shows a specific example of the styryl compound represented by the general formula (5).

As the distyryl compound, a compound represented by the following general formula (6) is preferable.

[0039]

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Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent an aryl group or an alkyl group which may be substituted, and R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group,
Represents an alkoxy group, and Ar ₄ represents an optionally substituted aryl group or an aromatic heterocyclic group.

Specific examples of the distyryl compound represented by the general formula (6) are shown in FIGS.

As the butadiene compound, a compound represented by the following general formula (7) is preferable.

[0043]

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However, R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ each represent an aryl group or an alkyl group which may be substituted, and R ₁₅ and R ₁₆ each represent a hydrogen atom.

FIG. 19 shows a specific example of the distyryl compound represented by the general formula (7).

Examples of the binder polymer include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, and copolymers thereof, polycarbonate, polyester, polyester carbonate, polysulfone, phenoxy, epoxy, and silicone resin. These may be used alone or as a mixture of two or more kinds, or a partially crosslinked thermosetting resin may be used. In particular, a mixture of a polycarbonate represented by the following general formula (8) or a polyester resin represented by the following general formula (8) and the following general formula (9) is preferable.

[0047]

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However, R ₂₇ and R ₂₈ each have an alkyl group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, and a substituent. Represents an aralkyl group having 7 to 17 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom, and X is directly bonded or substituted An alkylene group having 1 to 10 carbon atoms which may have a group, a cyclic alkylidene group having 1 to 10 carbon atoms which may have a substituent, and 6 to 12 carbon atoms which may have a substituent
Represents an arylene group, a sulfonyl group, a carbonyl group,
Z represents an alkylene group having 1 to 5 carbon atoms which may have a substituent, an arylene group having 6 to 12 carbon atoms, an arylene alkyl group having 7 to 17 carbon atoms, or a halogen atom, and Y represents a substituent. C1-5 alkyl group which may be substituted, C2-5 alkenyl group which may have a substituent, C1-5 alkoxy group which may have a substituent, and C1-5 which may have a substituent. E, f represents an alkyl ester group, an aryl ester group having 6 to 12 carbon atoms which may have a substituent, a carboxyl group, an aldehyde group, a hydroxyl group, a halogen atom, or a hydrogen atom;
Represents an integer of 1 to 4, and u represents an integer of 10 to 200.

FIG. 20 shows a specific example of the polycarbonate resin represented by the general formula (9).

[0050]

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Where g, h, and i are integers of 1 to 10,
v, w, x, and y represent an integer of 10 to 1,000.

The polyester resin of the general formula (9) is used in an amount of 0.05 to 0.5 parts by weight, preferably 0.2 to 0.3 parts by weight, based on the whole binder.

The compounds represented by formulas (2) to (7) are used in an amount of 0.2 to 1.5 parts by weight, preferably 0.3 to 1.2 parts by weight, based on the binder polymer. You.

The charge transport layer may contain various additives such as a leveling agent, an antioxidant, and a sensitizer, if necessary. Particularly, α-tocopherol is preferable as the antioxidant. The thickness of the charge transport layer is 10 to 60 μm, preferably 10 to 40 μm.

As the outermost surface layer, a conventionally known overcoat layer mainly composed of, for example, a thermoplastic or thermosetting polymer may be provided. Usually, the charge transport layer is formed on the charge generation layer, but the reverse is also possible. As a method for forming each layer, a known method such as sequentially applying a coating solution obtained by dissolving or dispersing a substance to be contained in a layer in a solvent can be applied.

In the case of the dispersion type photosensitive layer, the phthalocyanine compound is dispersed in the charge transporting layer having the above-described compounding ratio. The particle size in that case must be small enough,
Preferably, it is used at 1 μm or less. If the amount of the charge generating substance dispersed in the photosensitive layer is too small, the sensitivity becomes insufficient, and if the amount is too large, adverse effects such as lowering of the charging property and lowering of the sensitivity are caused, and 0.5 to 50% by weight, preferably 1 to 20% by weight. Used in weight percent. The thickness of the photosensitive layer is 5 to 50 μm, preferably 10 to 40 μm. Also in this case, a known plasticizer for improving film formability, flexibility, mechanical strength, etc., an additive for suppressing residual potential, a dispersion auxiliary for improving dispersion stability, and a coating property. Leveling agents and surfactants, such as silicone oils, fluorine-based oils, and other additives, may be added. Particularly, dimethylpolysiloxane is preferable as the leveling agent.

The electrophotographic photoreceptor of the present invention has the general formula (1)
Is used as the charge generating substance, and the general formulas (2), (3), (4), (5), (6),
The charge transporting material shown in (7) is used as a charge transporting material, and various modes are conceivable in this embodiment. The structure of the photoreceptor is schematically shown in FIGS.

FIG. 1 shows a photosensitive layer 4 on a conductive support 1.
A function-separated type photoreceptor comprising a laminate of a charge generation layer 5 having a charge generation material 2 as a main component dispersed in a binder and a charge transport layer 6 having a charge transport material 3 as a main component dispersed in a binder It shows the configuration of FIG.

FIG. 2 shows the photosensitive layer 4 ′ on the conductive support 1.
Shows a configuration of a photoconductor composed of a single layer in which a charge generation material 2 and a charge transport material 3 are dispersed in a binder.

FIG. 3 shows a structure in which an intermediate layer 7 is provided between the conductive support 1 and the same photosensitive layer 4 as in FIG. is there.

FIG. 4 shows a single-layer photosensitive member in which an intermediate layer 7 is provided between the conductive support 1 and the same photosensitive layer 4 'as in FIG.

[0062]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The production method and potential characteristics of a photoreceptor using these materials will be described more specifically with reference to the following examples.

(Production Example 1) o-phthalodinitrile 40
g, titanium tetrachloride 18 g, α-chloronaphthalene 500
The mixture was heated and stirred at 200 to 250 ° C. for 3 hours in a nitrogen atmosphere, allowed to react, allowed to cool to 100 to 130 ° C., filtered while hot, and heated to 100 ° C., and then heated to 100 ° C.
1 to obtain a crude product of dichlorotitanium phthalocyanine.

This crude product is washed at room temperature with 200 ml of α-chloronaphthalene, then with 200 ml of methanol, and further washed with 500 ml of methanol for 1 hour under hot suspension. The crude product obtained after filtration is stirred and dissolved in 100 ml of concentrated sulfuric acid, and the insoluble matter is collected by filtration.

The sulfuric acid solution was poured into 3000 ml of water,
The precipitated crystals are collected by filtration and, in 500 ml of water, have a pH of 6 to
After repeating hot suspension washing until 7, the wet cake was treated again with dichloromethane, washed with methanol, and dried to obtain the crystals of the present invention.

FIG. 5 shows the X-ray diffraction spectrum of this crystal. A maximum diffraction peak is shown at a Bragg angle (2θ ± 0.2 °) of 9.4 °, and 7.4 °, 9.7 °, and 27.3.
゜ has a diffraction peak, which indicates that it is a crystalline oxotitanyl phthalocyanine used in the electrophotographic photoreceptor of the present invention.

(Comparative Production Example 1) A crude product of dichlorotitanium phthalocyanine was obtained in the same manner as in Production Example 1, and this crude product was treated with α-chloronaphthalene 20 at room temperature.
After washing with 0 ml and then with 200 ml of methanol, hot washing with 500 ml of methanol is further performed for 1 hour. The crude product obtained after filtration was repeatedly heated and washed in 500 ml of water until the pH reached 6 to 7, and then dried to obtain a crystal of Comparative Production Example 1.

FIG. 7 shows the X-ray diffraction spectrum of this crystal. A maximum diffraction peak is shown at a Bragg angle (2θ ± 0.2 °) of 27.3 °, and 7.4 °, 9.7 ° and 27.
It has a diffraction peak at 3 °.
It can be seen that this is the oxotitanyl phthalocyanine of the crystal type described in JP-A-6.

(Production Example 2) Crystals of oxotitanyl phthalocyanine obtained in Comparative Production Example 1 were mixed with methyl ethyl ketone, milled together with glass beads having a diameter of 2 mm by a paint conditioner (manufactured by Red Level Co.), and washed with methanol. After drying, the crystals of the present invention were obtained.

FIG. 6 shows the X-ray diffraction spectrum of this crystal. It shows the maximum diffraction peak at a Bragg angle (2θ ± 0.2 °) of 9.7 °, and 7.4 °, 9.4 ° and 27.3.
゜ has a diffraction peak, which indicates that it is a crystalline oxotitanyl phthalocyanine used in the electrophotographic photoreceptor of the present invention.

Example 1 An aluminum-evaporated polyester film was used as a conductive support. On this support, 6 parts by weight of copolymerized nylon (CM8000, manufactured by Toray Industries, Inc.) were mixed with 47 parts by weight of methyl alcohol and 47 parts by weight of chloroform. The solution dissolved in the mixed solvent was applied and dried to form an intermediate layer having a thickness of 1 μm.

As a charge generating substance, 1 part by weight of the crystalline oxotitanyl phthalocyanine having the X-ray diffraction pattern shown in FIG. 5 obtained in Production Example 1 and polybutyral (ESLEK BL manufactured by Sekisui Chemical Co., Ltd.) as a binder
-1) 1 part by weight and 70 parts by weight of methyl ethyl ketone were mixed and dispersed with glass beads having a diameter of 2 mm by a paint conditioner (manufactured by Red Level Co.), and the obtained solution was applied on the intermediate layer and dried. Thus, a charge generation layer having a thickness of 0.4 μm was formed.

An enamine compound (N
o. 2-1) 10 parts by weight, 8 parts by weight of a polycarbonate resin (No. 8-1) as a binder, 2 parts by weight of a polyester resin (9), 0.2 part by weight of α-tocopherol as an antioxidant, and as a leveling agent 0.0002 parts by weight of polydimethylsiloxane was mixed, and a 15 wt% solution was prepared using methylene chloride as a solvent. The solution was applied on a charge generation material film to form a charge transfer layer having a dry film thickness of 25 μm.

As described above, a laminated electrophotographic photosensitive member sample 1 comprising a charge generation layer and a charge transport layer was obtained.

(Examples 2, 3, 4, and 5) The hydrazone compound (No. 3-1), the styryl compound (No. 5-1), and the distyryl compound (No. 6) were used as the charge transport materials.
1), using the butadiene compound (No. 7-1), in the same manner as in Example 1 to obtain the laminated electrophotographic photosensitive member samples 2, 3, 4,
5 was obtained.

(Example 6) As the charge generating substance, except that the crystalline oxotitanyl phthalocyanine having the X-ray diffraction pattern shown in FIG. 6 obtained in Production Example 2 was used.
A laminated electrophotographic photosensitive member sample 6 was obtained in the same manner as in Example 1.

(Examples 7, 8, 9, and 10) The hydrazone compound (No. 3-1), the styryl compound (No. 5-1), and the distyryl compound (No. 6) were used as the charge transport materials.
1), using the butadiene compound (No. 7-1), in the same manner as in Example 6, to obtain the laminated electrophotographic photosensitive member samples 7, 8,
9, 10 were obtained.

Comparative Example 1 The same procedure as in Example 1 was repeated except that the oxotitanyl phthalocyanine crystal having the X-ray diffraction pattern shown in FIG. 7 obtained in Comparative Production Example 1 was used as the charge generating material. Photoreceptor sample 1
1 was obtained.

Comparative Example 2 A laminated photoreceptor sample 12 was obtained in the same manner as in Example 1 except that a triphenylamine compound represented by the following general formula (10) was used as the charge transporting substance.

[0080]

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(Comparative Example 3) Polycarbonate resin (manufactured by Mitsubishi Gas Chemical Company) as a binder polymer for the charge generation layer
A laminated photoreceptor sample 13 was obtained in the same manner as in Example 1 except that PCZ-200) was used.

Comparative Example 4 A laminated photoreceptor sample 14 was obtained in the same manner as in Example 1 except that α-tocopherol was not added to the charge generation layer.

Comparative Example 5 A laminated photoreceptor sample 15 was prepared in the same manner as in Example 1 except that polydimethylsiloxane was not added to the charge generation layer. No film was obtained.

FIG. 21 shows a photoreceptor sample obtained as described above. The produced function-separated laminated electrophotographic photoreceptor is an electrostatic recording paper tester (Kawaguchi Electric; EPA-820).
The electrophotographic characteristics were evaluated according to 0). The measurement conditions were as follows: applied voltage: -6 kV, static: No. 3 and monochromatic light of 780 nm (irradiation light: 10
μW / cm ²⁾ required to attenuate the -350V from -700V by exposure i.e. half-life exposure E _1/2 (.mu.J
/ Cm ² ).

Further, a commercially available digital copying machine (AR5130 manufactured by Sharp Corporation) was remodeled, and the photosensitive member shown in FIG. 21 was used for the drum portion, and a continuous blank copy (Non Copy Agi) was performed.
ng) was performed 30,000 times, and before and after the measurement, the initial charging potential V ₀ (−volt) and the residual potential V _R (−volt) were measured. Further, the half-exposure amount E1 _{/ 2} after the continuous blank copy was measured again using the electrostatic recording paper test apparatus.

Further, the degree of reduction in the thickness of the photoreceptor was evaluated using an abrasion tester manufactured by Suga Test Instruments Co., Ltd. The measurement conditions were as follows: abrasive = aluminum oxide # 2000, load = 200 g
f, the number of times of friction = 10000 times. The results are shown in FIG.

Example 11 1 part by weight of the crystalline oxotitanyl phthalocyanine of Production Example 1 of the present invention as a charge generating substance, and an enamine compound (No.
2-1) 20 parts by weight, 16 parts by weight of a polycarbonate resin (No. 8-1) as a binder, 4 parts by weight of a polyester resin (9), 0.4 part by weight of α-tocopherol as an antioxidant, and a leveling agent 0.0004 parts by weight of polydimethylsiloxane and methylene chloride 16
The mixture was mixed with glass beads having a diameter of 2 mm for about 90 minutes using a paint conditioner (manufactured by Red Level Co., Ltd.).

Next, the dispersion was applied to a conductive support provided with an intermediate layer similar to that of Example 1, to obtain a single-layer type photoreceptor sample 1 comprising a photosensitive layer having a dry film thickness of 25 μm. .

(Examples 12, 13, 14, and 15) As charge transporting substances, hydrazone compounds (No. 3-1), styryl compounds (No. 5-1), and distyryl (No. 6) were used.
1) and single-layer type electrophotographic photoreceptor samples 2, 3, 4, and 5, respectively, using butadiene compound (No. 7-1) in the same manner as in Example 11.

Comparative Example 6 A single-layer type was prepared in the same manner as in Example 11 except that the oxotitanyl phthalocyanine crystal having the X-ray diffraction pattern shown in FIG. 7 and obtained in Comparative Production Example 1 was used as the charge generating substance. An electrophotographic photosensitive member sample 6 was obtained.

Comparative Example 7 A single-layer photosensitive member sample 7 was obtained in the same manner as in Example 11 except that the triphenylamine compound represented by the general formula (10) was used as the charge transporting substance.

Comparative Example 8 A single-layer photosensitive member sample 8 was obtained in the same manner as in Example 11, except that a polycarbonate resin (PCZ-200 manufactured by Mitsubishi Gas Chemical Company) was used as the binder polymer for the charge generation layer.

Comparative Example 9 A single-layer photosensitive member sample 9 was obtained in the same manner as in Example 11 except that α-tocopherol was not added to the charge generation layer.

Comparative Example 10 A single-layer type photoreceptor sample 10 was prepared in the same manner as in Example 11, except that polydimethylsiloxane was not added to the charge generation layer. No coating was obtained.

FIG. 23 shows a photoreceptor sample obtained as described above.

The produced single-layer type electrophotographic photoreceptor was also measured by using an electrostatic recording paper tester under the same measuring conditions and an applied voltage of +6 k.
V, static: No. 3, 780 nm monochromatic light (irradiation light: 10 μW / c)
m ² ), the amount of exposure required to attenuate from +700 V to +350 V, that is, half-exposure amount E _1/2 (μJ / cm ² )
Was measured.

Further, a commercially available digital copying machine (AR5130 manufactured by Sharp Corporation) was modified to use the photosensitive member shown in FIG. 23 for the drum portion, and to make a continuous blank copy (Non Copy Agi).
ng) was performed 30,000 times, and before and after that, the initial charging potential V ₀ (+ volt) and the residual potential V _R (+ volt) were measured. Further, the half-life exposure amount E1 _{/ 2} after continuous blank copy was measured using the electrostatic recording paper test apparatus.

Further, the degree of reduction in the thickness of the photoreceptor was evaluated using an abrasion tester manufactured by Suga Test Instruments Co., Ltd. The measurement conditions were as follows: abrasive = aluminum oxide # 2000, load = 200 g
f, the number of times of friction = 10000 times. Figure 2 shows the result.
It is shown in FIG.

[0099]

As is apparent from the above, the present invention provides an electrophotographic photosensitive member having extremely high spectral sensitivity in a long wavelength region and high durability. Therefore, the present invention is suitable for a photoreceptor such as a laser printer or a digital copier using a semiconductor laser beam as a light source, which has been remarkably developed recently.

[Brief description of the drawings]

FIG. 1 is a diagram showing a function-separated type photoconductor in which a photosensitive layer is composed of a charge generation layer and a charge transport layer.

FIG. 2 shows a photosensitive layer comprising an intermediate layer, a charge generation layer and a charge transport layer.
FIG. 3 is a diagram showing a function-separated type photoconductor composed of layers.

FIG. 3 is a diagram illustrating a single-layer type photoconductor in which a charge generation material is dispersed in a charge transport layer.

FIG. 4 is a diagram showing a single-layer type photoreceptor having an intermediate layer and a charge transport material in which a charge generation material is dispersed.

FIG. 5 is an X-ray spectrum diagram of the phthalocyanine obtained in Production Example 1 of the present invention.

FIG. 6 is an X-ray spectrum diagram of the phthalocyanine obtained in Production Example 2 of the present invention.

FIG. 7: X of phthalocyanine obtained in Comparative Example Production Example 1
It is a line spectrum figure.

FIG. 8 is a view showing a specific example of an enamine compound according to the present invention.

FIG. 9 is a view showing a specific example of an enamine compound according to the present invention.

FIG. 10 is a view showing a specific example of an enamine compound according to the present invention.

FIG. 11 is a view showing a specific example of an enamine compound according to the present invention.

FIG. 12 is a view showing a specific example of an enamine compound according to the present invention.

FIG. 13 is a view showing a specific example of a hydrazone compound according to the present invention.

FIG. 14 is a view showing a specific example of a styryl compound according to the present invention.

FIG. 15 is a view showing a specific example of a distyryl compound according to the present invention.

FIG. 16 is a view showing a specific example of a distyryl compound according to the present invention.

FIG. 17 is a view showing a specific example of a distyryl compound according to the present invention.

FIG. 18 is a view showing a specific example of a distyryl compound according to the present invention.

FIG. 19 is a view showing a specific example of a distyryl compound according to the present invention.

FIG. 20 is a view showing a specific example of the polycarbonate resin according to the present invention.

FIG. 21 is a diagram illustrating a photoconductor sample used in this example.

FIG. 22 is a diagram illustrating characteristics of a photoconductor used in this example.

FIG. 23 is a diagram illustrating a photoreceptor sample used in this example.

FIG. 24 is a diagram illustrating characteristics of the photoconductor used in the present example.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 conductive support 2 charge generating material 3 charge transporting material 4, 4 ′ photosensitive layer 5 charge generating layer 6 charge transfer layer 7 intermediate layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 69/00 C08L 69/00 G03G 5/05 101 G03G 5/05 101 104 104 5/147 504 5/147 504

Claims (14)

[Claims] 1. An X-ray diffraction spectrum represented by the following general formula (1): Bragg angle (2θ ± 0.2 °)
Exhibit a maximum diffraction peak at 9.4 ° and at least
A crystalline oxotitanyl phthalocyanine having diffraction peaks at 7.4 °, 9.7 ° and 27.3 °, and at least one of an enamine compound, a hydrazone compound, a styryl compound, a distyryl compound and a butadiene compound; An electrophotographic photoreceptor comprising: Embedded image (X in the formula represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and m represents an integer of 0 to 4.) 2. In the X-ray diffraction spectrum represented by the general formula (1), the Bragg angle (2θ ± 0.2 °)
9.7 ° shows the maximum diffraction peak and at least
A crystalline oxotitanyl phthalocyanine having diffraction peaks at 7.4 °, 9.4 °, and 27.3 °, and at least one of an enamine compound, a hydrazone compound, a styryl compound, a distyryl compound, and a butadiene compound; An electrophotographic photoreceptor comprising: 3. A charge generation layer containing oxotitanyl phthalocyanine as a charge generation material on a conductive support, and an enamine-based compound, a hydrazone-based compound, a styryl-based compound, a distyryl-based compound, and a butadiene-based compound as a charge-transporting material. 3. An electrophotographic photoreceptor comprising a photosensitive layer in which a charge transport layer containing at least one of the following is laminated, wherein the oxotitanyl phthalocyanine is a crystalline oxotitanyl phthalocyanine crystal according to claim 1 or 2. 4. An electrophotographic photoconductor according to claim 3, wherein an intermediate layer is provided between said conductive support and said photosensitive layer. 5. The method according to claim 1, wherein the enamine compound is a compound represented by the following general formula (2).
3. The electrophotographic photosensitive member according to any one of 3. Embedded image (Wherein, Ar ₁ may have an arylene group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. A heterocyclic alkyl group, n is an integer of 2 to 4.) 6. The electrophotographic photosensitive member according to claim 1, wherein the hydrazone compound is a compound represented by the following general formula (3) or (4). Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ each represent an optionally substituted alkyl group, aralkyl group, or aryl group;
R ₅ represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group; R ₁ and R ₂ may combine to form a ring;
One of R ₁ and R ₂ may be combined with R ₅ to form a ring. ) (Where A, B and R ₇ represent a hydrogen atom, a lower alkyl group, a dialkylamino group, a lower arakoxy group, a phenoxy group, or an arylalkoxy group, and R ₆ represents a hydrogen atom, a lower alkyl group, an allyl group phenyl) Represents a group or an aralkyl group, q and r represent an integer of 1 or 2, and p represents 0 or 1.) 7. The method according to claim 1, wherein the styryl compound is a compound represented by the following general formula (5).
The electrophotographic photosensitive member according to any one of the above. Embedded image (In the formula, Ar ₂ and Ar ₃ represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group or a heterosubstituted alkyl group which may have a substituent, or hydrogen. R ₈ , R ₉ , and R ₁₀ each represent an optionally substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group, a dialkylamino group, or a hydrogen atom. 8. The method according to claim 1, wherein the distyryl compound is a compound represented by the following general formula (6).
3. The electrophotographic photosensitive member according to any one of 3. Embedded image (Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent an optionally substituted aryl or alkyl group, R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group, or an alkoxy group, and Ar ₄ represents Represents an aryl group or an aromatic heterocyclic group which may be substituted.) 9. The butitadiene compound represented by the following general formula (7)
A compound represented by the formula:
2. The electrophotographic photosensitive member according to any one of 2, 3 and 4. Embedded image (In the formula, R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ each represent an optionally substituted aryl group or an alkyl group, and R ₁₅ and R ₁₆ each represent a hydrogen atom.) 10. An electrophotographic photosensitive member having a photosensitive layer containing a binder polymer on a conductive support, wherein the binder polymer contained in the photosensitive layer is a polymer of a vinyl compound or a copolymer thereof, polyester, polycarbonate. 4. The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor is a polyarylate, polysulfone, polyvinyl butyral, phenoxy resin, cellulosic resin, urethane resin or epoxy resin. 11. The electrophotographic photoreceptor according to claim 10, wherein the binder polymer contains at least one kind of polycarbonate resin represented by the following general formula (8). Embedded image (Wherein, R ₂₇ and R ₂₈ each have an alkyl group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, Carbon number 7
To 17 aralkyl groups, alkenyl groups having 2 to 5 carbon atoms,
X represents an alkoxy group having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom, and X represents a directly-bonded or an alkylene group having 1 to 10 carbon atoms which may have a substituent, Represents a cyclic alkylidene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms which may have a substituent, a sulfonyl group, or a carbonyl group, and Z represents 1 carbon atom which may have a substituent. Alkylene group of 5 to 6, carbon number of 6 to
12 represents an arylene group, an arylene alkyl group having 7 to 17 carbon atoms, or a halogen atom, and Y represents an alkyl group having 1 to 5 carbon atoms which may have a substituent, or a carbon number which may have a substituent. 2-5 alkenyl group, C1-C5 alkoxy group, C1-C5 alkyl ester group which may have a substituent, C6-C12 aryl ester group which may have a substituent , Carboxyl group, aldehyde group, hydroxyl group,
Represents a halogen atom or a hydrogen atom, e and f represent an integer of 1 to 4, and u represents an integer of 10 to 200. ) 12. The binder polymer contains at least one polyester resin represented by the following general formula (9), and the ratio of the polyester resin to the whole binder is 5% by weight or more and 50% by weight or less. The electrophotographic photosensitive member according to claim 10, wherein: Embedded image (Where g, h, and i are integers from 1 to 10, v, w, x,
y is an integer from 10 to 1000. ) 13. The method according to claim 1, wherein the photosensitive layer contains α-tocopherol as an antioxidant and the weight ratio of the antioxidant / charge transfer material is 0.1 / 100 or more and 5/100 or less. Item 11. The electrophotographic photosensitive member according to Item 10. 14. The method according to claim 10, wherein the surface layer contains dimethylpolysiloxane, and the weight ratio of the dimethylpolysiloxane / binder polymer is from 0.001 / 100 to 5/100. Electrophotographic photoreceptor.