JPH06236063A - Electrophotoreceptor, electrophotographic device and device unit with same - Google Patents

Abstract

PURPOSE:To provide an electrophotoreceptor having a protective layer having excellent transparency and excellent uniformity of conductivity so that excellent picture images can be stably obtd. even for repeated use, and to provide an electrophotographic device and a device unit having the same body. CONSTITUTION:This electrophotoreceptor has a photosensitive layer on a conductive supporting body, and has a protective layer on the photosensitive layer. The protective layer contains conductive particles and resin obtd. by polymn. of compd. having two ion polymerizable functional groups. The electrophotographic device and a facsimile equipment have this electrophotographic sensitive body.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
Specifically, it relates to an electrophotographic photoreceptor having a protective layer containing a specific resin and conductive particles. The present invention also relates to an electrophotographic apparatus and apparatus unit having the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Needless to say, an electrophotographic photosensitive member is provided with required sensitivity, electric characteristics, optical characteristics, etc. according to an electrophotographic process to be applied. Since electrical or mechanical external force such as corona charging, toner development, transfer to paper and cleaning is directly applied to the surface of the body, durability against them is required.

Specifically, durability is required against abrasion and scratches on the surface of the photoconductor due to rubbing, and deterioration of the surface of the photoconductor due to ozone which tends to occur during corona charging under high humidity. In addition, there is a problem that toner adheres to the surface of the photoconductor due to repeated toner development and cleaning, and it is required to improve the cleaning property of the surface of the photoconductor.

Attempts have been made to provide a surface protective layer containing a resin as a main component on the photosensitive layer in order to satisfy various characteristics required for the surface of the photosensitive member as described above. For example, Japanese Patent Laid-Open No. 57-30843 proposes a protective layer in which resistance is controlled by adding metal oxide particles as conductive particles.

[0005]

However, the conventionally used methods may not sufficiently disperse the metal oxide particles in the binder resin, which may adversely affect the conductivity and transparency of the protective layer. As a result, image defects due to unevenness of the protective layer, increase in residual potential after repeated use,
Further, there may be a problem that the sensitivity is lowered. In order to impart excellent transparency and conductivity uniformity to the protective layer, it is very useful to disperse the ultrafine particle powder (primary particle size: 0.1 μm or less). Dispersion stability is worse than ordinary fine powder (primary particle size 0.5 μm or more), secondary aggregation progresses over time, and dispersed particle size increases,
There is a problem that the transparency and the uniformity of conductivity are likely to decrease.

With the recent trend toward higher image quality and higher durability, electrophotographic photoreceptors satisfying the above characteristics at a higher level have been studied.

An object of the present invention is to provide an electrophotographic photosensitive member having a protective layer having excellent transparency and excellent conductivity uniformity.

Another object of the present invention is to provide an electrophotographic photosensitive member which can stably obtain an excellent image even when it is repeatedly used.

Another object of the present invention is to provide an electrophotographic apparatus and apparatus unit having the electrophotographic photosensitive member as described above.

[0010]

That is, the present invention provides an electrophotographic photoreceptor having a photosensitive layer on a conductive support and a protective layer on the photosensitive layer, wherein the protective layer is an ionic polymerizable functional group. An electrophotographic photoreceptor comprising a resin obtained by polymerization of a compound having two or more groups and conductive particles.

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

Preferred examples of the ionically polymerizable functional group in the present invention include epoxies, vinyl ethers, vinyls having an electron-donating group, cyclic ethers, thiaridine rings and cyclic polyorganosiloxanes. . Preferred specific examples are given below, but the invention is not limited thereto. The state of polymerization is also shown.

[0013]

[Outer 1]

[0014]

[Outside 2]

Next, preferable examples of the compound having two or more groups as described above are shown, but the compounds are not limited to these.

[0016]

[Outside 3]

[0017]

[Outside 4]

[0018]

[Outside 5]

[0019]

[Outside 6]

The compound having an ionically polymerizable functional group is polymerized by being irradiated with light in the presence of a photopolymerization initiator to form a resin.

The photopolymerization initiator used may be any compound as long as it is a compound capable of liberating a Lewis acid which initiates the polymerization of an ionically polymerizable compound upon irradiation with light.
Preferred examples include aromatic diazonium salts, aromatic halonium salts, and photosensitive aromatic onium salts of Group IVa or Va elements.

Such an aromatic diazonium salt has the following formula

[0023]

[Outside 7]

(Wherein R ¹ and R ² represent a hydrogen element, an alkyl group or an alkoxy group, R ³ represents a hydrogen atom, an aromatic group, an amide group or an aromatic group connected by a sulfur atom, and M Represents a metal or a metalloid, Q represents a halogen atom, a represents an integer of 1 to 6, and a = (bc).
And b is an integer satisfying c <b ≦ 8, and c is 2
~ 7 indicates an integer equal to the valence of M. ).
Preferred specific examples are shown below.

[0025]

[Outside 8]

The aromatic halonium salt has the following formula [(R ⁴ ) _d (R ⁵ ) _e X] _f ⁺ [MQ] _g- ^(gh) (wherein R ⁴ is a monovalent aromatic organic group). , R ⁵ represents a divalent aromatic organic group, X represents a halogen atom, M represents a metal or metalloid, Q represents a halogen atom, and d
Represents an integer of 0 to 2, e represents an integer of 0 or 1,
(D + e) is equal to the valence of 2 or X, g is an integer greater than or equal to 8 and less than or equal to 8, and f is f = g × (g−h).
Meet ). Preferred specific examples are shown below.

[0027]

[Outside 9]

Further, such Group IVa element or Va
The photosensitive aromatic onium salt of a group element is represented by the following formula [(R ⁶ ) _i (R ⁷ ) _j (R ⁸ ) _k Y] _p ⁺ [MQ _m ] ^-(mn) (wherein R ⁶ is a monovalent group). R ⁷ represents a monovalent aliphatic organic group, R ⁸ represents a polyvalent organic group selected from an aliphatic organic group and an aromatic organic group, and Y represents S, Se and Te. Represents a Group IVa element selected from the group consisting of or a Group Va element selected from the group consisting of N, P, As, Sb and Bi, M represents a metal or metalloid, Q represents a halogen atom, i Represents an integer of 0 to 4, j and k represent integers of 0 to 2, (i + j + k) is equal to the valence of Y, and is 3 when Y is a Group IVa element and Y is Va.
When it is a group element, it is 4, m is an integer of 8 or less, which is larger than n, and p satisfies p = m−n. Specific examples of preferred onium salts of Group IVa elements represented by the formula () are shown below.

[0029]

[Outside 10]

Specific preferred examples of onium salts of Group Va elements are shown below.

[0031]

[Outside 11]

The amount of these photopolymerization initiators added is preferably 0.01 to 50% by weight, more preferably 0.1 to 30% by weight, based on the ionic polymerizable compound.

The light used may be any light as long as it is an electromagnetic wave having sufficient energy to initiate the polymerization reaction, and examples thereof include ultraviolet rays, X-rays and electron beams, which are easy to handle. From the viewpoint of, it is particularly preferable that the ultraviolet ray is used. The wavelength range of such ultraviolet rays is usually 200 to 5
00 nm, preferably 250 to 400 nm. As the light source, a high pressure and low pressure mercury lamp or an alkali halide lamp is preferable. Further, if necessary, it is possible to heat the photoconductor during or after the irradiation of ultraviolet rays.

The polymerization reaction for obtaining the resin used in the present invention is an ionic polymerization reaction and does not generate a radical. Therefore, even if the layer in contact with the protective layer contains a charge transporting substance, the radical is generated. It does not adversely affect the charge transport material. Further, since ionic polymerization is not adversely affected by oxygen, it is possible to increase the degree of polymerization in the vicinity of the surface of the photoreceptor as compared with radical polymerization, and to obtain better mechanical strength and surface lubricity. You can Furthermore, since the ion-polymerizable compound used in the present invention has two or more functional groups, it can form a crosslinked structure when polymerized, and can have very excellent mechanical strength. In the present invention, the ionically polymerizable compound preferably has 3 or more functional groups because a stronger crosslinked structure can be obtained.

Further, in the present invention, two or more kinds of ion-polymerizable compounds may be used. At this time, for example, a compound having only one ionically polymerizable functional group such as phenyl glycidyl ether or t-butyl glycidyl ether can be used. Further, in the present invention, two or more resins obtained by using the ionically polymerizable compound of the present invention can be mixed and used, and other resins may be mixed and used. Such other resins include polyester, polycarbonate, polystyrene,
Polyvinyl chloride, cellulose, fluororesin, polyethylene, polypropylene, polyurethane, acrylic resin, epoxy resin, silicone resin, alkyd resin and vinyl chloride
Examples thereof include vinyl acetate copolymer.

On the other hand, the conductive particles used in the present invention are
It preferably has a volume resistance of 10 ⁸ Ω · cm or less, particularly 10 ⁵ Ω · cm or less. Specific examples thereof include metals, metal oxides, carbon black and the like, but metal oxides are preferable in terms of transparency and the like. Such metal oxides include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide,
Ultrafine particles such as tin-doped indium oxide, antimony-doped tin oxide and zirconium oxide can be used. These metal oxides may be used alone or in combination of two or more, and when two or more kinds are mixed, they may be in the form of solid solution or fusion.

The content of the conductive particles is preferably 5 to 90% by weight, and particularly preferably 10 to 80% by weight, based on the total weight of the protective layer. When the content of the conductive particles is less than 5% by weight, the resistance of the protective layer becomes too high, which may cause an increase in residual potential and generation of fog. When it is more than 90% by weight, the resistance of the protective layer may be increased. May become too low, resulting in a decrease in charging ability, occurrence of pin poles, and further image blurring.

Further, as described above, when the particles are dispersed in the protective layer, it is necessary to make the particle diameter smaller than the wavelength of the exposure light in order to prevent the scattering of the exposure light by the dispersed particles.
Further, in order to make the conductivity uniform, the smallest possible particles must be dispersed uniformly. The average particle diameter of the primary particles before dispersion of the conductive particles used in the present invention is 0.1 μm.
It is preferably m or less, and particularly preferably 0.05 μm or less.

The ion-polymerizable compound used in the present invention has two or more ion-polymerizable functional groups having a relatively high affinity for the conductive particles, and thus the conductive particles have good dispersibility and dispersion stability. Since it is high, it is possible to uniformly disperse the ultrafine particles as described above, and it is possible to have extremely excellent transparency and conductivity uniformity. In the present invention, the ionically polymerizable compound preferably has three or more functional groups, because more excellent dispersibility and dispersion stability can be obtained.

In Table 1, tin oxide particles (1) average particle size of primary particles before dispersion, (2) average particle size in coating liquid immediately after dispersion, and (3) coating left standing for 1 month after dispersion. The average particle size in the working liquid is shown. The coating liquid is the following formula

[0041]

[Outside 12] 60 parts (parts by weight, the same applies hereinafter) of 30 parts, 30 parts of tin oxide containing antimony and 30 parts of toluene
Parts are mixed and dispersed by a sand mill for 48 hours. The average particle size of the primary particles before dispersion is 200,000 times by an electron microscope (TEM), and is the average value of the particle size of any 100 particles having a particle size of 0.005 μm or more, The average particle size of the dispersed particles in the coating liquid is a value obtained by measurement using Horiba CAPA-700 manufactured by Horiba Ltd.

[0042]

[Table 1]

As can be seen from these results, in the present invention, the particle size after dispersion is very close to the particle size of the primary particles, the particles are very well dispersed, and there is no significant change in particle size over time. Not seen, showing good dispersibility.

The volume resistivity of the protective layer in the present invention is 1
It is preferably 0 ¹⁵ to 10 ⁹ Ω · cm, and particularly 1
It is preferably 0 ¹⁴ to 10 ¹⁰ Ω · cm. Further, the film thickness is preferably 0.1 to 10 μm, and particularly preferably 0.5 to 7 μm.

The protective layer in the present invention may also be formed by applying a solution in which conductive particles are dispersed in an ionic polymerizable compound using a suitable solvent onto the photosensitive layer, followed by drying and curing. It may be formed by dispersing the conductive particles in a state of low molecular weight component such as an oligomer using a mixer, coating on the photosensitive layer, and then drying and curing, but the former is preferable in terms of dispersibility. preferable. Examples of the coating method include a spray coating method, a beam coating method, and a dip coating method by selecting a solvent.

Further, in the present invention, in order to further improve the dispersibility, adhesiveness and environmental stability, it is preferable to add a coupling agent, an antioxidant or the like to the protective layer. Among such coupling agents, a coupling agent containing a fluorine atom having excellent water repellency is particularly preferable. The addition amount of the coupling agent is preferably 0.01 to 50% by weight, more preferably 0.05 to 30% by weight, and further preferably 0.1 to 20% with respect to the ionically polymerizable compound. It is preferably in the weight%.

The constitution of the photosensitive layer of the electrophotographic photosensitive member of the present invention is a so-called single layer type containing both a charge generating substance and a charge transporting substance, or a charge transporting layer containing a charge transporting substance and a charge generating substance. Any of the so-called laminated type, which is functionally separated into the contained charge generation layer, may be used. Examples of the structure of the laminated type photosensitive layer include one in which a charge generation layer and a charge transport layer are laminated in this order on a conductive support, and one in which a conductive support, a charge transport layer and a charge generation layer are laminated in this order. Can be mentioned.

The charge generation layer comprises azo pigments such as monoazo pigments, disazo pigments and trisazo pigments; quinone pigments; quinocyanine pigments; perylene pigments; indigo pigments such as indigo and thioindigo pigments; azurenium salt pigments; and phthalocyanine pigments. A charge generating substance such as a pigment is dispersed in a binder resin such as polyvinyl butyral, polyvinyl benzal, polyarylate, polycarbonate, polyester, polystyrene, polyvinyl acetate, acrylic resin, polyurethane, polyvinylpyrrolidone, ethyl cellulose and cellulose acetate butyrate. It is formed by applying this dispersion and drying. The thickness of the charge generation layer is preferably 5 μm or less, and particularly preferably 0.
It is preferably from 05 to 2 μm.

The charge transport layer comprises a polycyclic aromatic compound having a structure such as biphenylene, anthracene, pyrene and phenanthrene in the main chain or side chain; a nitrogen-containing cyclic compound such as indole, carbazole, oxadiazole and pyrazoline; hydrazone It is formed by applying a coating liquid in which a compound; and a charge transport substance such as a styryl compound are dissolved in a resin having film-forming properties, and drying. Examples of the film-forming resin include polyester, polycarbonate, acrylic resin, polyarylate, acrylonitrile-styrene copolymer, polymethacrylic acid ester, polystyrene, poly-N-vinylcarbazole, and polyvinylanthracene. The thin film of the charge transport layer is preferably 5 to 40 μm, and particularly 10 to 3
It is preferably 0 μm.

Even when the photosensitive layer is of a single layer type, the same substances as described above can be used, but as the charge transporting substance, a charge transfer complex composed of a combination of poly-N-vinylcarbazole and trinitrofluorene, etc. is further used. It can also be used. The film thickness is preferably 5 to 40 μm, and particularly preferably 10 to 30 μm.

In the present invention, an intermediate layer may be provided between the photosensitive layer and the protective layer in order to further improve the adhesiveness and coatability. The materials used are casein,
Polyvinyl alcohol, nitrocellulose, ethylene-
Acrylic acid copolymer, alcohol soluble polyamide,
Examples thereof include polyurethane, zetatin, aluminum oxide and the like. The film thickness is preferably 0.1 μm to 10 μm, and particularly preferably 0.3 μm to 2 μm.

The conductive support used in the present invention may be any one as long as it has conductivity, for example, metals and alloys such as aluminum, aluminum alloy, copper, chromium, nickel, zinc and stainless steel; aluminum. A metal foil such as copper or copper laminated on a plastic film; aluminum, indium oxide, tin oxide, etc. deposited on a plastic film; or a conductive material is applied alone or with an appropriate binder resin to form a conductive layer. Examples include metal, plastic film, and paper. As such a conductive substance,
Metal powders such as aluminum, copper, nickel and silver, metal foils and short metal fibers; conductive metal oxides such as antimony oxide, indium oxide and tin oxide; polypyrrole,
Polymer conductive materials such as polyaniline and polymer electrolytes; carbon fibers, carbon black and graphite powders; organic and inorganic electrolytes; or conductive powders whose surfaces are coated with these conductive substances. The conductive support may have any shape such as a drum shape, a sheet shape, or a belt shape, depending on the applied electrophotographic apparatus.

Further, in the present invention, an undercoat layer having a barrier function and an adhesive function may be provided between the conductive support and the photosensitive layer. Examples of the material used include those similar to the intermediate layer between the protective layer and the photosensitive layer,
The film thickness is preferably 0.1 to 5 μm, and 0.5 to
It is preferably 3 μm. The subbing layer can also contain conductive particles such as metal, metal oxide and carbon black, and the subbing layer containing the conductive particles on the conductive support and the subbing layer not containing it. Can be laminated in this order. In this case, the thickness of the undercoat layer containing the conductive particles is preferably 0.1 μm to 50 μm, and particularly preferably 0.5 to 40 μm.

The various layers described above use an appropriate solvent,
It can be formed by applying after a coating method such as a dip coating method, a spray coating method, a beam coating method, a spinner coating method, a roller coating method, a Meyer bar coating method and a blade coating method, and then drying.

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

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 denotes a drum-shaped electrophotographic 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 photoconductor 1 is uniformly charged on its peripheral surface by a charging means 2 at a predetermined positive or negative potential in the course of rotation, and then an image exposure means (not shown) exposes an exposure image L (slit). Exposure and laser beam scanning exposure). In this way, electrostatic latent images corresponding to the exposed images are sequentially formed on the peripheral surface of the photoconductor.

The formed electrostatic latent image is then developed by the developing means 4.
The toner developed image is transferred to a transfer material P, which is fed from a sheet feeding unit (not shown) between the photoconductor 1 and the transfer unit 5 in synchronization with the rotation of the photoconductor 1. 5 are sequentially transferred.

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.

The surface of the photoconductor 1 after the image transfer is cleaned by the cleaning means 6 to remove the residual toner after transfer, and is then discharged by the pre-exposure means 7 for repeated image formation.

In the present invention, among the above-mentioned electrophotographic photosensitive member 1, charging means 2, developing means 4, cleaning means 6 and the like, a plurality of components are integrally combined as an apparatus unit, and The unit may be detachably attached to the apparatus body. For example, at least one of the charging unit 2, the developing unit 4, and the cleaning unit 6 is integrally supported together with the photosensitive member to form a unit, and a unit that is detachably attached to the apparatus body by using a guide unit such as a rail of the apparatus body. Good as a unit.

In the case of using the electrophotographic apparatus 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 reads the original with a sensor. The signal is converted into a signal, and the laser beam is scanned, the LED array is driven, or the liquid crystal shutter array is driven in accordance with the signal to irradiate the photoconductor with light.

On the other hand, when used as a printer for a facsimile, the optical image exposure L becomes an exposure for printing the received data. FIG. 2 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 is the printer 1
9 is controlled. 14 is a telephone.

The image received from the line 15 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 12, and then the image information is decoded by the CPU 17 and the image memory 16 is sequentially processed. Stored in. 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. Upon receiving the image information of one page from the CPU 17, the printer controller 18 controls the printer 19 to record the image information of the page. CPU1
7 is receiving the next page while the printer 19 is recording.

Images are received and recorded as described above.

[0067]

【Example】

Example 1 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide (parts by weight, the same applies hereinafter), 25 parts of phenol resin (weight average molecular weight 30,000),
Methyl cellosolve 20 parts, methanol 5 parts and silicone oil (polydimethylsiloxane-polyoxyalkylene copolymer, weight average molecular weight 3,000) 0.002
Part was dispersed for 2 hours with a sand mill using φ1 mm glass beads to obtain a conductive layer coating material. The above coating material was applied by dipping onto an aluminum cylinder (φ30 mm × 260 mm) and dried at 140 ° C. for 30 minutes to form a conductive layer having a film thickness of 20 μm.

Next, 10 parts of alcohol-soluble copolymer nylon (weight average molecular weight 29,000) and 30 parts of methoxymethylated 6 nylon (weight average molecular weight 32,000) 30
Parts were dissolved in a mixed solvent of 260 parts of methanol and 40 parts of butanol. This solution was applied onto the conductive layer by dip coating and dried to form an undercoat layer having a film thickness of 1 μm.

Next, the disazo pigment 4 represented by the following formula
Department,

[0070]

[Outside 13] 2 parts of polyvinyl butyral (butyralization rate 68%, weight average molecular weight 24,000) and cyclohexanone 34
After being dispersed for 12 hours with a sand mill using φ1 mm glass beads, 60 parts of tetrahydrofuran was added to obtain a charge generation layer coating material. This coating material was spray-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, 10 parts of a styryl compound of the following formula:

[0072]

[Outside 14] And polycarbonate (weight average molecular weight 46,000)
10 parts was dissolved in a mixed solvent of 20 parts of dichloromethane and 40 parts of monochlorobenzene. This solution was applied onto the charge generation layer by dip coating and dried at 120 ° C. for 60 minutes to form a charge transport layer having a film thickness of 18 μm.

Next, the ionic polymerizable compound 6 of Compound Example 3
0 part, 30 parts of tin oxide ultrafine particles having an average primary particle diameter of 0.04 μm before dispersion, 0.1 part of triphenylsulfonium hexafluoroantimonate as a photoinitiator and 300 parts of toluene are dispersed in a sand mill for 48 hours. Thus, a protective layer solution was obtained. This solution was applied on the above charge transport layer by beam coating, dried and then photocured with a high pressure mercury lamp at a light intensity of 8 mW / cm ² for 20 seconds, and further heated at 100 ° C. for 30 minutes to form a protective layer. did. The thickness of the protective layer was 4 μm. The protective layer solution had good dispersibility, and the surface of the protective layer was a uniform and even surface. The average particle diameter of the tin oxide particles dispersed in the protective layer solution was measured according to the measuring method shown in Table 1 above, and was found to be 0.04 μm.

The electrophotographic photosensitive member thus obtained was manufactured by Kawaguchi Electric Co., Ltd. under the trade name of electrostatic copying paper tester Model SP-.
After being negatively charged by a corona discharge of -5 KV using 428 and holding for 1 second in a dark place, an illuminance of 2 using a halogen lamp.
It was exposed for 10 seconds with looks and examined for charging characteristics. The charging characteristics include the surface potential (dark part potential) and the exposure amount (E) required to attenuate the surface potential after leaving it in the dark for 1 second to 1/2.
1/2), that is, the sensitivity and the residual potential were measured.

Further, the obtained photoreceptor is mounted on a positive development type electrophotographic copying machine in which the processes of charging-exposure-developing-transfer-cleaning are repeated in a cycle of 1.5 seconds.
A durability test was carried out repeatedly for 10,000 times. The images obtained before and after the durability test are visually evaluated, and the eddy current type film thickness meter manufactured by KETT is used to measure the film thickness of the photoreceptor before and after the durability test to determine the amount of abrasion of the surface of the photoreceptor. I asked. The results are shown in Table 2.

Examples 2 to 4 Instead of the ionically polymerizable compound of Compound Example 3, Compound Example 1,
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 11 and 18 were used. The results are shown in Table 2.

Example 5 A conductive layer and an undercoat layer were formed on an aluminum cylinder in the same manner as in Example 1.

Next, the charge transport material 10 represented by the following formula
Department,

[0079]

[Outside 15] And polycarbonate (weight average molecular weight 25,000)
10 parts was dissolved in a mixed solvent of 20 parts of dichloromethane and 40 parts of monochlorobenzene. This solution was applied onto the undercoat layer by dip coating and dried at 120 ° C. for 60 minutes to form a charge transport layer having a film thickness of 20 μm.

Next, the disazo pigment 4 represented by the following formula
Department,

[0081]

[Outside 16] Polyvinyl benzal (80% benzal conversion rate, weight average molecular weight 11,000) 2 parts and cyclohexanone 30
Parts were dispersed in a sand mill using φ1 mm glass beads for 20 hours, and then 60 parts of methyl ethyl ketone was added to obtain a charge generation layer coating material. This coating material was spray-coated on the charge transport layer and dried at 80 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.10 μm.

Next, 60 parts of the ion-polymerizable compound of Compound Example 20, 30 parts of tin oxide ultrafine particles having an average primary particle diameter of 0.04 μm before dispersion, and triphenylsulfonium hexafluoroantimonate 0 as a photoinitiator A protective layer solution was obtained by dispersing 0.06 part and 300 parts of toluene in a ball mill for 24 hours. This solution was applied onto the charge generation layer by beam coating, dried, and then photocured with a high pressure mercury lamp at a light intensity of 8 mW / cm ² for 30 seconds, and further heated at 80 ° C. for 60 minutes to form a protective layer. did. The film thickness of the protective layer was 4.5 μm. The protective layer solution had good dispersibility, and the surface of the protective layer was a uniform and even surface. Further, the average particle size of the tin oxide particles dispersed in the protective layer solution was measured in the same manner as in Example 1 and found to be 0.04 μm.

The charging characteristics of the obtained electrophotographic photosensitive member were evaluated in the same manner as in Example 1. However, the polarity of charging was positive.

Further, regarding the obtained photoconductor, Example 1
An image output durability test was conducted in the same manner as in. However, instead of a positive development type electrophotographic copying machine, a reversal development type laser printer that repeats the process of charging-laser exposure-development-transfer-cleaning in a cycle of 1.5 seconds is used.
The charge was positive. The results are shown in Table 2.

Example 6 30 parts of compound example 7 as a protective layer solution, compound example 22
30 parts, the average particle size of the primary particles before dispersion is 0.04 μm
Electrophotographic exposure was carried out in the same manner as in Example 5 except that a mixed solution of 50 parts of tin oxide ultrafine particles, 0.1 part of 2-methylthioxanthone and 300 parts of toluene as a photoinitiator was dispersed in a sand mill for 24 hours. The body was created and evaluated.
The results are shown in Table 2.

Example 7 The solution for the protective layer was prepared by using the ion-polymerizable compound 5 of Compound Example 17.
5 parts, 30 parts of tin oxide ultrafine particles having an average primary particle size of 0.04 μm before dispersion, 0.1 part of triphenylsulfonium hexafluoroantimonate as a photoinitiator, 5 parts of a coupling agent represented by the following formula

[0087]

[Outside 17] And an electrophotographic photosensitive member were prepared and evaluated in the same manner as in Example 1 except that 300 parts of toluene was dispersed in a sand mill for 48 hours. The results are shown in Table 2. The average particle size of tin oxide particles in the protective layer solution is 0.04 μm.
Met.

Example 8 The solution for the protective layer was prepared by using the ionic polymerizable compound 4 of the compound example 22.
5 parts, 45 parts of tin oxide ultrafine particles having an average primary particle size of 0.04 μm before dispersion, triphenylsulfonium hexafluoroantimonate as a photoinitiator 0.06 part,
8 parts of coupling agent represented by the following formula

[0089]

[Outside 18] An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 5, except that 300 parts of toluene and 300 parts of toluene were dispersed in a sand mill for 24 hours. The results are shown in Table 2. The average particle size of tin oxide particles in the protective layer solution is 0.04 μm.
Met.

Comparative Example 1 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the protective layer was not formed. As a result, as shown in Table 2, the initial electrophotographic characteristics were good, but when a durability test was carried out, image defects caused by abrasion and scratches of the charge transport layer occurred at about 30,000 sheets.

Comparative Example 2 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that a monofunctional compound represented by the following formula was used instead of the ionically polymerizable compound of Compound Example 3. At this time, the average particle diameter of the tin oxide particles in the protective layer solution was 0.13 μm. The results are shown in Table 2.

[0092]

[Outside 19]

Comparative Example 3 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 5 except that the binder resin in the protective layer was replaced with polycarbonate (weight average molecular weight 46,000). The results are shown in Table 2.

Comparative Example 4 An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the protective layer did not use ultrafine tin oxide particles and the protective layer had a thickness of 1 μm. As a result, as shown in Table 2, the residual potential was high in the initial stage, the image was slightly fogged, and image defects due to abrasion or scratches on the surface of the photoconductor occurred at about 80,000 sheets. .

Comparative Example 5 A radical polymerizable compound represented by the following formula was used in place of the ionic polymerizable compound,

[0096]

[Outside 20] 2-Methyl-1- [4- (methylthio) as photoinitiator
An electrophotographic photosensitive member was prepared in the same manner as in Example 5 except that 5 parts of [phenyl] -2-morpholinopropane-1 was used.
evaluated. The result is that the sensitivity is low, as shown in Table 2.
The residual potential was also high, and the image was fogged even in the initial stage. Therefore, the image displaying durability test was not conducted.

[0097]

[Table 2]

[0098]

As described above, according to the present invention, an electron having a protective layer having excellent transparency and excellent conductivity uniformity and capable of stably obtaining an excellent image even when repeatedly used. A photographic photosensitive member, an electrophotographic apparatus having the electrophotographic photosensitive member, and an apparatus unit can be provided.

[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 of the Present Invention 1a Axis 2 Charging Means 3 Exposure Unit 4 Developing Means 5 Transfer Means 6 Cleaning Means 7 Pre-Exposure Means 8 Image Fixing Means L Optical Image Exposure P Transfer Materials 10 Image Reading Parts 11 Controllers 12 Reception Circuits 13 Transmission circuit 14 Telephone 15 Line 16 Image memory 17 CPU 18 Printer controller 19 Printer

Front page continuation (72) Inventor Shoji Amamiya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Haruyuki Tsuji 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Michiyo Sekiya 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Masaaki Yamagami 133-702 Matsushima, Tsuruga City, Fukui Prefecture

Claims (7)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer on a conductive support and a protective layer on the photosensitive layer, wherein the protective layer is obtained by polymerizing a compound having two or more ion-polymerizable functional groups. An electrophotographic photoreceptor comprising the obtained resin and conductive particles. 2. The electrophotographic photosensitive member according to claim 1, wherein the resin has a crosslinked structure. 3. The compound has an ionic polymerizable functional group of 3
The electrophotographic photosensitive member according to claim 1, which has one or more. 4. The electrophotographic photosensitive member according to claim 1, wherein the protective layer is formed by curing a compound and conductive particles. 5. The electrophotographic photosensitive member according to claim 1, wherein the protective layer contains a coupling agent. 6. A facsimile comprising an electrophotographic apparatus having the electrophotographic photosensitive member according to claim 1 and a receiving unit for receiving image information from a remote terminal. 7. 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.