JPH06295086A - Electrophotographic sensitive body, electrophotographic device with the same and device unit - Google Patents

Abstract

PURPOSE:To provide an electrophotographic sensitive body having excellent potential characteristics, capable of giving an image having high image quality even after repeated use and also having excellent characteristics with respect to pause memory and transfer memory and to provide an electrophotographic device with the electrophotographic sensitive body and a device unit. CONSTITUTION:In an electrophotographic sensitive body with a photosensitive layer and a protective layer on the electric conductive substrate, the protective layer contains electric conductive particles, fluorine atom-contg. resin particles, a bonding resin and at least one kind of fluorine atom-contg. compd. selected among a fluorine-contg. surfactant, a fluorine-contg. silane coupling agent, fluorine-contg. silicone oil and a fluorine-contg. graft polymer. The objective electrophotographic sensitive body is provided and the objective electrophotographic device with this electrophotographic sensitive body and the objective device unit are provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member having a protective layer, and more specifically, to an electrophotographic photosensitive member having high image uniformity and high durability, excellent sliding property and improved electrophotographic characteristics. The present invention relates to an electrophotographic apparatus and an apparatus unit having the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Electrophotographic photoreceptors are used for charging, exposing, developing,
Means such as transfer, cleaning and charge removal are repeatedly applied. The electrostatic latent image formed by charging and exposure becomes a toner image by a fine particle developer called toner. Further, this toner image is transferred onto a transfer material such as paper by the transfer means, but not all the toner is transferred, and a part thereof remains on the surface of the photoconductor.

When the amount of the residual toner is large, the image on the transfer material becomes a so-called "blurred" state in which a transfer failure occurs unevenly, so that not only the image uniformity is lacked but also the fusion of the toner to the photosensitive member and the filming are performed. Occurs. For these problems, it is required to improve the releasability of the surface layer of the photoconductor.

Further, the electrophotographic photosensitive member is required to have durability against the above-mentioned electric and mechanical external forces, since it is directly applied thereto. Specifically, it is required to have durability against abrasion and scratches on the surface due to rubbing, and deterioration of the surface layer due to adhesion of ozone and active substances such as NOx generated during charging.

Attempts have been made to provide various protective layers in order to satisfy the above-mentioned characteristics required for the electrophotographic photosensitive member. Above all, many protective layers containing a resin as a main component have been proposed. For example, Japanese Patent Application Laid-Open No. 57-30846 proposes a protective layer capable of controlling resistance by adding a metal oxide as a conductive powder to a resin.

Dispersing a metal oxide in a protective layer for an electrophotographic photoreceptor controls the electric resistance of the protective layer itself and prevents an increase in residual potential in the photoreceptor due to repeated electrophotographic processes. Is the main purpose, while the suitable resistance value of the protective layer for the electrophotographic photoreceptor is 10 ¹⁰ to 10 ¹⁵ o.
It is known to be hm · cm. However,
When the resistance value is in the above range, the electric resistance of the protective layer is easily affected by ion conduction, and therefore the electric resistance tends to largely change due to changes in the environment. In particular, when the metal oxide is dispersed in the film, the water absorption of the surface of the metal oxide is high, so that the resistance of the protective layer falls within the above range in the entire environment and when the electrophotographic process is repeated. It has been very difficult to keep within.

Particularly under high humidity, active substances such as ozone and NOx generated by charging are repeatedly deposited on the surface, which causes a reduction in the resistance of the surface of the photoconductor and a reduction in the releasability of the toner. There have been problems such as occurrence of flow and insufficient image uniformity.

Generally, when particles are dispersed in a protective layer, the particle size of the particles is smaller than the wavelength of the incident light, that is, 0.
It is preferably 3 μm or less. However, metal oxide particles usually tend to agglomerate in a resin solution and are difficult to uniformly disperse, and secondary agglomeration and precipitation easily occur once dispersed, so that a fine dispersion film of fine particles having a particle size of 0.3 μm or less should be formed. It was very difficult to produce stably. Further, it is preferable to disperse an ultrafine particle having a particularly small particle size (primary particle diameter of 0.1 μm or less) from the viewpoint of improving transparency and conductivity uniformity. However, dispersibility and dispersion stability of such an ultrafine particle. Tended to get worse.

In order to make up for the above drawbacks, for example, Japanese Patent Laid-Open No.
No. 306857 discloses a fluorine-containing silane coupling agent, a titanate coupling agent or C ₇ F ₁₅ NC.
A protective layer containing a compound such as O is disclosed in JP-A-62-29.
No. 5066, there is disclosed a protective layer in which a fine metal powder or a fine metal oxide powder having improved dispersibility and moisture resistance is dispersed in a binder resin by a water repellent treatment.
Japanese Patent Publication No. 67 proposes a protective layer in which a titanate coupling agent, a fluorine-containing silane coupling agent, and a fine metal oxide powder surface-treated with acetoalkoxyaluminum diisopropylate are dispersed in a binder resin. .

However, also in these protective layers, the releasing property of the binder resin used in the protective layer itself, the durability against abrasion and scratches due to rubbing, and the durability against active substances such as ozone and NOx are sufficient. However, the present situation is that no protective layer having satisfactory electrophotographic characteristics has yet been obtained as a protective layer that meets the recent demand for higher image quality.

Furthermore, with the recent development of high durability and high image quality of the photoconductor, a photoconductor pause memory phenomenon has been pointed out as a new problem. The pause memory phenomenon is basically one of deterioration phenomena caused by corona products, but after the copying is completed, the rotation of the photoconductor is stopped, and the charging ability of the portion stopped near the corona charger is lowered, This is a phenomenon in which the image density decreases only in that portion in the case of normal development, and increases in the case of reverse development. This phenomenon is likely to occur after the photoconductor has been used for a long time, and has become a more serious problem as the life of the photoconductor is extended.

In addition, in a recent reversal development system compatible with digitalization, since the primary charging and the transfer charging have opposite polarities, so-called transfer memory having different charging properties depending on the presence / absence of transfer occurs, which causes uneven density on an image. It's very easy to appear.

[0013]

SUMMARY OF THE INVENTION The present invention is to provide an electrophotographic photosensitive member which meets the above-mentioned demand.

That is, firstly, the object of the present invention is to provide a surface layer having excellent releasability and excellent durability against abrasion, scratches, etc., and to obtain a high quality image. An object is to provide an electrophotographic photosensitive member that can be maintained.

Secondly, it is an object of the present invention to provide an electrophotographic photosensitive member which is free from deterioration of surface resistance due to adhesion of an active substance caused by repeated use and which can maintain high quality image quality even under high humidity. .

Thirdly, it is to provide an electrophotographic photosensitive member exhibiting stable electrophotographic characteristics in which residual potential is not accumulated and sensitivity is not lowered even when it is repeatedly used.

Fourthly, it is to provide an electrophotographic photosensitive member in which a transfer memory hardly occurs even in a reversal developing system.

Fifth, to provide an electrophotographic photosensitive member which does not cause a pause memory phenomenon.

Sixth, to provide an electrophotographic apparatus and an apparatus unit having the electrophotographic photosensitive member as described above.

[0020]

That is, the present invention provides an electrophotographic photoreceptor having a photosensitive layer and a protective layer on a conductive support, the protective layer comprising conductive particles, fluorine atom-containing resin particles and a binder. An electron containing a resin and containing a fluorine atom-containing compound selected from the group consisting of a fluorine-based surfactant, a fluorine-based silane coupling agent, a fluorine-based silicone oil and a fluorine-based graft polymer. It is a photographic photoreceptor.

The present invention is also an electrophotographic apparatus and apparatus unit having the above electrophotographic photosensitive member.

Examples of the conductive particles used in the present invention include metals, metal oxides and carbon black. The metals include aluminum, zinc, copper, chrome,
Examples thereof include nickel, stainless steel, silver, and the like, or those obtained by vapor-depositing these metals on the surface of plastic particles. As the metal oxide, zinc oxide, titanium oxide,
Examples thereof include tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony-doped tin oxide and antimony-doped zirconium oxide. These may be used alone or in combination of two or more. Two
When using in combination of two or more species, even if simply mixed,
It may be in the form of solid solution or fusion.

The average particle size of the conductive particles used in the present invention is preferably 0.3 μm or less, and particularly preferably 0.1 μm or less, from the viewpoint of the transparency of the protective layer.

In the present invention, among the above-mentioned conductive particles, it is particularly preferable to use a metal oxide in terms of transparency.

The fluorine atom-containing resin particles used in the present invention include tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylenepropylene resin, vinyl fluoride resin, vinylidene fluoride resin, and difluorodichloride. One or two of ethylene resins and their copolymers
It is preferable to appropriately select one or more kinds, but tetrafluoroethylene resin and vinylidene fluoride resin are particularly preferable. The molecular weight of the resin particles and the particle size of the particles can be appropriately selected and are not particularly limited.

In the present invention, in order to prevent the conductive particles and the fluorine atom-containing resin particles from coagulating each other in the resin solution, a fluorine-containing surfactant, a fluorine-containing silane coupling agent and a fluorine-containing compound are added to the protective layer. Contains silicone oil or a fluorine-based graft polymer. By containing the fluorine atom-containing compound as described above, the dispersibility and dispersion stability of the conductive particles and the fluorine atom-containing resin particles in the resin solution are remarkably improved, and a coating liquid having very good dispersibility was gotten.

The addition amount of these fluorine atom-containing compounds is
It is preferably from 1 to 100% by weight, and particularly preferably from 5 to 50% by weight, based on the weight of the conductive particles used.

Preferred examples of the fluorinated silane coupling agent, fluorinated silicone oil, fluorinated surfactant and fluorinated graft polymer which can be used in the present invention are shown below, but the compounds are not limited to these compounds. is not.

The preferred fluorine-based silane coupling agent is CF ₃ CH ₂ CH ₂ Si (OCH ₃ ).
₃ , C ₄ F ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₆ F
₁₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₈ F ₁₇ CH ₂ C
H ₂ Si (OCH ₃ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si
(OCH ₂ CH ₂ OCH ₃ ) ₃ , C ₁₀ F ₂₁ Si (OCH
₃ ) ₃ , C ₆ F ₁₃ CONHSi (OCH ₃ ) ₃ , C ₈ F
₁₇ CONHSi (OCH ₃ ) ₃ , C ₇ F ₁₅ CONHCH
_{2 CH 2 CH 2 Si (OCH} 3) 3, C 7 F 15 CONH
CH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , C ₇ F ₁₅ C
OOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₇ F ₁₅
COSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₈ F
₁₇ SO ₂ NHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ )
₃ ,

[0030]

[Outer 1] C ₈ F ₁₇ CH ₂ CH ₂ SCH ₂ CH ₂ Si (OCH ₃ )
₃ , C ₁₀ F ₂₁ CH ₂ CH ₂ SCH ₂ CH ₂ Si (OCH
₃ ) ₃ ,

[0031]

[Outside 2]

[0032]

[Outside 3] Etc.

The preferred fluorinated silicone oil is

[0034]

[Outside 4] Is mentioned. Here, R in the formula is -CH ₂ CH ₂ CF ₃
And m and n are positive integers.

Preferred fluorine-containing surfactants are X-SO ₂ NRCH ₂ COOH and X-SO ₂ NRC.
H ₂ CH ₂ O (CH ₂ CH ₂ O) _n H (n = 5, 10,
_{15), X-SO 2 N} (CH 2 CH 2 CH 2 OH) 2,
X-RO (CH ₂ CH ₂ O) _n (n = 5, 10, 1
5), X- (RO) _n (n = 5 to 20), X- (RO)
_n R (n = 5 to 20),

[0036]

[Outside 5] _{X-COOH, X-CH 2} CH 2 COOH, X-ORC
_{OOH, X-ORCH 2 COOH,} X-SO 3 H, X-
ORSO ₃ H, X-CH ₂ CH ₂ OH,

[0037]

[Outside 6]

[0038]

[Outside 7]

[0039]

[Outside 8] Etc. Here, R is an alkyl group in the formula, an allyl group, an aralkyl group, X is _{-CF 3, -C 4 F 9,} -C
₈ shows a fluorinated carbon group such as ₈ F ₁₇ .

The preferred fluorine-based graft polymer is

[0041]

[Outside 9]

The binder resin which can be used in the protective layer of the present invention includes polycarbonate resin, polyester resin, polyarylate resin, polystyrene resin, polyethylene resin, polypropylene resin, polyurethane resin, acrylic resin, epoxy resin, silicone resin, Examples thereof include cellulose resins, polyvinyl chloride resins, phosphazene resins, melamine resins, and vinyl chloride-vinyl acetate copolymers. These resins can be used alone or in combination of two or more kinds.

Among the above resins, the surface hardness of the protective layer,
A curable resin is preferably used from the viewpoints of abrasion resistance, dispersibility of fine particles, and stability after dispersion. That is, the conductive particles and the fluorine atom-containing resin particles described above are dispersed in a solution containing a monomer or an oligomer that is cured by heat or light to prepare a coating solution for a protective layer, and the solution is coated on the photosensitive layer. The cured protective layer is more preferable in terms of dispersibility hardness and abrasion resistance.

The monomer or oligomer which is cured by heat or light has, for example, a functional group which causes a polymerization reaction at the end of the molecule by the energy of heat or light, and the number of repeating structural units of the molecule is about 2 to 20. A relatively large molecule is an oligomer, and a smaller molecule is a monomer. Examples of the functional group that causes the polymerization reaction include acryloyl group, methacryloyl group, groups having a carbon-carbon double bond such as vinyl group, silanol groups, those that cause ring-opening polymerization such as cyclic ether groups, or phenol and formaldehyde. Examples include those in which two or more kinds of molecules react to cause polymerization.

The ratio of the conductive metal oxide particles in the protective layer is one of the factors that directly determines the resistance of the protective layer, and the resistance of the protective layer is in the range of 10 ¹⁰ to 10 ¹⁵ ohm · cm. Preferably there is.

The proportion of the fluorine atom-containing resin particles in the protective layer is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, based on the total weight of the protective layer. If the proportion of the fluorine atom-containing resin particles is more than 70% by weight, the mechanical strength of the protective layer tends to decrease, and if the proportion of the fluorine atom-containing resin particles is less than 5% by weight, the releasability of the protective layer surface and the protective layer The abrasion resistance and scratch resistance may become insufficient.

In the present invention, additives such as a radical scavenger and an antioxidant may be added to the protective layer for the purpose of further improving dispersibility, binding property and weather resistance.

The thickness of the protective layer of the present invention is 0.2 to 10 μm.
Is preferable, and more preferably 0.5 to 6 μm.

Next, the photosensitive layer will be described. The constitution of the photosensitive layer of the electrophotographic photosensitive member of the present invention is a single layer type containing both the charge generating substance and the charge transporting substance in the same layer, or the charge generating layer and the charge transporting layer are laminated on a conductive support. It is either a laminated type. The laminated photosensitive layer will be described below.

As the constitution of the laminated type photosensitive layer, there are one in which a charge generating layer and a charge transporting layer are laminated in this order on a conductive support, and conversely, one in which a charge transporting layer and a charge generating layer are laminated in this order. .

The conductive support used in the present invention may be any one as long as it has conductivity. For example, a metal such as aluminum, copper, chromium, nickel, zinc or stainless is molded into a drum or sheet. A metal foil such as aluminum or copper laminated on a plastic film, aluminum, indium oxide, tin oxide or the like deposited on a plastic film, or a conductive substance applied alone or with a binder resin to form a conductive layer. Examples include metal, plastic film, and paper.

The charge-transporting layer of the multi-layer type photoreceptor is formed by using a coating solution prepared by dissolving a charge-transporting substance such as a pyrazoline compound, a hydrazone compound, a styryl compound and a triarylamine compound in a resin having a film-forming property. .

Examples of the resin having such a film-forming property include polyester, polycarbonate, polystyrene and polymethacrylic acid ester. The thickness of the charge transport layer is 5 to 40 μm, preferably 10 to 30 μm.

The charge generating layer of the multi-layer type photoconductor includes azo pigments such as Sudan red and Diane blue; quinone pigments such as pyrene quinone and anthanthrone; quinocyanine pigments; perylene pigments; indigo pigments such as indigo and thioindigo; and phthalocyanine pigments. Dispersing the charge generating substance in a binder resin such as polyvinyl butyral, polystyrene, polyvinyl acetate and acrylic resin,
It is formed by coating this dispersion or vacuum-depositing the pigment. The thickness of such a charge generation layer is 5
It is not more than μm, preferably 0.05 to 3 μm.

In the present invention, in order to further improve the adhesiveness between the photosensitive layer and the protective layer, 0.1 to 0.1% is provided between these layers.
An intermediate layer of about 5 μm can be provided.

In the present invention, an undercoat layer having a barrier function and an adhesive function can be provided between the conductive support and the photosensitive layer. The subbing layer can be formed of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, alcohol-soluble amide, polyurethane, gelatin and the like. The thickness of the undercoat layer is 0.1
μm to 0.3 μm is preferable.

The electrophotographic photosensitive member of the present invention can be applied not only to electrophotographic apparatuses in general such as copying machines, laser printers, LED printers and liquid crystal shutter type printers, but also to displays, recording, and electrophotographic technology.
It can be widely applied to devices such as light printing, plate making, and facsimile.

FIG. 1 shows a schematic structure of an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention.

In the figure, reference numeral 1 is a drum type photosensitive member of the present invention, which is rotationally driven around a shaft 1a in a direction of an arrow at a predetermined peripheral speed. The photosensitive member 1 receives uniform charging of a positive or negative predetermined potential on the peripheral surface of the photosensitive member 1 by the charging unit 2 during its rotation process, and then an optical image exposure L (slit exposure) by an image exposing unit (not shown) in the exposure unit 3.・ Laser beam scanning exposure, etc.)
Receive. As a result, electrostatic latent images corresponding to the exposed image are sequentially formed on the peripheral surface of the photoconductor.

The electrostatic latent image is then toner-developed by the developing means 4, and the toner-developed image is synchronized with the rotation of the photoconductor 1 between the photoconductor 1 and the transfer means 5 from a paper feeding portion (not shown). The transfer material P is sequentially transferred to the transferred and fed transfer material P.

The transfer material P which has received the image transfer is separated from the surface of the photoconductor and is introduced into the image fixing means 8 where it is subjected to the image fixing and printed out as a copy.

After the image transfer, the surface of the photoconductor 1 is cleaned by the cleaning means 6 to remove residual toner after transfer, and is further discharged by the pre-exposure means 7 to be repeatedly used for image formation. It

As the uniform charging means 2 for the photoconductor 1, a corona charging device is generally widely used. In addition, the transfer device 5
Corona transfer means are also widely used. In the present invention, among the above-described components such as the photoconductor, the developing unit, and the cleaning unit, a plurality of components are integrally combined and configured as an apparatus unit, and this unit is configured to be detachable from the apparatus main body. May be. For example, at least one of a charging unit, a developing unit, and a cleaning unit is integrally supported with a photoconductor to form a unit, which is a single unit that is detachably attached to the apparatus body, and a guide unit such as a rail of the apparatus body is used. It may be detachable.
At this time, the above device unit may be provided with a charging unit and / or a developing unit.

When the electrophotographic apparatus is used as a copying machine or a printer, the light image exposure L irradiates the photoconductor with reflected light or transmitted light from the original, or the original is read by a sensor and converted into a signal. According to this signal, the laser beam is scanned, the LED array is driven, or the liquid crystal shutter array is driven to irradiate the photoconductor with light.

When used as a facsimile printer, the optical image exposure L becomes an exposure for printing the received data. The figure is a block diagram showing an example of this case.

The controller 11 controls the image reading section 10 and the printer 19. The entire controller 11 is CP
It is controlled by U17. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 13. The data received from the partner station is sent to the printer 19 through the receiving circuit 12. Predetermined image data is stored in the image memory. The printer controller 18 controls the printer 19. 14 is a telephone.

The image received from the line 15 (image information from the remote terminal connected through the circuit) is demodulated by the receiving circuit 12, and then the CPU 17 decodes the image information to sequentially decode the image memory 16. Stored in. And
When the image of at least one page is stored in the memory 16, the image of that page is recorded. The CPU 17 reads the image information of one page from the memory 16 and sends the decoded image information of one page to the printer controller 18. When the printer controller 18 receives one page of image information from the CPU 17, the printer controller 18 controls the printer 19 to record the image information of the page.

The CPU 17 is receiving the next page while the printer 19 is recording.

The image is received and recorded as described above.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[0071]

【Example】

(Example 1) On an aluminum cylinder, 10 parts of alcohol-soluble polyamide resin (Amilan CM-8000, manufactured by Toray Industries, Inc.) (parts by weight, the same applies hereinafter) and methoxymethylated 6 nylon resin (Toresin EF-30T, Teikoku). A solution obtained by dissolving 30 parts of Kagaku Co., Ltd. in a mixed solvent of 150 parts of methanol and 150 parts of butanol is applied by dip coating and dried at 90 ° C. for 10 minutes to form an undercoat layer having a film thickness of 1 μm. did.

Next, the following equation

[0073]

[Outside 10] Into a solution in which 4 parts of the disazo pigment represented by, 2 parts of butyral resin (S-REC BL-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of cyclohexanone are dispersed in a sand mill for 48 hours, 100 parts of tetrahydrofuran (THF) is added As a result, a dispersion liquid for the charge generation layer was obtained. This dispersion was dip-coated on the undercoat layer and dried at 80 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.15 μm.

Next, the following equation

[0075]

[Outside 11] A solution obtained by dissolving 10 parts of a triarylamine compound represented by the formula and 10 parts of a polycarbonate resin (Iupilon Z-200, manufactured by Mitsubishi Gas Chemical Co., Inc.) in a mixed solvent of 20 parts of dichloromethane and 50 parts of monochlorobenzene is charged as described above. A charge transport layer having a film thickness of 20 μm was formed by dip coating on the generation layer and drying at 120 ° C. for 60 minutes.

Next, a dispersion liquid for the protective layer was prepared by the following procedure.

The following formula as a binder resin

[0078]

[Outside 12] 25 parts of an acrylic curable monomer represented by the following formula, 2.0 parts of 2-methylthioxanthone as a photopolymerization initiator, and an antimony-containing tin oxide fine particle (T
1, 45 parts of Mitsubishi Materials Co., Ltd. and 300 parts of toluene were mixed and dispersed in a sand mill for 72 hours into a dispersion liquid, and tetrafluoroethylene resin particles (Lubron L-).
2, manufactured by Daikin Industries, Ltd.) and fluorine-based silane coupling agent (C ₄ F ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ) 20
The parts were mixed and dispersed for 4 hours with a sand mill to obtain a dispersion liquid for the protective layer. This dispersion was spray-coated on the charge transport layer, dried, and then irradiated with ultraviolet rays for 20 seconds with a high-pressure mercury lamp at a light intensity of 800 mW / cm ² to form a protective layer having a thickness of 6 μm.

(Example 2) The amount of tetrafluoroethylene resin particles in the dispersion liquid for the protective layer used in Example 1 was changed to 45 parts,
Further, a photoconductor was prepared in the same manner as in Example 1 except that the amount of the fluorinated silane coupling agent was changed to 35 parts.

Example 3 A photoreceptor was prepared in the same manner as in Example 1 except that an intermediate layer formed by the following method was provided between the charge transport layer and the protective layer used in Example 1.

A ligroin solution of a silicone resin (AY42-441, manufactured by Toray Silicone Co., Ltd.) was applied by spraying so that the film thickness after drying would be 0.2 μm.

Example 4 CF ₃ was used in place of the fluorine-based silane coupling agent in the dispersion liquid for the protective layer used in Example 1.
A photoconductor was prepared in the same manner as in Example 1 except that CH ₂ CH ₂ Si (OCH ₃ ) ₃ was used.

Example 5 A fluorine-based graft polymer 10 represented by the following structural formula was used in place of 20 parts of the fluorine-based silane coupling agent in the dispersion liquid for the protective layer used in Example 1.
A photoconductor was prepared in the same manner as in Example 1 except that parts were used.

[0084]

[Outside 13]

Example 6 A fluorine-modified silicone oil (FL-100, Shin-Etsu Chemical Co., Ltd.) was used in place of the fluorine-based silane coupling agent in the dispersion liquid for the protective layer used in Example 1.
A photoconductor was prepared in the same manner as in Example 1 except that

(Example 7) A fluorine-based surfactant (C ₄ F ₉ SO ₂ NCH ₃ CH ₂ COOH) was used in place of the fluorine-based silane coupling agent in the dispersion liquid for the protective layer used in Example 1. A photoconductor was prepared in the same manner as in Example 1 except that it was used.

(Example 8) Example 8 was repeated except that tetrafluoroethylene resin particles (Daiflon, manufactured by Daikin Industries, Ltd.) were used in place of the tetrafluoroethylene resin particles in the dispersion liquid for the protective layer used in Example 1. A photoconductor was prepared in the same manner as in Example 1.

Example 9 A fluorine-based silane coupling agent (C ₄ F ₉ CH ₂ CH ₂ Si) was used instead of 20 parts of the fluorine-based silane coupling agent in the dispersion liquid for the protective layer used in Example 1.
(OCH ₃ ) ₃ ) 10 parts and a fluorine-based surfactant (C ₄
A photoconductor was prepared in the same manner as in Example 1 except that 10 parts of F ₉ SO ₂ NCH ₃ CH ₂ COOH) was used.

Example 10 The following structural formula was used instead of the acrylic curable monomer in the formulation for the protective layer used in Example 1.

[0090]

[Outside 14] By using an acrylic curable monomer represented by the following formula, and further adding a fluorine-based silane coupling agent to C ₈ F ₁₇ CH ₂ CH ₂ SCH ₂
A photoconductor was prepared in the same manner as in Example 1 except that CH ₂ Si (OCH ₃ ) ₃ was used instead.

Example 11 A positive charging photoreceptor was prepared in the same manner as in Example 1 except that the charge generation layer and the charge transport layer were laminated in reverse.

Example 12 In place of the antimony-containing tin oxide fine particles used in Example 1, barium sulfate fine particles were coated with oxygen-deficient tin oxide to give 0.1 μm conductive particles (Pastran IV / P-1, Mitsui). Metal Mining Co., Ltd.
A photoconductor was prepared in the same manner as in Example 1 except that

Examples 1 to 12 prepared as described above
The electrophotographic photoconductor of No. 1 was attached to a copying machine that repeats the process of charging, exposing, developing, transferring, and cleaning in a cycle of 1.5 seconds, and was kept at 20 ° C. and 50% humidity under normal temperature and normal humidity (N /
N) Image evaluation under 10 ° C., 15% low temperature and low humidity (L / L) and 35 ° C., 85% high temperature and high humidity (H / H), and 50,000 sheets under normal temperature and normal humidity Repeated image forming durability test was carried out. As a result, it was possible to obtain an image free from unevenness and black spots due to bleeding, etc., as compared with the photoconductors shown in Comparative Examples described later. Moreover, even in the repeated image forming durability test of 50,000 sheets, a stable and good image can be maintained without fusion and filming, and the durability against the abrasion and scratches on the surface was remarkably improved. The results are shown in Table 1. The dark portion potential is the surface potential of the photoconductor when discharged at a corona discharge voltage of -5 KV (however, +5 KV in the case of Example 7), and the larger the value, the better the charging ability. The sensitivity is indicated by the exposure amount required to attenuate the surface potential from 700 V to 200 V in absolute value.

Furthermore, in order to measure the pause memory phenomenon,
The photoconductor was attached to a modified machine of Canon Copier NP-3825, and the dark potential (V _D ) and light potential (V) of the photoconductor were attached.
_The latent image conditions were set so that _L ) was -650V and -150V, respectively. Next, after the continuous copying of 10,000 sheets, the potential was measured and the rate of change of V _D and V _L was obtained (for example, the rate of change in V _D is 2% means 650).
2% of V, that is, 13V is changed). Then, the photoconductor was left in the copying machine, and after 24 hours, the difference (ΔV _D ) in absolute value between the surface potential of the photoconductor located immediately below the corona charger and the potential of the other part was measured. The results are shown in Table 1.

(Examples 13 to 19) Next, in order to evaluate the transfer memory, photoconductors were prepared in which the charge generation layers of Examples 1 to 7 were changed as follows (undercoat layer, charge transport layer). The layers and the protective layer were prepared in the same manner as in Examples 1 to 7).

Oxytitanium phthalocyanine 4.5
Part, butyral resin (S-REC, BL-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of cyclohexanone were dispersed in a sand mill for 36 hours, and 100 parts of tetrahydrofuran was added to the solution to form a dispersion liquid for the charge generation layer. Got This dispersion is applied onto the undercoat layer by dip coating at 80 ° C.
By drying for 15 minutes, a charge generation layer having a film thickness of 0.15 μm was formed. (Examples 13 to 19 correspond to the charge generation layer differences of Examples 1 to 7 in order.) Example 13
The photosensitive drums Nos. 19 to 19 are mounted on a laser beam printer (a modified model of LBP-SX manufactured by Canon Inc.) which is a reversal development type electrophotographic printer equipped with a semiconductor laser. The so-called transfer memory | V _d1 |-| V _d2 | was measured with the charging voltage as V _dl and the primary charging voltage when the transfer current was ON as V _d2 . The results are shown in Table 2.

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1 except that the protective layer was not provided, and the same evaluation was carried out.

As a result, as shown in Table 1, the electrophotographic characteristics were good at the initial stage, but when it was subjected to durability, the charging ability was lowered and a good image could not be obtained from around 10,000 sheets.

(Comparative Example 2) Example 1 was repeated except that the fluorine atom-containing resin particles were not dispersed in the protective layer.
A photoconductor was prepared and evaluated in the same manner as in.

As a result, as shown in Table 1, the image was out of focus from the beginning, image blur occurred under high temperature and high humidity, and image deletion was observed due to durability.

(Comparative Example 3) A photoconductor was prepared in the same manner as in Example 1 except that the fluorine-based silane coupling agent used in the protective layer was not used, and the same evaluation was carried out.

As a result, as shown in Table 1, a good image was obtained, but the image deletion was observed when the number of sheets became close to 50,000.

Comparative Example 4 A photoconductor was prepared in the same manner as in Example 1 except that the fluorine-based silane coupling agent and the fluorine atom-containing resin particles used in the protective layer in Example 1 were not used. An evaluation was made.

As a result, as shown in Table 1, the image was out of focus from the beginning, image blur occurred under high temperature and high humidity, and image deletion was observed due to durability.

Comparative Example 5 A photoconductor was prepared in the same manner as in Example 11 except that the protective layer was not provided, and the same evaluation was performed.

As a result, as shown in Table 1, image blurring occurs under high temperature and high humidity, and the electrophotographic sensitivity remarkably decreases from about 10,000 sheets due to abrasion of the charge generating layer.
The contrast of the image disappeared and a good image could not be obtained.

Table 1 shows the measurement results of the resting memory phenomenon of Comparative Examples 1 to 5. In each case, the potential fluctuation under the charger was extremely large as compared with the Examples.

(Comparative Example 6) A photoconductor was prepared in the same manner as in Example 13 except that the protective layer was not provided, and the same evaluation was carried out. The results are shown in Table 2.

(Comparative Example 7) A photoconductor was prepared in the same manner as in Example 13 except that the fluorine atom-containing resin particles were not dispersed in the protective layer, and the same evaluation was carried out. The results are shown in Table 2.

Comparative Example 8 A photoconductor was prepared in the same manner as in Example 13 except that the fluorine-based silane coupling agent used in the protective layer was not used, and the same evaluation was carried out. The results are shown in Table 2.

(Comparative Example 9) A photoconductor was prepared in the same manner as in Example 13 except that the fluorine-based silane coupling agent and the fluorine atom-containing resin particles used in the protective layer in Example 13 were not used. An evaluation was made. The results are shown in Table 2.
Shown in.

(Comparative Example 10) A photoconductor was prepared in the same manner as in Example 19 except that the fluorine-containing surfactant used in the protective layer was not used, and the same evaluation was carried out.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

As described above, the electrophotographic photoreceptor of the present invention has excellent electrophotographic characteristics with almost no decrease in sensitivity or increase in residual potential.

Further, since the surface releasability, abrasion resistance and environmental stability of the protective layer are extremely excellent, it is possible to provide a stable image having good image quality even if it is repeatedly used.

Further, it is possible to provide an electrophotographic photosensitive member which is extremely excellent in terms of the rest memory and the transfer memory.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having an electrophotographic photosensitive member of the present invention.

FIG. 2 is a diagram showing an example of a block diagram of a facsimile having the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 1 Electrophotographic Photoreceptor 1a Axis 2 Charging Means 3 Exposure Part 4 Developing Means 5 Transfer Device 6 Cleaning Means 7 Pre-Exposure Means 8 Image Fixing Means L Optical Image Exposure P Transfer Material

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Michiyo Sekiya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (4)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer and a protective layer on a conductive support, wherein the protective layer contains conductive particles, fluorine atom-containing resin particles and a binder resin,
An electrophotographic photoreceptor containing a fluorine atom-containing compound selected from the group consisting of a fluorine-based surfactant, a fluorine-based silane coupling agent, a fluorine-based silicone oil, and a fluorine-based graft polymer. 2. The electrophotographic photosensitive member according to claim 1, wherein the fluorine atom-containing resin particles are selected from the group consisting of tetrafluoroethylene resin particles and vinylidene fluoride resin particles. 3. An electrophotographic photosensitive member according to claim 1, comprising means for forming an electrostatic latent image, means for developing the formed electrostatic latent image, and means for transferring the developed image to a transfer material. Characteristic electrophotographic device. 4. 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, which are integrally supported and detachable from the apparatus main body. A device unit characterized by.