JP4630806B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. In particular, the present invention relates to an electrophotographic photosensitive member containing a compound obtained by polymerizing a specific hole transporting compound and a specific compound having an arylene ether group in a photosensitive layer, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. .

  Conventionally, inorganic materials such as selenium, cadmium sulfide and zinc oxide have been known as photoconductive materials used for electrophotographic photoreceptors. On the other hand, polyvinylcarbazole, phthalocyanine and azo pigments, which are organic materials, tend to be inferior in terms of photoconductive properties and durability compared to inorganic materials, but attention is paid to advantages such as high productivity and non-pollution properties. Has been widely used. These electrophotographic photoreceptors are often used as function-separated electrophotographic photoreceptors in which a charge generation layer and a charge transport layer are laminated in order to satisfy both electrical and mechanical properties.

  On the other hand, as a matter of course, the electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the applied electrophotographic process. In particular, in an electrophotographic photosensitive member that is repeatedly used, the surface of the electrophotographic photosensitive member is directly subjected to electrical and mechanical external forces such as charging, image exposure, toner development, transfer to paper, and cleaning treatment. Therefore, durability and stability against them are required. Specifically, durability against the occurrence of surface wear and scratches due to rubbing, surface degradation resistance against ozone and nitrogen oxides during charging, and the like are required.

  In general, the surface of the electrophotographic photosensitive member is a thin resin layer, and the characteristics of the resin are very important. In recent years, an acrylic resin, a polycarbonate resin, or the like has been selected as a resin that satisfies the above-described conditions to some extent, and has been widely put into practical use as a charge transport layer mixed with a charge transport material.

  However, since the surface layer as described above is a thermoplastic polymer, its mechanical strength is limited. In addition, since a large amount of a low-molecular charge transport material is contained for the purpose of satisfying the electrical characteristics, it is not sufficient in terms of wear resistance, and various studies have been made to overcome these problems.

  As an example, it is effective to use a curable resin as a surface protective layer (see, for example, Patent Documents 1 and 2). A surface layer using an ultraviolet curable resin and a thermosetting resin is disclosed, which shows improved durability. Among them, curable acrylic resins are used as various hard coats because of their high reactivity and high curing speed, and they have sufficient durability even when they are used for the surface layer of an electrophotographic photoreceptor. It is shown that it can be obtained (for example, refer to Patent Document 3).

  There is an attempt to use a curable resin as a resin for the charge transport layer (see, for example, Patent Document 4). As shown in this document, by hardening and crosslinking the charge transport layer using a curable resin as the resin for the charge transport layer, the mechanical strength is increased, and the abrasion resistance and scratch resistance during repeated use are improved. .

  In Patent Documents 5 and 6, a charge transport material having a carbon-carbon double bond is reacted with heat or light energy to be chemically bonded to a charge transport matrix, whereby the surface layer of the electrophotographic photosensitive member is mechanically bonded. Disclosed is a method for improving the mechanical strength. Furthermore, Patent Document 7 discloses a method for improving the mechanical strength of the surface layer of an electrophotographic photosensitive member by introducing a group having a charge transporting ability into a thermoplastic polymer chain.

  However, when the mechanical strength of the surface layer of the electrophotographic photosensitive member is increased and the abrasion resistance during repeated use is improved, the image flow under high humidity is caused by adhesion of charged products generated when the electrophotographic photosensitive member is charged. Is likely to occur. In order to prevent this image flow, Patent Document 8 discloses a method of adding an antioxidant to an electrophotographic photosensitive member. In addition, if the image forming apparatus is left for several hours after continuous use and then used further, the image of the portion corresponding to a part of the electrophotographic photosensitive member at the position of the charger as the charging means becomes darker than the surroundings. A phenomenon called black belt occurs. In particular, this phenomenon is particularly noticeable when the charging machine is a corona charger such as a corotron or scorotron that uses corona charging. In order to prevent the black belt under the charger, Patent Documents 9 and 10 disclose a method of adding an antioxidant to the electrophotographic photosensitive member.

A high-hardness surface layer having a compound obtained by polymerizing a hole transporting compound having a chain polymerization functional group has high mechanical strength. However, since the amount of abrasion generated after a certain period of use is small, an electrophotographic photosensitive member having a high hardness surface layer composed of a compound obtained by polymerizing a hole transporting compound having a chain polymerization functional group is an image as described above. Potentially has problems with flow and black under charger. As a means to prevent problems such as image flow and black belt under the charger, the conventional method of adding an antioxidant inhibits polymerization, so the degree of cure is lowered, and durability and life are reduced. ,There's a problem. Moreover, the phenomenon that the image flow is further deteriorated occurred, and the problem could not be solved.
JP-A-51-66834 JP-A 64-72167 JP-A 61-5253 JP-A-2-127852 JP-A-5-216249 Japanese Patent Laid-Open No. 7-72640 JP-A-8-248649 Japanese Patent Laid-Open No. 04-308551 JP 2001-356501 A JP 2002-072515 A JP 54-143645 A Tadahiro Miwa, “Chemistry of basic synthetic resins (new edition)” (Gihodo Publishing, July 25, 1995 (1st edition, 8th edition)) 24 pages

  The present invention has been made in view of the above-described problems, and has excellent durability and long life, and does not cause problems such as image flow under high humidity and black belt under a charger. It is an object to provide a body, a process cartridge, and an electrophotographic apparatus.

The present invention is an electrophotographic photosensitive member having a support and a photosensitive layer provided on the support, wherein the outermost surface layer of the electrophotographic photosensitive member includes the following compound (A) and the following compound (B An electrophotographic photoreceptor characterized in that it is a layer containing a polymer obtained by polymerizing
Compound (A): a hole transporting compound having two or more chain polymerizable functional groups in the same molecule;
Compound (B): Compound represented by the following structural formula (4)
(In Structural Formula (4), P represents a chain polymerizable reactive group. R ₄₀₁ and R ₄₀₂ each independently represents an organic residue that is not a monovalent hydroxyl group. P, q, r, and s are: The integer of 0-5 is shown, However, the sum of p and q and the sum of r and s are 2-5.)

The process cartridge and the electrophotographic apparatus according to the present invention include the above-described electrophotographic photosensitive member , charging means for charging the surface of the electrophotographic photosensitive member, and an electrostatic latent image formed on the surface of the electrophotographic photosensitive member. At least one means selected from the group consisting of developing means for developing with toner to form a toner image on the surface of the electrophotographic photosensitive member, and cleaning means for removing transfer residual toner on the surface of the electrophotographic photosensitive member Is a process cartridge that can be attached to and detached from the main body of the electrophotographic apparatus .
The present invention also provides an electrostatic latent image on the surface of the electrophotographic photosensitive member by exposing the surface of the electrophotographic photosensitive member to the above-described electrophotographic photosensitive member, charging means for charging the electrophotographic photosensitive member, and the surface of the charged electrophotographic photosensitive member. Exposure means for forming an image, developing means for developing an electrostatic latent image formed on the surface of the electrophotographic photosensitive member with toner to form a toner image on the surface of the electrophotographic photosensitive member, and electrophotographic photosensitive member An electrophotographic apparatus comprising transfer means for transferring a toner image formed on the surface of the toner image onto a transfer material.

  According to the present invention, in an electrophotographic photosensitive member having a highly curable, highly durable and long-life surface layer, the degree of curing is not impaired, and there is no problem of image flow or occurrence of a black belt under a charger, and it is highly durable and highly durable. An electrophotographic photosensitive member having an excellent lifetime can be provided.

  The electrophotographic photoreceptor according to the present invention has a structure in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated in this order on a conductive support, or a charge generation layer. The charge transport layer may be reversely laminated. Further, the electrophotographic photoreceptor according to the present invention may have a single layer structure in which a charge generation material and a charge transport material are dispersed in the same layer. In the former stacked type, the charge transporting layer may be composed of two or more layers. In the latter single layer type, a charge transport layer may be further formed on the photosensitive layer containing the charge generation material and the charge transport material in the same layer, and further on the charge generation layer or the charge transport layer. A protective layer may be formed.

Even when taking any configuration, the outermost layer of the electrophotographic photosensitive member according to the present invention is a layer having containing a polymer obtained by polymerizing the following compounds (A) and (B) Features.

Compound (A): a hole transporting compound having two or more chain polymerizable functional groups in the same molecule Compound (B): having a chain polymerizable functional group and an arylene ether group, having no hydroxyl group and having a chain at least it has a functional group represented by the following structural formula (1), and compounds having no hole transporting function between the polymerizable functional group and arylene ether groups
Details of the compound (A) and the compound (B) will be described later.

(In structural formula (1), v and w represent integers of 0 to 5. However, the sum of v and w is 2 to 5.)

(Support)
In the electrophotographic photoreceptor according to the present invention, the support may be any one having conductivity. For example, a metal or alloy such as aluminum, copper, chromium, nickel, zinc, and stainless steel formed into a drum shape or a sheet shape, or a metal foil such as aluminum and copper laminated on a plastic film may be used. In addition, examples include aluminum, indium oxide, tin oxide, and the like deposited on a plastic film, a metal, a plastic film, paper, and the like provided with a conductive layer by applying a conductive material alone or with a binder resin.

(Underlayer)
In the electrophotographic photoreceptor according to the present invention, an undercoat layer having a barrier function and an adhesive function may be provided between the support and the photosensitive layer. The undercoat layer is used to improve the adhesion of the photosensitive layer, improve coating properties, protect the support, cover defects on the support, improve charge injection from the support, and protect against electrical breakdown of the photosensitive layer. Formed.

  Examples of the material for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, and copolymer nylon. . In addition, glue and gelatin are listed. The undercoat layer is formed by applying a solution prepared by dissolving these materials in a solvent suitable for each of the materials onto a support and drying it. The film thickness is preferably 0.1 to 2 μm.

(Charge generation material, charge generation layer)
When the electrophotographic photoreceptor according to the present invention has a laminated photosensitive layer, the charge generation layer is composed of at least a charge generation material and a binder resin. Examples of the charge generating material include selenium-tellurium, pyrylium, thiapyrylium dyes, and various central metals and crystal systems. Specific examples include phthalocyanine compounds having crystal types such as α, β, γ, ε, and X type. Moreover, anthanthrone pigment, dibenzpyrenequinone pigment, pyranthrone pigment, trisazo pigment, disazo pigment, monoazo pigment, indigo pigment, quinacridone pigment, asymmetric quinocyanine pigment, quinocyanine and the like can be mentioned. Furthermore, the amorphous silicon etc. of patent document 11 are mentioned.

  Examples of the binder resin include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene. In addition, examples include polyvinyl alcohol, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin.

  As a method for producing the charge generation layer, first, the charge generation material described above, such as a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an adrider, and a roll mill, together with 0.3 to 4 times the amount of binder resin and solvent are used. Disperse well by method. The obtained dispersion is applied and dried, or formed as a single composition film such as a vapor-deposited film of a charge generating material. The film thickness is preferably 5 μm or less, and particularly preferably 0.1 to 2 μm.

(Charge transport material, charge transport layer)
In the electrophotographic photoreceptor according to the present invention, the above-mentioned compound (A) or an appropriate charge transporting material is used as the charge transporting material contained in the charge transporting layer constituting the laminated photosensitive layer or the single-layered photosensitive layer. Can do. Examples of suitable charge transporting materials include polymer compounds having a heterocyclic ring or condensed polycyclic aromatics such as poly-N-vinylcarbazole and polystyrylanthracene. In addition, heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole and carbazole, triarylalkane derivatives such as triphenylmethane, and triarylamine derivatives such as triphenylamine can be given. Furthermore, low molecular weight compounds such as phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, and hydrazine derivatives are exemplified. The charge transport layer is composed of these charge transport materials and a binder resin.

  As the binder resin, the binder resin mentioned in the above charge generation layer can be used. In the case of a single layer in which the charge generation material and the charge transport material are dispersed in the same layer, the charge generation material and the charge generation material are composed of a charge transport material, a charge generation material, and a binder resin.

As described above, the electrophotographic photosensitive member according to the present invention has the following compound (A) as the outermost surface layer, regardless of whether the photosensitive layer constituting the electrophotographic photosensitive member is a multilayer type or a single layer type. and wherein the compound (B) and the polymerization to obtain the polymer is a layer having free.

Compound (A): a hole transporting compound having two or more chain polymerizable functional groups in the same molecule Compound (B): having a chain polymerizable functional group and an arylene ether group, having no hydroxyl group and having a chain at least it has a functional group represented by the following structural formula (1), and compounds having no hole transporting function between the polymerizable functional group and arylene ether groups

(In structural formula (1), v and w represent integers of 0 to 5. However, the sum of v and w is 2 to 5.)

  In the present invention, the compound (A) means a compound having a hole transport function and having two or more chain polymerizable functional groups in the same molecule. The compound (A) preferably has a triarylamine structure in that it has a hole transport function. There are various structures exhibiting a hole transport function, but a triarylamine structure is most preferable in order to obtain the best effects of the present invention. In particular, a triphenylamine structure which is unsubstituted or substituted with a substituent other than a hydroxyl group is preferable.

  On the other hand, as the chain-polymerizable functional group, an optimal group may be selected from a functional group group capable of general addition reaction, condensation reaction, dehydration reaction, polymerization reaction, crosslinking reaction and the like. In particular, from the viewpoint of reaction efficiency and the like, a polymerization or crosslinkable reactive group is preferable. Examples of the polymerization or crosslinkable reactive group include chain polymerizable functional groups such as radical polymerization or ionic polymerization, sequential polymerizable functional groups such as addition condensation, polycondensation, and polyaddition. In particular, a chain polymerizable functional group is preferable from the viewpoint of reaction efficiency. Here, the chain polymerizable functional group will be described in detail.

  When the polymer formation reaction is largely divided into chain polymerization and sequential polymerization, in the present invention, chain polymerization refers to the former polymerization reaction mode. Specifically, for example, as described in Non-Patent Document 1, such as unsaturated polymerization, ring-opening polymerization and isomerization polymerization in which the reaction proceeds mainly via an intermediate such as a radical or an ion. That means. Here, specific examples of unsaturated polymerization or ring-opening polymerizable functional groups that occupy most of them and have a wide application range are shown.

  Unsaturated polymerization is a reaction in which unsaturated groups such as C═C, C≡C, C═O, C═N, and C≡N are polymerized by radicals, ions, etc., but mainly C═C. It is a reaction between each other. Specific examples of the unsaturated polymerizable functional group are shown in Table 1, but are not limited thereto.

Specific examples of unsaturated polymerizable functional groups

  In the table, R represents a substituted or unsubstituted alkyl group, aralkyl group, aryl group, or hydrogen atom. Examples of the substituted or unsubstituted alkyl group include substituted or unsubstituted products such as a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the substituted or unsubstituted aralkyl group include substituted or unsubstituted products such as a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, and a thienyl group. Examples of the substituted or unsubstituted aryl group include substituted or unsubstituted compounds such as a phenyl group, a naphthyl group, and an anthryl group.

  Ring-opening polymerization is a reaction in which unstable cyclic structures with distortions such as carbocycles, oxo rings, and nitrogen heterocycles are activated by the action of a catalyst, and at the same time, the polymerization is repeated to produce a chain polymer. Say. In this case, basically, most of the ions act as active species. Specific examples of the ring-opening polymerizable functional group are shown in Table 2, but are not limited thereto.

Specific examples of ring-opening polymerizable functional groups

  In the table, R is as defined in the unsaturated polymerizable functional group described above.

  In the present invention, the above compound (A) preferably has no hydroxyl group. When the compound (A) has a hydroxyl group, it is considered that there is a tendency to adsorb moisture in the atmosphere of the electrophotographic photosensitive member, and the effect of the present invention is small.

  Moreover, it is preferable that a compound (A) does not have an arylene ether group.

On the other hand, in the present invention, the above-mentioned compound (B) has a chain polymerizable functional group and an arylene ether group, has no hydroxyl group, and at least the following structure between the chain polymerizable functional group and the arylene ether group: having a functional group represented by the formula (1), and a compound having no hole transporting function.

(In structural formula (1), v and w represent an integer of 0 to 5. However, the sum of v and w is 2 to 5. )

  The compound (B) preferably has 2 to 4 arylene ether groups. When the number is less than 2, the effect of the present invention is reduced for the reason that the part of the structural formula (1) is considered to be difficult to cut. On the other hand, when the number exceeds four, the three-dimensional structure of the compound (B) with respect to the compound (A) becomes large, and as a result, the hole transport function becomes small, resulting in a detrimental effect that the sensitivity is lowered.

Compound (B) is preferably a Ru of compound represented by the following structural formula (2).

(In the structural formula (2), P is shows the chain polymerizable reactive group. X is n-valent (n is shows the organic residue of an integer of 2 to 4). _R 201 ~R _204, respectively independently, hydrogen atom, or, shows the monovalent hydroxyl group such have organic residues. v and w, is the sum of the. Here, v and w represent an integer of 0 to 5, at 2-5 Yes. )

The compound (B) is preferably a Ru of compound represented by the following structural formula (3).

(In the structural formula (3), P is shows the chain polymerizable reactive group. _R 301 _{to R 310} are independently a hydrogen atom, or, shows the monovalent hydroxyl group such have an organic residue . p, q, r and s represents an integer of 0 to 5. However, the sum of the sum and r and s of p and q is 2-5.)

Further, the compound (B) is preferably a Ru of compound represented by the following structural formula (4).

(In the structural formula (4), P is shows the chain polymerizable reactive group. _{R 401} and _{R 402} are each independently a have organic residues in a monovalent hydroxyl, p, q, r and s represents an integer of 0 to 5. However, the sum of p and q and the sum of r and s are 2 to 5. )

Incidentally, those examples of the organic residue as defined substituent X of shows the compounds by the above structural formula (2) to (4), is not particularly limited, except the n hydrogen atoms from an alkane or cycloalkane preferable. The organic residue as defined substituents _{R 401} and _{R 402} and _R 301 _{to R 310} of shown the compounds by the above structural formula (2) to (4), is not particularly limited, an alkyl group is preferable A methyl group is more preferable. Furthermore, the above-mentioned arylene ether group is preferably a phenylene ether group which is unsubstituted or substituted with a substituent other than a hydroxyl group.

  In any case, the outermost surface layer of the electrophotographic photosensitive member according to the present invention is preferably subjected to polymerization / crosslinking reaction after applying the solution containing the compound (A) and the compound (B). In particular, it is also possible to form a surface layer using a mixture or the like that is dispersed or dissolved in a solvent again after reacting a solution containing the compound (A) and the compound (B) in advance to obtain a cured product. is there.

  In the electrophotographic photoreceptor according to the present invention, when the layer corresponding to the outermost surface layer of the electrophotographic photoreceptor is a charge transport layer, the amount of the compound (A) used as the charge transport material is the amount of the cured charge transport layer. It is preferable that the hole transporting group is contained in an amount of 20% by mass or more based on the total mass. In particular, the content is more preferably 40% by mass or more. In addition, this positive hole transportable group means the thing corresponding to the compound obtained by substituting all the substituents which comprise a compound (A) with hydrogen. For example, when triarylamine is used as the compound (A), it means that all the substituents are replaced with hydrogen. When the hole transporting group is less than 20% by mass, the charge transporting ability is lowered, and problems such as a reduction in sensitivity and an increase in residual potential are likely to occur. The thickness of the charge transport layer is preferably 1 to 50 μm, and more preferably 3 to 30 μm.

  In this case, it is preferable that the mass of a compound (A) is 20-70 mass% with respect to both total mass, and it is more preferable that it is 25-60 mass%. When the amount of the compound (A) is less than 20% by mass, the charge transport ability is lowered, and problems such as a reduction in sensitivity and an increase in residual potential are likely to occur. On the other hand, when the amount of the compound (A) exceeds 70% by mass, the amount of the compound (B) is relatively small, and problems such as image flow under high humidity and a black belt under a charger are likely to occur. The total thickness of the charge transport layer combined with the upper surface protective layer is preferably 1 to 50 μm, and particularly preferably 5 to 30 μm.

Further, in the present invention, in the case of any of the above are also compounds (A) and (B) and a photosensitive layer having containing the resulting polymer by polymerizing a charge transport material other than the compound (A) May be included.

  When the photosensitive layer constituting the electrophotographic photoreceptor according to the present invention is a monolayer type photosensitive layer, it may be formed by polymerizing / crosslinking a solution containing the compound (A), the charge generating material and the compound (B). Good. Alternatively, it may be formed by applying a solution containing the compound (A) and the compound (B) on a monolayer type photosensitive layer having a charge generation material and a charge transport material, and then polymerizing / crosslinking.

  Although the example of the compound (A) in this invention is shown below, it is not limited to these.

  Moreover, although the example of the compound (B) in this invention is shown below, it is not limited to these.

(Additive)
The photosensitive layer constituting the electrophotographic photoreceptor according to the present invention may have various additives depending on the purpose.

  In addition to the outermost surface layer described above, examples of the method for applying the coating solution for each layer of the electrophotographic photoreceptor according to the present invention include a dip coating method, a spray coating method, a curtain coating method, and a spin coating method. Of these, the dip coating method is preferable from the viewpoint of efficiency / productivity. Also, vapor deposition, plasma, and other known film forming methods can be appropriately selected.

(polymerization)
In the present invention, as a method for polymerizing the above-mentioned additives, it is preferable to use high energy radiation such as heat, ultraviolet rays, γ rays, and electron beams, and a polymerization initiator may be used in some cases. However, the initiators may be appropriately selected so as not to adversely affect the electrophotographic characteristics. In particular, it is preferable to use a high energy beam such as an electron beam because it does not require an initiator and has a high polymerization efficiency.

(Thermal polymerization)
When carrying out the polymerization reaction with heat, there are cases where the polymerization reaction proceeds only with thermal energy and there are cases where a polymerization initiator is required, but in order to advance the reaction efficiently at a lower temperature, an initiator is added. It is preferable to do.

  The polymerization initiator used in this case may be any one having a half-life at room temperature or higher. Specific examples include peroxides such as ammonium persulfate, dicumyl peroxide, benzoyl peroxide, cyclohexane peroxide, t-butyl hydroperoxide and di-t-butyl peroxide, and azo such as azobisbutyronitrile. Compounds. The addition amount of the polymerization initiator is about 0.01 to 10 parts by mass with respect to 100 parts by mass of the compound having a chain polymerizable functional group, and the temperature of the reaction system is from room temperature to 200 ° C. depending on the initiator. You may select suitably between.

(Light (ultraviolet light) polymerization)
When the polymerization reaction is performed with ultraviolet rays, the reaction may proceed only with light energy, but generally a photopolymerization initiator is used in combination.

  In this case, the polymerization initiator mainly refers to an agent that absorbs ultraviolet rays having a wavelength of 400 nm or less to generate active species such as radicals and ions and starts polymerization. Specific examples include radical polymerization initiators such as acetophenone, benzoin, benzophenone, and thioxanthone, and ion polymerization initiators such as diazonium compounds, sulfonium compounds, iodonium compounds, and metal complex compounds. In recent years, a polymerization initiator that absorbs light in the infrared / visible region at a wavelength of 400 nm or more to generate the previous active species has been announced, and the polymerization reaction by light in the infrared / visible region is utilized using them. You may go. The addition amount of the initiator is about 0.01 to 50 parts by mass with respect to 100 parts by mass of the compound having a chain polymerizable functional group. In the present invention, the above-described heat and photopolymerization initiator may be used in combination.

(Process cartridge and electrophotographic apparatus)
Next, a process cartridge and an electrophotographic apparatus having the above-described electrophotographic photoreceptor according to the present invention will be described. FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus using a process cartridge having an electrophotographic photosensitive member according to the present invention. In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member according to the present invention, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. The electrophotographic photosensitive member 1, in the rotation process, positive or on the peripheral surface thereof by a static-unit 3 receives the uniform charging of a predetermined negative potential, then the slit exposure or laser beam scanning exposure or the like of an exposure unit (not shown) The exposure light 4 is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the electrophotographic photoreceptor 1 . When using a static-unit 3 as a scorotron or the corona charger such as a corotron, problems mentioned of the above-described problems are likely to occur. Therefore, the effect of the present invention is a band conductor means 3 obtained particularly pronounced in the case of the corona charger.

The electrostatic latent image thus formed is then developed with toner by the developing means 5. Thereafter, toner over image is generated, the paper feeding unit transferred has been fed in synchronism with the rotation of the electrophotographic photosensitive member 1 between the (not shown) between the electrophotographic photosensitive member 1 and the transfer means 6 material 7 Then, the images are sequentially transferred by the transfer means 6. The transfer material 7 that has received the image transfer is separated from the surface of the electrophotographic photosensitive member, introduced into the image fixing means 8, and subjected to image fixing, and printed out as a copy (copy).

The surface of the electrophotographic photosensitive member 1 after the image transfer is cleaned by removing the transfer residual toner by the cleaning unit 9, and is further subjected to charge removal processing by the pre-exposure light 10 from the pre-exposure unit (not shown). After that, it is repeatedly used for image formation. Incidentally, when the strip conductor means 3 is a contact charging means using a charging roller or the like, pre-exposure is not necessarily required.

The process cartridge according to the present invention, the electrophotographic photosensitive member 1 described above, strip conductor means 3, and integrally coupled to the one or more components of the components such as the developing means 5 and cleaning means 9 as a process cartridge structure do it. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, strip conductor means 3, and a cartridge integrally supported to form at least one with the electrophotographic photosensitive member 1 of the developing means 5 and cleaning means 9, the apparatus main body by using a guiding means 12 such as a rail of the electrophotographic apparatus body The process cartridge container 11 can be attached and detached.

  The exposure light 4 may be reflected light or transmitted light from an original when the electrophotographic apparatus is a copying machine or a printer. The exposure light 4 may be light emitted by reading a document with a sensor, converting it into a signal, scanning with a laser beam performed according to this signal, driving an LED array, driving a liquid crystal shutter array, and the like.

  The electrophotographic photosensitive member according to the present invention can be used not only for electrophotographic copying machines but also widely for electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making.

  Examples according to the present invention are illustrated below, but the present invention is not limited thereto. “Part” means “part by mass”.

( Reference Example 1)
A paint for the conductive layer was prepared by the following procedure. First, the following components were dispersed for 2 hours in a sand mill apparatus using φ1 mm glass beads to prepare a paint.

Conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide
50 parts phenol resin 25 parts methyl cellosolve 20 parts methanol 5 parts silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, weight average molecular weight 3000)
0.002 parts This coating material was applied on a φ30 mm aluminum cylinder by a dip coating method and dried at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 16 μm.

  Next, 5 parts of N-methoxymethylated nylon was dissolved in 95 parts of methanol to prepare an undercoat layer coating material. This paint was applied onto the above-mentioned conductive layer by a dip coating method and dried at 100 ° C. for 20 minutes to form a 0.5 μm undercoat layer.

  Next, 5 parts of the following (5), 2 parts of polyvinyl butyral resin, and 60 parts of cyclohexanone were dispersed for 24 hours in a sand mill apparatus using φ1 mm glass beads. To this, 60 parts of tetrahydrofuran was added to obtain a charge generation layer coating material. This paint was applied on the undercoat layer by the dip coating method and dried at 100 ° C. for 15 minutes to form a charge generation layer having a thickness of 0.25 μm.

  Subsequently, 6 parts of tetrafluoroethylene resin particles (Lublon L-2, manufactured by Daikin Industries) and 50 parts of monochlorobenzene were dispersed in a sand mill apparatus using glass beads. In this tetrafluoroethylene resin particle dispersion, Compound Example No. 30 parts of Compound No. 253, Compound Example No. 30 parts of compound 7 were added and dissolved. 30 parts of dichloromethane was added thereto to prepare a charge transport layer coating material.

  This paint is coated on the above-described charge generation layer by dip coating, and the resin is cured by irradiating with an electron beam under the conditions of an acceleration voltage of 150 kV and a dose of 24 Mrad to form a charge transport layer having a film thickness of 15 μm. A photoreceptor was obtained.

  The produced electrophotographic photoreceptor was evaluated for initial electrophotographic characteristics, images during repeated use, and images after standing for a certain period after repeated use. The initial electrophotographic characteristics and durability were evaluated by attaching this photoreceptor to Canon Inc. LBP-SX. The initial photoreceptor characteristics [dark part potential Vd, bright part potential Vl and residual potential Vsl (potential when a light amount 4.5 times the amount of exposure light was irradiated)] were measured in an environment of 33 ° C./87%. Further, in this environment, 1500 sheets per day were durable, and after 15 hours or more, 1500 sheets per day were durable on the next day, and this was repeated until a total of 15000 sheets was tested. It was. After leaving it for 15 hours, output an image and check for the occurrence of visual image defects (image flow, black under charger) according to the criteria of <image flow> and <black under charger> described below. Observed. Further, the amount of photoconductor scraping was measured. The results are shown in Table 96. The electrophotographic photosensitive member according to the present invention was good in both the characteristics of the photosensitive member and the image, the amount of shaving during durability was small, and the image flow and the black belt under the charger were not generated throughout the durability. In addition, the amount of chipping was measured using an eddy current film thickness measuring device (manufactured by FISCHER, PERMASCOPE TYPE E111). Thereafter, the same measurement was performed.

<Image flow>
The reproducibility of the character image and the image of the pattern in which one dot is arranged in a Keima-like pattern as shown in FIG. The best one was 11, the worst one was 0, and 4 or less considered that the effect of the present invention was not obtained.

<Black belt under charger>
The reproducibility of the character image and 1 dot image was evaluated in 12 stages of 11 to 0. The best one was 11, the worst one was 0, and 4 or less considered that the effect of the present invention was not obtained.

( Reference Examples 2-5)
In Reference Example 1, Compound Example No. 7 instead of 30 parts of the compound, Compound Example No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Reference Example 1 except that 30 parts of the compounds of 5, 6, 8 and 10 were used. The results are shown in Table 96.

( Reference Examples 6-8)
In Reference Example 1, Compound Example No. 7 instead of 30 parts of the compound, Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1, except that 30 parts of the compounds of 3, 9, and 12 were used. The results are shown in Table 96.

(Examples 9 to 10)
In Reference Example 1, Compound Example No. 7 instead of 30 parts of the compound, Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1 except that 30 parts of the compounds 13 and 14 were used. The results are shown in Table 96.

( Reference Examples 11-12)
In Reference Example 1, compound example No. of compound (A). An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1 except that 30 parts of the compounds of the following structural formulas (6) and (7) were used instead of 30 parts of the compound of 253. The results are shown in Table 96.

(Comparative Examples 1-5)
In Reference Example 1, Compound Example No. 7 instead of 30 parts of the compound, Compound Example No. An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1 except that 30 parts of the compounds 1 to 5 were used. The results are shown in Table 97.

1 shows an example of a schematic configuration of an electrophotographic apparatus using a process cartridge having an electrophotographic photosensitive member according to the present invention. It is a figure which shows the image pattern for demonstrating this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 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 container 12 Guide means

Claims (7)

An electrophotographic photosensitive member having a support and a photosensitive layer provided on the support, wherein the outermost surface layer of the electrophotographic photosensitive member polymerizes the following compound (A) and the following compound (B): An electrophotographic photosensitive member characterized by being a layer containing a polymer obtained by:
Compound (A): a hole transporting compound having two or more chain polymerizable functional groups in the same molecule;
Compound (B): Compound represented by the following structural formula (4)
(In Structural Formula (4), P represents a chain polymerizable reactive group. R ₄₀₁ and R ₄₀₂ each independently represents an organic residue that is not a monovalent hydroxyl group. P, q, r, and s are: The integer of 0-5 is shown, However, the sum of p and q and the sum of r and s are 2-5.) The electrophotographic photosensitive member according to claim 1, wherein the compound (A) is a compound having no hydroxyl group. The compound (A), an electrophotographic photosensitive member according to claim 1 or 2 which is a compound having no arylene ether group. The compound (A), an electrophotographic photosensitive member according to any one of claims 1 to 3 which is a compound having a triarylamine structure. Polymerization of the The electrophotographic photosensitive member according to any one of claims 1 to 4 which is carried out the polymerization by irradiation with an electron beam. In an electrophotographic photosensitive member according to any one of claims 1 to 5, a charging means for charging the surface of the electrophotographic photosensitive member, an electrostatic latent image formed on the surface of the electrophotographic photoconductor toner Developing means for developing and forming a toner image on the surface of the electrophotographic photosensitive member; and at least one means selected from the group consisting of cleaning means for removing residual toner on the surface of the electrophotographic photosensitive member. A process cartridge which is integrally supported and detachable from an electrophotographic apparatus main body. The electrophotographic photosensitive member according to any one of claims 1 to 5, a charging means for charging the electrophotographic photoreceptor, the electrophotographic photosensitive member is subjected to exposure with respect to the charged surface of the electrophotographic photosensitive member Exposure means for forming an electrostatic latent image on the surface, developing means for developing the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with toner to form a toner image on the surface of the electrophotographic photosensitive member, and An electrophotographic apparatus comprising transfer means for transferring a toner image formed on the surface of an electrophotographic photosensitive member to a transfer material.