JP2000242021A - Electrophotographic photoreceptor, image forming device using the same, image forming method, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic photoreceptor having good electrification characteristics and high sensitivity, free from the peeling of a film and also having high wear resistance by enhancing the adhesiveness of a surface protective layer comprising an organosilicon compound to a photosensitive layer, to obtain an image forming device using the photoreceptor, to provide an image forming method and to obtain a process cartridge. SOLUTION: When a photosensitive layer and a surface protective layer are successively laminated on an electrically conductive substrate to obtain an electrophotographic photoreceptor, the surface protective layer is formed of a layer containing a siloxane resin having structural units having electric charge transferring performance and also having a crosslinked structure and an adhesive layer comprising a resin containing hydrolyzable groups or hydroxyl groups is disposed between the photosensitive layer and the surface protective layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photosensitive member, an image forming apparatus using the same, an image forming method, and a process cartridge.

[0002]

2. Description of the Related Art In recent years, in order to write data processed by digital signal processing, an electrophotographic image forming method for forming an electrostatic latent image by exposing a dot light on an organic photoreceptor and forming an image by a reversal developing method has been actively used. Began to take place.

[0003] The electrophotographic photosensitive member used in such a system is required to be stable over a long period of use and to be able to cope with writing requiring high resolution. In general, organic photoreceptors have a wider range of material choices than inorganic photoreceptors, so they can easily respond to various exposure light sources and have excellent potential stability. Technology has been.

On the other hand, the organic photoreceptor is weak in strength, and is liable to cause defects due to wear and tear of the photosensitive layer, and improvement in durability is required. The surface protective layer obtained by crosslinking an organosilicon compound having excellent surface strength is formed of an organic photoreceptor (OP
C), which has attracted attention as a technique that can improve the durability against scratches and abrasion, which has been a problem in the past.

[0005] However, a crosslinked film made of an organosilicon compound generally has poor adhesion to the photosensitive layer, and has been considered to cause film peeling and increased wear.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the adhesiveness between a surface protective layer made of an organosilicon compound and a photosensitive layer, to provide good charge characteristics, high sensitivity, no film peeling and abrasion resistance. An object of the present invention is to provide a high electrophotographic photosensitive member, and an image forming apparatus, an image forming method, and a process cartridge using the same.

[0007]

Means for Solving the Problems The present inventors have examined the above problem and found that a hydrolyzable group or a hydrolyzable group or a photosensitive protective layer was provided between a surface protective layer formed by crosslinking an organosilicon compound and a photosensitive layer. It has been found that by providing a layer made of a resin containing a hydroxyl group, the adhesiveness can be greatly improved, and the present invention has been made.

That is, the object of the present invention is achieved by adopting one of the following constitutions.

[1] In an electrophotographic photosensitive member having a photosensitive layer and a surface protective layer sequentially laminated on a conductive support, the surface protective layer has a structural unit having a charge transporting property and has a crosslinked structure. An electrophotographic photoreceptor comprising a layer containing a siloxane-based resin, and an adhesive layer made of a resin containing a hydrolyzable group or a hydroxyl group provided between the photosensitive layer and the surface protective layer.

[2] The surface protective layer contains a resin layer obtained by reacting an organosilicon compound having a hydroxyl group or a hydrolyzable group with a compound having a hydroxyl group and a structural unit having charge transport performance. The electrophotographic photosensitive member according to [1], which is characterized in that:

[3] The electrophotographic photoreceptor according to [1] or [2], wherein the surface protective layer contains colloidal silica.

[4] The electrophotographic photoreceptor according to any one of [1] to [3], wherein the surface protective layer contains an antioxidant.

[5] The electrophotographic photosensitive member according to [4], wherein the surface protective layer contains a hindered phenol compound or a hindered amine compound as an antioxidant.

[6] The method according to any one of [1] to [5], wherein the adhesive layer is a resin layer containing a hydroxyl group.
Item.

[7] The electrophotographic photosensitive member according to any one of [1] to [6], wherein the hydroxyl group-containing resin is a phenoxy resin or a modified product thereof.

[8] In an electrophotographic photosensitive member in which a photosensitive layer and a surface protective layer are sequentially laminated on a conductive support, the surface protective layer comprises a layer containing a siloxane-based resin having a crosslinked structure. An electrophotographic photoreceptor comprising an adhesive layer made of a resin containing a hydrolyzable group or a hydroxyl group between a photosensitive layer and a surface protective layer.

[0017]

[9] The electrophotographic photosensitive member according to [8], wherein the surface protective layer contains colloidal silica.

[10] The adhesive layer is a resin layer containing a hydroxyl group, [8] or

[9] The electrophotographic photosensitive member according to the above.

[11] The electrophotographic photosensitive member according to [10], wherein the hydroxyl-containing resin is a phenoxy resin or a modified product thereof.

[12] The electron according to any one of [1] to [11], wherein the uppermost layer of the photosensitive layer is a charge transport layer, and the charge transport layer is a layer containing polycarbonate. Photoreceptor.

[13] The electrophotographic photosensitive member according to any one of [1] to [12], which has steps of charging, image exposure, development, transfer / separation, and cleaning, and is developed by a reversal development method. And forming an image.

[14] Using the electrophotographic photoreceptor according to any one of [1] to [12], forming an image through a process including charging, image exposure, development, transfer / separation, and cleaning. An image forming apparatus comprising:

[15] Using an electrophotographic photosensitive member,
In a process cartridge used for image formation through the steps of image exposure, development, transfer / separation, and cleaning,
It is manufactured by combining the electrophotographic photosensitive member according to any one of [1] to [12] with at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device. A process cartridge characterized by the above-mentioned.

The adhesive layer in the present invention is provided between the photosensitive layer and the surface protective layer, and aims at improving the adhesiveness between the two layers. The adhesive layer may be composed of a single layer or a plurality of layers.The adhesive layer contains a charge transporting substance to supplement the charge transporting performance, and an additive such as an antioxidant for preventing deterioration and an ultraviolet absorber. May be.

The thickness of the adhesive layer is 0.01 to 10 μm.
m, and preferably 0.1 to 5 μm. When the thickness of the adhesive layer is less than 0.01 μm, the adhesiveness is insufficient, and when the thickness is more than 10 μm, the sensitivity may be reduced.

As the resin used for the adhesive layer, a resin having a hydrolyzable group or a hydroxyl group is used. Examples of the hydrolyzable group include an alkoxy group, an aryloxy group and a halogen atom, and an alkoxy group having 1 to 4 carbon atoms is particularly preferable. The hydrolyzable group and the hydroxyl group may be contained in the repeating unit of the resin, or may be contained in a part of the polymer chain.

Specific examples of the resin containing a hydrolyzable group or a hydroxyl group include an alkoxy-modified acrylic resin, an alkoxy-modified methacrylate resin, a polyester resin, a butyral resin, a formal resin, a phenoxy resin, an epoxy resin, and a polyvinyl alcohol resin. No. Phenoxy resin, acrylic resin, methacrylic resin, and the like are particularly preferably used in terms of adhesiveness to the photosensitive layer, but are not particularly limited thereto.

Incidentally, the surface protective layer has a meaning usually used, and in the present invention, is a layer containing a siloxane-based resin having a crosslinked structure.

As the siloxane resin having a cross-linked structure, a three-dimensional network structure is formed by adding a catalyst or a cross-linking agent to a monomer, oligomer or polymer having a siloxane bond in the structural unit in advance to form a new chemical bond, or A three-dimensional network structure is formed from monomers, oligomers, and polymers by siloxane bonds. The structural unit used here is, for example, one capable of forming a three-dimensional network structure by, for example, a condensation reaction of an alkoxysilane or a condensation reaction of a silanol, and a three-dimensional network structure such as colloidal silica. Particles may be included.

In the present invention, the hydrolyzable group in the organosilicon compound having a hydroxyl group or a hydrolyzable group includes a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group and a butoxy group. Methoxyethoxy group. Among them, a hydrolyzable group represented by -OR is preferable, and R is an atomic group forming an alkoxy group, and preferably has 1 to 6 carbon atoms. For example,
Examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a methoxyethyl group.

The organosilicon compound used as a raw material of the curable resin containing a siloxane bond in the present invention generally has a high organosilicon compound content when the number n of the hydrolyzable groups bonded to the silicon atom is 1. The molecular reaction is suppressed. When n is 2, 3 or 4, a polymerization reaction is likely to occur, and especially when 3 or 4, the crosslinking reaction can be advanced to a high degree. Therefore, by controlling these, it is possible to control the preservability of the obtained coating layer liquid, the hardness of the coating layer, and the like.

The structural unit having the charge transporting property indicates a property having the electron or hole drift mobility alone. Another definition of the compound having a structural unit having a charge transporting property of the present invention is an ordinary Time-
It can also be expressed as a compound that can obtain a detection current due to charge transport by a known method capable of detecting charge transport performance such as the Of-Flight method.

For example, as the hole transport type, oxazole,
Oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidine, styryl, hydrazone, benzidine, pyrazoline, stilbene, amine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine, aminostilbene, poly -N-vinylcarbazole, poly-1-vinylpyrene,
Compounds having a structural unit such as poly-9-vinylanthracene and derivatives thereof are exemplified.

As the electron transport type, succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, nitrobenzene, dinitrobenzene, trinitrobenzene, tetranitrobenzene Nitrobenzene, nitrobenzonitrile, picryl chloride, quinone chlorimide,
Chloranil, bromanil, benzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone,
1-chloroanthraquinone, dinitroanthraquinone,
4-nitrobenzophenone, 4,4'-dinitrobenzophenone, 4-nitrobenzalmalone dinitrile, α-
Cyano-β- (p-cyanophenyl) -2- (p-chlorophenyl) ethylene, 2,7-dinitrofluorene,
2,4,7-trinitrofluorenone, 2,4,5,7
-Tetranitrofluorenone, 9-fluorenylidenedicyanomethylenemalononitrile, polynitro-9-fluoronylidenedicyanomethylenemalonodinitrile, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid,
3,5-dinitrobenzoic acid, pentafluorobenzoic acid,
5-nitrosalicylic acid, 3,5-dinitrosalicylic acid,
Examples include compounds having a structural unit such as phthalic acid and merit acid and derivatives thereof, but are not limited to these structures.

That is, a charge transporting compound represented by the following general formula, which can be typically combined with a curable organosilicon compound to form a resin layer.

X— (R—OH) _mm ≧ 1 wherein X: a structural unit having charge transporting ability, R: a single bond, each substituted or unsubstituted alkylene or arylene group, m: preferably 1 to 1 5

Among them, the following are typical ones. For example, a triarylamine-based compound is a compound having a triarylamine structure such as triphenylamine and having a hydroxyl group bonded to a carbon atom via a carbon atom constituting the group.

1. Triarylamine compounds

[0039]

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2. Hydrazine compounds

[0041]

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3. Stilbene compounds

[0043]

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4. Benzidine compound

[0045]

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5. Butadiene compound

[0047]

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6 Other compounds

[0049]

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The surface protective layer of the present invention preferably contains an antioxidant, particularly a hindered phenol compound or a hindered amine compound. This is because the effect of the present invention becomes more remarkable by including these compounds.

Next, specific examples of the compounds of the present invention will be shown.

[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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The layer constitution of the electrophotographic photoreceptor of the present invention is not particularly limited, but a photosensitive layer such as a charge generation layer, a charge transport layer, or a charge generation / charge transport layer, and a resin layer of the present invention formed thereon. It is preferable to adopt a painted configuration.

The charge generating substance (CGM) contained in the photosensitive layer of the present invention is used alone or together with a suitable binder resin to form a layer. Representative examples of the charge generating substance include pyrylium dyes, thiopyrylium dyes, phthalocyanine pigments, anthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, azo pigments, trisazo pigments, and disazo pigments. Pigments, indigo pigments, quinacridone pigments, cyanine pigments and the like.

The charge transport material (C) contained in the photosensitive layer
TM) includes, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazoline derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds, benzidine compounds, pyrazoline derivatives, stilbenes Compound,
Amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, etc. These charge transport materials (CTM) are usually used to form a layer together with a binder.

The binder resin contained in the photosensitive layer having a single-layer structure and the charge generation layer (CGL) and the charge transport layer (CTL) in the case of a multilayer structure include polycarbonate resin,
Polyester resin, polystyrene resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl butyral resin, polyvinyl acetate resin, styrene-butadiene resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-maleic anhydride Copolymer resins, urethane resins, silicone resins, epoxy resins, silicon-alkyd resins, phenol resins, polysilane resins, polyvinyl carbazole, and the like can be used.

In the present invention, the ratio between the charge generating substance and the binder resin in the charge generating layer is 1: 5 to 5: 1 by weight.
Is preferred. The thickness of the charge generation layer is preferably 5 μm or less, particularly preferably 0.05 to 2 μm.

The charge transport layer is formed by dissolving the charge transport material and the binder resin in a suitable solvent, and applying and drying the solution. The mixing ratio of the charge transport material and the binder resin is preferably from 3: 1 to 1: 3 by weight.

The thickness of the charge transport layer is preferably 5 to 50 μm, particularly preferably 10 to 40 μm. When a plurality of charge transport layers are provided, the thickness of the upper layer of the charge transport layer is 10 μm.
m or less, and preferably smaller than the total thickness of the charge transport layer provided below the charge transport layer.

The solvent or dispersion medium used in the present invention includes n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, Benzene, toluene,
Xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2
-Trichloroethane, 1,1,1-trichloroethane,
Examples include trichloroethylene, tetrachloroethane, tetrahydrofuran, dioxolan, dioxane, methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve and the like. Although the present invention is not limited to these, dichloromethane, 1,2-dichloroethane, methyl ethyl ketone and the like are preferably used. In addition, these solvents can be used alone or as a mixed solvent of two or more kinds.

Next, the conductive support of the electrophotographic photoreceptor of the present invention includes: 1) a metal plate such as an aluminum plate or a stainless steel plate; 2) a support such as paper or a plastic film;
A thin metal layer such as aluminum, palladium, or gold provided by lamination or vapor deposition. 3) On a support such as paper or plastic film,
Examples thereof include those in which a layer of a conductive compound such as a conductive polymer, indium oxide, or tin oxide is provided by coating or vapor deposition.

The coating method for producing the electrophotographic photoreceptor of the present invention includes dip coating, spray coating,
A coating method such as a circular amount control type coating is used, but the coating process on the upper layer side of the photosensitive layer is performed by spray coating or a circular amount control type in order to minimize dissolution of the lower layer film and to achieve a uniform coating process. A typical example is a circular slide hopper type. It is preferable to use a coating method such as coating. The spray coating is described in detail in, for example, JP-A-3-90250 and JP-A-3-269238, and the circular amount control type coating is described in, for example, JP-A-58-18.
No. 9061 discloses this in detail.

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

Examples of the material for the intermediate layer include casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, and phenol resin polyamides (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethyl And an intermediate layer using polyurethane, gelatin, and aluminum oxide, or a curable intermediate layer using a metal alkoxide, an organic metal chelate, or a silane coupling agent as disclosed in JP-A-9-68870. The thickness of the intermediate layer is preferably from 0.1 to 10 μm, particularly preferably from 0.1 to 10 μm.
5 μm is preferred.

The shape of the support may be a drum shape, a sheet shape, or a belt shape, and may be any shape as long as it is optimal for the applied electrophotographic apparatus.

The electrophotographic photoreceptor of the present invention can be applied to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers. It can be widely applied to devices such as light printing, plate making, and facsimile.

FIG. 1 is a sectional view of an image forming apparatus equipped with the electrophotographic photosensitive member of the present invention.

In FIG. 1, reference numeral 10 denotes a photoreceptor drum (photoreceptor) serving as an image carrier, and an organic photosensitive layer is applied on the drum.
A photoreceptor coated with the resin layer of the present invention thereon is grounded and driven to rotate clockwise. Reference numeral 12 denotes a scorotron charger, which applies uniform charging to the peripheral surface of the photosensitive drum 10 by corona discharge. Prior to the charging by the charger 12, in order to eliminate the history of the photoconductor in the previous image formation, exposure by the exposure unit 11 using a light emitting diode or the like may be performed to remove electricity from the peripheral surface of the photoconductor.

After the photosensitive member is uniformly charged, the image exposing unit 13 performs image exposure based on the image signal. The image exposure device 13 in this figure uses a laser diode (not shown) as an exposure light source. The light on the photosensitive drum is scanned by the light whose optical path is bent by the reflection mirror 132 through the rotating polygon mirror 131, the fθ lens, and the like, and an electrostatic latent image is formed.

The electrostatic latent image is then developed by the developing device 14. Developing devices 14 each having a built-in developer composed of toner and carrier such as yellow (Y), magenta (M), cyan (C), black (K), etc., at the periphery of the photosensitive drum 10.
First, development of the first color is performed by a developing sleeve 141 which rotates with a built-in magnet and holding a developer. The developer comprises, for example, a carrier in which an insulating resin is coated around a ferrite core, and a toner in which a pigment corresponding to a color and a charge control agent, silica, titanium oxide, etc. are added using polyester as a main material. The developer is regulated to a layer thickness of 100 to 600 μm on the developing sleeve 141 by a layer forming means (not shown), and is conveyed to a developing area to be developed. At this time, normally, a DC and / or AC bias voltage is applied between the photosensitive drum 10 and the developing sleeve 141 to perform the development.

In the color image formation, after the visualization of the first color is completed, the image forming process of the second color is started, and the uniform charging is performed again by the scorotron charger 12 to form the latent image of the second color. It is formed by the exposure device 13. An image forming process similar to that for the second color is performed for the third color and the fourth color, and a visible image of four colors is formed on the peripheral surface of the photosensitive drum 10.

On the other hand, in a monochrome electrophotographic apparatus,
Reference numeral 4 is composed of one kind of black toner and can form an image by one development.

After the image is formed, the recording paper P is fed to the transfer area by the rotation of the paper feed roller 17 at the time when the transfer timing is adjusted.

In the transfer area, a transfer roller (transfer device) 1 is mounted on the peripheral surface of the photosensitive drum 10 in synchronization with the transfer timing.
8, the multicolor image is transferred collectively by sandwiching the fed recording paper P.

Next, the recording paper P is neutralized by a separation brush (separator) 19 brought into pressure contact with the transfer roller almost at the same time, and is separated by the peripheral surface of the photosensitive drum 10 to be conveyed to the fixing device 20 where it is heated. 201 and pressure roller 2
After the toner is welded by heating and pressurizing 02, the toner is discharged to the outside of the apparatus via the discharge roller 21. The transfer roller 18 and the separation brush 19 are retracted and separated from the peripheral surface of the photosensitive drum 10 after the recording paper P has passed to prepare for the formation of the next toner image.

On the other hand, the photosensitive drum 10 from which the recording paper P has been separated removes and cleans the residual toner by pressing the blade 221 of the cleaning unit 22 and receives the charge removal by the exposure unit 11 and the charge by the charger 12 again. The next image forming process is started. When a color image is formed on the photoconductor by superimposition, the blade 221 moves immediately after the cleaning of the photoconductor surface and retreats from the peripheral surface of the photoconductor drum 10.

Reference numeral 30 denotes a detachable cartridge in which a photosensitive member, a charger, a transfer device / separator, and a cleaning device are integrated.

The electrophotographic image forming apparatus is constructed by integrally combining the above-described photoreceptor, a developing device, a cleaning device, and other components as a process cartridge, and this unit is configured to be detachable from the apparatus main body. You may.
Also, a process cartridge is formed by integrally supporting at least one of a charger, an image exposing unit, a developing unit, a transfer or separating unit, and a cleaning unit together with a photoreceptor. It may be configured to be detachable using a guide means such as a rail of the apparatus body.

When the image forming apparatus is used as a copying machine or a printer, the image exposure is performed by irradiating the photosensitive member with reflected light or transmitted light from the original, or by reading the original with a sensor and converting it into a signal. Scanning of a laser beam, driving of an LED array, or driving of a liquid crystal shutter array is performed by irradiating the photosensitive member with light.

When used as a facsimile printer, the image exposure unit 13 performs exposure for printing received data.

[0098]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

A photoreceptor was prepared as described below.

Example 1 <Intermediate layer> A polyamide resin (Amilan CM-8000: manufactured by Toray Industries, Inc.) 60 g methanol 1600 ml 1-butanol 400 ml was mixed and dissolved to prepare an intermediate layer coating solution. This coating solution is applied on a cylindrical aluminum substrate by a dip coating method,
An intermediate layer having a thickness of 0.3 μm was formed.

<Charge Generating Layer> A-type titanyl phthalocyanine 60 g Silicone resin solution (KR5240, 15% xylene-butanol solution: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2,000 ml were mixed, and dispersed using a sand mill for 10 hours. A generating layer coating solution was prepared. This coating solution was applied on the intermediate layer by a dip coating method to form a 0.2 μm-thick charge generation layer.

<Charge Transporting Layer> Charge transporting substance (D1) 200 g Bisphenol Z-type polycarbonate (Iupilon Z200: manufactured by Mitsubishi Gas Chemical Company) 300 g 1,2-Dichloroethane 2000 ml was mixed and dissolved to prepare a charge transporting layer coating solution. did. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a thickness of 20 μm.

[0103]

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<Adhesive Layer> 60 g of silyl acrylate (PC-7A: manufactured by Shin-Etsu Chemical Co., Ltd.) and 2,000 ml of 2-butanone were mixed and dissolved to prepare a coating solution for an adhesive layer. This coating solution is applied on the charge transporting layer,
A heat treatment was performed for a minute to form an adhesive layer having a thickness of 0.3 μm.

<Surface protective layer> On top of this, 80 mol% of methylsiloxane units and 20 of methyl-phenylsiloxane units
Molecular sieve 4A was added to a methanol solution of polysiloxane consisting of mol%, and the mixture was allowed to stand for 15 hours to be dehydrated. 10 parts by weight of this solution was dissolved in 10 parts by weight of toluene, and 1 part by weight of methyltrimethoxysilane and 0.2 part by weight of dibutyltin acetate were added to obtain a uniform solution.

6 parts by weight of dihydroxymethyltriphenylamine (Exemplified Compound T-1) was added thereto and mixed, and this solution was applied as a protective layer having a dry film thickness of 1 μm.
The resultant was cured by heating at 0 ° C. for 1 hour to prepare a photoreceptor of Example 1.

Example 2 A photoconductor was prepared in the same manner as in Example 1, except that the adhesive layer was changed as follows.

<Adhesive Layer> Polyester (Byron 200: manufactured by Toyobo Co., Ltd.) 60 g 2-butanone 2000 ml was mixed and dissolved to prepare an adhesive layer coating solution. Using this coating solution, a coating was applied on the charge transport layer to a thickness of 0.3 μm.
Was formed.

Example 3 A photoconductor was prepared in the same manner as in Example 1, except that the adhesive layer was changed as follows.

<Adhesive Layer> A phenoxy resin (PKHJ: manufactured by Union Carbide) 60 g 2-butanone 2000 ml was mixed and dissolved to prepare an adhesive layer coating solution. Using this coating solution, a coating was applied on the charge transport layer to a thickness of 0.3 μm.
Was formed.

Example 4 A photoconductor was prepared by the same way as that of Example 1 except that 4- [2- (triethoxysilyl) ethyl] triphenylamine was used instead of dihydroxymethyltriphenylamine. .

Example 5 A photoconductor was prepared by the same way as that of Example 1 except that 1 part by weight of colloidal silica was added to the coating solution for the surface protective layer.

Example 6 An adhesive layer was produced in the same manner as in Example 1. 60 parts by weight of KP-85 (manufactured by Shin-Etsu Chemical Co., Ltd.) composed of a commercially available organosilicon compound and 60 parts by weight of 2-propanol were added thereto and uniformly dissolved. 6 parts by weight of compound T-1) was added and mixed, and this solution was applied so as to form a protective layer having a dry film thickness of 1 μm, and dried at 110 ° C. for 1 hour to prepare a photoreceptor.

Example 7 An adhesive layer was produced in the same manner as in Example 1. 60 parts by weight of a commercially available organosilicon compound KP-854 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 60 parts by weight of 2-propanol were added thereto and uniformly dissolved, and dihydroxytriphenylamine (exemplary example) was obtained in the same manner as in Example 1. 6 parts by weight of compound T-1) was added and mixed, and this solution was applied so as to form a protective layer having a dry film thickness of 1 μm, and dried at 110 ° C. for 1 hour to prepare a photoreceptor.

Example 8 An adhesive layer was manufactured in the same manner as in Example 1. 60 parts by weight of x-40-2269 (manufactured by Shin-Etsu Chemical Co., Ltd.) composed of a commercially available organosilicon compound and 60 parts by weight of 2-propanol were added thereto and uniformly dissolved, and dihydroxytriphenylamine was obtained in the same manner as in Example 1. (Exemplary Compound T-1) 6 parts by weight were added and mixed, and this solution was applied so as to form a protective layer having a dry film thickness of 1 μm, and dried at 110 ° C. for 1 hour to prepare a photoreceptor.

Example 9 In the surface protective layer of Example 1, hindered phenol (1-
32) A photoconductor was prepared by the same way as that of Example 1 except that 0.3 part by weight was added.

Example 10 In the surface protective layer of Example 1, hindered amine (2-1)
A photoconductor was prepared in the same manner as in Example 1, except that 0.3 part by weight was added.

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1, except that the adhesive layer was not used.

<Evaluation> Adhesion Test 100 cross-cut scratches were formed on the photoreceptor in accordance with the JIS standard, and a peeling tape was attached to the photoreceptor. After peeling, the number of cross-cuts remaining in 100 cross-cuts was counted.

[0120] 2. The electrophotographic characteristics and thickness loss were evaluated using the above photoconductors with a digital copier Kon manufactured by Konica Corporation.
The ica 7060 was modified and mounted on an evaluator having an appropriate exposure amount, the initial charging potential was set to -650 V, a 50,000 copy actual photographing test was performed, and the fluctuation amount of the exposed portion potential was measured.
The thickness loss of the photoreceptor after 50,000 copies was measured.

Table 1 shows the results.

[0122]

[Table 1]

The photoreceptors of Examples 1 to 10 in the present invention all show good characteristics, but it can be seen that Comparative Example 1 is inferior in adhesiveness and film thickness loss characteristics.

Example 11 <Intermediate layer> A polyamide resin (Amilan CM-8000: manufactured by Toray Industries, Inc.) 60 g methanol 1600 ml 1-butanol 400 ml was mixed and dissolved to prepare an intermediate layer coating solution. This coating solution is applied on a cylindrical aluminum substrate by a dip coating method,
An intermediate layer having a thickness of 0.3 μm was formed.

<Charge Generation Layer> Y-type titanyl phthalocyanine 60 g Silicone resin solution (KR5240, 15% xylene-butanol solution: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2000 ml was mixed, and dispersed by using a sand mill for 10 hours. A generating layer coating solution was prepared. This coating solution was applied on the intermediate layer by a dip coating method to form a 0.2 μm-thick charge generation layer.

<Charge Transporting Layer> Charge transporting substance (D1) 200 g Bisphenol Z-type polycarbonate (Iupilon Z200: manufactured by Mitsubishi Gas Chemical Company) 300 g 1,2-Dichloroethane 2000 ml was mixed and dissolved to prepare a charge transporting layer coating solution. did. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a thickness of 20 μm.

<Adhesive Layer> 60 g of silyl acrylate (PC-7A: manufactured by Shin-Etsu Chemical Co., Ltd.) and 2,000 ml of 2-butanone were mixed and dissolved to prepare a coating solution for an adhesive layer. This coating solution is applied on the charge transporting layer,
A heat treatment was performed for a minute to form an adhesive layer having a thickness of 0.3 μm.

<Surface protective layer> On top of this, 80 mol% of methylsiloxane units and 20 of methyl-phenylsiloxane units
Molecular sieve 4A was added to a methanol solution of polysiloxane consisting of mol%, and the mixture was allowed to stand for 15 hours to be dehydrated. 10 parts by weight of this solution was dissolved in 10 parts by weight of toluene, and 1 part by weight of methyltrimethoxysilane and 0.2 part by weight of dibutyltin acetate were added to obtain a uniform solution.

This solution was applied as a protective layer having a dry film thickness of 1 μm, and was heated and cured at 120 ° C. for 1 hour to produce a photoreceptor of Example 11.

Example 12 A photoconductor was prepared by the same way as that of Example 11 except that the adhesive layer was changed as described below.

<Adhesive Layer> Polyester (Byron 200: manufactured by Toyobo Co., Ltd.) 60 g 2-butanone 2000 ml was mixed and dissolved to prepare an adhesive layer coating solution. Using this coating solution, a coating was applied on the charge transport layer to a thickness of 0.3 μm.
Was formed.

Example 13 A photoconductor was prepared by the same way as that of Example 11 except that the adhesive layer was changed as described below.

<Adhesive Layer> A phenoxy resin (PKHJ: manufactured by Union Carbide Co., Ltd.) 60 g 2-butanone 2000 ml was mixed and dissolved to prepare an adhesive layer coating solution. Using this coating solution, a coating was applied on the charge transport layer to a thickness of 0.3 μm.
Was formed.

Example 14 A photoconductor was prepared by the same way as that of Example 11 except that 1 part by weight of colloidal silica was added to the coating solution for the surface protective layer.

Example 15 In the same manner as in Example 11, an adhesive layer was produced. 60 parts by weight of a commercially available organosilicon compound KP-85 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 60 parts by weight of 2-propanol are added and uniformly dissolved, and this solution becomes a protective layer having a dry film thickness of 1 μm. And dried at 110 ° C. for 1 hour to prepare a photoreceptor.

Example 16 In the same manner as in Example 11, an adhesive layer was manufactured. 60 parts by weight of a commercially available organosilicon compound KP-854 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 60 parts by weight of 2-propanol are added and uniformly dissolved, and this solution is used as a protective layer having a dry film thickness of 1 μm. And dried at 110 ° C for 1 hour.
A photoreceptor was produced.

Example 17 In the same manner as in Example 11, an adhesive layer was manufactured. 60 parts by weight of a commercially available organosilicon compound x-40-2269 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 60 parts by weight of 2-propanol were added and uniformly dissolved, and the solution was dried to form a protective layer having a dry film thickness of 1 μm. And dried at 110 ° C. for 1 hour to prepare a photoreceptor.

Comparative Example 2 A photoconductor was prepared by the same way as that of Example 11 except that the adhesive layer was not used.

<Evaluation> The same evaluation as in Examples 1 to 10 and Comparative Example 1 was performed.

Table 2 shows the results.

[0141]

[Table 2]

As is clear from the results shown in Table 1, Comparative Example 2, which is not the present invention, is inferior in adhesiveness and film thickness loss characteristics.

[0143]

According to the present invention, an electrophotographic photoreceptor having improved adhesion properties between a surface protective layer made of an organosilicon compound and a photosensitive layer, having good charging characteristics, high sensitivity, no film peeling and high abrasion resistance can be obtained. An image forming apparatus, an image forming method, and a process cartridge using the same can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view of an image forming apparatus according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 10 Photosensitive drum (or photoreceptor) 11 Exposure part using light emitting diode etc. 12 Charging device 13 Image exposing device 14 Developing device 17 Paper feed roller 18 Transfer roller (transfer device) 19 Separation brush (separator) 20 Fixing device 21 Discharge roller 22 Cleaning device 30 Removable process cartridge in which photoconductor, charging device, transfer device / separator and cleaning device are integrated.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 C08L 83/04 C08L 83/04 G03G 5/05 101 G03G 5/05 101 15 / 08 502 15/08 502A (72) Inventor Yoko Kitahara 2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica Corporation (72) Inventor Masahiko Kurachi 2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica Corporation (72) Inventor Kazuhisa Shida 2970 Ishikawacho, Hachioji-shi, Tokyo Konica Corporation F-term (reference) 2H068 AA03 AA04 AA10 AA35 BA05 BA12 BB25 BB30 BB32 CA06 FA27 FC01 FC05 FC08 FC11 FC15 2H077 AD36 EA03 GA13 GA17 4J002 CP091 CP017EJ0JEJ0JEJ037 EL127 EU077 EU087 EU187 EU197 EV077 EW067 EW087 EW127 FD077 GP03

Claims (15)

[Claims] 1. An electrophotographic photoreceptor comprising a photosensitive layer and a surface protective layer sequentially laminated on a conductive support, wherein the surface protective layer has a structural unit having charge transport performance and has a crosslinked structure. Consisting of a layer containing a siloxane-based resin,
An electrophotographic photoreceptor, wherein an adhesive layer made of a resin containing a hydrolyzable group or a hydroxyl group is provided between the photosensitive layer and the surface protective layer. 2. The surface protective layer comprises a resin layer obtained by reacting an organosilicon compound having a hydroxyl group or a hydrolyzable group with a compound having a hydroxyl group and a structural unit having charge transport performance. The electrophotographic photosensitive member according to claim 1, wherein 3. The electrophotographic photoreceptor according to claim 1, wherein said surface protective layer contains colloidal silica. 4. The electrophotographic photoconductor according to claim 1, wherein the surface protective layer contains an antioxidant. 5. The electrophotographic photoreceptor according to claim 4, wherein said surface protective layer contains a hindered phenol compound or a hindered amine compound as an oxidizing agent. 6. The electrophotographic photosensitive member according to claim 1, wherein the adhesive layer is a resin layer containing a hydroxyl group. 7. The electrophotographic photoreceptor according to claim 1, wherein the hydroxyl group-containing resin is a phenoxy resin or a modified product thereof. 8. An electrophotographic photoreceptor comprising a photosensitive layer and a surface protective layer sequentially laminated on a conductive support, wherein the surface protective layer comprises a layer containing a siloxane-based resin having a crosslinked structure. An electrophotographic photoreceptor comprising an adhesive layer made of a resin containing a hydrolyzable group or a hydroxyl group provided between the layer and the surface protective layer. 9. The electrophotographic photoconductor according to claim 8, wherein the surface protective layer contains colloidal silica. 10. The electrophotographic photosensitive member according to claim 8, wherein the adhesive layer is a resin layer containing a hydroxyl group. 11. The electrophotographic photoreceptor according to claim 10, wherein the resin containing a hydroxyl group is a phenoxy resin or a modified product thereof. 12. The electrophotographic photoreceptor according to claim 1, wherein an uppermost layer of the photosensitive layer is a charge transport layer, and the charge transport layer is a layer containing polycarbonate. . 13. An electrophotographic photoreceptor according to claim 1, comprising the steps of charging, image exposure, development, transfer / separation, and cleaning, and developing by reversal development to form an image. An image forming method characterized by forming. 14. An image forming method using the electrophotographic photoreceptor according to claim 1 through a process including charging, image exposure, development, transfer / separation, and cleaning. Image forming apparatus. 15. The process cartridge according to claim 1, wherein the process cartridge comprises an electrophotographic photosensitive member and is used for forming an image through steps of charging, image exposure, development, transfer / separation, and cleaning. A process cartridge comprising a combination of a photographic photosensitive member and at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device.