JP2012113238A - Electrophotographic photoreceptor, method for manufacturing electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having excellent wear resistance and electric characteristics and significantly improved scratch resistance in an electrophotographic photoreceptor having a surface layer containing a curable resin that is obtained by polymerizing a compound having a polymerizable functional group.SOLUTION: The electrophotographic photoreceptor has a surface layer containing a curable resin that is obtained by polymerizing a compound having a polymerizable functional group, wherein the surface layer contains a compound (amide derivative) having a specified structure.

Description

  The present invention relates to an electrophotographic photosensitive member and a method for manufacturing the same, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  An electrophotographic photosensitive member using an organic photoconductive substance (organic electrophotographic photosensitive member) has a good film forming property and can be produced by coating. Therefore, it has the advantage of providing an electrophotographic photosensitive member that is highly productive and inexpensive. Have been extensively studied. In particular, many attempts have been made to improve the mechanical durability of the electrophotographic photosensitive member for the purpose of extending the life of the electrophotographic photosensitive member and improving the image quality. Among them, an electrophotographic photosensitive member having a surface layer to which a curable resin is applied has been put to practical use in a high-speed copying machine or the like that requires high durability because of its high wear resistance.

  Also known is a technique of adding an additive to the surface layer of the electrophotographic photosensitive member for the purpose of improving mechanical durability such as scratch resistance and abrasion resistance of the electrophotographic photosensitive member.

  Patent Documents 1 to 3 disclose a technique in which a specific amine compound is further contained in the surface layer of an electrophotographic photosensitive member containing a curable resin obtained by polymerizing a radical polymerizable monomer mixture. These techniques are intended to improve image blur without causing a decrease in hardness (decrease in mechanical durability) due to polymerization inhibition by containing a specific amine compound in the surface layer.

JP 2007-272191 A JP 2007-272192 A JP 2007-279678 A

  However, as a result of the study by the present inventors, it has been found that the amine compounds described in Patent Documents 1 to 3 cause deterioration of the electrical characteristics of the electrophotographic photosensitive member. Further, the mechanical durability such as scratch resistance is not sufficient. The term “scratch” as used herein refers to a scratch with a clear appearance on the surface of the electrophotographic photosensitive member caused by local mechanical stress on the surface of the electrophotographic photosensitive member. It can be recognized as a scratch image (scratched white spots or black streaks).

  An object of the present invention is to provide an electrophotographic photosensitive member having a surface layer containing a curable resin obtained by polymerizing a compound having a polymerizable functional group, which is excellent in wear resistance and electrical characteristics, and has large scratch resistance. An object of the present invention is to provide an improved electrophotographic photosensitive member and a method for producing the same.

  Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  The present invention provides an electrophotographic photosensitive member having a surface layer containing a curable resin obtained by polymerizing a compound having a polymerizable functional group, the surface layer containing a compound represented by the following general formula (1) An electrophotographic photosensitive member characterized in that:

(In Formula (1), Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group, and the substituent is limited to a substituted or unsubstituted aryl group, a hydroxy group, or a fluorine atom. , N is an integer selected from 0 to 17.)

  In addition, the present invention forms a coating film using a surface layer coating liquid containing a compound having a polymerizable functional group and the compound represented by the general formula (1), and the polymerization contained in the coating film It is a method for producing an electrophotographic photoreceptor having a step of forming a surface layer by polymerizing a compound having a functional functional group.

  Further, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, and is detachable from the main body of the electrophotographic apparatus. A process cartridge.

  The present invention also provides an electrophotographic apparatus having the electrophotographic photosensitive member, and a charging unit, an exposure unit, a developing unit, and a transfer unit.

  JP-A-61-035452 and JP-A-01-137260 disclose single-layer electrophotographic photoreceptors formed of a photoconductive composition containing an amino compound or an amide compound. There is no suggestion of improving scratch resistance.

  Japanese Patent Application Laid-Open No. 58-102239 describes that the film properties of polyvinylcarbazole are improved by adding an amide compound to the electrophotographic photosensitive member, but specific verification has been made. Absent. Furthermore, when the present inventors conducted a verification experiment, when a urea compound specifically disclosed in JP-A-63-097959 is incorporated in the surface layer containing a curable resin, an electrophotography is obtained. It has been found that the scratch resistance and wear resistance of the photoreceptor are lowered and the electrical characteristics are greatly deteriorated.

  According to the present invention, in an electrophotographic photosensitive member having a surface layer containing a curable resin obtained by polymerizing a compound having a polymerizable functional group, it is excellent in wear resistance and electrical characteristics, and has large scratch resistance. An improved electrophotographic photosensitive member and a method for producing the same can be provided.

  Further, according to the present invention, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member can be provided.

It is a figure which shows an example of the layer structure of an electrophotographic photoreceptor. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention.

  Although the detailed mechanism of manifestation of the effect of the present invention is unknown, the present inventors presume as follows.

That is, the compound represented by the general formula (1) has a chemical structure in which the aryl groups (Ar ¹ and Ar ² ) in the molecule can easily be arranged to face each other. Then, according to the external pressure applied to the electrophotographic photosensitive member that induces scratches, the distance between the aryl groups facing each other is shortened (the aryl groups overlap each other), thereby acting as a kind of molecular level spring, and the external pressure is quickly applied. I think that it can be converted into thermal energy accompanying chemical structural changes. In addition, it is speculated that since the opposing aryl groups also act as conductive paths having anisotropy, the adverse effect of the deterioration of electrical characteristics can be solved.

On the other hand, among the compounds disclosed in JP-A-61-035452, JP-A-01-137260 and JP-A-58-102239, those having an aryl group are short in nitrogen atoms. It does not have a structure in which alkyl groups (R ₁ and R ₂ : alkyl groups having 1 to 3 carbon atoms) are directly bonded. Therefore, aryl groups do not overlap each other. Therefore, it is presumed that the effect of the action as a spring derived from the overlapping of the above aryl groups cannot be obtained.

  An electrophotographic photoreceptor generally has a support and a photosensitive layer formed on the support.

  In the present invention, the photosensitive layer of the electrophotographic photosensitive member may be a single-layer type photosensitive layer containing a charge transport material and a charge generation material in the same layer, or a charge generation layer containing a charge generation material and a charge generation material. It may be a laminated photosensitive layer (FIGS. 1A and 1B) separated into a charge transport layer containing a transport material. From the viewpoint of electrophotographic characteristics, a laminated photosensitive layer is preferable. In FIG. 1, 101 is a support, 102 is an undercoat layer, 103 is a charge generation layer, 104 is a charge transport layer, and 105 is a protective layer. The undercoat layer is also called an intermediate layer or a barrier layer.

  In the present invention, the surface layer of the electrophotographic photosensitive member means a layer located on the outermost surface. For example, in the case of the electrophotographic photosensitive member having the layer structure shown in FIG. 1A, the surface layer of the electrophotographic photosensitive member is the charge transport layer 104. In the case of the electrophotographic photosensitive member having the layer structure shown in FIG. 1B, the surface layer of the electrophotographic photosensitive member is the protective layer 105.

  As described above, the surface layer of the electrophotographic photoreceptor of the present invention contains a curable resin obtained by polymerizing a compound having a polymerizable functional group (a compound having at least one polymerizable functional group). When polymerizing a compound having a polymerizable functional group, a polymerization initiator may be used as necessary. The polymerization of the compound having a polymerizable functional group can be performed using heat, light (such as ultraviolet rays) or radiation (such as an electron beam). Among these, it is not always necessary to use a polymerization initiator, polymerization using radiation is preferable, and polymerization using an electron beam is more preferable. In addition, when a compound having a polymerizable functional group is polymerized using an electron beam, it may be heated in an inert gas atmosphere after irradiating the electron beam in an inert gas atmosphere for the purpose of removing the polymerization inhibiting action due to oxygen. preferable. Examples of the inert gas include nitrogen and argon.

  In the present invention, the surface layer of the electrophotographic photoreceptor further contains a compound (amide derivative / amide compound) represented by the following general formula (1).

  N in the general formula (1) is an integer of 0 to 17. n is preferably 0, 1 or 2. When n is 18 or more, it works as a factor that inhibits the densification of the structure (three-dimensional network structure) of the curable resin forming the surface layer, and sufficient film strength of the surface layer may not be obtained. If the film strength of the surface layer is not sufficient, sufficient wear resistance and scratch resistance cannot be obtained.

Ar ¹ and Ar ² in the general formula (1) each independently represent a substituted or unsubstituted aryl group. However, when Ar ¹ and Ar ² are substituted aryl groups, the substituent of the aryl group is an unsubstituted aryl group, an aryl group substituted with an alkyl group, an aryl group substituted with a carboxy group, or an aryl group substituted with a cyano group , An aryl group substituted with a hydroxy group, an aryl group substituted with a nitro group, an aryl group substituted with a fluorine atom, an aryl group substituted with a chlorine atom, an aryl group substituted with a bromine atom, a hydroxy group, or a fluorine atom. Ar ¹ and Ar ² are preferably an unsubstituted fluorenyl group or an alkyl group-substituted fluorenyl group, and more preferably a 9,9-dimethylfluorenyl group.

  Examples of the aryl group include a phenyl group, a naphthyl group, and a fluorenyl group.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

  In the present invention, the surface layer of the electrophotographic photosensitive member preferably contains 1 to 20% by mass of the compound represented by the general formula (1) with respect to the total mass of the surface layer. When there is too little content, the effect of this invention may become small. Moreover, when there is too much content, the densification of the structure (three-dimensional network structure) of the curable resin which forms a surface layer will be suppressed, and when the film | membrane intensity | strength of a surface layer becomes low, or the said general formula from a surface layer The compound represented by (1) may be easily precipitated.

  The compound represented by the general formula (1) may contain only one type or two or more types in the surface layer of the electrophotographic photosensitive member.

  The compound represented by the general formula (1) can be synthesized from a suitable aniline derivative and benzoyl chloride derivative as described in, for example, JP-A-2005-255981.

  Specific examples (exemplary compounds) of the compound represented by the general formula (1) are listed below, but the present invention is not limited thereto.

  Among the compounds, a compound represented by the structural formula (A-10) and a compound represented by the structural formula (A-22) are more preferable. Hereinafter, the compounds represented by the structural formulas (A-1) to (A-22) are also referred to as exemplary compounds (A-1) to (A-22), respectively.

  Further, the compound having a polymerizable functional group used for the surface layer of the electrophotographic photosensitive member of the present invention is a compound that can form a curable resin by polymerization. Specifically, for example, an olefin compound (a compound having only one double bond C = C) or a halogenated olefin compound (having only one double bond C = C, a halogen X (X is F , Cl, Br or I)), diene compounds (compounds having two or more double bonds C = C), acetylene compounds (compounds having one or more triple bonds C≡C), and the like. , A styrene compound (C = C-Ar (Ar is an aromatic ring or aromatic heterocyclic ring) structure), a vinyl compound (a compound having a vinyl group C = C-), an acrylic acid compound (C = C-CO-Z (Z is a compound having an O, S or N) or C = C-CN structure), a cyclic ether compound (a cyclic compound having an -O- bond in the ring), a lactone compound ( -CO-O- bond in the ring A cyclic compound.), A lactam compound (a cyclic compound having a —NH—CO— bond in the ring), a cyclic amine compound (a cyclic compound having a —NH— bond in the ring), a cyclic sulfide compound (S in the ring). A cyclic compound having an atom.), A cyclic carbonate compound (a cyclic compound having a —O—CO—O— bond in the ring), a cyclic acid anhydride (a cyclic compound having a —CO—O—CO— bond in the ring) ), A cyclic imino ether compound (a cyclic compound having a —N═C—O— bond in the ring), and an amino acid-N-carboxylic acid anhydride (—O—CO—N═C—CO— bond in the ring). And cyclic imide compounds (cyclic compounds having a —CO—NH—CO— bond, —NH—CO—O— bond or —NH—CO—NH— bond in the ring), Phosphorus compounds (having P atoms in the ring Cyclic compounds, cyclic silicon-containing compounds (cyclic compounds having a Si atom in the ring), cyclic olefin compounds (cyclic compounds in which the ring is composed of carbon or carbon multiple bonds), phenolic compounds (aromatic hydroxyl structure). ), Melamine / urea compounds (melamines or urea derivatives), diamine compounds (including diamine derivatives and polyamines), dicarboxylic acid compounds (dicarboxylic acid (ester) derivatives), oxycarbons Acid compounds (oxycarboxylic acid (ester) derivatives), aminocarboxylic acid compounds (aminocarboxylic acid (ester) derivatives), diol compounds (polyols having two or more free OH groups), diisocyanate compounds (Iso (thio) cyanate derivatives) and sulfur-containing compounds (sulfur-containing (S ) Monomers. ), Phosphorus-containing compounds (phosphorus-containing (P) monomers), aromatic ether compounds (compounds in which aromatic hydrocarbon groups are bonded with oxygen), dihalogen compounds (carbon-halogens other than acid halides) A compound having a plurality of bonds), an aldehyde compound (a compound having an aldehyde group), a diketone compound, a carbonic acid derivative compound, an aniline derivative compound, a silicon compound, and the like.

  Moreover, it is preferable that the compound which has the said polymeric functional group is a compound shown by following General formula (2) from a viewpoint of an electrical property.

In the general formula (2), A ¹ represents a charge transporting group, P ¹ represents a group represented by the following general formula (3), and m represents a positive integer.

In the general formula (3), Y ¹ represents a hydrogen atom or a methyl group.

Examples of the structure of P ¹ include a structure in which a hydrogen adduct obtained by replacing the site bonded to P ^{1 of} A ¹ with a hydrogen atom becomes triarylamine, hydrazone, pyrazoline, or carbazole. Preferably, the hydrogen adduct obtained by substituting a hydrogen atom for the site bonded to P ^{1 of} A ¹ is a structure represented by the following general formula (4).

In the general formula (4), Ar ^{3 to} Ar ⁵ each independently represents an unsubstituted aryl group or an alkyl group-substituted aryl group.

  Examples of the aryl group include a phenyl group, a naphthyl group, and a fluorenyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

Furthermore, from the viewpoint of forming a sufficient three-dimensional network structure on the surface layer of the electrophotographic photoreceptor, the compound having a polymerizable functional group is a charge transporting compound having two or more polymerizable functional groups. Is preferred. More preferably, in the general formula (4), the binding site of A ¹ to P ¹ is present in any two of Ar ^{3 to} Ar ⁵ . This structure has a monoamine structure with good polymerization efficiency, and has an excessive number of polymerizable functional groups that can easily increase the internal stress of the surface layer and easily cause scratches.

  The compound having a polymerizable functional group may be used alone or in combination of two or more when forming a surface layer containing a curable resin.

  The support for the electrophotographic photosensitive member may be any conductive one (conductive support). For example, a support made of metal such as aluminum, stainless steel, or nickel, or a conductive film on the surface is provided. Metal, plastic, paper support and the like. Examples of the shape of the support include a cylindrical shape and a film shape. Among these, a cylindrical aluminum support is excellent in terms of mechanical strength, electrophotographic characteristics, and cost. The raw tube may be used as a support, but the surface of the raw tube is supported by physical treatment such as cutting or honing, anodizing treatment, chemical treatment using acid, etc. It may be used as a body. A support having a surface roughness of 0.1 μm or more and 3.0 μm or less in terms of Rz value by performing physical processing such as cutting and honing on the raw tube has an excellent interference fringe suppression function. .

  A conductive layer (not shown in FIG. 1) can be provided between the support and the photosensitive layer or the undercoat layer described below, if necessary. The conductive layer is not always necessary when the support itself has an interference fringe suppression function. However, the conductive layer is used as a support in the form of a bare tube, and a conductive layer is formed on the conductive tube. A fringe suppression function can be provided. For this reason, it is very useful in terms of productivity and cost. For the conductive layer, inorganic particles such as tin oxide, indium oxide, titanium oxide, and barium sulfate are dispersed in a suitable solvent together with a curable resin such as a phenol resin. Can be formed by coating the resulting coating film on a support and heating and drying the resulting coating film. The thickness of the conductive layer is preferably 10 μm or more and 30 μm or less from the viewpoint of the interference fringe suppressing function and the coating of defects on the support.

  An undercoat layer may be provided on the support or the conductive layer for the purpose of ensuring adhesion to the support, protecting the photosensitive layer from electrical breakdown, and improving the carrier injection property of the photosensitive layer. .

  The undercoat layer can be formed by applying an undercoat layer coating solution obtained by dissolving a resin in a solvent, and drying the resulting coating film.

  Examples of the resin used for the undercoat layer include acrylic resin, allyl resin, alkyd resin, ethyl cellulose resin, ethylene-acrylic acid copolymer, epoxy resin, casein resin, silicone resin, gelatin resin, phenol resin, butyral resin, polyacrylate. , Polyacetal, polyamideimide, polyamide, polyallyl ether, polyimide, polyurethane, polyester, polyethylene, polycarbonate, polystyrene, polysulfone, polyvinyl alcohol, polybutadiene, polypropylene, urea resin, agarose resin, cellulose resin and the like.

  Examples of the solvent used in the coating solution for the undercoat layer include benzene, toluene, xylene, tetralin, chlorobenzene, dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, propyl acetate, methyl formate, and formic acid. Ethyl, acetone, methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, propylene glycol monomethyl ether, dioxane, methylal, tetrahydrofuran, water, methanol, ethanol, n-propanol, isopropanol, butanol, methyl cellosolve, methoxypropanol, dimethylformamide, dimethyl Examples include acetamide and dimethyl sulfoxide.

  The thickness of the undercoat layer is preferably from 0.1 μm to 5 μm.

  A photosensitive layer is provided on the support, the conductive layer or the undercoat layer.

  Examples of the charge generating substance include azo pigments such as monoazo, bisazo, trisazo, and tetrakisazo, phthalocyanine pigments such as gallium phthalocyanine and oxytitanium phthalocyanine, and perylene pigments. Among these, gallium phthalocyanine is preferable from the viewpoint of characteristic stability during environmental changes. Furthermore, from the viewpoint of high sensitivity, crystalline hydroxygallium having strong peaks at positions of 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° of the Bragg angle 2θ in CuKα characteristic X-ray diffraction A phthalocyanine crystal is more preferable.

  When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin for the charge generation layer include polyvinyl butyral, polyarylate, polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyvinyl pyridine, and cellulose. Examples thereof include insulating resins such as resin, urethane resin, epoxy resin, agarose resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. Moreover, organic photoconductive polymers, such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene, can also be used.

  Examples of the solvent used in the charge generation layer coating solution include toluene, xylene, tetralin, chlorobenzene, dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, propyl acetate, methyl formate, ethyl formate, Acetone, methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, propylene glycol monomethyl ether, dioxane, methylal, tetrahydrofuran, water, methanol, ethanol, n-propanol, isopropanol, butanol, methyl cellosolve, methoxypropanol, dimethylformamide, dimethylacetamide, Examples thereof include dimethyl sulfoxide.

  The charge generation layer can be formed by applying a charge generation layer coating solution containing a charge generation material and, if necessary, a binder resin, and drying the resulting coating film. The coating solution for the charge generation layer may be prepared by adding only the charge generation material to the solvent and then dispersing and then adding the binder resin. Alternatively, the charge generation material and the binder resin may be added to the solvent together and dispersed. May be prepared.

  The thickness of the charge generation layer is preferably 0.05 μm or more and 5 μm or less.

  Examples of the charge transport material include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triallylmethane compounds, and the like.

  When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin for the charge transport layer include polyvinyl butyral, polyarylate, polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, and polyvinylpyridine. Insulating resins such as cellulose resin, urethane resin, epoxy resin, agarose resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. Moreover, organic photoconductive polymers, such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene, can also be used.

  Examples of the solvent used in the charge transport layer coating solution include toluene, xylene, tetralin, chlorobenzene, dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, propyl acetate, methyl formate, ethyl formate, Acetone, methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, propylene glycol monomethyl ether, dioxane, methylal, tetrahydrofuran, water, methanol, ethanol, n-propanol, isopropanol, butanol, methyl cellosolve, methoxypropanol, dimethylformamide, dimethylacetamide and Examples thereof include dimethyl sulfoxide.

  The charge transport layer can be formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and, if necessary, a binder resin in a solvent, and drying the obtained coating film. .

  The thickness of the charge transport layer is preferably 5 μm or more and 40 μm or less.

  The structure of the surface layer of the electrophotographic photosensitive member of the present invention is as described above. Further, the surface layer may contain conductive particles, an ultraviolet absorber, an abrasion resistance improver, and the like. Examples of the conductive particles include metal oxides such as tin oxide particles. Examples of the wear resistance improver include fluorine atom-containing resin particles, alumina particles, and silica particles.

  The film thickness of the surface layer is preferably 0.5 μm or more and 20 μm or less.

  Examples of the solvent used in the surface layer coating solution include toluene, xylene, tetralin, chlorobenzene, dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, methyl acetate, ethyl acetate, propyl acetate, methyl formate, ethyl formate, and acetone. , Methyl ethyl ketone, cyclohexanone, diethyl ether, dipropyl ether, propylene glycol monomethyl ether, dioxane, methylal, tetrahydrofuran, water, methanol, ethanol, n-propanol, isopropanol, butanol, 1,1,2,2,3,3,4 -Heptafluorocyclopentane, 4-methylmorpholine, N, N'-dimethylcyclohexylamine, methyl cellosolve, methoxypropanol, dimethylformamide , Dimethylacetamide, and dimethyl sulfoxide.

  When the layer structure of the electrophotographic photosensitive member is the layer structure shown in FIG. 1A, the surface layer having the charge transporting capability is formed on the charge generation layer, and the layer structure shown in FIG. In this case, the surface layer is formed on the charge transport layer.

  Moreover, when forming each said layer, application | coating methods, such as a dip coating method (dipping method), a spray coating method, a spinner coating method, a bead coating method, a blade coating method, a beam coating method, can be used.

  FIG. 2 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 2, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 at a predetermined peripheral speed (process speed) in the direction of an arrow. In the rotation process, the electrophotographic photosensitive member 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by a charging unit (primary charging unit) 3. Next, the exposure light 4 intensity-modulated in response to a time-series electric digital image signal of target image information output from an exposure means (not shown) such as slit exposure or laser beam scanning exposure is received. In this way, electrostatic latent images corresponding to target image information are sequentially formed on the surface of the electrophotographic photosensitive member 1.

  The formed electrostatic latent image is then visualized as a toner image by regular development or reversal development with toner contained in the developing means 5. The toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is sequentially transferred onto the transfer material 7 by the transfer means 6. Here, the transfer material 7 is taken out from a sheet feeding unit (not shown) in synchronization with the rotation of the electrophotographic photosensitive member 1 and fed between the electrophotographic photosensitive member 1 and the transfer means 6. Further, a bias voltage having a polarity opposite to the charge held in the toner is applied to the transfer means 6 from a bias power source (not shown). The transfer means may be an intermediate transfer type transfer means having a primary transfer member, an intermediate transfer member, and a secondary transfer member.

  The transfer material 7 that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member, conveyed to the fixing means 8, and subjected to a fixing process of the toner image, whereby an electrophotographic image forming product (print, copy) is obtained. Printed out of the device.

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by removing the deposits such as transfer residual toner by the cleaning means 9. The transfer residual toner can be collected by a developing device or the like. Further, after being subjected to charge removal processing by pre-exposure light 10 from pre-exposure means (not shown), it is repeatedly used for image formation. Note that when the charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.

  In the present invention, a plurality of components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6, and the cleaning unit 9 may be housed in a container to form a process cartridge. The process cartridge may be detachably attached to an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one means selected from the group consisting of charging means 3, developing means 5, transfer means 6 and cleaning means 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and the rail of the electrophotographic apparatus main body. The process cartridge 11 can be detachably attached to the main body of the electrophotographic apparatus using the guide means 12 such as the above.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to these. In the examples, “part” means “part by mass”.

<Example 1>
50 parts of titanium oxide particles coated with tin oxide containing 10% by weight of antimony oxide, 25 parts of resol type phenol resin, 20 parts of methyl cellosolve, 5 parts of methanol, and silicone oil (polydimethylsiloxane / polyoxyalkylene) A coating solution for a conductive layer was prepared by placing 0.002 part of a copolymer (average molecular weight 3000) in a sand mill using glass beads having a diameter of 0.8 mm for 2 hours.

  The conductive layer coating solution is dip-coated on an aluminum cylinder (outer diameter 30 mm, drawing tube) as a support, and the resulting coating film is dried for 30 minutes at 140 ° C., so that the film thickness is 20 μm. A layer was formed.

  Next, 2.5 parts of nylon 6-66-610-12 quaternary nylon copolymer (trade name: CM8000, manufactured by Toray Industries, Inc.) and N-methoxymethylated 6 nylon resin (trade name: Toresin EF) An undercoat layer coating solution was prepared by dissolving 7.5 parts of -30T (manufactured by Nagase ChemteX) in a mixed solvent of 100 parts of methanol and 90 parts of butanol. The undercoat layer coating solution was dip-coated on the conductive layer, and the resulting coating film was dried at 100 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.7 μm.

  Next, a Bragg angle 2θ ± 0 in CuKα characteristic X-ray diffraction was added to a solution obtained by dissolving 5 parts of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) in 130 parts of cyclohexanone. 11 parts of a crystalline form of hydroxygallium phthalocyanine crystal (charge generating material) having strong peaks at 7.3 ° and 28.1 ° of 2 ° were added. To this, 500 parts of glass beads having a diameter of 1 mm were added and dispersed for 2 hours under the condition of 1800 rpm while cooling with cooling water at 18 ° C. A coating solution for a charge generation layer was prepared by adding 300 parts of ethyl acetate and 160 parts of cyclohexanone to the liquid after the dispersion treatment and diluting. The average particle size (median) of hydroxygallium phthalocyanine crystals in the charge generation layer coating solution is measured using a centrifugal particle size measuring device (trade name: CAPA700) manufactured by Horiba, Ltd. based on the liquid phase precipitation method. As a result, it was 0.22 μm.

  This charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 110 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.15 μm.

  Next, 5 parts of a compound (charge transport material) represented by the following structural formula (5),

5 parts of a compound (charge transport material) represented by the following structural formula (6),

A coating solution for a charge transport layer was prepared by dissolving 10 parts of polycarbonate (trade name: Iupilon Z400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in a mixed solvent of 70 parts of monochlorobenzene and 30 parts of dimethoxymethane. The charge transport layer coating solution was dip-coated on the charge generation layer, and the resulting coating film was dried at 100 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm.

  Next, 45 parts of a compound represented by the following structural formula (7),

And 5 parts of exemplary compound (A-19) is dissolved in 25 parts of n-propanol, and 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, Nippon Zeon) A protective layer coating solution was prepared by adding 25 parts by Co., Ltd. This protective layer coating solution was dip coated on the charge transport layer, and the resulting coating film was heat treated at 50 ° C. for 5 minutes. Thereafter, the coating film was irradiated with an electron beam for 1.5 seconds under conditions of an acceleration voltage of 75 kV and an absorbed dose of 19000 Gy in a nitrogen atmosphere. Subsequently, the coating film was heat-treated at 125 ° C. for 30 seconds in a nitrogen atmosphere. The oxygen concentration from the electron beam irradiation to the heat treatment for 30 seconds was 19 ppm. Next, the coating film was heat-treated at 100 ° C. for 15 minutes in the air to form a protective layer having a thickness of 5 μm.

  Thus, an electrophotographic photosensitive member having a support, a conductive layer, an undercoat layer, a charge generation layer, a charge transport layer and a protective layer, and the protective layer being a surface layer was produced (manufactured). This electrophotographic photosensitive member is referred to as an electrophotographic photosensitive member 1.

<Example 2>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that Example Compound (A-19) was changed to Example Compound (A-20) in Example 1. This is referred to as an electrophotographic photoreceptor 2.

<Example 3>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the exemplified compound (A-19) was changed to the exemplified compound (A-11) in Example 1. This is referred to as an electrophotographic photoreceptor 3.

<Example 4>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that Example Compound (A-19) was changed to Example Compound (A-6) in Example 1. This is referred to as an electrophotographic photoreceptor 4.

<Example 5>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that Example Compound (A-19) was changed to Example Compound (A-7) in Example 1. This is referred to as an electrophotographic photoreceptor 5.

<Example 6>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the exemplified compound (A-19) was changed to the exemplified compound (A-10) in Example 1. This is referred to as an electrophotographic photoreceptor 6.

<Example 7>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared as follows. This is referred to as an electrophotographic photoreceptor 7.

  45 parts of a compound represented by the following structural formula (8),

And 5 parts of exemplary compound (A-10) is dissolved in 25 parts of n-propanol, and 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, Nippon Zeon) A protective layer coating solution was prepared by adding 25 parts by Co., Ltd.

<Example 8>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer coating solution was prepared as follows. This is referred to as an electrophotographic photoreceptor 8.

  22.5 parts of dipentaerythritol hexaacrylate (trade name: DPHA, manufactured by Daicel Cytec Co., Ltd.) (compound having a polymerizable functional group and no charge transport structure), the above structural formula ( 82.5) and 5 parts of exemplified compound (A-10) are dissolved in 25 parts of n-propanol, and 1,1,2,2,3,3,4-heptafluoro is further dissolved. A coating solution for protective layer was prepared by adding 25 parts of cyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.).

<Example 9>
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the protective layer was formed as follows. This is referred to as an electrophotographic photoreceptor 9.

  Compound represented by the following structural formula (9)

(Treatment amount 7%) Antimony-doped tin oxide ultrafine particles 25 parts and ethanol 150 parts were placed in a sand mill and dispersed for 66 hours. Further, polytetrafluoroethylene particles (average particle size 0.18 μm) 10 parts were added and dispersed for 2 hours to obtain a dispersion. Thereafter, 10 parts of a resol type phenol resin (trade name: PL-4804, containing an amine compound other than ammonia, manufactured by Gunei Chemical Co., Ltd.) and 5 parts of the exemplified compound (A-10) are dissolved in the dispersion. Thus, a protective layer coating solution was prepared. This protective layer coating solution was dip coated on the charge transport layer, and the resulting coating film was heat treated at 150 ° C. for 60 minutes to form a protective layer having a thickness of 5 μm.

<Example 10>
A solution obtained by adding 1 part of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) (photopolymerization initiator) to the coating solution for protective layer prepared in Example 8 A protective layer coating solution was obtained. This protective layer coating solution was dip coated on the charge transport layer, and the resulting coating film was heat treated at 50 ° C. for 5 minutes. Thereafter, the coating film was irradiated with light for 20 seconds under the condition of irradiation intensity: 500 mW / cm ² using a metal halide lamp, and heat-treated at 130 ° C. for 30 minutes to form a protective layer having a thickness of 5 μm. Except for this, an electrophotographic photosensitive member was produced in the same manner as in Example 8. This is referred to as an electrophotographic photoreceptor 10.

<Comparative example 1>
In Example 1, the exemplary compound (A-19) is represented by the following structural formula (10)

An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the above was changed. This is referred to as an electrophotographic photoreceptor C1.

<Comparative example 2>
In Example 1, the exemplary compound (A-19) is represented by the following structural formula (11)

An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the above was changed. This is referred to as an electrophotographic photoreceptor C2.

<Comparative Example 3>
In Example 1, the exemplary compound (A-19) is represented by the following structural formula (12)

An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the above was changed. This is referred to as an electrophotographic photoreceptor C3.

<Comparative example 4>
In Example 1, the exemplary compound (A-19) is represented by the following structural formula (13)

An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the above was changed. This is referred to as an electrophotographic photoreceptor C4.

<Comparative Example 5>
In Example 1, the exemplified compound (A-19) is represented by the following structural formula (14)

An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the above was changed. This is designated as an electrophotographic photoreceptor C5.

<Comparative Example 6>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that Example Compound (A-19) was not used in Example 1. This is designated as an electrophotographic photoreceptor C6.

<Comparative Example 7>
In Example 7, an electrophotographic photosensitive member was produced in the same manner as in Example 7 except that the exemplified compound (A-10) was not used. This is designated as an electrophotographic photoreceptor C7.

<Comparative Example 8>
In Example 8, an electrophotographic photosensitive member was produced in the same manner as in Example 8 except that the exemplified compound (A-10) was not used. This is designated as an electrophotographic photoreceptor C8.

<Comparative Example 9>
In Example 9, an electrophotographic photosensitive member was produced in the same manner as in Example 9 except that the exemplified compound (A-10) was not used. This is designated as an electrophotographic photoreceptor C9.

<Paper pass durability evaluation>
The electrophotographic photosensitive members 1 to 10 and C1 to C9 are mounted on an electrophotographic copying machine (trade name: iR4570) manufactured by Canon Inc., and the dark part potential is −750 V in an environment of 27 ° C./75% RH. The light passage potential was set to -160 V, and a paper passing durability test of 200,000 sheets was performed. At that time, the presence or absence of image defects (scratched images) due to the occurrence of scratches on the surface of the electrophotographic photosensitive member was visually confirmed for every 10,000 sheets. Further, regarding the electrophotographic photosensitive members 1 to 6 and C1 to C6, the magnitude of the bright portion potential fluctuation amount after passing 20,000 sheets (= the bright portion potential after passing 20,000 sheets−the initial bright portion potential). It was confirmed. Further, regarding the electrophotographic photoreceptors 1 to 6 and C1 to C6, the wear amount (μm) of the surface layer after passing 50,000 sheets was confirmed. The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 101 Support body 102 Undercoat layer 103 Charge generation layer 104 Charge transport layer 105 Protective layer 1 Electrophotographic photosensitive member 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (9)

An electrophotographic photosensitive member having a surface layer containing a curable resin obtained by polymerizing a compound having a polymerizable functional group, wherein the surface layer contains a compound represented by the following general formula (1) An electrophotographic photoreceptor.

(In the general formula (1), Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group, provided that the substituent of the aryl group is an unsubstituted aryl group or an alkyl group-substituted aryl. Group, carboxy group substituted aryl group, cyano group substituted aryl group, hydroxy group substituted aryl group, nitro group substituted aryl group, fluorine atom substituted aryl group, chlorine atom substituted aryl group, bromine atom substituted aryl group , A hydroxy group, or a fluorine atom, n is an integer of 0 to 17.)   The electrophotographic photosensitive member according to claim 1, wherein n in the general formula (1) is 0, 1 or 2. The electrophotographic photoreceptor according to claim 1, wherein Ar ¹ and Ar ² in the general formula (1) are an unsubstituted fluorenyl group or an alkyl group-substituted fluorenyl group. The electrophotographic photosensitive member according to claim 1, wherein the compound having a polymerizable functional group is a compound represented by the following general formula (2).

(In General Formula (2), A ¹ represents a charge transporting group, P ¹ represents a group represented by the following General Formula (3), and m represents a positive integer.

(In general formula (3), Y ¹ represents a hydrogen atom or a methyl group.) A hydrogen adduct in which m in the general formula (2) is 2 and the site bonded to P ¹ of A ^{1 in} the general formula (2) is replaced with a hydrogen atom is represented by the following general formula (4). The electrophotographic photosensitive member according to claim 4, wherein the electrophotographic photosensitive member is a compound and the bonding site of A ¹ to P ¹ is present in any two of Ar ^{3 to} Ar ⁵ .

(In general formula (4), Ar ^{3 to} Ar ⁵ each independently represents an unsubstituted aryl group or an alkyl group-substituted aryl group.) A compound having a polymerizable functional group formed by using a coating liquid for a surface layer containing a compound having a polymerizable functional group and a compound represented by the following general formula (1), and having the polymerizable functional group contained in the applied film A method for producing an electrophotographic photosensitive member, comprising a step of forming a surface layer by polymerizing a surface layer.

(In the general formula (1), Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group, provided that the substituent of the aryl group is an unsubstituted aryl group or an alkyl group-substituted aryl. Group, carboxy group substituted aryl group, cyano group substituted aryl group, hydroxy group substituted aryl group, nitro group substituted aryl group, fluorine atom substituted aryl group, chlorine atom substituted aryl group, bromine atom substituted aryl group , A hydroxy group, or a fluorine atom, n is an integer of 0 to 17.)   The method for producing an electrophotographic photosensitive member according to claim 6, wherein the polymerization is performed by irradiating the coating film with an electron beam.   An electrophotographic photosensitive member according to any one of claims 1 to 5 and at least one means selected from the group consisting of a charging means, a developing means, a transfer means and a cleaning means are integrally supported, and an electrophotographic A process cartridge that is detachable from the main unit.   An electrophotographic apparatus comprising: the electrophotographic photosensitive member according to claim 1; and a charging unit, an exposure unit, a developing unit, and a transfer unit.

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