JP2000105479A - Electrophotographic photo-receptor, process cartridge, and electrophotographic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the electrophotographic photoreceptor superior in sensitivity characteristics and small in light memory and good in repetition characteristics in the semiconductor wave-length region of 380-500 nm. SOLUTION: The electrophotographic photoreceptor is irradiated with semiconductor laser beams of 380-500 nm wavelength and provided on a substrate with a photosensitive layer containing gallium phthalocyanine or oxytitanium- phthalocyanine having an intense peak in a diffraction angle of 27.2±0.2 deg. in the CuK αcharacteristic X-ray diffraction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photoreceptor,
More particularly, the present invention relates to an electrophotographic photosensitive member, a process cartridge, and an electrophotographic apparatus suitable for a short-wavelength semiconductor laser capable of increasing the resolution of an image.

[0002]

2. Description of the Related Art At present, a semiconductor laser having an oscillation wavelength around 800 nm or around 680 nm is mainly used in an electrophotographic apparatus using a laser as a light source such as a laser printer. In recent years, various approaches for achieving higher resolution have been made due to a growing need for higher image quality of output images. The wavelength of the laser is also deeply involved in the high resolution, and as described in JP-A-9-240051, the shorter the oscillation wavelength of the laser, the smaller the spot diameter of the laser becomes. A high-resolution latent image can be formed.

There are several techniques for shortening the laser oscillation wavelength.

One is to use a nonlinear optical material and reduce the wavelength of a laser beam to a half by using second harmonic generation (SHG) (Japanese Patent Laid-Open Nos. 9-275242 and 9-275242). 189930 and JP-A-5-313033). In this system, a GaAs-based semiconductor laser or a YAG laser, which has already been established and can output high power, can be used as a primary light source, so that the life can be extended and the power can be increased.

The other uses a wide-gap semiconductor, and can reduce the size of the device as compared with a device using SHG. ZnSe based semiconductor laser (Japanese Unexamined Patent Publication No.
321409 and JP-A-6-334272)
And GaN-based semiconductor lasers (for example, JP-A-8-088441 and JP-A-7-335975) have been the subject of much research because of their high luminous efficiency.

[0006] In these semiconductor lasers, it is difficult to optimize the element structure, crystal growth conditions, electrodes, and the like, and it is difficult to perform long-term oscillation at room temperature, which is essential for practical use, due to defects in the crystal.

[0007] However, technological innovations such as the base have progressed, and 19
In October 1997, Nichia reported a continuous oscillation (at 50 ° C.) for 1150 hours with a GaN-based semiconductor laser, and practical use is imminent.

[0008]

Problems to be Solved by the Invention
No. 1 discloses a photoreceptor suitable for a laser of 400 to 500 nm, which is a monolayer using α-type titanyl phthalocyanine or a laminated photoreceptor having a charge generation layer as the outermost surface layer. According to these studies, when this material is used, there is a problem that the sensitivity is poor and the memory for light near 400 nm is particularly large, so that the potential fluctuation of the photoconductor when used repeatedly is large. I understood.

An object of the present invention is to provide an electrophotographic photosensitive member having high sensitivity characteristics even in a wavelength range of 380 to 500 nm, a small optical memory, and a small potential fluctuation upon repeated use, and a process cartridge having the same. Another object of the present invention is to provide an electrophotographic apparatus capable of practically and stably obtaining a high-quality output image by using the photosensitive member and a short-wavelength laser.

[0010]

According to the present invention, there is provided an electrophotographic photoreceptor having a photosensitive layer on a support, wherein the electrophotographic photoreceptor is irradiated with a semiconductor laser having a wavelength of 380 to 500 nm; The layer has a diffraction angle of 2 in the gallium phthalocyanine compound or CuKα characteristic X-ray diffraction.
An electrophotographic photosensitive member containing oxytitanium phthalocyanine having a strong peak at 7.2 # ± 0.2 °.

Further, the present invention is a process cartridge having the above electrophotographic photosensitive member.

Further, the present invention is an electrophotographic apparatus having the above electrophotographic photosensitive member and a short wavelength semiconductor laser as an exposure light source.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The gallium phthalocyanine compound (hereinafter referred to as GaPc) used in the present invention is represented by the following formula.

[0014]

Embedded image (Wherein X represents Cl, Br, I and OH, and Y ₁ , Y
₂ , Y ₃ and Y ₄ represent Cl or Br, and n, m, k
And p show the integer of 0-4. In the present invention, GaPc having any crystal form can be used, but it is preferably hydroxygallium phthalocyanine (hereinafter, referred to as HOGaPc), and particularly, CuKα disclosed in JP-A-5-263007 and the like. Diffraction angle in characteristic X-ray diffraction (2θ ± 0.
The crystalline form of HOGaPc having strong peaks at 7.4 ° and 28.2 ° in 2) is particularly preferable because it has high sensitivity and the present invention effectively works.

The oxytitanium phthalocyanine (hereinafter referred to as TiOPc) used in the present invention is represented by the following formula.

[0016]

Embedded image (Wherein X ₁ , X ₂ , X ₃ and X ₄ represent Cl or Br, and a, b, c and d each represent an integer of 0 to _4. ) TiOPc used in the present invention has CuKα characteristic X Any crystal may be used as long as it has a crystal form having a strong peak at a diffraction angle of 27.2 ° ± 0.2 ° in the line diffraction, and among them, those having the following crystal forms are preferable.

That is, the diffraction angles (2θ ± 0.2 °) in the CuKα characteristic X-ray diffraction disclosed in JP-A-3-128973 are 9.0 °, 14.2 °, 23.
Preferably, it is a crystalline form having strong peaks at 9 ° and 27.1 °.

[0018] In addition, there are strong peaks at the diffraction angles (2θ ± 0.2 °) of 9.6 ° and 27.3 ° in the CuKα characteristic X-ray diffraction disclosed in JP-A-5-188614 and the like. Preferably, it is in a crystalline form.

Further, the diffraction angles (2θ ± 0.2 °) of 9.5 °, 9.7 °, and 11.1 in the CuKα characteristic X-ray diffraction disclosed in JP-A-64-17066 and the like.
7 °, 15.0 °, 23.5 °, 24.1 ° and 27.
It is preferable that the crystal form has a strong peak at 3 °.

Among these, in particular, the diffraction angle (2θ ± 0.2 °) of 9.0 °, 1 ° in the CuKα characteristic X-ray diffraction.
Crystal forms with strong peaks at 4.2 °, 23.9 ° and 27.1 ° are preferred.

The reason why the remarkable effect of the present invention can be obtained is not clear, but it is not clear that GaPc and TiO having a specific crystal form are used.
It is considered that Pc is unlikely to generate photo memory even for short-wavelength light having high energy, and has high quantum efficiency when short-wavelength light is used. Can be This Ga
The characteristics of Pc and TiOPc are completely unexpected from characteristics using long-wavelength light conventionally known.

Next, the electrophotographic photosensitive member of the present invention will be described in detail.

The structure of the photoreceptor may be any known structure as shown in FIGS. 1, 2 and 3, but is preferably the structure of FIG. In the figure, a is a support, b is a photosensitive layer, c is a charge generation layer, d is a charge transport layer, e
Represents a charge generation material. Japanese Patent Application Laid-Open No. 9-240051 discloses that in a photoreceptor in which a charge generation layer and a charge transport layer are laminated in this order on a support as shown in FIG. 1, light of 400 to 500 nm is absorbed by the charge transport material, and Although light does not reach the layer, there is no sensitivity in principle, but this is not always the case, and a charge transport material that is transparent to the laser oscillation wavelength is used as the charge transport material for the charge transport layer. If used, sufficient sensitivity can be obtained even with the photoreceptor having the above configuration, and the photoreceptor can be used.

Hereinafter, a method of preparing a function-separated type photoconductor in which a charge generation layer and a charge transport layer are laminated on a support will be described.

The charge generation layer is made of Ga as a charge generation material.
It is formed by applying a liquid obtained by dispersing Pc or TiOPc together with a binder resin in a suitable solvent onto a support by a known method, and drying the liquid. Its film thickness is 5μ
m, particularly preferably 0.1 to 1 μm.

The binder resin used is selected from a wide range of insulating resins or organic photoconductive polymers, and includes polyvinyl butyral, polyvinyl benzal, polyarylate, polycarbonate, polyester, phenoxy resin, cellulose resin, and acrylic resin. And polyurethane, and the like. These resins may have a substituent, and the substituent is preferably a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a trifluoromethyl group, or the like. The amount of the binder resin used is preferably 80 to the total weight of the charge generation layer.
% By weight, more preferably 40% by weight or less.

The solvent used is preferably selected from those which dissolve the binder resin and do not dissolve the charge transport layer and the undercoat layer described below. Specifically, ethers such as tetrahydrofuran and 1,4-dioxane, ketones such as cyclohexanone and methyl ethyl ketone,
Amines such as N, N-dimethylformamide; esters such as methyl acetate and ethyl acetate; aromatics such as toluene, xylene and chlorobenzene; methanol;
Alcohols such as ethanol and 2-propanol,
Examples include aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, and trichloroethylene.

The charge transport layer is stacked on or below the charge generation layer, and has a function of receiving charge carriers from the charge generation layer in the presence of an electric field and transporting the carriers. The charge transport layer is formed by applying a solution prepared by dissolving a charge transport material in a solvent together with an appropriate binder resin as required, and drying the solution. The film thickness is preferably from 5 to 40 μm, and particularly preferably from 15 to 30 μm.

The charge transporting material includes an electron transporting substance and a hole transporting substance.
Electron withdrawing substances such as 4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone, chloranil, and tetracyanoquinodimethane, and those obtained by polymerizing these electron withdrawing substances. .

Examples of the hole transporting substance include polycyclic aromatic compounds such as pyrene and anthracene, carbazole, indole, oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole and triazole. Heterocyclic compound such as a compound, a hydrazone compound, a styryl compound, a benzidine compound, a triarylmethane compound and a triphenylamine compound, or a polymer having a group consisting of these compounds in a main chain or a side chain (for example, Poly
N-vinylcarbazole and polyvinylanthracene).

These charge transporting materials can be used alone or in combination of two or more. When the charge transport material does not have a film forming property, an appropriate binder can be used. Specifically, insulating resin such as acrylic resin, polyarylate, polycarbonate, polyester, polystyrene, acrylonitrile styrene copolymer, polyacrylamide, polyamide and chlorinated rubber, or organic photoconductive such as poly-N-vinylcarbazole and polyvinylanthracene And the like.

However, when used for the photoreceptor having the configuration shown in FIG. 1, it is necessary to select a charge transporting material or a binder resin which is transparent to the oscillation wavelength of the semiconductor laser used as described above.

The support has conductivity, and examples thereof include aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold and platinum. In addition, plastics (eg, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, etc.) and conductive particles (eg, carbon black and silver particles) formed by coating these metals or alloys by vacuum evaporation are suitable. A support coated on a plastic, a metal or an alloy as described above, or a support in which conductive particles are impregnated in plastic or paper together with a binder resin can be used. Examples of the shape include a drum shape, a sheet shape, and a belt shape.

In the present invention, an undercoat layer having a barrier function and an adhesive function may be provided between the support and the photosensitive layer.

Further, a protective layer can be provided for the purpose of protecting the photosensitive layer from external mechanical and chemical adverse effects.

Incidentally, additives such as an antioxidant and an ultraviolet absorber may be used in the photosensitive layer as required.

The exposure means in the present invention only needs to have a semiconductor laser having an oscillation wavelength of 380 to 500 nm as an exposure light source, and other configurations are not particularly limited. Other configurations of the semiconductor laser are not particularly limited as long as the oscillation wavelength is within the above range. In the present invention, the oscillation wavelength of the semiconductor laser is preferably 400 to 450 nm from the viewpoint of electrophotographic characteristics.

The charging means, developing means, transfer means and cleaning means in the present invention are not particularly limited.

FIG. 4 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 rotatably driven around an axis 2 in a direction of an arrow at a predetermined peripheral speed. The photoreceptor 1 rotates during the rotation process.
The peripheral surface thereof is uniformly charged at a predetermined positive or negative potential by the primary charging means 3, and then receives exposure light 4 from exposure means (not shown) using a semiconductor laser having an oscillation wavelength of 380 to 500 nm. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then developed
The toner-developed image developed by the toner image is transferred 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 and fed to a transfer material 7 fed therefrom. The image is sequentially transferred by the transfer unit 6.

The transfer material 7 which has undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing to be 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 the cleaning means 9, and the pre-exposure light 1 from the pre-exposure means (not shown).
After the charge is removed by 0, the image is repeatedly used for image formation. In the figure, since the primary charging means 3 is a contact charging means using a charging roller, pre-exposure is not necessarily required.

In the present invention, a plurality of components such as the above-described electrophotographic photosensitive member 1, the primary charging unit 3, the developing unit 5, and the cleaning unit 9 are integrally connected as a process cartridge. The process 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, which can be attached to and detached from the apparatus main body using a guide unit such as a rail 12 of the apparatus main body. The process cartridge 11 can be used.

Next, a production example of GaPc used in the present invention will be described. Hereinafter, parts in Production Examples and Examples are parts by weight.

[Production Example 1] o-phthalodinitrile 73
Parts, 25 parts of gallium trichloride and α-chloronaphthalene 4
After reacting 00 parts under nitrogen atmosphere at 200 ° C. for 4 hours,
The product was filtered at 130 ° C. The product obtained is converted to N, N
After dispersing and washing at 130 ° C. for 1 hour using dimethylformamide, the mixture was filtered, washed with methanol and dried to obtain 45 parts of chlorogallium phthalocyanine. The elemental analysis values of this compound were as follows.

Elemental analysis value (C ₃₂ H ₁₆ N ₈ ClGa) CH N Cl Experimental value (%) 61.8 2.7 18.3 6.3 Calculated value (%) 62.2 2.6 18.1 5.7 [Production Example 2] 15 parts of chlorogallium phthalocyanine obtained in Production Example 1 was dissolved in 450 parts of concentrated sulfuric acid at 10 ° C, dropped into 2300 parts of ice water with stirring, reprecipitated, and filtered. After dispersed and washed with 2% ammonia water, sufficiently washed with ion-exchanged water, separated by filtration and dried to obtain a low-crystalline HOGaP.
13 parts of c were obtained. The elemental analysis values of this compound were as follows.

Elemental analysis value (C ₃₂ H ₁₇ N ₈ OGa) CH N Cl Experimental value (%) 62.8 2.6 18.3 0.5 Calculated value (%) 64.1 2.9 18.7 [Preparation Example 3] Milling treatment was performed at room temperature (22 ° C) for 24 hours together with 5 parts of the chlorogallium phthalocyanine obtained in Preparation Example 1 and 300 parts of glass beads having a diameter of 1 mm.
200 parts of benzyl alcohol was added, and a milling treatment was further performed at room temperature (22 ° C.) for 6 hours. The solid content was taken out from this dispersion and dried to obtain 4.5 parts of chlorogallium phthalocyanine. This chlorogallium phthalocyanine has a diffraction angle (2θ ± 0.2 °) in X-ray diffraction.
Had strong peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 °. This chlorogallium phthalocyanine is described in JP-A-5-98181.

[Production Example 4] HOGa obtained in Production Example 2
Milling treatment was performed for 6 hours at room temperature (22 ° C.) with 10 parts of Pc and 300 parts of N, N-dimethylformamide together with 450 parts of 1 mmφ glass beads.

The solid content was taken out from this dispersion, replaced with methanol, and dried to obtain 9.2 parts of HOGaPc. This HOGaPc has a diffraction angle (2θ ± 0.2 °) of 7.4 ° and 28.2 ° in CuKα characteristic X-ray diffraction.
Had a strong peak. This HOGaPc is described in JP-A-5-263007.

[Production Example 5] HOGa obtained in Production Example 2
Milling treatment was performed for 6 hours at room temperature (22 ° C.) with 10 parts of Pc and 300 parts of N, N-dimethylformamide together with 450 parts of 1 mmφ glass beads.

A solid content was taken out from this dispersion, replaced with methanol, washed and dried to obtain 9.2 parts of HOGaPc. This HOGaPc has a diffraction angle (2θ ± 0.2 °) of 7.6 °, 16.4 ° in CuKα characteristic X-ray diffraction,
It had strong peaks at 25.0 ° and 26.5 °.
This HOGaPc is described in JP-A-5-263007.

[Production Example 6] HOGa obtained in Production Example 2
Milling of 10 parts of Pc and 300 parts of chloroform together with 450 parts of 1 mmφ glass beads at room temperature (22 ° C.)
The operation was performed for 6 hours.

The solid content was taken out from the dispersion and dried to obtain 9.2 parts of HOGaPc. This HOGaPc has a diffraction angle (2θ ± 0.2) in CuKα characteristic X-ray diffraction.
°) at 6.9 °, 16.5 ° and 26.7 °. This HOGaPc is disclosed in JP-A-6-27.
No. 9698.

Next, a production example of TiOPc used in the present invention will be described.

[Production Example 7] o-phthalodinitrile 5.0
Parts, 2.0 parts of titanium tetrachloride were added to α-chloronaphthalene 10
In 0 parts, the mixture was heated and stirred at 200 ° C. for 3 hours, cooled to 50 ° C., and the precipitated crystals were separated by filtration to obtain a paste of dichlorotitanium phthalocyanine. Then, add this to 100
The mixture was washed with 100 parts of N, N-dimethylformamide heated to 100 ° C while stirring, and then washed with 100 parts of methanol at 60 ° C.
The washing was repeated twice and filtered. Further, the obtained paste was stirred at 80 ° C. for 1 hour in 100 parts of deionized water and filtered to obtain blue TiOPc crystals. Yield 4.3 parts.

Next, the crystals were dissolved in 30 parts of concentrated sulfuric acid, dropped into 300 parts of deionized water at 20 ° C. with stirring to reprecipitate, filtered, and sufficiently washed with water.
Pc was obtained. Amorphous TiOP thus obtained
c 4.0 parts in 100 parts of methanol at room temperature (22 ° C.)
The suspension was stirred for 8 hours, filtered, and dried under reduced pressure to obtain low crystalline TiOPc. Next, 2.0 parts of this TiOPc
-40 parts of butyl ether was added, 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 then with water, and dried to obtain the novel crystalline TiOPc of the present invention. Yield 1.8 parts. This TiOP
c is the diffraction angle (2θ ± 0.2 °) in X-ray diffraction.
It had strong peaks at 0 °, 14.2 °, 23.9 ° and 27.1 °.

[Production Example 8] According to the production example disclosed in Japanese Patent Application Laid-Open No. Sho 64-17066, the diffraction angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction is 9.5.
Crystalline form of TiOPc with strong peaks at °, 9.7 °, 11.6 °, 14.9 °, 24.0 ° and 27.3 °
I got

[Production Example 9] According to the production example disclosed in Japanese Patent Application Laid-Open No. 5-188614, the diffraction angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction is 9.6 °.
And a crystalline form of TiOP having a strong peak at 27.3 °
c was obtained.

Comparative Example 1 JP-A-61-23924
According to a production example disclosed in US Pat. No. 8,728,592 (USP 4,728,592), a so-called α-type is called.
27.2 ° ± 2 ° of diffraction angle in CuKα characteristic X-ray diffraction
A crystalline form of TiOPc having no strong peak at 0.2 ° was obtained.

[0062]

Next, the present invention will be described with reference to examples.

Example 1 5 parts of methoxymethylated nylon (average molecular weight: 32,000) and alcohol-soluble copolymerized nylon (average molecular weight: 29.0) were placed on an aluminum substrate.
00) A solution prepared by dissolving 10 parts in 95 parts of methanol was applied with a Meyer bar, and dried to obtain a film having a thickness of 1 μm.
Was formed.

Next, 4 parts of the GaPc compound obtained in Production Example 3 was mixed with 95 parts of cyclohexanone in butyral resin (butyralization degree: 63 mol%, weight average molecular weight: 100,000).
Was added to the liquid in which the parts had been dissolved, and the mixture was dispersed with a sand mill for 20 hours. The thickness of this dispersion after drying on the undercoat layer is 0.2
The resultant was applied with a Meyer bar to a thickness of μm to form a charge generation layer.

Next, 5 parts of a charge transporting material having the following structural formula

[0066]

Embedded image And 5.5 parts of bisphenol Z-type polycarbonate resin (number average molecular weight: 20,000) are dissolved in 40 parts of chlorobenzene, and this solution is dried on the charge generation amount to a film thickness of 20 parts.
The mixture was applied with a Meyer bar to a thickness of μm to form a charge transport layer, and an electrophotographic photosensitive member of Example 1 was prepared.

The electrophotographic photoreceptor thus prepared was applied to an electrostatic copying paper tester (Kawaguchi Electric: EPA-810).
0) was evaluated as follows.

(Sensitivity) Charged by a corona charger so that the surface potential of the photoreceptor becomes -700 V, and then exposed with a monochromatic light of 400 nm separated by a monochromator, and required to attenuate the surface potential to -350 V. And the sensitivity (E1 / 2) was determined. Similarly, at 450 nm, 50
Sensitivity at 0 nm monochromatic light was measured.

(Repeatability) Next, the initial dark portion potential (V
d) and the initial light portion potential (V1) are -700 V, respectively.
Charging and exposure were repeated 3,000 times using a monochromatic light of 400 nm set at around -200 V, and the fluctuation amounts (ΔVd, ΔV1) of Vd and V1 were measured.

(Photo Memory) Initial Vd, 4
The initial V1 with the monochromatic light of 00 nm is -700 V, respectively.
It was set around -200V. Next, after irradiating a part of the photoreceptor with monochromatic light of 400 nm having a light intensity of 20 μW / cm ² for 15 minutes, Vd and V1 of the photoreceptor were measured again. The difference (ΔVd _PM ) and the difference (ΔV1 _PM ) between V1 of the non-irradiated part and the irradiated part were measured.

Table 1 shows the above results.

In the table below, a minus sign in the repetition characteristics and the photo memory indicates a decrease in the absolute value of the potential, and a plus sign indicates an increase in the absolute value of the potential.

Examples 2 to 4 and Comparative Example 1 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the materials shown in Table 1 were used as the charge generating materials. Table 1 shows the results.

[0074]

[Table 1] Examples 5 to 8 and Comparative Example 2 Examples 1 to 4 and Comparative Example 1 except that the vertical relationship between the charge generation layer and the charge transport layer was reversed.
An electrophotographic photoreceptor was prepared in the same manner as in Example 1, and the initial sensitivity was measured in the same manner as in Example 1. However, the charge transport material was replaced with a compound having the following structural formula, and the charge polarity was positive.

[0075]

Embedded image These results are summarized in Table 2.

[0076]

[Table 2] From the above results, the electrophotographic photoreceptor used in the present invention has extremely excellent sensitivity in the oscillation wavelength region of the short-wavelength laser of 400 to 500 nm as compared with the electrophotographic photoreceptor of the comparative example, and has a high light sensitivity to short-wavelength light. It can be seen that the memory is small and the potential and sensitivity stability when used repeatedly are excellent.

[Examples 9 to 12] 50 parts of titanium oxide powder coated with tin oxide containing 10% antimony oxide,
Resol type phenol resin 25 parts, methyl cellosolve 2
0 parts, 5 parts of methanol and 0.002 parts of silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3,000) were dispersed in a sand mill using φ1 mm glass beads for 2 hours to prepare a paint for a conductive layer. Prepared. By dip-coating this paint on an aluminum cylinder and drying at 140 ° C for 30 minutes,
A conductive layer having a thickness of 20 μm was formed.

6-66-610-12 5 parts of a quaternary polyamide copolymer resin were obtained by mixing 70 parts of methanol and 25 parts of butanol.
Of the mixed solvent. This solution was applied onto the conductive layer by dip coating and dried to form an undercoat layer having a thickness of 0.8 μm.

Next, the charge generation materials 10 shown in Table 3
Part is polyvinyl butyral resin (trade name: Esrec B
MS, Sekisui Chemical Co., Ltd.) 5 parts of cyclohexanone 100
The mixture was added to the solution dissolved in the mixture, dispersed by a sand mill using φ1 mm glass beads for 20 hours, and further diluted with 100 parts of methyl ethyl ketone. This liquid 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 0.2 μm.

Next, 9 parts of a charge transporting material represented by the following structural formula and 10 parts of a bisphenol Z-type polycarbonate resin (number average molecular weight: 20,000) were mixed with monochlorobenzene 6
Dissolved in 0 parts. This solution was applied onto the charge generation layer by dip coating, and dried at a temperature of 110 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm. Thus, electrophotographic photoreceptors of Examples 9 to 12 were prepared.

[0081]

Embedded image The electrophotographic photoreceptor produced in this way was used as a Canon printer LBP-20 equipped with a pulse modulator.
00 remodeling machine (Hitachi Metals Co., Ltd. equipped with all solid blue SHG laser ICD-430 / oscillation wavelength of 430 nm. Also available from reversal development system for charging-exposure-development-transfer-cleaning that can support 600 dpi equivalent image input. (Remodeled into a Carlson type electrophotographic system.) Dark section potential Vd = -650 V, bright section potential V1 =
At -200 V, an image of one dot and one space and a character (5 points) image were output, and the obtained image was visually evaluated.

[Comparative Example 3] The light source of the evaluator was set to an oscillation wavelength of 78.
Image evaluation was performed in the same manner as in Example 9, except that the GaAs semiconductor laser of 0 nm was used. Table 3 shows the results.

[0083]

[Table 3] From these results, it can be seen that the electrophotographic apparatus of the present invention is excellent in dot reproducibility and character reproducibility and can obtain a high-resolution output image.

[Examples 13 to 15] Table 4 shows charge generation materials.
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the above-mentioned components were replaced with those described in Example 1. Table 4 shows the results.

[0085]

[Table 4] [Examples 16 to 18] An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 5, except that the charge generating materials were changed to those shown in Table 5. Table 5 shows the results.

[0086]

[Table 5] From the above results, the electrophotographic photoreceptor used in the present invention has extremely excellent sensitivity in the oscillation wavelength region of the short-wavelength laser of 400 to 500 nm as compared with the electrophotographic photoreceptor of the comparative example, and has a high light sensitivity to short-wavelength light. It can be seen that the memory is small and the potential and sensitivity stability when used repeatedly are excellent.

[Examples 19 to 21] Table 6 shows charge generation materials.
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 9 except that the above-mentioned components were replaced with those described in Example 9. Table 6 shows the results.

[0088]

[Table 6] From these results, it can be seen that the electrophotographic apparatus of the present invention is excellent in dot reproducibility and character reproducibility and can obtain a high-resolution output image.

[0089]

As described above, according to the present invention, the use of a charge-generating substance having a specific structure allows 380 to 500
It is possible to provide an electrophotographic photosensitive member having excellent sensitivity characteristics, a small optical memory, and excellent repetition characteristics in the oscillation wavelength region of a semiconductor laser having a short wavelength of around nm. By combining the above, it is possible to provide a process cartridge and an electrophotographic apparatus capable of forming a high-resolution image and stably being used repeatedly.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a layer configuration of an electrophotographic photoreceptor of the present invention.

FIG. 2 is a cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a cross-sectional view illustrating an example of a layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 4 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member according to the present invention.

[Explanation of symbols]

 Reference Signs List a Support b Photosensitive layer c Charge generation layer d Charge transport layer e Charge generation material 1 Electrophotographic photoreceptor 2 Axis 3 Primary charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Image fixing means 9 Cleaning means 10 Before Exposure light 11 Process cartridge 12 Rail

Claims (27)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a support, wherein the electrophotographic photosensitive member is irradiated with a semiconductor laser beam having a wavelength of 380 to 500 nm, and the photosensitive layer has a gallium phthalocyanine compound or CuKα characteristic. An electrophotographic photosensitive member containing oxytitanium phthalocyanine having a strong peak at a diffraction angle of 27.2 # ± 0.2 ° in X-ray diffraction. 2. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer contains a gallium phthalocyanine compound. 3. The electrophotographic photosensitive member according to claim 1, wherein the gallium phthalocyanine compound is hydroxygallium phthalocyanine. 4. The method according to claim 1, wherein the hydroxygallium phthalocyanine is C
Diffraction angle in uKα characteristic X-ray diffraction (2θ ± 0.2 °)
4. The electrophotographic photosensitive member according to claim 3, which has strong peaks at 7.4 ° and 28.2 °. 5. The electrophotographic photoreceptor according to claim 1, wherein the photosensitive layer contains oxytitanium phthalocyanine having a strong peak at a diffraction angle of 27.2 # ± 0.2 ° in CuKα characteristic X-ray diffraction. 6. An oxytitanium phthalocyanine comprising Cu
6. The electron according to claim 1, having strong peaks at 9.0 #, 14.2 #, 23.9 # and 27.1 [deg.] Of diffraction angles (2 [theta] ± 0.2 [deg.]) In Kα characteristic X-ray diffraction. Photoreceptor. 7. An oxytitanium phthalocyanine comprising Cu
2. Strong peaks at 9.6 # and 27.3 ° of the diffraction angle (2θ ± 0.2 °) in Kα characteristic X-ray diffraction.
Or the electrophotographic photosensitive member according to 5. 8. The method according to claim 1, wherein the oxytitanium phthalocyanine is Cu.
9.5 #, 9.7 #, 11.7 #, 15.0 #, 23.5 of diffraction angles (2θ ± 0.2 °) in Kα characteristic X-ray diffraction
6. The electrophotographic photoreceptor according to claim 1, which has strong peaks at #, 24.1 # and 27.3 °. 9. The semiconductor laser beam has a wavelength of 400.
The electrophotographic photosensitive member according to any one of claims 1 to 8, wherein the thickness is from 450 to 450 nm. 10. A process cartridge which integrally supports an electrophotographic photosensitive member and at least one means selected from a charging means, a developing means and a cleaning means and is detachable from an electrophotographic apparatus main body. The body has a photosensitive layer on a support,
The semiconductor layer is irradiated with a semiconductor laser beam having a wavelength of 500 nm, and the gallium phthalocyanine compound or C
27.2 # ± 0. of diffraction angle in uKα characteristic X-ray diffraction.
A process cartridge containing oxytitanium phthalocyanine having a strong peak at 2 °. 11. The process cartridge according to claim 10, wherein the photosensitive layer contains a gallium phthalocyanine compound. 12. The process cartridge according to claim 10, wherein the gallium phthalocyanine compound is hydroxygallium phthalocyanine. 13. Hydroxygallium phthalocyanine has a diffraction angle (2θ ± 0.2) in CuKα characteristic X-ray diffraction.
The process cartridge according to claim 12, which has strong peaks at 7.4 ° and 28.2 ° in (°). 14. The photosensitive layer contains oxytitanium phthalocyanine having a strong peak at a diffraction angle of 27.2 # ± 0.2 ° in CuKα characteristic X-ray diffraction.
The process cartridge according to 1. 15. An oxytitanium phthalocyanine comprising C
Diffraction angle in uKα characteristic X-ray diffraction (2θ ± 0.2 °)
15. The process cartridge according to claim 10, wherein the process cartridge has strong peaks at 9.0 #, 14.2 #, 23.9 # and 27.1 °. 16. An oxytitanium phthalocyanine comprising C
Diffraction angle in uKα characteristic X-ray diffraction (2θ ± 0.2 °)
15. The process cartridge according to claim 10, which has strong peaks at 9.6 # and 27.3 °. 17. The method according to claim 17, wherein the oxytitanium phthalocyanine is C
Diffraction angle in uKα characteristic X-ray diffraction (2θ ± 0.2 °)
9.5 #, 9.7 #, 11.7 #, 15.0 #, 23.5
15. The process cartridge according to claim 10, which has strong peaks at #, 24.1 #, and 27.3 °. 18. The semiconductor laser beam has a wavelength of 40.
The process cartridge according to any one of claims 10 to 17, wherein the thickness is from 0 to 450 nm. 19. An electrophotographic apparatus having an electrophotographic photosensitive member, a charging unit, an exposing unit, a developing unit, and a transferring unit, wherein the exposing unit has a semiconductor laser having a wavelength of 380 to 500 nm as an exposure light source. The photographic photoreceptor has a photosensitive layer on a support, and the photosensitive layer is a gallium phthalocyanine compound or CuKα characteristic X.
An electrophotographic apparatus comprising oxytitanium phthalocyanine having a strong peak at a diffraction angle of 27.2 # ± 0.2 ° in line diffraction. 20. The electrophotographic apparatus according to claim 19, wherein the photosensitive layer contains a gallium phthalocyanine compound. 21. The electrophotographic apparatus according to claim 19, wherein the gallium phthalocyanine compound is hydroxygallium phthalocyanine. 22. Hydroxygallium phthalocyanine has a diffraction angle (2θ ± 0.2) in CuKα characteristic X-ray diffraction.
22. The electrophotographic apparatus according to claim 21, which has strong peaks at 7.4 ° and 28.2 ° in (°). 23. The photosensitive layer contains oxytitanium phthalocyanine having a strong peak at a diffraction angle of 27.2 # ± 0.2 ° in CuKα characteristic X-ray diffraction.
An electrophotographic apparatus according to claim 1. 24. An oxytitanium phthalocyanine comprising C
Diffraction angle in uKα characteristic X-ray diffraction (2θ ± 0.2 °)
24. The electrophotographic apparatus according to claim 19 or 23, wherein the electrophotographic apparatus has strong peaks at 9.0 #, 14.2 #, 23.9 # and 27.1 °. 25. An oxytitanium phthalocyanine comprising C
Diffraction angle in uKα characteristic X-ray diffraction (2θ ± 0.2 °)
The electrophotographic apparatus according to claim 19 or 23, wherein the electrophotographic apparatus has strong peaks at 9.6 # and 27.3 °. 26. An oxytitanium phthalocyanine comprising C
Diffraction angle in uKα characteristic X-ray diffraction (2θ ± 0.2 °)
9.5 #, 9.7 #, 11.7, 15.0 #, 23.5
The electrophotographic apparatus according to claim 19 or 23, wherein the electrophotographic apparatus has strong peaks at #, 24.1 #, and 27.3 °. 27. The oscillation wavelength of a semiconductor laser is 400 to
27. The electrophotographic apparatus according to claim 19, wherein the wavelength is 450 nm.