JP2002196520A - Electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having low residual potential, no defect in electrification, small photomemory, high image quality, high sensitivity characteristics and stable potential characteristics in repetitive use and to provide a process cartridge using the photoreceptor and an electrophotographic device. SOLUTION: In the electrophotographic photoreceptor having a photosensitive layer on a substrate, the photosensitive layer contains oxy-titanium phthalocyanine and silicon phthalocyanine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member having a photosensitive layer containing a specific compound as a charge generating material. The present invention also relates to a process cartridge having the electrophotographic photosensitive member and an electrophotographic apparatus.

[0002]

2. Description of the Related Art Conventionally, phthalocyanine pigments have been attracting attention and studied as electronic materials used for electrophotographic photosensitive members, solar cells, sensors, and the like, in addition to coloring purposes.

Further, in recent years, printers to which electrophotographic technology is applied have become widespread as terminal printers. These are mainly laser beam printers using laser light as a light source, and a semiconductor laser is used as the light source in terms of cost, size of the apparatus, and the like. Currently, mainly used semiconductor lasers have an oscillation wavelength of 790 to 820 nm, which is a long wavelength. Therefore, development of an electrophotographic photoreceptor having sufficient sensitivity to light of such a long wavelength has been advanced.

[0004] The sensitivity range of the electrophotographic photoreceptor varies depending on the type of charge generating material, and recently, as charge generating materials having sensitivity to long wavelengths, aluminum chlorophthalocyanine, chloroindium phthalocyanine, oxyvanadium phthalocyanine, hydroxygallium phthalocyanine. Many studies have been made on phthalocyanines such as chlorogallium phthalocyanine, magnesium phthalocyanine, oxytitanium phthalocyanine, and silicon phthalocyanine, and metal-free phthalocyanines.

Of these, oxytitanium phthalocyanine is disclosed in Japanese Patent Application Laid-Open Nos.
These are disclosed in, for example, Japanese Patent Application Laid-Open No. 1-239248, Japanese Patent Application Laid-Open No. 64-17066, and Japanese Patent Application Laid-Open No. 3-128973. Further, silicon phthalocyanine is disclosed in
No. 7536 and the like.

Further, a (panchromatic) electrophotographic photoreceptor having a wide sensitivity wavelength range using a phthalocyanine compound and an azo pigment in combination as a charge generating material has been proposed.
It is disclosed in JP-A-3-37666, JP-A-5-66596 and JP-A-7-128888.

[0007]

The electrophotographic photoreceptor using oxytitanium phthalocyanine has very high sensitivity and good chargeability, but has more excellent characteristics particularly in terms of residual potential, photo memory and potential stability. What they have is being considered.

As described above, it has been proposed to use a phthalocyanine compound and an azo pigment in combination. However, since the phthalocyanine compound and the azo pigment have different dispersibility, a complicated dispersing method is required. In many cases, the dispersion state is unstable, and from the viewpoint of further increasing the speed of the process or improving the image quality, sensitivity and potential stability during repeated use, residual potential and black spots due to poor charging, fogging, etc. Further, an electrophotographic photosensitive member having more excellent characteristics in terms of memory and the like against white light has been studied.

An object of the present invention is to provide an electrophotographic photoreceptor having a low residual potential, no charge defects, a small photo memory, high image quality, high sensitivity characteristics and stable potential characteristics when repeatedly used. is there.

It is another object of the present invention to provide a process cartridge and an electrophotographic apparatus using the electrophotographic photosensitive member.

[0011]

The present invention provides an electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer contains oxytitanium phthalocyanine and silicon phthalocyanine. is there.

According to the present invention, the electrophotographic photoreceptor of the present invention and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported and detachably mounted on the electrophotographic apparatus main body. A process cartridge characterized in that:

Further, the present invention is an electrophotographic apparatus comprising the electrophotographic photoreceptor of the present invention, charging means, exposure means, developing means and transfer means.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The preferred silicon phthalocyanine used in the present invention is represented by the following general formula (1):
, A dialkoxysilicon phthalocyanine represented by the following general formula (2), a dimerized dihydroxysilicon phthalocyanine represented by the following general formula (3), a disiloxysilicon phthalocyanine represented by the following general formula (4), and the like. But are not limited to these.

[Formula 6] General formula (1)

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent a halogen atom, and a, b, c and d each independently represent an integer of 0 to _4. ) Examples of the halogen atom of ₁ , X ₂ , X ₃ and X ₄ include a chlorine atom and a bromine atom.

[Formula 7] General formula (2) (Wherein, R ₁ and R ₂ represent an alkyl group which may have a substituent, X ₅ , X ₆ , X ₇ and X ₈ each independently represent a halogen atom, e, f, g and h represents an integer of independently 0-4.) the alkyl group for R ₁ and R _2, include such as methyl group and ethyl group are preferable carbon number is 8 or less, R ₁ and Examples of the substituent which R ₂ may have include a halogen atom such as a chlorine atom and a bromine atom. Examples of the halogen atom of X ₅ , X ₆ , X ₇ and X ₈ include a chlorine atom and a bromine atom.

[Formula 8] General formula (3) (Wherein X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ and X ₁₆ each independently represent a halogen atom;
j, k, l, m, n, o and p are each independently 0 to
Represents an integer of 4. Examples of the halogen atom for X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ and X ₁₆ include a chlorine atom and a bromine atom.

[Formula 9] General formula (4) (Wherein, R ₃ and R ₄ each independently represent an alkyl group, a cycloalkyl group, an aralkyl group,
Represents an aryl group. X ₁₇ , X ₁₈ , X ₁₉ and X ₂₀ each independently represent a halogen atom, and q, r, s and t each independently represent an integer of 0 to 4. Examples of the alkyl group for R ₃ and R ₄ include a methyl group and an ethyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aralkyl group include a benzyl group. Examples of the aryl group include a phenyl group and a naphthyl group and the like, R ₃
And the substituent which R ₄ may have include a halogen atom such as a chlorine atom and a nitrogen atom. Also,
Examples of the halogen atom for X ₁₇ , X ₁₈ , X ₁₉ and X ₂₀ include a chlorine atom and a bromine atom.

Preferred silicon phthalocyanines used in the present invention are 9.2 ° and 14.1 having a diffraction angle (2θ ± 0.3 °) in CuKα characteristic X-ray diffraction.
Dihydroxysilicon phthalocyanine with strong peaks at °, 15.3 °, 19.7 ° and 27.1 °, Cu
7.1 °, 9.3 °, 12.8 °, 15.8 °, 17.7 ° of diffraction angles (2θ ± 0.3 °) in Kα characteristic X-ray diffraction.
Dihydroxysilicon phthalocyanine with strong peaks at 2 °, 25.6 ° and 26.9 °, CuKα characteristic X
8.1 ° of diffraction angle (2θ ± 0.3 °) in line diffraction,
12.2 °, 13.0 °, 17.0 °, 18.7 °, 2
Dimethoxysilicon phthalocyanine with strong peaks at 3.3 °, 26.0 °, 27.8 ° and 30.4 °,
Diffraction angle in CuKα characteristic X-ray diffraction (2θ ± 0.3
°) 8.4 °, 10.9 °, 11.7 °, 14.6
°, 16.7 °, 17.2 °, 24.6 ° and 26.8
Diethoxysilicon phthalocyanine having a strong peak at °°, diffraction angle in CuKα characteristic X-ray diffraction (2θ ±
0.3 °), 6.9 °, 8.0 °, 10.6 °, 16.
Dimerized dihydroxysilicon phthalocyanine with strong peaks at 0 °, 26.3 ° and 27.4 °, and Cu
8.3 °, 12.3 °, 14.9 °, 23.2 °, 2 ° of diffraction angle (2θ ± 0.3 °) in Kα characteristic X-ray diffraction
Examples include, but are not limited to, diacetoxysilicon phthalocyanine having strong peaks at 5.0 ° and 27.5 °.

The oxytitanium phthalocyanine used in the present invention is represented by the following general formula (5).

[Formula 10] (In the formula, X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ each independently represent a halogen atom, and u, v, w and x each independently represent an integer of 0 to 4.) X ₂₁ , X Examples of the halogen atom of ₂₂ , ₂₃ and ₂₄ include a chlorine atom and a bromine atom. Preferred crystal forms of the oxytitanium phthalocyanine used in the present invention include those having the strongest peak at a diffraction angle (2θ) of 27.2 ° ± 0.2 ° in CuKα characteristic X-ray diffraction. Above all, the diffraction angle (2θ ± 0.2 °) of the CuKα characteristic X-ray diffraction of 9.0 °, 1 °
Crystal forms with strong peaks at 4.2, 23.9, and 27.1, 9.5, 9.7, 11.7, 15.
Crystal forms with strong peaks at 0 °, 23.5 °, 24.1 ° and 27.3 °, and 9.3 °, 10.6 °, 1
3.2 °, 15.1 °, 20.8 °, 26.3 ° and 2
Each of the crystal forms having a strong peak at 7.1 ° is preferred, but not limited thereto.

In the present invention, the content ratio of oxytitanium phthalocyanine to oxytitanium phthalocyanine silicon phthalocyanine is from 9: 1 to 1: 9 by mass.
It is particularly preferable that the ratio is 7: 3 to 3: 7. If the amount of oxytitanium phthalocyanine is too large, it tends to be insufficient in terms of residual potential, photo memory and potential stability.If the amount is too small, image defects such as black spots and fogging due to poor charging are likely to occur, and the potential stability is also insufficient. easy.

The photosensitive layer of the present invention may be of a laminated type having a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material, or both of the same and the same material. A single-layer type contained in the layer is exemplified.

Of these, the former is more preferable, and in the former case, there are two laminating orders. Among them, the constitution in which the charge generating layer and the charge transport layer are laminated in this order from the support side in terms of electrophotographic characteristics. Is preferred.

The charge generation layer contains silicon phthalocyanine, oxytitanium phthalocyanine and a binder resin as charge generation materials. When mixing charge generation materials,
Each material is dispersed in an appropriate binder resin and a solvent in the ratio in the above range, or individually dispersed liquids are mixed so as to have a predetermined ratio. When dispersed individually, the binder resin and the solvent may be different from each other. In the case of laminating, the liquids which are individually dispersed are applied so that the amount of the contained material becomes a predetermined ratio.

Examples of the binder resin used include polyester, acrylic resin, polyvinyl carbazole, phenoxy resin, polycarbonate, polyvinyl butyral, polyvinyl benzal, polystyrene, polyvinyl acetate, polysulfone, polyarylate, and vinylidene chloride-acrylonitrile copolymer. No.

The thickness of the charge generation layer is 0.01 to 15 μm,
Further, the thickness is preferably 0.05 to 5 μm, and the mass ratio of the charge generation material to the binder resin is preferably 10: 1 to 1:20.

The charge transport layer is formed mainly by applying a coating material in which a charge transport material and a binder resin are dissolved in a solvent, and drying. Examples of the charge transport material include various triarylamine compounds, hydrazone compounds, stilbenzene compounds, pyrazoline compounds, oxazole compounds, butadiene compounds, enamine compounds,
And thiazole compounds and triallylmethane compounds. The same resin as the charge generation layer can be used as the binder resin.

The thickness of the charge transporting layer is preferably 5 to 50 μm, more preferably 8 to 30 μm, and the mass ratio of the charge transporting material to the binder resin is 5: 1 to 1: 5, more preferably 3: 1 to 1: 5. 3 is preferred.

When the photosensitive layer is of a single-layer type, it can be formed by applying a paint containing the above-mentioned charge generating material, charge transport material and binder resin, and drying. The single-layer type preferably has a thickness of 10 to 30 μm.

The support may be any one having conductivity, such as metal such as aluminum and stainless steel, or metal provided with a conductive layer, plastic and paper.
Examples of the shape include a cylindrical shape and a film shape.

Further, an undercoat layer having a barrier function and an adhesive function can be provided between the support and the photosensitive layer.
Examples of the material of the undercoat layer include polyvinyl alcohol, polyethylene oxide, ethyl cellulose, methyl cellulose, casein, polyamide, glue, gelatin and the like. These are dissolved in an appropriate solvent and coated on a support. The thickness of the undercoat layer is 5 μm or less, and further 0.5
３3 μm is preferred.

Further, it is preferable to provide a conductive layer between the support and the undercoating layer for the purpose of covering unevenness and defects of the substrate, and for preventing interference fringes due to scattering when image input is laser light. It is. This can be formed by dispersing conductive powder such as carbon black, metal particles and metal oxide in a binder resin. The thickness of the conductive layer is preferably from 5 to 40 μm, particularly preferably from 10 to 30 μm.

As a method for applying these layers, dip coating, spray coating, spinner coating, bead coating, blade coating, beam coating, and the like can be used.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
RT printer, LED printer, LCD printer,
Electrophotographic application fields such as laser plate making and facsimile can also be widely used.

Next, the process cartridge and the electrophotographic apparatus of the present invention will be described. FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention.

In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around a shaft 2 in a direction of an arrow at a predetermined peripheral speed. During the rotation process, the photosensitive member 1
The peripheral surface is uniformly charged with a predetermined positive or negative potential by the primary charging means 3 and then receives exposure light 4 from exposure means (not shown) such as slit exposure or laser beam scanning exposure. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then transferred to developing means 5
The toner-developed image developed by the above-described process is transferred to a transfer material 7 fed from a paper supply unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1. The image is sequentially transferred by the transfer unit 6.

The transfer material 7 having undergone the image transfer is separated from the surface of the photoreceptor, introduced into the image fixing means 8 and subjected to image fixing, thereby being printed out of the apparatus as a copy. The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the untransferred toner by a cleaning unit 9, and further subjected to a static elimination process by a pre-exposure light 10 from a pre-exposure unit (not shown). Used repeatedly for image formation. Since the primary charging means 3 is a contact charging means using a charging roller as shown in the figure, pre-exposure is not necessarily required.

In the present invention, a plurality of components, such as the photosensitive member 1, the primary charging unit 3, the developing unit 5, and the cleaning unit 9, are integrally supported as a process cartridge. The cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5 and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and the process cartridge is detachable from the apparatus main body using guide means such as the rail 12 of the apparatus main body. It can be 11. When the electrophotographic apparatus is a copier or a printer, the exposure light 4 uses reflected light or transmitted light from the original, or reads the original with a sensor and converts it into a signal. , Light emitted by driving the LED array, driving the liquid crystal shutter array, and the like.

[0037]

EXAMPLES First, production examples of the phthalocyanine compound used in the present invention will be described.

Production Example 1 (Production of dihydroxysilicon phthalocyanine) Under nitrogen atmosphere, 29 g of 1,3-diiminoisoindoline and 51 g of silicon tetrachloride were added to 400 ml of quinoline in 21 ml.
After heating and stirring at 0 ° C. for 2 hours, the mixture was cooled to 150 ° C., and the precipitated crystals were filtered and the filter was washed with acetone. Next, this was stirred and washed under 200 ml of acetone heated under reflux, and the crystals were separated by filtration and dried to obtain 27.1 g of dichlorosilicon phthalocyanine.

Next, 8 g of the dichlorosilicon phthalocyanine was added to 100 g of a 90% aqueous solution of N-methylpyrrolidone.
And reacted at 130 ° C. for 6 hours. The reaction product was filtered hot, and the filter was washed with acetone. Further, the residue was washed with stirring under 200 ml of acetone, and the crystals were separated by filtration.
Dry to 6.2 g of dihydroxy silicon phthalocyanine
I got

The obtained dihydroxysilicon phthalocyanine had a diffraction angle (2θ ±) in CuKα characteristic X-ray diffraction.
0.3 °) of 9.2 °, 14.1 °, 15.3 °, 1
It had strong peaks at 9.7 ° and 27.1 °.

Production Example 2 (Production of dihydroxysilicon phthalocyanine) 10 g of dichlorosilicon phthalocyanine obtained in Production Example 1
Was added to a mixed solution of 200 ml of a 1% aqueous sodium hydroxide solution and 50 ml of pyridine, and reacted under heating and reflux for 2 hours. The reaction product was filtered hot and the filter was washed with acetone and then with deionized water. Further, the residue was repeatedly washed with 100 ml of deionized water five times, and then the crystals were separated by filtration and dried to obtain 6.1 g of dihydroxysilicon phthalocyanine.

The obtained dihydroxysilicon phthalocyanine had a diffraction angle (2θ ± 2) in CuKα characteristic X-ray diffraction.
0.3 °) 7.1 °, 9.3 °, 12.8 °, 15.
It had strong peaks at 8 °, 17.2 °, 25.6 ° and 26.9 °.

Production Example 3 (Production of dimethoxysilicon phthalocyanine) Dichlorosilicon phthalocyanine 1 synthesized in Production Example 1
0 g of sodium methoxide 2 g, methanol 100 m
1 and 100 ml of pyridine, and reacted under heating and reflux for 2 hours. The reaction product was filtered hot and the filter was washed with methanol, acetone and deionized water. Further, the residue was repeatedly washed with 100 ml of deionized water five times, and then the crystals were separated by filtration and dried to obtain 9.5 g of dimethoxysilicon phthalocyanine.

The obtained dimethoxysilicon phthalocyanine has a diffraction angle (2θ ±) in CuKα characteristic X-ray diffraction.
0.3 °) 8.1 °, 12.2 °, 13.0 °, 1
7.0 °, 18.7 °, 23.3 °, 26.0 °, 2
It had strong peaks at 7.8 ° and 30.4 °.

Production Example 4 (Production of diethoxy silicon phthalocyanine) Dichlorosilicon phthalocyanine 1 synthesized in Production Example 1
0 g of sodium ethoxide 2 g, methanol 100 m
1 and 100 ml of pyridine, and reacted under heating and reflux for 2 hours. The reaction product was filtered hot, and the filter was washed with ethanol, acetone and deionized water. Further, the residue was repeatedly washed with 100 ml of deionized water five times, and then the crystals were separated by filtration and dried to obtain 9.1 g of diethoxysilicon phthalocyanine.

The obtained diethoxysilicon phthalocyanine has a diffraction angle (2θ ±
0.3 °) of 8.4 °, 10.9 °, 11.7 °, 1
4.6 °, 16.7 °, 17.2 °, 24.6 ° and 2
It had a strong peak at 6.8 °.

Production Example 5 (Production of dimerized dihydroxysilicon phthalocyanine) Dichlorosilicon phthalocyanine 1 synthesized in Production Example 1
0 g was added to 100 ml of N-methylpyrrolidone.
The reaction was performed at 0 ° C. for 2 hours. The reaction product was filtered hot and the filter was washed with N-methylpyrrolidone and acetone. Further, the crystals were stirred and washed under 100 ml of acetone, and the crystals were separated by filtration and dried to obtain 6.0 g of dimerized dichlorosilicon phthalocyanine. 6 g of this dimerized dichlorosilicon phthalocyanine was added to 100 ml of aqueous ammonia and pyridine 1
The mixture was added to 00 ml of the mixture, and reacted under heating and reflux for 5 hours. The reaction product is filtered hot, acetone on the filter,
Each was washed with deionized water. Next, deionized water 10
After stirring in 0 ml, the crystals were separated by filtration and dried to obtain 4.3 g of dimerized dihydroxysilicon phthalocyanine.

The obtained dimerized dihydroxysilicon phthalocyanine has a diffraction angle (2θ ± 0.3 °) of 6.9 °, 8.0 °, 10.6 ° in CuKα characteristic X-ray diffraction.
°, 16.0 °, 26.3 ° and 27.4 ° had strong peaks.

Production Example 6 (Production of diacetoxysilicon phthalocyanine) 5 g of dimethoxysilicon phthalocyanine synthesized in Production Example 3 was added to 100 ml of acetic acid, and the reaction was carried out under heating and reflux for 3 hours. The reaction product is filtered hot, acetic acid on the filter,
After washing with deionized water and methanol, the crystals were separated by filtration and dried to obtain 4.8 g of diacetoxysilicon phthalocyanine.

The obtained diacetoxysilicon phthalocyanine has a diffraction angle (2θ ± 2) in CuKα characteristic X-ray diffraction.
0.3 °) 8.3 °, 12.3 °, 14.9 °, 2
It had strong peaks at 3.2 °, 25.0 ° and 27.5 °.

Production Example 7 (Production of oxytitanium phthalocyanine) Under a nitrogen atmosphere, in 100 g of α-chloronaphthalene, o-
After 5.0 g of phthalodinitrile and 2.0 g of titanium tetrachloride were heated and stirred at 200 ° C. for 3 hours, they were cooled to 50 ° C., and the precipitated crystals were separated by filtration to obtain dichlorotitanium phthalocyanine. Next, this was heated to 100 ° C. in N, N
The mixture was washed with stirring under 100 ml of dimethylformamide, and then washed twice with 100 ml of methanol at 60 ° C., followed by filtration. Further, the obtained paste was stirred in 100 ml of deionized water at 80 ° C. for 1 hour and filtered to obtain 4.3 g of oxytitanium phthalocyanine.

Next, the crystals were dissolved in 30 ml of concentrated sulfuric acid, dropped into 300 ml of deionized water at 20 ° C. with stirring, reprecipitated, filtered, washed sufficiently with water, and then mixed with amorphous oxytitanium. Phthalocyanine was obtained. 4.0 g of the obtained amorphous oxytitanium phthalocyanine was suspended and stirred in 100 ml of methanol at room temperature (22 ° C.) for 8 hours, filtered and dried under reduced pressure to obtain low-crystalline oxytitanium phthalocyanine. . Next, 40 ml of n-butyl ether was added to 2.0 g of the oxytitanium phthalocyanine, and milling was performed at room temperature (22 ° C.) for 20 hours together with 1 mmφ glass beads.

The solid was removed from the dispersion, washed thoroughly with methanol and deionized water, and dried to obtain oxytitanium phthalocyanine. Yield 1.8 g.

The obtained oxytitanium phthalocyanine has a diffraction angle (2θ ± 0.
2 °) 9.0 °, 14.2 °, 23.9 ° and 27.
It had a strong peak at 1 °.

Production Example 8 (Production of oxytitanium phthalocyanine) According to the production example disclosed in JP-A-64-17066, the diffraction angle (2θ) in CuKα characteristic X-ray diffraction was measured.
± 0.2 °) 9.5 °, 9.7 °, 11.7 °, 1
Crystalline forms of oxytitanium phthalocyanine having strong peaks at 5.0 °, 23.5, 24.1 ° and 27.3 ° were obtained.

Production Example 9 (Production of oxytitanium phthalocyanine) In a nitrogen atmosphere, o-
20 g of phthalodinitrile and 9 g of titanium tetrachloride were added to 22
After stirring at 0 ° C. for 3 hours, the mixture was cooled to room temperature and filtered to obtain dichlorotitanium phthalocyanine. This dichlorotitanium phthalocyanine was treated with concentrated ammonia water 150 m
After washing with acetone, each was washed with acetone and o-dichlorobenzene, filtered and titanyl phthalocyanine 10
g was obtained. The crystals are dissolved in 100 ml of concentrated sulfuric acid at 5 ° C. or lower, dropped into 2,000 ml of deionized water at 20 ° C. with stirring, reprecipitated, filtered, thoroughly washed with water, and dried to obtain amorphous oxytitanium phthalocyanine. I got This is α
Recrystallization from -chloronaphthalene gave 2 g of oxytitanium phthalocyanine.

The obtained oxytitanium phthalocyanine has a diffraction angle (2θ ± 0.
2 °) of 9.3 °, 10.6 °, 13.2 °, 15.1
°, 20.8 °, 26.3 ° and 27.1 °.

Example 1 50 parts by mass of titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts by mass of resole type phenol resin, 20 parts by mass of methyl cellosolve, 5 parts by mass of methanol and silicone oil (poly 0.02 parts by mass of a dimethylsiloxane polyoxyalkylene copolymer (average molecular weight 3000) was dispersed in a sand mill using a 1 mmφ glass bead for 2 hours to prepare a coating for a conductive layer. This coating material was applied on an aluminum cylinder by dip coating and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

A solution obtained by dissolving 5 parts by mass of a 6-66-610-12 quaternary polyamide copolymer in a mixed solvent of 70 parts by mass of methanol and 25 parts by mass of butanol was applied onto the conductive layer by dip coating. By drying for 1 minute, an undercoat layer having a thickness of 1 μm was formed.

Next, 4 parts by mass of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 and 4 parts by mass of the oxytitanium phthalocyanine crystal obtained in Production Example 8 were mixed with polyvinyl butyral (trade name: SREC BX-
1, 4 parts by mass of Sekisui Chemical Co., Ltd.)
Was added to the solution dissolved in 00 parts by mass and dispersed in a sand mill using 1 mmφ glass beads for 2 hours.
A part by mass of ethyl acetate was added for dilution. This dispersion was dip-coated on the undercoat layer and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

Next, a charge transport material represented by the following structural formula

[Outside 11]

10 parts by mass and 10 parts by mass of a bisphenol Z type polycarbonate resin (number average molecular weight 22,000) were dissolved in 60 parts by mass of monochlorobenzene. This solution was applied onto the charge generation layer by dip coating, and dried at 100 ° C. for 1 hour to form a charge transport layer having a thickness of 23 μm, thereby producing an electrophotographic photoreceptor (photoreceptor 1).

Example 2 The procedure of Example 1 was repeated except that 4 parts by mass of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 was replaced by 4 parts by mass of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 2. An electrophotographic photosensitive member (photosensitive member 2) was prepared in the same manner.

Example 3 The procedure of Example 1 was repeated except that 4 parts by weight of the dimethoxysilicon phthalocyanine crystal obtained in Production Example 3 was used instead of 4 parts by weight of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 1. An electrophotographic photosensitive member (photosensitive member 3) was prepared in the same manner.

Example 4 Example 1 was repeated except that 4 parts by weight of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 was replaced by 4 parts by weight of the diethoxysilicon phthalocyanine crystal obtained in Production Example 4. An electrophotographic photoreceptor (photoreceptor 4) was prepared in the same manner as described above.

Example 5 The procedure of Example 5 was repeated, except that 4 parts by mass of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 5 was used instead of 4 parts by mass of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 1. An electrophotographic photosensitive member (photosensitive member 5) was prepared in the same manner as in Example 1.

Example 6 The procedure of Example 1 was repeated except that 4 parts by mass of the oxytitanium phthalocyanine crystal obtained in Production Example 8 was used instead of 4 parts by mass of the oxytitanium phthalocyanine crystal obtained in Production Example 8. In the same manner, an electrophotographic photosensitive member (photosensitive member 6) was prepared.

Example 7 The procedure of Example 1 was repeated except that 4 parts by mass of the oxytitanium phthalocyanine crystal obtained in Production Example 8 was used instead of 4 parts by mass of the oxytitanium phthalocyanine crystal obtained in Production Example 8. An electrophotographic photosensitive member (photosensitive member 7) was prepared in the same manner.

(Example 8) The dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 and the oxytitanium phthalocyanine crystal obtained in Production Example 8 were replaced with 4 parts by mass of dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 An electrophotographic photoreceptor (photoreceptor 8) was prepared in the same manner as in Example 1, except that 0.8 parts by mass of a phthalocyanine crystal and 7.2 parts by mass of the oxytitanium phthalocyanine crystal obtained in Production Example 8 were used.

(Example 9) The dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 was replaced with 4 parts by mass of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 8 and the dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 was replaced with 4 parts by mass. An electrophotographic photoreceptor (photoreceptor 9) was prepared in the same manner as in Example 1, except that 7.2 parts by mass of the phthalocyanine crystal and 0.8 parts by mass of the oxytitanium phthalocyanine crystal obtained in Production Example 8 were used.

(Comparative Example 1) The dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 and the oxytitanium phthalocyanine crystal obtained in Production Example 8 were replaced with 4 parts by mass of dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 An electrophotographic photosensitive member (comparative photosensitive member 1) was prepared in the same manner as in Example 1, except that 8 parts by mass of phthalocyanine crystal was used.

Comparative Example 2 The oxytitanium obtained in Production Example 8 was replaced with 4 parts by mass of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 and 4 parts by mass of the oxytitanium phthalocyanine crystal obtained in Production Example 8. An electrophotographic photosensitive member (comparative photosensitive member 2) was prepared in the same manner as in Example 1, except that 8 parts by mass of phthalocyanine crystal was used.

Comparative Example 3 The oxytitanium phthalocyanine obtained in Production Example 8 was replaced with 4 parts by mass of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 1 and 4 parts by mass of the oxytitanium phthalocyanine crystal obtained in Production Example 8. 4 parts by mass of crystal and disazo pigment represented by the following structural formula

[Outside 12]

An electrophotographic photosensitive member (comparative photosensitive member 3) was prepared in the same manner as in Example 1 except that 4 parts by mass was used.

The photoreceptors 1 to 9 and the comparative photoreceptors 1 to 3 were set in a modified digital copying machine (GP-55, manufactured by Canon Inc.) and set so that the dark area potential became -700 V. , Irradiating a 780 nm laser beam to measure the amount of light required to lower the potential of -700 V to -150 V,
Sensitivity. Further, the potential when the light amount of ²⁰ cJ / m ² was irradiated was measured as the residual potential Vr. Table 1 shows the results.

[0076]

[Table 1]

Next, in an environment with a humidity of 80% and a temperature of 35 ° C., the initial dark part potential is -700 V, and the bright part potential is -150 V.
V, and perform a continuous paper passing durability test of 3000 sheets.
Fluctuation amount ΔV of dark portion potential and bright portion potential at the initial stage and after 3000 sheets
d and ΔVl were measured. A positive sign of the variation indicates an increase in the absolute value of the potential, and a negative sign indicates a decrease in the absolute value of the potential.
Further, the evaluation of black spots and fogging was carried out visually after the endurance. Table 2 shows the results.

[0078]

[Table 2]

Next, the unused photoreceptors 1 to 9 and the comparatively unused comparative photoreceptors 1 to 3 were put into a 1500 fluorescent lamp using a white fluorescent lamp.
Lux light was irradiated for 5 minutes, and the difference ΔVpm between the dark area potential 2 minutes after the irradiation and the dark area potential before the light irradiation was measured to evaluate the photo memory. Table 3 shows the results.

[0080]

[Table 3]

As is clear from the above results, the electrophotographic photoreceptor of the present invention has a low residual potential, has no image defects such as black spots and fog, has a small photo memory, has high sensitivity characteristics, and is stable when repeatedly used. It can be seen that it has the potential characteristics described above.

Example 10 The same procedures as in Example 1 were carried out except that 4 parts by mass of the diacetoxysilicon phthalocyanine crystal obtained in Production Example 6 was used instead of 4 parts by mass of the dihydroxysilicon phthalocyanine crystal obtained in Production Example 1. And an electrophotographic photoreceptor (photoreceptor 1
0) was prepared and evaluated. As a result, the sensitivity is 0.17c.
J / m ² , Vr is −15 V, black spots and fog are good,
ΔVd was −5 V, ΔVl was −5 V, and ΔVpm was −5 V.

[0083]

As described above, according to the present invention, an electrophotographic photoreceptor having a low residual potential, hardly causing poor charging, a small photo memory, and excellent sensitivity characteristics and potential stability. A process cartridge having an electrophotosensitive member and an electrophotographic apparatus can be provided.

[Brief description of the drawings]

FIG. 1 is a view showing a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hidetoshi Hirano 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Ichie Hama 3-30-2 Shimomaruko, Ota-ku, Tokyo Kyano Incorporated (72) Inventor Takashi Higashi 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H068 AA19 BA39 FA18 FA19 FA27 4C050 PA12 PA13

Claims (17)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the photosensitive layer contains oxytitanium phthalocyanine and silicon phthalocyanine. 2. The electrophotographic photoreceptor according to claim 1, wherein said silicon phthalocyanine is dihydroxysilicon phthalocyanine represented by the following general formula (1). [Formula 1] General formula (1) (In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent a halogen atom, and a, b, c and d each independently represent an integer of 0 to _4. ) 3. The electrophotographic photoreceptor according to claim 1, wherein said silicon phthalocyanine is a dialkoxysilicon phthalocyanine represented by the following general formula (2). [Formula 2] General formula (2) (Wherein, R ₁ and R ₂ each independently represent an alkyl group which may have a substituent, X ₅ , X ₆ , X ₇ and X ₈ each independently represent a halogen atom, e, f, g, and h each independently represent an integer of 0 to 4.) 4. The electrophotographic photosensitive member according to claim 1, wherein said silicon phthalocyanine is a dimerized dihydroxysilicon phthalocyanine represented by the following general formula (3). [Formula 3] General formula (3) (Wherein X ₉ , X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , X ₁₄ , X ₁₅ and X ₁₆ each independently represent a halogen atom;
j, k, l, m, n, o and p are each independently 0 to
Represents an integer of 4. ) 5. The electrophotographic photoreceptor according to claim 1, wherein said silicon phthalocyanine is disiloxysilicon phthalocyanine represented by the following general formula (4). [Formula 4] General formula (4) (Wherein, R ₃ and R ₄ each independently represent an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group which may have a substituent. X ₁₇ , X ₁₈ , X ₁₉ and X ₂₀ each represent Independently represents a halogen atom, and q, r, s and t each independently represent an integer of 0 to 4.) 6. The dihydroxysilicon phthalocyanine has a diffraction angle (2θ ± 0.2 in CuKα characteristic X-ray diffraction).
3 °) of 9.2 °, 14.1 °, 15.3 °, 19.7
The electrophotographic photoreceptor according to claim 2, which has strong peaks at ° and 27.1 °. 7. The dihydroxysilicon phthalocyanine has a diffraction angle (2θ ± 0.5.degree.) In CuKα characteristic X-ray diffraction.
3 °) 7.1 °, 9.3 °, 12.8 °, 15.8
3. The electrophotographic photoreceptor according to claim 2, wherein the electrophotographic photoreceptor has strong peaks at °, 17.2 °, 25.6 ° and 26.9 °. 8. The diffraction angle of the dialkoxysilicon phthalocyanine in CuKα characteristic X-ray diffraction (2θ ± 0.
3 °) 8.1 °, 12.2 °, 13.0 °, 17.0
°, 18.7 °, 23.3 °, 26.0 °, 27.8 °
4. The electrophotographic photoreceptor according to claim 3, wherein said photoreceptor is dimethoxysilicon phthalocyanine having a strong peak at 30.4 °. 9. The dialkoxysilicon phthalocyanine may have a diffraction angle (2θ ± 0.1) in CuKα characteristic X-ray diffraction.
3 °) 8.4 °, 10.9 °, 11.7 °, 14.6
°, 16.7 °, 17.2 °, 24.6 ° and 26.8
4. The electrophotographic photoreceptor according to claim 3, wherein the photoreceptor is a diethoxy silicon phthalocyanine having a strong peak at an angle of. 10. The dimerized dihydroxysilicon phthalocyanine has a diffraction angle (2) in CuKα characteristic X-ray diffraction.
θ ± 0.3 °), 6.9 °, 8.0 °, 10.6 °, 1
The electrophotographic photoreceptor according to claim 4, which has strong peaks at 6.0, 26.3, and 27.4. 11. The diacyloxysilicon phthalocyanine has a diffraction angle (2θ ± 2) in CuKα characteristic X-ray diffraction.
0.3 °) of 8.3 °, 12.3 °, 14.9 °, 2
6. The electrophotographic photoreceptor according to claim 5, wherein the photoreceptor is diacetoxysilicon phthalocyanine having strong peaks at 3.2 °, 25.0 ° and 27.5 °. 12. The oxytitanium phthalocyanine represented by the following general formula (5) and having a strongest peak at a diffraction angle (2θ) of 27.2 ° ± 0.2 ° in CuKα characteristic X-ray diffraction. 12. The electrophotographic photosensitive member according to any one of claims 1 to 11. [Formula 5] General formula (5) (In the formula, X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ each independently represent a halogen atom, and u, v, w and x each independently represent an integer of 0 to 4.) 13. The oxytitanium phthalocyanine has a diffraction angle (2θ ± 0.2) in CuKα characteristic X-ray diffraction.
゜) 9.0 ゜, 14.2 ゜, 23.9 ゜ and 27.1
The electrophotographic photoreceptor according to claim 12, which has a strong peak at ゜. 14. The oxytitanium phthalocyanine has a diffraction angle (2θ ± 0.2) in CuKα characteristic X-ray diffraction.
゜) 9.5 ゜, 9.7 ゜, 11.7 ゜, 15.0 ゜,
The electrophotographic photoreceptor according to claim 12, which has strong peaks at 23.5, 24.1 and 27.3. 15. The oxytitanium phthalocyanine has a diffraction angle (2θ ± 0.2) in CuKα characteristic X-ray diffraction.
゜) 9.3 °, 10.6 °, 13.2 °, 15.1
The electrophotographic photoreceptor according to claim 12, which has strong peaks at 20.8, 26.3, and 27.1. 16. An electrophotographic apparatus, wherein the electrophotographic photosensitive member according to claim 1 and at least one unit selected from the group consisting of a charging unit, a developing unit and a cleaning unit are integrally supported. A process cartridge which is detachable from a main body. 17. An electrophotographic apparatus comprising: the electrophotographic photosensitive member according to claim 1; a charging unit; an exposing unit; a developing unit; and a transfer unit.