JP2007086522A - Electrophotographic photoreceptor, and process cartridge and electrophotographic apparatus having the electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor excellent in mechanical strength and electric characteristics and capable of forming a stable image over a long period of time. <P>SOLUTION: The electrophotographic photoreceptor has, in particular, a first charge transport layer and a second charge transport layer in this order with the second charge transport layer as the outermost surface layer. The second charge transport layer contains a compound that is obtained by carrying out either polymerization or crosslinking or both of them on a curable charge transport compound expressed by general formula (1) and a curable compound having no charge transport property; and the charge transport component included in the second charge transport layer satisfies conditions expressed by K=L/M and K<0.95, wherein L represents a concentration of the charge transport component present from the surface of the electrophotographic photoreceptor to the depth at 40% of the film thickness of the second charge transport layer, M represents a concentration of the charge transport component present from the interface between the first charge transport layer and the second charge transport layer to the depth at 40% of the film thickness of the second charge transport layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrophotographic photosensitive member having a curable surface protective layer in which a charge transport component is distributed by continuous or stepwise concentration change. The present invention also relates to a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  In recent years, organic photoconductive substances having advantages such as pollution-free and high productivity have been widely used as materials used for electrophotographic photoreceptors. These electrophotographic photoreceptors are often used as function-separated 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, since various electric and mechanical external forces such as charging, exposure, toner development, transfer to paper and cleaning are directly applied to the surface layer of the photoreceptor to be used repeatedly, durability against them is required. .

  Specifically, sensitivity and potential decrease and residual potential increase due to degradation by active substances such as ozone, NOx, and nitric acid generated during charging. In addition, the surface is worn or scratched by rubbing. Durability against these is required.

As a means for solving these problems, for example, a photosensitivity containing a cured product of a charge transporting compound having a chain polymerizable functional group in the same molecule as disclosed in Patent Document 1 in the outermost surface layer. The body has been reported. By using such a curable film having charge transportability, it is theoretically possible to achieve both excellent mechanical strength and charge transport ability. However, since the curable film having the above-described charge transporting property is difficult to create a new surface due to abrasion due to its excellent mechanical strength, electrical deterioration is accumulated and a stable image can be provided over a long period of time. However, it is still difficult to get the full performance.
JP 2000-147813 A

  An object of the present invention is to provide an electrophotographic photoreceptor excellent in mechanical strength and electrical characteristics and capable of forming a stable image over a long period of time, and a process cartridge and an electrophotographic apparatus having the child photographic photoreceptor.

  As a result of intensive studies, the present inventors have found that the distribution of the charge transport component present in the curable surface protective layer under a specific condition solves the above-described problem.

That is, the present invention provides an electrophotographic photosensitive member having at least a charge generation layer, a first charge transport layer, and a second charge transport layer in this order on a conductive support, wherein the second charge transport layer is the outermost surface layer. The second charge transport layer is formed by polymerizing and / or crosslinking a curable charge transport compound represented by the following general formula (1) and a curable compound having no charge transport property. An electrophotographic photosensitive member characterized in that the charge transport component contained in the second charge transport layer contains the resulting compound and satisfies the following conditions.
K = L / M and K <0.95
(In the formula, L represents the concentration of the charge transport component existing from the surface of the electrophotographic photosensitive member to a depth of 40% of the thickness of the second charge transport layer, and M represents the first charge transport layer and the second charge transport layer). The concentration of the charge transport component existing from the interface of the transport layer to a depth of 40% of the thickness of the second charge transport layer is indicated in the compound represented by the following general formula (1). Of triphenylamine.)

(In the formula, A represents a charge transporting group having a triphenylamine skeleton, P ¹ and P ² represent a chain polymerizable functional group, Z represents an organic group which may have a substituent, a, b and d represent 0 or an integer of 1 or more, and a + b × d represents an integer of 1 or more, P ¹ and P ² may be the same or different, and when a is 2 or more, P ¹ may be the same And may be different. When d is 2 or more, P ² may be the same or different. When b is 2 or more, Z and P ² may be the same or different.

  The present invention also provides a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  According to the present invention, an electrophotographic photosensitive member having excellent mechanical strength and electrical characteristics can be produced, and a stable image can be continuously formed over a long period of time. In addition, according to the present invention, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member can be provided.

  Details of the present invention will be described below.

  In the present invention, the second charge transport layer of the electrophotographic photosensitive member having at least the charge generation layer, the first charge transport layer, and the second charge transport layer in this order on the conductive support is composed of a curable charge transport compound and a charge transport. Containing a compound obtained by polymerizing and / or cross-linking a curable compound having no property, and further containing a charge transport component contained in the second charge transport layer under specific distribution conditions It exists in.

  Here, the curable charge transport compound in the present invention refers to a compound in which at least one chain polymerizable functional group is chemically bonded to the charge transport compound as a functional group. In this case, all the chain-polymerizable functional groups may be the same or different, and the following general formula (1) is preferable.

(In the formula, A represents a charge transporting group having a triphenylamine skeleton, P ¹ and P ² represent a chain polymerizable functional group, Z represents an organic group which may have a substituent, a, b and d represent 0 or an integer of 1 or more, and a + b × d represents an integer of 1 or more, P ¹ and P ² may be the same or different, and when a is 2 or more, P ¹ may be the same And may be different. When d is 2 or more, P ² may be the same or different. When b is 2 or more, Z and P ² may be the same or different.

In addition, the chain polymerizable functional groups P ¹ and P ² in the general formula (1) can undergo unsaturated polymerization, ring-opening polymerization, isomerization polymerization, etc. in which the reaction proceeds via an intermediate such as a radical or an ion. An acrylic group and a methacryl group are particularly preferable from the viewpoint of polymerization characteristics and the like.

  The hole transporting group A in the general formula (1) may be any one as long as it has a triphenylamine skeleton and exhibits hole transporting properties.

  Hereinafter, typical examples of the curable charge transport compound and the curable compound having no charge transport property relating to the second charge transport layer of the present invention are listed in Table 1, but the present invention is not limited thereto. Among these, No. 1 to 13 are curable charge transport compounds represented by the general formula (1).

  Next, the charge transport component in the present invention refers to triphenylamine in the structure represented by the hole transporting group A. Depending on the structure of the hole transporting group A, there may be a plurality of triphenylamines. In such a case, all triphenylamines are regarded as charge transporting components. For example, Compound Example Nos. In the case of No. 2, the charge transport component is one triphenylamine. In case 3, the charge transport component is two triphenylamines.

  The second charge transport layer of the electrophotographic photosensitive member in the present invention is formed in a very short time and thus has high productivity, has a three-dimensional cross-linked structure, and has excellent mechanical strength after curing, and charge transport. Since it contains a component, it is characterized by excellent electrical characteristics.

  However, the second charge transport layer is difficult to create a new surface due to abrasion due to its excellent mechanical strength, and as a result, the charge transport component existing in the vicinity of the surface deteriorates due to charging and is accumulated without being eliminated. Especially when used continuously in a high temperature and high humidity environment, problems such as image flow may occur, and the mechanical properties are excellent, but the original electrical characteristics are fully exploited. It has not reached.

  However, it is possible to improve mechanical strength and electrical characteristics by distributing the charge transport component of the second charge transport layer described above so that the concentration on the surface side is lower than that on the support side. The reason has not yet been clarified, but in the charging process at the time of image formation, the charge transport component deteriorates mainly due to discharge, so the concentration of the charge transport component near the surface is reduced within a range that does not impair the electrophotographic characteristics. Thus, it is presumed that electrical deterioration can be suppressed to a minimum, and at the same time, the mechanical strength is improved because the plastic action is reduced. Furthermore, it is presumed that the charge transport property is improved by the high concentration distribution of the charge transport component in the vicinity of the interface between the first charge transport layer and the second charge transport layer, which contributes to the improvement of electrical characteristics.

  Next, a method for producing an electrophotographic photoreceptor according to the present invention will be specifically described.

  The electrophotographic photosensitive member may have any conductivity, such as aluminum, copper, chromium, nickel, zinc and stainless steel or alloy formed into a drum or sheet, aluminum, copper, etc. Metal foil laminated with plastic film, aluminum, indium oxide and tin oxide deposited on plastic film, metal with conductive layer applied alone or with binder resin, and plastic film And paper.

  In the present invention, an undercoat layer having a barrier function and an adhesive function can be provided on the conductive support.

  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 the photosensitive layer from electrical breakdown. Formed. Materials for the undercoat layer include polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, glue and gelatin. It has been known. These are dissolved in a solvent suitable for each and coated on a support. The film thickness at that time is preferably 0.1 to 2 μm. When the photoreceptor of the present invention is a function separation type photoreceptor, a charge generation layer and a charge transport layer are laminated. Examples of the charge generation material used in the charge generation layer include selenium-tellurium, pyrylium, thiapyrylium dyes, various central metals and crystal systems, specifically, crystal types such as α, β, γ, ε, and X types. Examples include phthalocyanine compounds, anthanthrone pigments, dibenzpyrenequinone pigments, pyranthrone pigments, trisazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanines, and amorphous silicones described in JP-A No. 54-143645. It is done.

  In the case of a function-separated type photoreceptor, the charge generation layer comprises the charge generation material 0.3 to 4 times the amount of binder resin and solvent on a mass basis, a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor, and the like. It is well dispersed by a method such as a roll mill, and is formed by applying a dispersion and drying, or formed as a single composition film such as a vapor deposition film of the charge generation material. The film thickness is preferably 5 μm or less, and particularly preferably in the range of 0.1 to 2 μm.

  Examples of using binder resins are polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, trifluoroethylene, polyvinyl alcohol, polyvinyl acetal. , Polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, epoxy resin and the like.

  In the present invention, the second charge transport layer is generally formed by applying a polymerization reaction after applying a solution containing a curable charge transport compound and a curable compound having no charge transport property, It is also possible to form the second charge transport layer by using a solution obtained by reacting the solution in advance to obtain a cured product and then again dispersing or dissolving in a solvent. As a method for applying these solutions, for example, dip coating, spray coating, curtain coating, spin coating, and the like are known. In order to distribute charge transporting components under specific conditions as in the present invention, spray coating is used. Although the method is most desirable, other film forming methods can be selected as appropriate.

  The coating solution for the second charge transport layer in the present invention can be polymerized by heat, light and radiation, and it is particularly preferable to polymerize by radiation. The greatest advantage of polymerization by radiation is that a polymerization initiator is not required, and the influence on the electrophotographic characteristics due to this can be eliminated. In addition, because it is an efficient polymerization reaction in a short time, productivity is also high, and furthermore, because of its good radiation permeability, it inhibits curing when a thick film or a shielding substance such as an additive is present in the film. The impact is very small. However, depending on the type of the central skeleton having the charge transporting property, the polymerization reaction may not easily proceed, and in this case, it is possible to add the polymerization initiator within a range that does not affect the polymerization reaction. The radiation used at this time is an electron beam and a γ-ray. When an electron beam is used, any type of accelerator such as a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type can be used. When an electron beam is used, the use conditions are very important in the photoreceptor of the present invention in order to develop electric characteristics and durability. In the present invention, the acceleration voltage is preferably 250 KV or less, and optimally 150 KV or less. The dose of the electron beam is preferably 200 kGy or less, more preferably 100 kGy or less. When the acceleration voltage of the electron beam exceeds the above, damage to the photoreceptor characteristics tends to increase. Also, when the electron beam dose is larger than the above range, care must be taken because the characteristics of the photoreceptor are liable to deteriorate.

  The first charge transport layer, which is the lower layer of the second charge transport layer, is a suitable charge transport material such as a polymer compound having a heterocyclic ring or condensed polycyclic aromatic compound such as poly-N-vinylcarbazole or polystyrylanthracene, or pyrazoline. , Heterocyclic compounds such as imidazole, oxazole, triazole, carbazole, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, hydrazone derivatives, etc. A solution in which a low molecular weight compound is dispersed / dissolved in a solvent together with a suitable binder resin (which can be selected from the aforementioned resin for charge generation layer) can be applied and dried by the above-mentioned known methods. In this case, the ratio of the charge transport material to the binder resin is preferably selected in the range of 30 to 100, preferably 50 to 100, when the total mass of both is 100. If the amount of the charge transport material is less than that, the charge transport ability is lowered, and problems such as a decrease in sensitivity and an increase in residual potential occur. The film thickness of the first charge transport layer is determined so that the total film thickness combined with the second charge transport layer on the upper layer is 1 to 50 μm, and is preferably adjusted in the range of 5 to 30 μm.

The charge transport component contained in the second charge transport layer must be distributed so as to satisfy the following conditions.
K = L / M and K <0.95
(In the formula, L represents the concentration of the charge transport component existing from the surface of the electrophotographic photosensitive member to a depth of 40% of the film thickness of the second charge transport layer, and M represents the charge transport layer and the second charge transport layer. The concentration of the charge transport component existing from the interface to the depth of 40% of the film thickness of the second charge transport layer is represented by triphenyl in the charge transport group in the curable charge transport compound. Means amine.)

In a distribution state that does not satisfy this condition, the plastic effect is not reduced, and the effect of suppressing electrical deterioration due to the charging process is insufficient, and it is difficult to provide a stable image over a long period of time. Further, it is desirable that the distribution is made so as to satisfy the following condition.
K = L / M and 0.25 <K <0.80

  Furthermore, various additives can be added to the photosensitive layer in the present invention as required. The additives include antioxidants, polymerization inhibitors, deterioration inhibitors such as UV absorbers and halogen compounds, lubricants such as tetrafluoroethylene resin and fluorocarbon, monofunctional or polyfunctional chain polymerizable functional groups. Examples thereof include a curability-imparting agent such as a polymerizable monomer having, a thermoplastic resin, a known charge transport compound, and a known charge generating substance.

  FIG. 1 schematically shows an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. In the figure, reference numeral 1 denotes an electrophotographic photosensitive member of the present invention on a drum, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. In the rotating process, the photosensitive member 1 is uniformly charged at a predetermined positive or negative potential on its peripheral surface by the primary charging unit 3, and then an image from an image exposure unit (not shown) such as slit exposure or laser beam scanning exposure. Exposure light 4 is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the photoreceptor 1. The formed electrostatic latent image is then developed with toner by the developing means 5, and the developed toner developed image is taken out in synchronization with the rotation of the photosensitive member 1 from a paper feeding unit (not shown) and fed onto the transfer 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 photosensitive member, introduced into the image fixing means 8, and subjected to image fixing, thereby being printed out as a copy (copy). After the image transfer, the surface of the photoreceptor 1 is cleaned by removing the transfer residual toner by the cleaning unit 9, and is further subjected to a charge removal process by the pre-exposure light 10 from the pre-exposure unit (not shown), and then repeatedly. Used for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary. In the present invention, a plurality of components such as the above-described electrophotographic photosensitive member 1, primary charging unit 3, developing unit 5, and cleaning unit 9 are integrally coupled as a 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, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, and can be attached to and detached from the apparatus main body using guide means such as a rail 12 of the apparatus main body. The process cartridge 11 can be obtained. Further, when the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is a reflected light or transmitted light from a document, or a signal is read by a sensor and converted into a signal, and a laser beam scanning performed according to this signal is performed. The light is emitted by driving the LED array and the liquid crystal shutter array.

  The electrophotographic photosensitive member of the present invention is not only used in electrophotographic copying machines but also widely used in electrophotographic application fields such as laser printers, CRT printers, LED printers, liquid crystal printers, facsimiles, and electrophotographic plate making systems. Can do.

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

  The following examples further illustrate the present invention. In the examples, “parts” represents parts by mass.

[Example 1]
First, a coating material for the conductive layer was prepared by the following procedure. 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide (mass parts, hereinafter the same), phenol resin 25 parts, methyl cellosolve 20 parts, methanol 5 parts and silicone compound (polydimethylsiloxane poly) An oxyalkylene copolymer (average molecular weight 3000) 0.002 part was prepared by dispersing for 2 hours in a sand mill using φ1 mm glass beads. This paint was applied on a φ30 mm aluminum cylinder by a dip coating method and dried at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 18 μm.

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

  Next, 3 parts of oxytitanium phthalocyanine having strong peaks at 9.0 degrees, 14.2, 23.9 degrees, and 27.1 degrees of black angle 2θ ± 0.2 degrees in CuKα characteristic X-ray diffraction , 3.5 parts of polyvinyl butyral (trade name S-REC BM2, manufactured by Sekisui Chemical Co., Ltd.) and 35 parts of cyclohexanone are dispersed for 2 hours in a sand mill using φ1 mm glass beads, and then 60 parts of ethyl acetate. Was added to prepare a charge generation layer coating material. This paint was applied on the intermediate layer by a dip coating method and dried at 90 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm.

  Next, 20 parts of a charge transport compound represented by the following structural formula,

And a polycarbonate resin having a repeating unit represented by the following structural formula (number average molecular weight 20000)

A first charge transport layer was formed on the charge generation layer using a coating solution prepared by dissolving 10 parts in a mixed solvent of 50 parts monochlorobenzene and 20 parts dichloromethane. At this time, the thickness of the first charge transport layer was 15 μm.

Next, 1.25 parts of fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) as a dispersant was added to 1,1,2,2,3,3,4-heptafluorocyclopentane. (Product name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) 37.5 parts and 1-propanol 37.5 parts, and then dissolved in tetrafluoroethylene resin powder (trade name: Lubron L-2, Daikin Industries, Ltd. (25 parts) was added, and a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA) was subjected to 3 treatments at a pressure of 5880 N / cm ² and uniformly dispersed. . This was subjected to pressure filtration with a 10 μm PTFE membrane filter to prepare a lubricant dispersion.

  Next, the following five types of paints were prepared.

  (1-1) Compound Example Nos. No. 4 curable charge transport compound, 30 parts; 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (1-1).

  (1-2) Compound Example Nos. No. 4 curable charge transport compound 25 parts, Compound Example No. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating liquid (1-2).

  (1-3) Compound Example Nos. No. 4 curable charge transport compound 15 parts, Compound Example No. 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (1-3).

  (1-4) Compound Example Nos. No. 4 curable charge transport compound, 7 parts; 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (1-4).

  (1-5) Compound Example Nos. No. 4 curable charge transport compound 5 parts, Compound Example No. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (1-5).

  After applying the coating liquids (1-1) to (1-5) described above on the first charge transport layer in this order by the spray coating method so that the film thickness of each layer is 1.0 μm, in nitrogen Curing was carried out under the conditions of an acceleration voltage of 150 kV and an electron beam dose of 50 kGy, and subsequently a heat treatment was carried out for 90 seconds under the condition that the temperature of the photoreceptor was 120 ° C. The oxygen concentration at this time was 10 ppm. Furthermore, the photoconductor was heat-treated for 20 minutes in a hot air drier adjusted to 100 ° C. in the atmosphere to form a second charge transport layer having a thickness of 5 μm, thereby preparing the photoconductor (1).

  The photoconductor (1) is mounted on a laser beam printer (LASER SHOT LBP-930: manufactured by Canon Inc.) modified so that the light amount and the charge setting can be changed, and in a high temperature and high humidity environment (32 ° C./85% RH) (H / H), continuous 15,000 sheets were passed through, and the presence or absence of visual image defects was observed. Furthermore, the film thickness of the electrophotographic photoreceptor was measured using an overcurrent film thickness meter (manufactured by Karl Fischer). And measured. The modified machine in the paper passing durability test was set to transfer current: +5.5 μA and process speed: 106 mm / sec. Further, the photodischarge characteristics were measured before and after the paper passing durability test, and the initial value and the amount of fluctuation (ΔVl) of Vr after the paper passing durability test were calculated. The results are shown in Table 2.

  From these results, the photoreceptor (1) has high mechanical strength in a continuous paper passing durability test in a high temperature and high humidity environment, does not cause image defects such as image flow, and does not change potential before and after continuous use. Since it was extremely small, it became clear that a clear image was stably obtained over a long period of time and had excellent electrical characteristics and mechanical strength.

[Example 2]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were performed in the same manner as in Example 1.

  Next, the following five types of paints were prepared.

  (2-1) Compound Example Nos. No. 4 curable charge transport compound, 30 parts; 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (2-1).

  (2-2) Compound Example Nos. No. 4 curable charge transport compound, no. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (2-2).

  (2-3) Compound Example Nos. No. 4 curable charge transport compound 15 parts, Compound Example No. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After the parts were mixed and stirred, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (2-3).

  (2-4) Compound Example Nos. No. 4 curable charge transport compound, 10 parts; 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (2-4).

  (2-5) Compound Example Nos. No. 4 curable charge transport compound 5 parts, Compound Example No. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (2-5).

  After coating the coating liquids (2-1) to (2-5) described above on the first charge transport layer in this order by the spray coating method so that the film thickness of each layer becomes 1.0 μm, in nitrogen Curing was carried out under the conditions of an acceleration voltage of 150 kV and an electron beam dose of 50 kGy, and subsequently a heat treatment was carried out for 90 seconds under the condition that the temperature of the photoreceptor was 120 ° C. The oxygen concentration at this time was 10 ppm. Furthermore, the photoconductor was heat-treated in a hot air dryer adjusted to 100 ° C. in the atmosphere for 20 minutes to form a second charge transport layer having a thickness of 5 μm, and the photoconductor (2) was prepared and carried out. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[Example 3]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were performed in the same manner as in Example 1.

  Next, the following five types of paints were prepared.

  (3-1) Compound Example Nos. No. 4 curable charge transport compound, 30 parts; 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (3-1).

  (3-2) Compound Example Nos. No. 4 curable charge transport compound 25 parts, Compound Example No. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (3-2).

  (3-3) Compound Example Nos. No. 4 curable charge transport compound, no. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (3-3).

  (3-4) Compound Example Nos. No. 4 curable charge transport compound 15 parts, Compound Example No. 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (3-4).

  (3-5) Compound Example Nos. No. 4 curable charge transport compound, 10 parts; 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (3-5).

  After applying the coating liquids (3-1) to (3-5) described above on the first charge transport layer in this order by the spray coating method so that the film thickness of each layer becomes 1.0 μm, in nitrogen Curing was carried out under the conditions of an acceleration voltage of 150 kV and an electron beam dose of 50 kGy, and subsequently a heat treatment was carried out for 90 seconds under the condition that the temperature of the photoreceptor was 120 ° C. The oxygen concentration at this time was 10 ppm. Further, the photoconductor was heated in the air at 100 ° C. in a hot air dryer for 20 minutes to form a second charge transport layer having a thickness of 5 μm, and the photoconductor (3) was prepared and carried out. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[Example 4]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were performed in the same manner as in Example 1.

  Next, the following five types of paints were prepared.

  (4-1) Compound Example Nos. No. 4 curable charge transport compound, 30 parts; 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (4-1).

  (4-2) Compound Example Nos. No. 4 curable charge transport compound 28 parts, Compound Example No. 14 parts of a curable compound having no charge transporting property, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (4-2).

  (4-3) Compound Example Nos. No. 4 curable charge transport compound 25 parts, Compound Example No. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (4-3).

  (4-4) Compound Example Nos. No. 4 curable charge transport compound, 22 parts; 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (4-4).

  (4-5) Compound Example Nos. No. 4 curable charge transport compound, no. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (4-5).

  After applying the coating liquids (4-1) to (4-5) described above on the first charge transport layer in this order by the spray coating method so that the film thickness of each layer becomes 1.0 μm, in nitrogen Curing was carried out under the conditions of an acceleration voltage of 150 kV and an electron beam dose of 50 kGy, and subsequently a heat treatment was carried out for 90 seconds under the condition that the temperature of the photoreceptor was 120 ° C. The oxygen concentration at this time was 10 ppm. Furthermore, the photoconductor was heat-treated in a hot air dryer adjusted to 100 ° C. in the atmosphere for 20 minutes to form a second charge transport layer having a film thickness of 5 μm, and a photoconductor (4) was prepared and carried out. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[Example 5]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were performed in the same manner as in Example 1.

  Next, the following five types of paints were prepared.

  (5-1) Compound Example Nos. No. 4 curable charge transport compound, 30 parts; 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (5-1).

  (5-2) Compound Example Nos. No. 4 curable charge transport compound 29 parts, Compound Example No. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (5-2).

  (5-3) Compound Example Nos. No. 4 curable charge transport compound 28 parts, Compound Example No. 14 parts of a curable compound having no charge transporting property, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (5-3).

  (5-4) Compound Example Nos. No. 4 curable charge transport compound 27 parts, Compound Example No. 14 parts of curable compound having no charge transport property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (5-4).

  (5-5) Compound Example Nos. No. 4 curable charge transport compound 26 parts, Compound Example No. 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After the parts were mixed and stirred, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (5-5).

  After applying the coating liquids (5-1) to (5-5) described above on the first charge transport layer in this order by the spray coating method so that the thickness of each layer becomes 1.0 μm, in nitrogen Curing was carried out under the conditions of an acceleration voltage of 150 kV and an electron beam dose of 50 kGy, and subsequently a heat treatment was carried out for 90 seconds under the condition that the temperature of the photoreceptor was 120 ° C. The oxygen concentration at this time was 10 ppm. Furthermore, the photoconductor was heat-treated in a hot air dryer adjusted to 100 ° C. in the atmosphere for 20 minutes to form a second charge transport layer having a film thickness of 5 μm, and a photoconductor (5) was prepared and carried out. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[Example 6]
The curable charge transport compound of Example 1 was identified as Compound Example No. 1 in Table 1. A photoconductor (6) was prepared and evaluated in the same manner as in Example 1 except that the curable charge transport compound was changed to 10. The results are shown in Table 2.

[Example 7]
The curable charge transport compound of Example 2 was identified as Compound Example No. 1 in Table 1. A photoconductor (7) was prepared and evaluated in the same manner as in Example 2 except that the curable charge transport compound was changed to 10. The results are shown in Table 2.

[Example 8]
The curable charge transport compound of Example 3 was identified as Compound Example No. 1 in Table 1. A photoconductor (8) was prepared and evaluated in the same manner as in Example 3 except that the curable charge transport compound was changed to 10. The results are shown in Table 2.

[Example 9]
The curable charge transport compound of Example 4 was identified as Compound Example No. 1 in Table 1. A photoconductor (9) was prepared and evaluated in the same manner as in Example 4 except that the curable charge transport compound was changed to 10. The results are shown in Table 2.

[Example 10]
The curable charge transport compound of Example 5 was identified as Compound Example No. 1 in Table 1. A photoconductor (10) was prepared and evaluated in the same manner as in Example 5 except that the curable charge transport compound was changed to 10. The results are shown in Table 2.

[Example 11]
The curable charge transport compound of Example 1 and the curable compound having no charge transport property are designated as Compound Example No. 1 in Table 1. 2 and Compound Example No. A photoconductor (11) was prepared and evaluated in the same manner as in Example 1 except that the number was changed to 16. The results are shown in Table 2.

[Example 12]
The curable charge transport compound of Example 2 and the curable compound having no charge transport property are shown in Compound Example No. 1 in Table 1. 2 and Compound Example No. A photoconductor (12) was prepared and evaluated in the same manner as in Example 2 except for changing to 16 respectively. The results are shown in Table 2.

[Example 13]
The curable charge transport compound of Example 3 and the curable compound having no charge transport property are shown in Compound Example No. 1 in Table 1. 2 and Compound Example No. A photoconductor (13) was prepared and evaluated in the same manner as in Example 3 except for changing to 16 respectively. The results are shown in Table 2.

[Example 14]
The curable charge transport compound of Example 4 and the curable compound having no charge transport property are shown in Compound Example No. 1 in Table 1. 2 and Compound Example No. A photoconductor (14) was prepared and evaluated in the same manner as in Example 4 except for changing to 16 respectively. The results are shown in Table 2.

[Example 15]
The curable charge transport compound of Example 5 and the curable compound having no charge transport property are shown in Compound Example No. 1 in Table 1. 2 and Compound Example No. A photoconductor (15) was prepared and evaluated in the same manner as in Example 5 except that each was changed to 16. The results are shown in Table 2.

[Example 16]
The curable charge transport compound of Example 11 was converted to Compound Example No. 1 in Table 1. A photoconductor (16) was prepared and evaluated in the same manner as in Example 11 except for changing to 7. The results are shown in Table 2.

[Example 17]
The curable charge transport compound of Example 12 was identified as Compound Example No. 1 in Table 1. A photoconductor (17) was prepared and evaluated in the same manner as in Example 12 except for changing to 7. The results are shown in Table 2.

[Example 18]
The curable charge transport compound of Example 13 was identified as Compound Example No. 1 in Table 1. A photoconductor (18) was prepared and evaluated in the same manner as in Example 13 except for changing to 7. The results are shown in Table 2.

[Example 19]
The curable charge transport compound of Example 14 was identified as Compound Example No. 1 in Table 1. A photoconductor (19) was prepared and evaluated in the same manner as in Example 14 except for changing to 7. The results are shown in Table 2.

[Example 20]
The curable charge transport compound of Example 15 was designated as Compound Example No. 1 in Table 1. A photoconductor (20) was prepared and evaluated in the same manner as in Example 15 except for changing to 7. The results are shown in Table 2.

[Example 21]
The curable charge transport compound of Example 18 was identified as Compound Example No. 1 in Table 1. A photoconductor (21) was prepared and evaluated in the same manner as in Example 18 except for changing to 9. The results are shown in Table 2.

[Example 22]
The curable charge transport compound of Example 8 was identified as Compound Example No. 1 in Table 1. A photoconductor (22) was prepared and evaluated in the same manner as in Example 8 except for changing to 8. The results are shown in Table 2.

[Example 23]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were the same as in Example 1.

  Next, the following five types of paints were prepared.

(23-1) Compound Example Nos. No. 11 curable charge transport compound, 30 parts; 15 parts of a curable compound having no charge transporting property, 0.2 part of a thermal polymerization initiator (the following structural formula A),
After mixing and stirring 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane and 24 parts of 1-propanol, a PTFE 5 μm membrane filter was used. Pressure filtration was performed to prepare a coating solution (23-1).

  (23-2) Compound Example Nos. No. 11 curable charge transport compound, 25 parts; 15 parts of a curable compound having no charge transporting property, 0.2 part of a thermal polymerization initiator (the following structural formula A), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution (23-2).

  (23-3) Compound Example Nos. No. 11 curable charge transport compound 20 parts, Compound Example No. 15 parts of a curable compound having no charge transporting property, 0.2 part of a thermal polymerization initiator (the following structural formula A), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution (23-3).

  (23-4) Compound Example Nos. 11 curable charge transport compound, Compound Example No. 15 parts of a curable compound having no charge transporting property, 0.2 part of a thermal polymerization initiator (the following structural formula A), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution (23-4).

  (23-5) Compound Example Nos. No. 11 curable charge transport compound, 10 parts; 15 parts of a curable compound having no charge transporting property, 0.2 part of a thermal polymerization initiator (the following structural formula A), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution (23-5).

  After coating the coating liquids (23-1) to (23-5) described above on the first charge transport layer in this order by the spray coating method so that the film thickness of each layer is 1.0 μm, the coating liquid is heated to 150 ° C. Then, a second charge transport layer having a film thickness of 5 μm was formed by heat curing for 1 hour to prepare a photoconductor (23), which was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 24]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were the same as in Example 1.

  Next, the following five types of paints were prepared.

(24-1) Compound Example Nos. No. 11 curable charge transport compound, 30 parts; 15 parts of a curable compound having no charge transporting property, 0.2 part of a photopolymerization initiator (the following structural formula B),
After mixing and stirring 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane and 24 parts of 1-propanol, a PTFE 5 μm membrane filter was used. The coating solution (24-1) was prepared by performing pressure filtration.

  (24-2) Compound Example Nos. No. 11 curable charge transport compound, 25 parts; 15 parts of a curable compound having no charge transporting property, 0.2 part of a photopolymerization initiator (the following structural formula B), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution (24-2).

  (24-3) Compound Example Nos. No. 11 curable charge transport compound 20 parts, Compound Example No. 15 parts of a curable compound having no charge transporting property, 0.2 part of a photopolymerization initiator (the following structural formula B), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution (24-3).

  (24-4) Compound Example Nos. 11 curable charge transport compound, Compound Example No. 15 parts of a curable compound having no charge transporting property, 0.2 part of a photopolymerization initiator (the following structural formula B), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution (24-4).

  (24-5) Compound Nos. No. 11 curable charge transport compound, 10 parts; 15 parts of a curable compound having no charge transporting property, 0.2 part of a photopolymerization initiator (the following structural formula B), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution (24-5).

After the coating liquids (24-1) to (24-5) described above are applied on the first charge transport layer in this order by the spray coating method so that the film thickness of each layer is 1.0 μm, a metal halide lamp is used. After curing for 60 seconds at a light intensity of 500 mW / cm ² , heat treatment is performed to form a second charge transport layer having a thickness of 5 μm, and a photoconductor (24) is produced. did. The results are shown in Table 2.

[Example 25]
The curable charge transport compound of Example 3 and the curable compound having no charge transport property are shown in Compound Example No. 1 in Table 1. 11 and no. A photoconductor (25) was prepared and evaluated in the same manner as in Example 3 except for changing to 15 respectively. The results are shown in Table 2.

[Example 26]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were performed in the same manner as in Example 1.

  Next, the following five types of paints were prepared.

  (26-1) Compound Example Nos. No. 7 curable charge transport compound, 30 parts; 16 parts of a curable compound having no charge transporting property, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating liquid (26-1).

  (26-2) Compound Example Nos. No. 7 curable charge transport compound 25 parts, Compound Example No. 16 parts of a curable compound having no charge transporting property, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (26-2).

  (26-3) Compound Nos. No. 7 curable charge transport compound 20 parts, Compound Example No. 16 parts of a curable compound having no charge transporting property, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (26-3).

  (26-4) Compound Example Nos. No. 7 curable charge transport compound 15 parts, Compound Example No. 16 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (26-4).

  (26-5) Compound Example Nos. No. 7 curable charge transport compound, 10 parts; 16 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution (26-5).

  The coating liquid (26-1) described above is applied onto the first charge transport layer by a dip coating method so that the film thickness becomes 1.0 μm, and in nitrogen, the acceleration voltage is 150 kV and the electron beam dose is 1 kGy. Precured under conditions. On the pre-cured layer thus formed, coating solutions (26-2) to (26-4) are similarly applied in this order, pre-cured in nitrogen, and further immersed in the coating solution (26-5). It was applied by a coating method, cured in nitrogen under the conditions of an acceleration voltage of 150 kV and an electron beam dose of 46 kGy, and subsequently subjected to a heat treatment for 90 seconds under the condition that the temperature of the photoreceptor becomes 120 ° C. The oxygen concentration at this time was 10 ppm. Further, the photoconductor was heated in the air at 100 ° C. in a hot air dryer for 20 minutes to form a second charge transport layer having a thickness of 5 μm, and a photoconductor (26) was prepared, Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 1]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were the same as in Example 1.

  Next, Compound Example Nos. No. 4 curable charge transport compound 30 parts and Compound Example No. 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution. This coating solution is applied onto the first charge transport layer by a dip coating method, cured in nitrogen under the conditions of an acceleration voltage of 150 kV and an electron beam dose of 50 kGy, and then the temperature of the photoreceptor is 90 ° C. Heat treatment was performed for 2 seconds. The oxygen concentration at this time was 10 ppm. Further, the photoconductor was heat-treated for 20 minutes in a hot air dryer adjusted to 100 ° C. in the air to form a second charge transport layer having a thickness of 5 μm, and a comparative photoconductor (1) was prepared. Evaluation was conducted in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 2]
The curable charge transport compound of Comparative Example 1 was identified as Compound Example No. 1 in Table 1. A comparative photoreceptor (2) was prepared and evaluated in the same manner as in Comparative Example 1 except that the curable charge transport compound was changed to 10. The results are shown in Table 2.

[Comparative Example 3]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were the same as in Example 1.

  Next, Compound Example Nos. No. 8 curable charge transport compound 30 parts and Compound Example No. 14 parts of curable compound having no charge transporting property, 16.2 parts of lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution. This coating solution is applied onto the first charge transport layer by a dip coating method, cured in nitrogen under the conditions of an acceleration voltage of 150 kV and an electron beam dose of 50 kGy, and then the temperature of the photoreceptor is 90 ° C. Heat treatment was performed for 2 seconds. The oxygen concentration at this time was 10 ppm. Further, the photoconductor was heat-treated for 20 minutes in a hot air dryer adjusted to 100 ° C. in the atmosphere to form a second charge transport layer having a thickness of 5 μm, and a comparative photoconductor (3) was prepared. Evaluation was conducted in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 4]
The curable charge transporting compound of Comparative Example 1 and the curable compound having no charge transporting property are designated as Compound Example No. 1 in Table 1. No. 2 curable charge transport compound and Compound Example No. 2 A comparative photoconductor (4) was prepared and evaluated in the same manner as in Comparative Example 1 except that it was changed to a curable compound having no charge transport property of 16. The results are shown in Table 4.

[Comparative Example 5]
The curable charge transport compound of Comparative Example 4 was converted into Compound Example No. A comparative photoreceptor (5) was prepared and evaluated in the same manner as in Comparative Example 4 except that the curable charge transport compound was changed to 7. The results are shown in Table 2.

[Comparative Example 6]
The curable charge transport compound of Comparative Example 4 was converted into Compound Example No. A comparative photoreceptor (6) was prepared and evaluated in the same manner as in Comparative Example 4 except that the curable charge transport compound was changed to 9. The results are shown in Table 2.

[Comparative Example 7]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were the same as in Example 1.

  Next, Compound Example Nos. No. 11 curable charge transport compound, 30 parts; 15 parts of a curable compound having no charge transporting property, 0.2 part of a thermal polymerization initiator (the following structural formula A), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution.

  The coating solution is applied onto the first charge transport layer by a dip coating method, and then heated and cured at 150 ° C. for 1 hour to form a second charge transport layer having a thickness of 5 μm. The comparative photoreceptor (7) Was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 8]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were the same as in Example 1.

  Next, Compound Example Nos. No. 11 curable charge transport compound, 30 parts; 15 parts of a curable compound having no charge transporting property, 0.2 part of a photopolymerization initiator (the following structural formula B), 16.2 parts of a lubricant dispersion, 1,1,2,2,3,3 , 4-Heptafluorocyclopentane and 24 parts of 1-propanol were mixed and stirred, followed by pressure filtration with a PTFE 5 μm membrane filter to prepare a coating solution.

This coating solution is applied onto the first charge transport layer by a dip coating method, and then cured for 60 seconds at a light intensity of 500 mW / cm ² using a metal halide lamp, followed by heat treatment, and a second film having a thickness of 5 μm. A charge transport layer was formed, a comparative photoreceptor (8) was prepared, and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 9]
The processes up to the formation of the first charge transport layer and the preparation of the lubricant dispersion were the same as in Example 1.

  Next, Compound Example Nos. No. 11 curable charge transport compound 30 parts and Compound Example No. 15 parts of a curable compound having no charge transport property, 16.2 parts of a lubricant dispersion, 24 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane, 1-propanol 24 After mixing and stirring the parts, pressure filtration was performed with a PTFE 5 μm membrane filter to prepare a coating solution. This coating solution is applied onto the first charge transport layer by a dip coating method, cured in nitrogen under the conditions of an acceleration voltage of 150 kV and an electron beam dose of 50 kGy, and then the temperature of the photoreceptor is 90 ° C. Heat treatment was performed for 2 seconds. The oxygen concentration at this time was 10 ppm. Further, the photoconductor was heat-treated for 20 minutes in a hot air dryer adjusted to 100 ° C. in the atmosphere to form a second charge transport layer having a thickness of 5 μm, and a comparative photoconductor (9) was prepared. Evaluation was conducted in the same manner as in Example 1. The results are shown in Table 2.

From the above experimental results, the charge transport component in the second charge transport layer is
K = L / M and K <0.95
(In the formula, L represents the concentration of the charge transport component existing from the surface of the electrophotographic photosensitive member to a depth of 40% of the film thickness in the second charge transport layer, and M represents the charge transport layer and the second charge transport layer). The concentration of the charge transport component existing from the interface of the layer to a depth of 40% of the film thickness of the second charge transport layer is represented by the charge transport group and the charge transport in the curable charge transport compound. Means both compounds.)
The electrophotographic photosensitive member distributed under the conditions satisfying the above conditions is excellent in mechanical strength and electrical characteristics, and can form a high-quality image stably over a long period of time.

1 is a schematic view showing an embodiment of a process cartridge having an electrophotographic photosensitive member of the present invention and an electrophotographic apparatus having the process cartridge. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Primary charging means 4 Image exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Image fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Rail

Claims (8)

In the electrophotographic photoreceptor having at least a charge generation layer, a first charge transport layer, and a second charge transport layer in this order on a conductive support, wherein the second charge transport layer is an outermost surface layer, the second charge The transport layer contains a compound obtained by polymerizing and / or crosslinking a curable charge transport compound represented by the following general formula (1) and a curable compound having no charge transport property. An electrophotographic photoreceptor, wherein the charge transport component contained in the second charge transport layer satisfies the following conditions.
K = L / M and K <0.95
(In the formula, L represents the concentration of the charge transport component existing from the surface of the electrophotographic photosensitive member to a depth of 40% of the thickness of the second charge transport layer, and M represents the first charge transport layer and the second charge transport layer). The concentration of the charge transport component existing from the interface of the transport layer to a depth of 40% of the thickness of the second charge transport layer is indicated in the compound represented by the following general formula (1). Of triphenylamine.)

(In the formula, A represents a charge transporting group having a triphenylamine skeleton, P ¹ and P ² represent a chain polymerizable functional group, Z represents an organic group which may have a substituent, a, b and d represent 0 or an integer of 1 or more, and a + b × d represents an integer of 1 or more, P ¹ and P ² may be the same or different, and when a is 2 or more, P ¹ may be the same And may be different. When d is 2 or more, P ² may be the same or different. When b is 2 or more, Z and P ² may be the same or different.   2. The electrophotographic photosensitive member according to claim 1, wherein in the general formula (1), a + b × d is 2 or more.   3. The electrophotographic photosensitive member according to claim 1, wherein at least one of the curable compounds has any one of an acryl group, a methacryl group, and a styrene group. 4. The electrophotographic photosensitive member according to claim 1, wherein L and M in claim 1 satisfy the following conditions.
K = L / M and 0.25 <K <0.80   The electrophotographic photosensitive member according to claim 1, wherein the second charge transport layer is cured by any one of heat, ultraviolet rays, and radiation.   The electrophotographic photosensitive member according to claim 1, wherein the second charge transport layer is cured by an electron beam.   7. The electrophotographic photosensitive member according to claim 1, a charging unit for charging the electrophotographic photosensitive member, and development for developing an electrostatic latent image formed on the charged electrophotographic photosensitive member. And a process cartridge mounted on the electrophotographic photosensitive member having a cleaning means for removing toner from the surface of the electrophotographic photosensitive member, the electrophotographic photosensitive member, the charging unit, the developing unit, and A process cartridge which integrally supports at least one means selected from the group consisting of the cleaning means and is detachably attached to the electrophotographic apparatus main body.   7. The electrophotographic photosensitive member according to claim 1, charging means for charging the electrophotographic photosensitive member, and exposure means for forming an electrostatic latent image on the charged electrophotographic photosensitive member by exposure. And developing means for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner, and transfer means for transferring the toner image formed on the electrophotographic photosensitive member to a transfer material. An electrophotographic device.