JP2013044818A - Electrophotographic photoreceptor, manufacturing method thereof, process cartridge, and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor that prevents scratches on the surface even after repeated use while preventing image deterioration.SOLUTION: The electrophotographic photoreceptor includes at least a conductive substrate and a photosensitive layer provided on the conductive substrate. The outermost layer is formed of a cured film of a composition containing one or more kinds of charge transport materials (A) represented by the following general formula (I). In the general formula (I), F denotes a charge transporting skeleton, D denotes a group represented by the following general formula (III), and m denotes an integer of 1-8. In the general formula (III), L denotes a divalent linking group containing one or more groups selected from the group consisting of -C(=O)-, -N(R)- and -S-, or a group formed by combining -C(=O)- with -O-, -N(R)- or -S-. R denotes a hydrogen atom, alkyl group, aryl group or aralkyl group.

Description

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

  In an electrophotographic image forming apparatus, the surface of an electrophotographic photosensitive member is charged to a polarity and a potential determined by a charging device, and the surface of the electrophotographic photosensitive member after charging is selectively discharged by image exposure. An electrostatic latent image is formed. Next, the latent image is developed as a toner image by attaching toner to the electrostatic latent image by a developing device, and the toner image is transferred to a recording medium by a transfer unit, and discharged as an image formed product.

  As an electrophotographic photoreceptor, it has been proposed to provide a protective layer on the surface from the viewpoint of improving strength. Examples of the material system for forming the protective layer include a material in which conductive powder is dispersed in a phenol resin (for example, see Patent Document 1), an organic-inorganic hybrid material (for example, see Patent Document 2), an alcohol-soluble charge transporting material, and the like. The thing by a phenol resin (for example, refer patent document 3) etc. are disclosed. Further, a cured film of an alkyl etherified benzoguanamine / formaldehyde resin and an electron-accepting carboxylic acid or an electron-accepting polycarboxylic acid anhydride (see, for example, Patent Document 4), iodine, an organic sulfonic acid compound, or a second chloride is added to the benzoguanamine resin. A cured film doped with iron or the like (see, for example, Patent Document 5), a cured film of a specific additive and a phenol resin, melamine resin, benzoguanamine resin, siloxane resin, or urethane resin (for example, see Patent Document 6) is disclosed. ing.

  In recent years, a protective layer made of an acrylic material has attracted attention. For example, a film obtained by applying and curing a liquid containing a photocurable acrylic monomer (see, for example, Patent Document 7), a monomer having a carbon-carbon double bond, a charge transfer material having a carbon-carbon double bond, and a binder Disclosed is a film formed by reacting a resin mixture with a carbon-carbon double bond of the monomer and a carbon-carbon double bond of the charge transfer material by heat or light energy (see, for example, Patent Document 8). Has been.

Furthermore, a film made of a compound obtained by polymerizing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule is disclosed (for example, see Patent Document 9). In addition, a technique of using a polymer of a charge transport material having a chain polymerizable functional group for a protective layer is disclosed (for example, see Patent Document 10).
These acrylic materials are strongly affected by curing conditions, curing atmospheres, and the like, and are formed, for example, by a film formed by heating after irradiation with radiation in a vacuum or an inert gas (see, for example, Patent Document 11) or inert. A film (for example, see Patent Document 12) cured by heating in a gas is disclosed.
In addition, a cross-linked product of a charge transporting compound in which a styrene skeleton is linked with an ether group as a chain polymerizable group is disclosed (Patent Documents 13 and 14).

Japanese Patent No. 3287678 JP 2000-019749 A JP 2002-82469 A Japanese Patent Laid-Open No. 62-251757 Japanese Patent Laid-Open No. 7-146564 JP 2006-84711 A JP-A-5-40360 JP-A-5-216249 JP 2000-206715 A JP 2001-175016 A Japanese Patent Laid-Open No. 2004-12986 Japanese Patent Laid-Open No. 7-72640 Japanese Patent No. 2546739 Japanese Patent No. 2852464

  SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member that hardly causes scratches on the surface even when used repeatedly and that causes little deterioration in image quality.

In order to achieve the above object, the following invention is provided.
The invention of claim 1 has at least a conductive substrate and a photosensitive layer provided on the conductive substrate, and the outermost surface layer is one or more kinds of charge transports represented by the following general formula (I) An electrophotographic photosensitive member which is a layer comprising a polymerized or cured film of a composition containing the material (A).

(In general formula (I), F represents a charge transporting skeleton. D represents a group represented by the following general formula (III). M represents an integer of 1 to 8.)

(In General Formula (III), L represents —C (═O) —, —N (R) —, —S—, or —C (═O) —, and —O—, —N (R) —). Or a divalent linking group containing one or more groups selected from the group consisting of a combination of -S-, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

The invention according to claim 2 is the electrophotographic photoreceptor according to claim 1, wherein the charge transport material (A) represented by the general formula (I) is a charge transport material represented by the following general formula (II).

(In the general formula (II), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group. Ar ⁵ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group. D is synonymous with D in formula (I), c1 to c5 each represents an integer of 0 to 2, and the sum of c1 to c5 is an integer of 1 to 8. k is 0 or 1 .)

  The invention according to claim 3 is the electrophotographic photoreceptor according to claim 1 or 2, wherein L in the general formula (III) is a divalent linking group containing -C (= O) -O-. .

The invention according to claim 4 is the electrophotographic photosensitive member according to any one of claims 1 to 3, wherein the general formula (III) is a compound represented by the following general formula (IV).

(In general formula (IV), p represents an integer of 0 or more and 4 or less.)

  The invention according to claim 5 is the electrophotographic photosensitive member according to any one of claims 1 to 4, wherein m in the general formula (I) represents an integer of 2 or more and 6 or less.

  The invention according to claim 6 is the electrophotographic photosensitive member according to claim 5, wherein m in the general formula (I) represents an integer of 3 or more and 6 or less.

  The invention according to claim 7 is the electrophotographic photosensitive member according to claim 6, wherein m in the general formula (I) represents an integer of 4 or more and 6 or less.

  In the invention according to claim 8, the outermost surface layer is a layer made of a film obtained by polymerizing or curing the composition containing the charge transport material (A) by heat, light, or electron beam. The electrophotographic photosensitive member according to claim 7.

  According to a ninth aspect of the present invention, there is provided a process cartridge comprising at least the electrophotographic photosensitive member according to any one of the first to eighth aspects and detachable from the image forming apparatus.

  According to a tenth aspect of the present invention, there is provided an electrophotographic photosensitive member according to any one of the first to eighth aspects, a charging device for charging the electrophotographic photosensitive member, and a surface of the charged electrophotographic photosensitive member. A latent image forming apparatus that forms an electrostatic latent image, a developing apparatus that develops the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with a developer containing toner, and forms a toner image; and the electrophotographic apparatus An image forming apparatus comprising: a transfer device that transfers a toner image formed on the surface of the photoreceptor to a recording medium.

  The invention of claim 11 includes a step of applying a coating liquid comprising a composition containing the charge transport material (A) represented by the general formula (I) to a surface to be coated to form a coating film, and And a step of heating the film at 100 ° C. to 170 ° C. for polymerization or curing to obtain an outermost surface layer.

  According to the first aspect of the present invention, the outermost surface layer is formed on the surface even after repeated use, as compared with a case where the outermost surface layer is a polymerized or cured film of a composition not containing the charge transporting material represented by the general formula (I). There is provided an electrophotographic photosensitive member that is less likely to be scratched and has little image quality deterioration.

  According to the invention of claim 2, the compound represented by the general formula (I) is less likely to be scratched on the surface even when used repeatedly as compared with the case where the compound represented by the general formula (II) is not used. An electrophotographic photosensitive member with little image quality deterioration is provided.

  According to the invention of claim 3, L in the general formula (III) is on the surface even when it is repeatedly used, compared to the case where L is a divalent linking group not containing —C (═O) —O—. There is provided an electrophotographic photosensitive member that is less likely to be scratched and has little image quality deterioration.

  According to the invention of claim 4, the general formula (III) is less likely to be scratched on the surface even when it is repeatedly used and the image quality is less deteriorated than when the general formula (III) is not a compound represented by the following general formula (IV). An electrophotographic photoreceptor is provided.

  According to the fifth, sixth, and seventh aspects of the invention, compared to the case where m in the general formula (I) is not within the above range, the surface is less likely to be scratched even when used repeatedly, and the image quality is less deteriorated. A photographic photoreceptor is provided.

  According to invention of Claim 8, the said outermost surface layer is a layer which consists of a film | membrane which polymerized or hardened | cured the composition containing the said charge transport material (A) by methods other than a heat | fever, light, or an electron beam. As compared with a certain case, an electrophotographic photosensitive member is provided which is less likely to be scratched on the surface even when used repeatedly and has little image quality deterioration.

  According to the ninth and tenth aspects of the present invention, when an outermost surface layer is an electrophotographic photosensitive member that is a polymerized or cured film of a composition that does not include the charge transporting material represented by the general formula (I). In comparison, it is possible to provide a process cartridge and an image forming apparatus which are less likely to be scratched on the surface even when used repeatedly and have little image quality deterioration.

  According to the eleventh aspect of the present invention, compared to the case of producing an electrophotographic photosensitive member by a method of forming an outermost surface layer using a coating liquid that does not contain the charge transport material (A) represented by the general formula (I). Thus, an electrophotographic photosensitive member is provided which is less likely to be scratched on the surface even when used repeatedly and has little deterioration in image quality.

1 is a schematic partial cross-sectional view showing an electrophotographic photosensitive member according to an embodiment. 1 is a schematic partial cross-sectional view showing an electrophotographic photosensitive member according to an embodiment. 1 is a schematic partial cross-sectional view showing an electrophotographic photosensitive member according to an embodiment. 1 is a schematic configuration diagram illustrating an image forming apparatus according to an embodiment. It is a schematic block diagram which shows the image forming apparatus which concerns on other embodiment. (A) thru | or (C) is a figure which shows the image pattern used for image evaluation, respectively. It is IR spectrum of compound A-15. It is IR spectrum of compound A-43.

Hereinafter, embodiments of the present invention will be described in detail.
Although the surface of the electrophotographic photosensitive member is polymerized or cured, the mechanical strength of the photosensitive member by repeated use is improved, but the image quality itself and the stability of the image quality by repeated use are not sufficient. The reason for this is not clear, but by curing, the intermolecular distance and conformation of the chemical structure responsible for charge transport properties change from the state before curing, or by curing, the chain polymerizable group It is considered that the peripheral chemical structure and the chemical structure responsible for charge transporting are aggregated to change the film state before curing. Moreover, in addition to the charge transporting material having a chain polymerizable functional group, when the film containing the binder resin is cured, the structure of the charge transporting material and the compatibility of the binder resin are reduced by curing. It is considered as a factor.
Thus, it is important to achieve both mechanical strength and image quality with the aim of extending the life of the electrophotographic photosensitive member.

The electrophotographic photoreceptor according to the exemplary embodiment (hereinafter may be simply referred to as “photoreceptor”) includes at least a conductive substrate and a photosensitive layer provided on the conductive substrate, and is an outermost surface layer. And having a structure in which one or more charge transporting skeletons and one or more styrene skeletons not conjugated to the charge transporting skeleton are linked in the same molecule, and the charge transporting skeleton and the -C (= O)-, -N (R)-, -S-, or -C (= O)-in addition to -O-, -N (R)-, Or a layer (Oc) made of a polymerized or cured film of a composition containing one or more charge transporting materials (A) containing one or more groups selected from the group combining -S- Have.
According to the above-described embodiment, an electrophotographic photosensitive member is provided that is less likely to be scratched on the surface even when used repeatedly and has little image quality deterioration.
In addition, the styrene skeleton contained in the charge transport material (A) of the present embodiment refers to a structure in which a vinyl group (—CH═CH ₂ ) is directly connected to a benzene ring. A substituent may be substituted for the hydrogen atom of the benzene ring, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and the like, but preferably no substituent.

(Estimated factors that produce effects)
Although the cause of the effect of the photoconductor of the present embodiment has not been clarified, the cause of little deterioration in image quality due to repeated use is estimated as follows. It is considered that a photoreceptor having a polymerized or cured film as the outermost surface causes film shrinkage due to polymerization or curing, and aggregation of the structure around the charge transport structure and the chain polymerizable group. Therefore, if the surface of the photoreceptor is subjected to mechanical stress by repeated use, the film itself is worn out or the chemical structure in the molecule is cut, and the above-mentioned film contraction and aggregation state change greatly, and as a photoreceptor The electrical characteristics of the image will change, causing image quality degradation. On the other hand, in this embodiment, a styrene skeleton is used as the chain polymerizable group, and is compatible with the aryl group that is the main skeleton of the charge transport agent, and the charge transport structure due to film shrinkage and curing, around the chain polymerizable group Since aggregation of the structure is considered to be suppressed, image quality deterioration due to repeated use is suppressed.

Furthermore, in this embodiment, the charge transporting skeleton and the styrene skeleton are connected via a linking group including a specific group such as —C (═O) —, —N (R) —, and —S—. Thus, it is considered that the strength in the polymerized or cured film is further improved by the interaction between the specific group and the nitrogen atom in the charge transporting skeleton or the interaction between the specific groups.
The specific groups such as -C (= O)-, -N (R)-, and -S- are caused by the polarity and hydrophilicity, and cause the charge transportability and image quality deterioration under high humidity conditions. However, in this embodiment, since a styrene skeleton having a higher hydrophobicity than (meth) acryl or the like is used as the chain polymerizable group, deterioration in image quality such as deterioration in charge transport and ghost as described above is observed. I can't.

[Electrophotographic photoreceptor]
Hereinafter, the configuration of the electrophotographic photosensitive member of the present embodiment will be described.
The photoreceptor according to the exemplary embodiment includes at least a conductive substrate and a photosensitive layer provided on the conductive substrate, and the outermost surface layer includes one or more charge transporting skeletons in the same molecule. -C (= O)-, -N (R)-, having a structure in which one or more styrene skeletons are linked, and in the linking group that links the charge transporting skeleton and the styrene skeleton, One or more types including one or more groups selected from -S-, or -C (= O)-and a group further combining -O-, -N (R)-, or -S- As long as it has a layer (Oc) made of a polymerized or cured film of a composition containing the charge transporting material (A), the layer structure is not particularly limited.

  The photosensitive layer according to the present embodiment may be a function-integrated type photosensitive layer having both charge transport capability and charge generation capability, or a function-separated type photosensitive layer including a charge transport layer and a charge generation layer. Also good. Furthermore, other layers such as an undercoat layer may be provided.

Hereinafter, the configuration of the photoreceptor according to the present embodiment will be described with reference to FIGS. 1 to 3, but the present embodiment is not limited to FIGS. 1 to 3.
FIG. 1 is a schematic view showing an example of the layer structure of the photoreceptor according to the present embodiment. The photoreceptor shown in FIG. 1 has a layer structure in which an undercoat layer 4, a charge generation layer 2A, a charge transport layer 2B-1, and a charge transport layer 2B-2 are laminated on a substrate 1 in this order. 2 is composed of three layers, a charge generation layer 2A and charge transport layers 2B-1 and 2B-2 (first embodiment). In the photoreceptor shown in FIG. 1, the charge transport layer 2B-2 corresponds to the layer (Oc) of this embodiment containing the reactive compound represented by the general formula (I). Hereinafter, the layer of the present embodiment in the first aspect is referred to as a layer (Oc1) of the present embodiment. The charge transport layer 2B-2 serving as the outermost surface layer also functions as a protective layer for protecting the charge transport layer 2B-1.

  FIG. 2 is a schematic view showing another example of the layer structure of the photoreceptor according to this embodiment. 2 has a layer structure in which an undercoat layer 4, a charge generation layer 2A, and a charge transport layer 2B are laminated in this order on a substrate 1, and the photosensitive layer 2 includes the charge generation layer 2A and the charge transport layer. It is composed of two layers 2B (second embodiment). In the photoreceptor shown in FIG. 2, the charge transport layer 2B corresponds to the layer (Oc) of this embodiment containing the reactive compound represented by the general formula (I). Hereinafter, the layer of this embodiment in the second aspect is referred to as a layer (Oc2) of this embodiment.

  FIG. 3 is a schematic view showing another example of the layer structure of the photoreceptor according to this embodiment. 3 has a layer structure in which an undercoat layer 4 and a photosensitive layer 6 are laminated in this order on a substrate 1, and the photosensitive layer 6 includes a charge generation layer 2A and a charge transport layer shown in FIG. This is a layer in which the functions of 2B are integrated (third mode). In the photoreceptor shown in FIG. 3, the function-integrated photosensitive layer 6 corresponds to the layer (Oc) of this embodiment containing the reactive compound represented by the general formula (I). The layer of the present embodiment is referred to as a layer (Oc3) of the present embodiment.

  Hereinafter, each of the first to third aspects will be described as an example of the photoreceptor according to the present exemplary embodiment.

-Conductive substrate-
Any conductive substrate may be used as long as it is conventionally used. For example, thin films (eg, metals such as aluminum, nickel, chromium, stainless steel, and films of aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, indium tin oxide (ITO), etc.) And a plastic film coated or impregnated with a conductivity-imparting agent, a plastic film coated or impregnated with a conductivity-imparting agent, and the like. The shape of the substrate is not limited to a cylindrical shape, and may be a sheet shape or a plate shape.
The conductive base particles preferably have conductivity with a volume resistivity of less than 10 ⁷ Ω · cm, for example.

  When a metal pipe is used as the conductive substrate, the surface may be left as it is, and processing such as mirror cutting, etching, anodizing, rough cutting, centerless grinding, sand blasting, wet honing has been performed in advance. May be.

-Undercoat layer-
The undercoat layer is provided as necessary for the purpose of preventing light reflection on the surface of the conductive substrate and preventing inflow of unnecessary carriers from the conductive substrate to the photosensitive layer.

The undercoat layer includes, for example, a binder resin and, if necessary, other additives.
As the binder resin contained in the undercoat layer, acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, Known polymer resin compounds such as polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol resin, phenol-formaldehyde resin, melamine resin, urethane resin, and charge transporting group Examples thereof include charge transporting resins having a conductive resin such as polyaniline. Among these, resins that are insoluble in the upper coating solvent are preferably used, and phenol resins, phenol-formaldehyde resins, melamine resins, urethane resins, epoxy resins, and the like are particularly preferably used.

  The undercoat layer may contain a metal compound such as a silicon compound, an organic zirconium compound, an organic titanium compound, or an organic aluminum compound.

  The ratio between the metal compound and the binder resin is not particularly limited, and is set within a range in which desired electrophotographic photoreceptor characteristics can be obtained.

  In the undercoat layer, resin particles may be added to the undercoat layer in order to adjust the surface roughness. Examples of the resin particles include silicone resin particles and cross-linked polymethyl methacrylate (PMMA) resin particles. The surface may be polished after forming the undercoat layer for adjusting the surface roughness. As a polishing method, buffing, sandblasting, wet honing, grinding, or the like is used.

  Here, the constitution of the undercoat layer includes a constitution containing at least a binder resin and conductive particles. Note that the conductive particles preferably have conductivity with a volume resistivity of less than 107 Ω · cm, for example.

Examples of the conductive particles include metal particles (particles such as aluminum, copper, nickel, and silver), conductive metal oxide particles (particles such as antimony oxide, indium oxide, tin oxide, and zinc oxide), and conductive substance particles. (Carbon fiber, carbon black, particles of graphite powder) and the like. Among these, conductive metal oxide particles are preferable. You may mix and use 2 or more types of electroconductive particle.
In addition, the conductive particles may be subjected to a surface treatment with a hydrophobizing agent (for example, a coupling agent) or the like to adjust the resistance.
The content of the conductive particles in the undercoat layer is, for example, desirably from 10% by mass to 80% by mass, and more desirably from 40% by mass to 80% by mass with respect to the binder resin.

In forming the undercoat layer, an undercoat layer forming coating solution in which the above components are added to a solvent is used.
In addition, as a method of dispersing particles in the coating solution for forming the undercoat layer, a media dispersing machine such as a ball mill, a vibrating ball mill, an attritor, a sand mill, a horizontal sand mill, a stirring, an ultrasonic dispersing machine, a roll mill, a high-pressure homogenizer Medialess dispersers are used. Here, examples of the high-pressure homogenizer include a collision method in which the dispersion liquid is dispersed by liquid-liquid collision or liquid-wall collision in a high-pressure state, and a penetration method in which a fine flow path is dispersed in a high-pressure state. .

  Examples of the method for applying the coating solution for forming the undercoat layer onto the conductive substrate include dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating, and curtain coating. It is done.

  The thickness of the undercoat layer is preferably 15 μm or more, and more preferably 20 μm or more and 50 μm or less.

  Here, although not shown, an intermediate layer may be further provided between the undercoat layer and the photosensitive layer. As the binder resin used for the intermediate layer, acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl In addition to polymer resins such as acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, melamine resin, zirconium, titanium, aluminum, manganese, silicon atom, etc. An organometallic compound containing These compounds may be used alone or as a mixture or polycondensate of a plurality of compounds. Among these, an organometallic compound containing zirconium or silicon is preferable in that it has a low residual potential, a small potential change due to the environment, and a small potential change due to repeated use.

  In forming the intermediate layer, a coating solution for forming an intermediate layer in which the above components are added to a solvent is used. As the coating method for forming the intermediate layer, usual methods such as a dip coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, a knife coating method, and a curtain coating method are used.

  In addition to improving the coatability of the upper layer, the intermediate layer also serves as an electrical blocking layer, but if the film thickness is too large, the electrical barrier becomes too strong and the potential increases due to desensitization or repetition. May cause. Therefore, when forming the intermediate layer, it is preferable to set the film thickness within the range of 0.1 μm to 3 μm. In this case, the intermediate layer may be used as the undercoat layer.

-Charge generation layer-
The charge generation layer includes, for example, a charge generation material and a binder resin. Examples of such a charge generating material include phthalocyanine pigments such as metal-free phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, dichlorotin phthalocyanine, and titanyl phthalocyanine. Chlorogallium phthalocyanine crystal having strong diffraction peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 °, at least 7.7 Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray Metal-free phthalocyanine crystals having strong diffraction peaks at °, 9.3 °, 16.9 °, 17.5 °, 22.4 ° and 28.8 °, Bragg angle with respect to CuKα characteristic X-ray (2θ ± 0.2 °) at least 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, Hydroxygallium phthalocyanine crystal having strong diffraction peaks at 5.1 ° and 28.3 °, Bragg angle (2θ ± 0.2 °) to CuKα characteristic X-ray of at least 9.6 °, 24.1 ° and 27.2 A titanyl phthalocyanine crystal having a strong diffraction peak at 0 ° can be mentioned. In addition, examples of the charge generation material include quinone pigments, perylene pigments, indigo pigments, bisbenzimidazole pigments, anthrone pigments, quinacridone pigments, and the like. These charge generation materials may be used alone or in combination of two or more.

Examples of the binder resin constituting the charge generation layer include polycarbonate resin such as bisphenol A type or bisphenol Z type, acrylic resin, methacrylic resin, polyarylate resin, polyester resin, polyvinyl chloride resin, polystyrene resin, acrylonitrile-styrene. Copolymer resin, acrylonitrile-butadiene copolymer, polyvinyl acetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride Examples thereof include resins, silicone resins, phenol-formaldehyde resins, polyacrylamide resins, polyamide resins, poly-N-vinylcarbazole resins. These binder resins may be used alone or in combination of two or more.
The mixing ratio of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10, for example.

  When forming the charge generation layer, a coating solution for forming a charge generation layer in which the above components are added to a solvent is used.

  As a method for dispersing particles (for example, charge generation material) in the coating solution for forming the charge generation layer, a media dispersion machine such as a ball mill, a vibration ball mill, an attritor, a sand mill, a horizontal sand mill, an agitation, an ultrasonic dispersion machine, a roll mill, etc. Medialess dispersers such as high-pressure homogenizers are used. Examples of the high-pressure homogenizer include a collision method in which the dispersion liquid is dispersed by liquid-liquid collision or liquid-wall collision in a high-pressure state, and a penetration method in which a fine flow path is dispersed in a high-pressure state.

  Examples of the method for applying the charge generation layer forming coating liquid on the undercoat layer include dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating, and curtain coating. It is done.

  The thickness of the charge generation layer is desirably set in the range of 0.01 μm to 5 μm, more desirably 0.05 μm to 2.0 μm.

-Charge transport layer 2B-1 (in the case of the first embodiment)-
The charge transport layer 2B-1 is the case of the first embodiment, and is configured to include a charge transport material and, if necessary, a binder resin.
Examples of the charge transport material include oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1- [ Pyrazoline derivatives such as pyridyl- (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline, triphenylamine, N, N′-bis (3,4-dimethylphenyl) biphenyl- Aromatic tertiary amino compounds such as 4-amine, tri (p-methylphenyl) aminyl-4-amine, dibenzylaniline, N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine Aromatic tertiary diamino compounds such as 3- (4'-dimethylaminophenyl) -5,6-di- (4'-methoxyphenyl) -1,2,4 1,2,4-triazine derivatives such as triazine, hydrazone derivatives such as 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline, 6-hydroxy-2,3- Benzofuran derivatives such as di (p-methoxyphenyl) benzofuran, α-stilbene derivatives such as p- (2,2-diphenylvinyl) -N, N-diphenylaniline, enamine derivatives, carbazole derivatives such as N-ethylcarbazole, poly -Hole transport materials such as -N-vinylcarbazole and its derivatives, quinone compounds such as chloranil and broanthraquinone, tetraanoquinodimethane compounds, 2,4,7-trinitrofluorenone, 2,4,5,7 -Fluorenone such as tetranitro-9-fluorenone Examples thereof include an electron transport material such as a compound, a xanthone compound, and a thiophene compound, and a polymer having a group consisting of the above-described compounds in a main chain or a side chain. These charge transport materials may be used alone or in combination of two or more.

As the binder resin constituting the charge transport layer 2B-1, for example, polycarbonate resin such as bisphenol A type or bisphenol Z type, acrylic resin, methacrylic resin, polyarylate resin, polyester resin, polyvinyl chloride resin, polystyrene resin, Acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene copolymer resin, polyvinyl acetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinyl acetate -Insulating resins such as maleic anhydride resin, silicone resin, phenol-formaldehyde resin, polyacrylamide resin, polyamide resin, chlorine rubber, and polyvinylcarbazole, polyvinyl Anthracene, organic photoconductive polymers such as polyvinyl pyrene, and the like. These binder resins may be used alone or in combination of two or more.
The mixing ratio between the charge transport material and the binder resin is preferably 10: 1 to 1: 5, for example.

  The charge transport layer 2B-1 is formed using a coating liquid for forming the charge transport layer 2B-1 in which the above components are added to a solvent.

As a method of applying the coating liquid for forming the charge transport layer 2B-1 on the charge generation layer, dip coating method, push-up coating method, wire bar coating method, spray coating method, blade coating method, knife coating method, curtain coating method Ordinary methods such as are used.
The film thickness of the charge transport layer 2B-1 is desirably set in the range of 5 μm or more and 50 μm or less, more desirably 10 μm or more and 40 μm or less.

-Charge transport layer 2B-2 (corresponding to the layer (Oc1) of the present embodiment in the first mode)-
The layer (Oc1) of the present embodiment has a structure in which one or more charge transporting skeletons and one or more styrene skeletons are linked in the same molecule, and the charge transporting skeletons and the styrene skeletons. -C (= O)-, -N (R)-, -S-, or -C (= O)-in addition to -O-, -N (R)-, or- It is a layer formed of a polymerized or cured film of a composition containing one or more charge transport materials (A) containing one or more groups selected from a group in which S- is combined.

Hereinafter, the composition for forming the charge transport layer 2B-2 will be described.
The composition for forming the charge transport layer 2B-2 contains at least one charge transport material (A) of the present embodiment. The charge transport material (A) of the present embodiment has a structure in which one or more charge transporting skeletons and one or more styrene skeletons are linked in the same molecule, and the charge transporting skeletons and the -C (= O)-, -N (R)-, -S-, or -C (= O)-in addition to -O-, -N (R)-, Or it will not specifically limit if it is a compound containing one or more groups selected from the group which combined -S-. Here, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
Examples of the charge transporting skeleton in the charge transport material (A) of the present embodiment include those described in the charge transport layer 2B-1. The charge transporting skeleton preferably includes an arylamine skeleton, and more preferably includes a triarylamine skeleton.
Hereinafter, a more preferable structure of the charge transporting material (A) of the present embodiment is represented by the general formula (II).

In general formula (II), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylene group, D is a group represented by the general formula (III). In the general formula (III), L represents —C (═O) —, —N (R) —, —S—, or —C (═O) —, and —O—, —N (R) —, Or the group which combined -S-, The bivalent coupling group containing 1 or more groups selected from is shown. R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. C1 to c5 in the general formula (II) each represents an integer of 0 or more and 2 or less, and may be different from each other. However, the sum total of c1 to c5 in the formula (II) is an integer of 1 to 8. k is 0 or 1.

The total number of styrene skeletons in the general formula (I) corresponds to m. The total number of styrene skeletons in the general formula (II) corresponds to a value of c1 + c2 + k × (c3 + c4) + c5.
The lower limit of the total number of styrene skeletons in the general formulas (I) and (II) is preferably 2 or more, and more preferably 4 or more, from the viewpoint of obtaining a crosslinked film (cured film) with higher strength. In general, if the number of chain polymerizable groups in one molecule is too large, as the polymerization (crosslinking) reaction proceeds, the molecules become difficult to move and the chain polymerization reactivity decreases, and the ratio of unreacted chain polymerizable groups decreases. Therefore, the upper limit of the total number of styrene skeletons in the general formula (I) is preferably 7 or less, and more preferably 6 or less.

  D in the general formula (II) is a group represented by the general formula (III), and L is -C (= O)-, -N (R)-, -S-, or -C (= A divalent group including one or more groups selected from the group (O)-further combined with -O-, -N (R)-, or -S- (hereinafter referred to as a specific group (Lx)). Represents a linking group. Here, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

The specific group (Lx) includes —C (═O) —, —N (R) —, —S—, —C (= from the viewpoint of the balance between the strength of the polymerized or cured film and the polarity (hydrophobicity). O) —O—, —C (═O) —N (R) —, —C (═O) —S—, —O—C (═O) —O—, —O—C (═O) — N (R)-is preferable, and -N (R)-, -S-, -C (= O) -O-, -C (= O) -N (H)-, -C (= O)- O- is more preferable, and -C (= O) -O- is most preferable.
L in the general formula (III) is not particularly limited as long as it contains the specific group (Lx). For example, the specific group (Lx) and a saturated hydrocarbon (linear, branched, Specific examples thereof include a divalent group formed by combining an oxygen atom with a residue of an aromatic hydrocarbon or an aromatic hydrocarbon. L is preferably formed by combining the specific group (Lx), a linear saturated hydrocarbon residue, and an oxygen atom.
The total number of carbon atoms contained in L in the general formula (III) is preferably 1 or more and 20 or less, more preferably 2 or more and 10 or less, from the viewpoint of the density of the styrene skeleton in the molecule and the chain polymerization reactivity.

In general formula (II), Ar ^{1 to} Ar ⁴ each independently represent a substituted or unsubstituted aryl group. Ar ^{1 to} Ar ⁴ may be the same or different. Here, as a substituent in the substituted aryl group, a substituent other than D is substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. A phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, a halogen atom, and the like.

Ar ^{1 to} Ar ⁴ are preferably any one of the following structural formulas (1) to (7). The following structural formulas (1) to (7) are shown together with “— (D) c” which can be connected to Ar ^{1 to} Ar ⁴ . Here, “-(D) c” is synonymous with “-(D) c1 to (D) c4” in the general formula (II), and preferred examples are also the same.

In the structural formula (1), R ⁰¹ is a phenyl group substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. , An unsubstituted phenyl group, and one selected from the group consisting of an aralkyl group having 7 to 10 carbon atoms.
In the structural formulas (2) and (3), R ^{02 to} R ⁰⁴ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 or more carbon atoms. 1 type selected from the group consisting of a phenyl group substituted with 4 or less alkoxy groups, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom. M represents an integer of 1 to 3.
In the structural formula (7), Ar represents a substituted or unsubstituted arylene group.
Here, as Ar in Formula (7), what is shown by following Structural formula (8) or (9) is desirable.

In the structural formulas (8) and (9), R ⁰⁵ and R ⁰⁶ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 or more carbon atoms. 1 represents one selected from the group consisting of a phenyl group substituted with 4 or less alkoxy groups, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, and q is 1 to 3 Represents an integer.

  In the structural formula (7), Z ′ represents a divalent organic linking group, and is preferably represented by any one of the following structural formulas (10) to (17). P represents 0 or 1.

In the structural formulas (10) to (17), R ⁰⁷ and R ⁰⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 or more carbon atoms. 1 represents one selected from the group consisting of a phenyl group substituted with 4 or less alkoxy groups, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, and W represents a divalent group. , R and s each independently represents an integer of 1 to 10, and t represents an integer of 1 to 3.

  W in the structural formulas (16) to (17) is preferably any one of divalent groups represented by the following (18) to (26). However, in formula (25), u represents an integer of 0 or more and 3 or less.

In general formula (II), Ar ⁵ is a substituted or unsubstituted aryl group when k is 0, and this aryl group is the same as the aryl group exemplified in the description of Ar ^{1 to} Ar ^4. Can be mentioned. Ar ⁵ is a substituted or unsubstituted arylene group when k is 1, and the arylene group includes a hydrogen atom at a target position from the aryl group exemplified in the description of Ar ^{1 to} Ar ^4. And an arylene group without one

  Specific examples of the compound represented by the general formula (I) are shown below. In addition, the compound shown by general formula (I) is not limited at all by these.

  First, as specific examples of the charge transporting skeleton F in the case where the total number of D in the general formula (I) is 1, “(1) -1” to “(1) -25” are shown, but are not limited thereto. is not. In addition, the part of * in each structure shows connecting with D in general formula (I).

Next, as specific examples of the charge transporting skeleton F in the case where the total number of D in the general formula (I) is 2, “(2) -1” to “(2) -29” are shown, but are not limited thereto. It is not a thing.
In addition, the part of * in each structure shows connecting with D in general formula (I).

Next, specific examples of the charge transporting skeleton F in the case where the total number of D in the general formula (I) is 3 are “(3) -1” to “(3) -29”, but are not limited thereto. It is not a thing.
In addition, the part of * in each structure shows connecting with D in general formula (I).

  Next, specific examples of the charge transporting skeleton F in the case where the total number of D in the general formula (I) is 4 or more include “(4) -1” to “(4) -31”. It is not something that can be done. In addition, the part of * in each structure shows connecting with D in general formula (I).

Next, “(III) -1” to “(III) -66” are shown as specific examples of D in the general formula (I) or the general formula (II), that is, the group represented by the formula (III). In addition, it shows that the part of * in each structure connects with the charge transporting skeleton F in the general formula (I) or Ar ^{1 to} Ar ⁵ in the general formula (II).

Next, although the specific example of the novel reactive compound shown by general formula (I) is shown below, this embodiment is not limited to these.
The “CTM skeleton structure” in the following table corresponds to the charge transporting skeleton F in the general formula (I).

  An example of the synthesis route of the charge transport material (A) used in this embodiment is shown below.

  Two or more kinds of the charge transport material (A) of this embodiment may be used in the composition for forming the charge transport layer 2B-2. For example, in the charge transport material (A) of the present embodiment, a compound having a total number of styrene skeletons in one molecule of 4 or more and a compound having a total number of styrene skeletons in one molecule of 1 to 3 are included. When used in combination, the strength of the polymerized or cured film can be adjusted without reducing the charge transport performance. In that case, a compound in which the total number of styrene skeletons in one molecule is 4 or more in the charge transporting material (A) of the present embodiment with respect to the total content of the charge transporting material (A) of the present embodiment. Is preferably 5% by mass or more, and more preferably 20% by mass or more.

The content of the charge transport material (A) of the present embodiment is preferably 40% by mass or more, preferably 50% by mass or more, based on the total solid content of the composition for forming the charge transport layer 2B-2. 60 mass% or more is still more preferable.
Next, components other than the charge transport material (A) of the present embodiment among the components constituting the composition for forming the charge transport layer 2B-2 will be described.

  The composition for forming the charge transport layer 2B-2 may contain a charge transport agent (B) having a chain polymerizable functional group other than the charge transport material (A) of the present embodiment. Examples of the charge transfer agent (B) include compounds described in paragraphs [0060] to [0099] of JP-A-2000-206715, and paragraphs [0066] to [0080] of JP-A-2011-70023. And the like. The content of the charge transport agent (B) is usually 0% by mass or more and 40% by mass or less, and 0% by mass or more and 30% by mass with respect to the total solid content of the composition for forming the charge transport layer 2B-2. The following is desirable, and more preferably 0% by mass or more and 20% by mass or less.

  The composition for forming the charge transport layer 2B-2 may include the charge transport material and the binder resin mentioned in the description of the charge transport layer 2B-1. The content is usually 0% by mass or more and 40% by mass or less, and preferably 0% by mass or more and 30% by mass or less, based on the total solid content of the composition for forming the charge transport layer 2B-2. More preferably, it is 0% by mass or more and 20% by mass or less.

The composition for forming the charge transport layer 2B-2 may contain the following surfactant from the viewpoint of ensuring film forming properties.
Examples of the surfactant include (A) a structure formed by polymerizing an acrylic monomer having a fluorine atom, (B) a structure having a carbon-carbon double bond and a fluorine atom, (C) an alkylene oxide structure, and (D) carbon. -A surfactant containing in the molecule thereof one or more types of structures having a carbon triple bond and a hydroxyl group.
This surfactant needs to contain 1 or more types of the structure of (A) thru | or (D) in the molecule | numerator, and may contain 2 or more types.

  Hereinafter, the structures (A) to (D) and the surfactant having the structure will be described.

(A) Structure formed by polymerizing an acrylic monomer having a fluorine atom (A) The structure formed by polymerizing an acrylic monomer having a fluorine atom is not particularly limited, but an acrylic monomer having a fluoroalkyl group is polymerized. The structure is preferably a structure obtained by polymerizing an acrylic monomer having a perfluoroalkyl group.

  Specific examples of the surfactant having the structure (A) include Polyflow KL-600 (manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF-351, EF-352, EF-801, EF-802, and EF- 601 (manufactured by JEMCO).

(B) Structure having a carbon-carbon double bond and a fluorine atom (B) The structure having a carbon-carbon double bond and a fluorine atom is not particularly limited, but in the following structural formulas (B1) and (B2) It is desirable that the group be at least one of them.

As the surfactant having the structure (B), a compound having a group represented by at least one of the structural formulas (B1) and (B2) in the side chain of the acrylic polymer, or the following structural formulas (B3) to (B3) to The compound represented by any one of (B5) is desirable.
When the surfactant having the structure (B) is a compound having at least one of the structural formulas (B1) and (B2) in the side chain of the acrylic polymer, the acrylic structure and the other components in the composition Since it has the property of being easily adapted, an outermost surface layer that is nearly uniform can be formed.
In addition, when the surfactant having the structure (B) is a compound represented by any one of the structural formulas (B3) to (B5), it tends to prevent repelling during coating. Defects can be suppressed.

In the structural formulas (B3) to (B5), v and w each independently represent an integer of 1 or more, R ′ represents a hydrogen atom or a monovalent organic group, and Rf each independently represents a structural formula (B1). Or represents the group shown by (B2).
In the structural formulas (B3) to (B5), examples of the monovalent organic group represented by R ′ include an alkyl group having 1 to 30 carbon atoms and a hydroxyalkyl group having 1 to 30 carbon atoms.

The following are mentioned as a commercial item of surfactant which has the structure of (B).
For example, as a compound represented by any one of structural formulas (B3) to (B5), the following are possible: 100, 100C, 110, 140A, 150, 150CH, AK, 501, 250, 251, 222F, FTX-218, 300, 310, 400SW, 212M, 245M, 290M, FTX-207S, FTX-211S, FTX-220S, FTX-230S, FTX-209F, FTX-213F, FTX-222F, FTX-233F, FTX-245F, FTX- 208G, FTX-218G, FTX-230G, FTX-240G, FTX-204D, FTX-280D, FTX-212D, FTX-216D, FTX-218D, FTX-220D (manufactured by Neos Corporation), etc. It is done.
Moreover, as a compound which has at least one of Structural formula (B1) and (B2) in the side chain of an acrylic polymer, KB-L82, KB-L85, KB-L97, KB-L109, KB-L110, KB-F2L , KB-F2M, KB-F2S, KB-F3M, KB-FaM (manufactured by Neos Corporation) and the like.

-(C) alkylene oxide structure (C) As an alkylene oxide structure, an alkylene oxide and a polyalkylene oxide are included. Specific examples of the alkylene oxide include ethylene oxide and propylene oxide, and the alkylene oxide may be a polyalkylene oxide having a repeating number of 2 to 10,000.
Examples of the surfactant (C) having an alkylene oxide structure include polyethylene glycol, polyether antifoaming agent, and polyether-modified silicone oil.
The polyethylene glycol preferably has an average molecular weight of 2000 or less, and the polyethylene glycol having an average molecular weight of 2000 or less includes polyethylene glycol 2000 (average molecular weight 2000), polyethylene glycol 600 (average molecular weight 600), polyethylene glycol 400 (average molecular weight). 400), polyethylene glycol 200 (average molecular weight 200), and the like.
In addition, PE-M, PE-L (above, manufactured by Wako Pure Chemical Industries, Ltd.), antifoam No. 1. Antifoaming agent No. 1 Polyether antifoaming agents such as 5 (above, manufactured by Kao Corporation) are also suitable examples.

(C) As the surfactant containing a fluorine atom in the molecule in addition to the alkylene oxide structure, those having an alkylene oxide or polyalkylene oxide in the side chain of the polymer having a fluorine atom, and alkylene oxide or polyalkylene oxide Examples thereof include those in which the terminal is substituted with a substituent containing a fluorine atom.
(C) Specific examples of surfactants containing a fluorine atom in the molecule in addition to the alkylene oxide structure include, for example, Megafac F-443, F-444, F-445, F-446 (and above, Dainippon Ink, Inc.). Chemical Industry Co., Ltd.), Footgent 250, 251, 222F (above, manufactured by Neos), POLY FOX PF636, PF6320, PF6520, PF656 (above, made by Kitamura Chemical Co., Ltd.).

  (C) Specific examples of the surfactant containing a silicone structure in the molecule in addition to the alkylene oxide structure include KF351 (A), KF352 (A), KF353 (A), KF354 (A), KF355 (A ), KF615 (A), KF618, KF945 (A), KF6004 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF4440, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460 (manufactured by GE Toshiba Silicon Corporation), BYK- 300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 341, 344, 345, 346, 347, 348, 370, 375, 377, 378, UV3500, UV3510, UV3570, etc. (above, Kkukemi Japan Co., Ltd.) and the like.

-(D) Structure having a carbon-carbon triple bond and a hydroxyl group (D) The structure having a carbon-carbon triple bond and a hydroxyl group is not particularly limited, and examples of the surfactant having this structure include the following compounds. It is done.
(D) Examples of the surfactant having a structure having a carbon-carbon triple bond and a hydroxyl group include compounds having a triple bond and a hydroxyl group in the molecule. Specifically, for example, 2-propyn-1-ol, 1-butyn-3-ol, 2-butyn-1-ol, 3-butyn-1-ol, 1-pentyn-3-ol, 2-pentyn-1-ol, 3-pentyn-1-ol, 4- Pentyn-1-ol, 4-pentyn-2-ol, 1-hexyn-3-ol, 2-hexyn-1-ol, 3-hexyn-1-ol, 5-hexyn-1-ol, 5-hexyne- 3-ol, 1-heptin-3-ol, 2-heptin-1-ol, 3-heptin-1-ol, 4-heptin-2-ol, 5-heptin-3-ol, 1-octin-3- All, 1-o Chin-3-ol, 3-octyn-1-ol, 3-nonin-1-ol, 2-decyn-1-ol, 3-decyn-1-ol, 10-undecin-1-ol, 3-methyl- 1-butyn-3-ol, 3-methyl-1-penten-4-in-3-ol, 3-methyl-1-pentyn-3-ol, 5-methyl-1-hexyn-3-ol, 3- Ethyl-1-pentyn-3-ol, 3-ethyl-1-heptin-3-ol, 4-ethyl-1-octin-3-ol, 3,4-dimethyl-1-pentyn-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3,6-dimethyl-1-heptin-3-ol, 2,2,8,8-tetramethyl-3,6-nonadiin-5-ol, 4,6 -Nonadecadiin-1-ol, 10,12-pe Tacosadin-1-ol, 2-butyne-1,4-diol, 3-hexyne-2,5-diol, 2,4-hexadiyne-1,6-diol, 2,5-dimethyl-3-hexyne-2, 5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, (+)-1,6-bis (2-Chlorophenyl) -1,6-diphenyl-2,4-hexadiyne-1,6-diol, (-)-1,6-bis (2-chlorophenyl) -1,6-diphenyl-2,4-hexadiyne -1,6-diol, 2-butyne-1,4-diol bis (2-hydroxyethyl), 1,4-diacetoxy-2-butyne, 4-diethylamino-2-butyn-1-ol, 1,1-diphenyl -2-propyne 1-ol, 1-ethynyl-1-cyclohexanol, 9-ethynyl-9-fluorenol, 2,4-hexadiindiyl-1,6-bis (4-phenylazobenzenesulfonate), 2-hydroxy-3- Butynoic acid, 2-hydroxy-3-butynoic acid ethyl ester, 2-methyl-4-phenyl-3-butyn-2-ol, methyl propargyl ether, 5-phenyl-4-pentyn-1-ol, 1-phenyl- 1-propyn-3-ol, 1-phenyl-2-propyne-1-ol, 4-trimethylsilyl-3-butyn-2-ol, 3-trimethylsilyl-2-propyne-1-ol and the like can be mentioned.
Moreover, the compound (For example, Surfynol 400 series (made by Shin-Etsu Chemical Co., Ltd.) etc.) which alkylene oxides, such as ethylene oxide, added to a part or all of the hydroxyl group of said compound are mentioned.

  (D) As the surfactant having a structure having a carbon-carbon triple bond and a hydroxyl group, a compound represented by any one of the following general formulas (D1) and (D2) is desirable.

In the general formulas (D1) and (D2), R ^a , R ^b , R ^c , and R ^d each independently represent a monovalent organic group, and x, y, and z are each independently An integer of 1 or more is shown.
Among the compounds represented by the general formula (D1) or (D2), those in which R ^a , R ^b , R ^c and R ^d are alkyl groups are preferable. More preferably, at least one of R ^a and R ^b and at least one of R ^c and R ^d are branched alkyl groups. Furthermore, z is preferably 1 or more and 10 or less. x and y are each preferably 1 or more and 500 or less.

  Surfinol 400 series (made by Shin-Etsu Chemical Co., Ltd.) is mentioned as a commercial item of the compound shown by general formula (D1) or (D2).

The surfactants having the structures (A) to (D) described above may be used singly or in combination of two or more. In the case of using a mixture of a plurality of types, a surfactant having a structure different from the surfactant having the structure of (A) to (D) may be used in combination as long as the effect is not impaired.
Examples of the surfactant that can be used in combination include the following surfactants having a fluorine atom and surfactants having a silicone structure.
That is, as the surfactant having a fluorine atom that can be used in combination with the surfactant having the structure of (A) to (D), perfluoroalkylsulfonic acid (for example, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, etc.) ), Perfluoroalkyl carboxylic acids (for example, perfluorobutane carboxylic acid, perfluoro octane carboxylic acid, etc.), and perfluoroalkyl group-containing phosphate esters. Perfluoroalkylsulfonic acids and perfluoroalkylcarboxylic acids may be salts thereof and amide-modified products thereof.
Examples of commercially available perfluoroalkyl sulfonic acids include Megafac F-114 (manufactured by Dainippon Ink & Chemicals, Inc.), F-top EF-101, EF102, EF-103, EF-104, EF-105, and EF. -112, EF-121, EF-122A, EF-122B, EF-122C, EF-123A (manufactured by JEMCO), FT 100, 100C, 110, 140A, 150, 150CH, AK, 501 ( As mentioned above, the Neos company) etc. are mentioned.
Examples of commercially available perfluoroalkylcarboxylic acids include Megafac F-410 (Dainippon Ink Chemical Co., Ltd.), F-Top EF-201, EF-204 (above, JEMCO).
As commercial products of perfluoroalkyl group-containing phosphates, MegaFac F-493, F-494 (above, manufactured by Dainippon Ink & Chemicals, Inc.) F-top EF-123A, EF-123B, EF-125M, EF -132 (above, manufactured by JEMCO).

  In addition, the surfactant having a fluorine atom that can be used in combination with the surfactant having the structure of (A) to (D) is not limited to the above, and for example, a fluorine atom-containing betaine structure compound (for example, Factent 400SW, Neos) and surfactants having amphoteric ion groups (for example, Footent SW (manufactured by Neos)) are also preferably used.

  Examples of the surfactant having a silicone structure that can be used in combination with the surfactant having the structure of (A) to (D) include general silicone oils such as dimethyl silicone, methylphenyl silicone, diphenyl silicone, and derivatives thereof. Can be mentioned.

The content of the surfactant is desirably 0.01% by mass or more and 1% by mass or less, more desirably 0.02% by mass or more, based on the total solid content of the composition for forming the charge transport layer 2B-2. 0.5% by mass or less. When the content of the surfactant is less than 0.01% by mass, the coating film defect preventing effect tends to be insufficient. Further, when the content of the surfactant exceeds 1% by mass, a polymerized or cured film obtained by separating the surfactant from the curing component (a compound represented by the general formula (I), other monomers, oligomers, etc.) The strength of the steel tends to decrease.
The surfactant having the structures (A) to (D) is preferably contained in an amount of 1% by mass or more, and more preferably 10% by mass or more.

In addition, the composition used for forming the charge transport layer 2B-2 has no charge transport ability for the purpose of controlling the viscosity, film strength, flexibility, smoothness, cleaning property, etc. of the composition. A radical polymerizable monomer, oligomer or the like may be added.
Examples of the monofunctional radical polymerizable monomer include isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate , Phenoxypolyethyleneglycol Lumpur acrylate, phenoxy polyethylene glycol methacrylate, hydroxyethyl o- phenylphenol acrylate, and the like o- phenylphenol glycidyl ether acrylate.

  Examples of the bifunctional radical polymerizable monomer include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 2-n-butyl-2-ethyl- 1,3-propanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dioxane glycol diacrylate, polytetramethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane Examples include methanol diacrylate, tricyclodecane methanol dimethacrylate, divinylbenzene, and diallylpropyl isocyanurate.

  Examples of the tri- or more functional radical polymerizable monomer include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol acrylate, trimethylolpropane EO-added triacrylate, glycerin PO-added triacrylate, and trisacryloyloxyethylphosphine. Fate, pentaerythritol tetraacrylate, ethoxylated isocyanuric triacrylate, triallyl isocyanuric acid, trivinylcyclohexane, trivinylbenzene, and the like.

  Moreover, as a radically polymerizable oligomer, an epoxy acrylate type, a urethane acrylate type, and a polyester acrylate type oligomer are mentioned, for example.

  The radically polymerizable monomer or oligomer having no charge transporting ability is preferably contained in an amount of 0 to 50% by mass, more preferably 0 to 40% by mass, based on the total solid content of the composition. More preferably, the content is from 0 to 30% by mass.

Here, the cured film (crosslinked film) constituting the charge transport layer 2B-2 can be obtained by curing the composition containing the above components by various methods such as heat, light, and electron beam. If necessary, a thermal polymerization initiator and a photopolymerization initiator may be added to the composition.
In order to balance characteristics such as mechanical strength, thermosetting is desirable. Usually, when curing a general acrylic paint or the like, an electron beam that cures without a catalyst and photopolymerization that cures in a short time are preferably used. However, in the electrophotographic photosensitive member, since the photosensitive layer which is the surface of the outermost layer contains a photosensitive material, it is difficult to damage the photosensitive material, and in order to improve the surface properties of the obtained cured film, It is desirable to perform thermosetting that allows the reaction to proceed. Thermal curing may be performed without a catalyst, but it is desirable to use a thermal radical initiator as a catalyst.

  The thermal radical initiator is not particularly limited, but is preferably one having a 10-hour half-life temperature of 40 ° C. or higher and 110 ° C. or lower in order to suppress damage to the photosensitive material in the photosensitive layer during formation of the charge transport layer 2B-2. .

Commercially available products of thermal radical initiators include V-30 (10-hour half-life temperature: 104 ° C.), V-40 (same: 88 ° C.), V-59 (same: 67 ° C.), V-601 (same as above: 66 ° C), V-65 (same: 51 ° C), V-70 (same: 30 ° C), VF-096 (same: 96 ° C), Vam-110 (same: 111 ° C), Vam-111 (same: 111 ° C.), VE-073 (same as above: 73 ° C.) (Wako Pure Chemical Industries, Ltd.), OTAZO-15 (same as 61 ° C.), OTAZO-30 (same as 57 ° C.), AIBN (same as 65 ° C.) Azo initiators such as AMBN (same: 67 ° C.), ADVN (same: 52 ° C.), ACVA (same: 68 ° C.) (above, manufactured by Otsuka Chemical Co., Ltd.);
Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Perbutyl H, Park Mill H, Park Mill P, Permenta H, Per Octa H, Perbutyl C, Perbutyl D, Perhexyl D, Parroyl IB, Parroyl 355, Parroyl L , Parroyl SA, Niper BW, Niper BMT-K40 / M, Parroyl IPP, Parroyl NPP, Parroyl TCP, Parroyl OPP, Parroyl SBP, Parkmill ND, Perocta ND, Perhexyl ND, Perbutyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl PV, Perhexa 250, Perocta O, Perhexyl O, Perbutyl O, Perbutyl L, Perbutyl 355, Perhexyl I, Perbutyl I, Perbutyl E, Perhexa 5Z, perbutyl A, perhexyl Z, perbutyl ZT, perbutyl Z (manufactured by NOF Chemical Co., Ltd.), Kayaketal AM-C55, Trigonox 36-C75, Laurox, Parkardox L-W75, Percadox CH-50L, Trigonox TMBH, Kayakumen H, Kayabutyl H-70, Percadox BC-FF, Kaya Hexa AD, Parka Dox 14, Kaya Butyl C, Kaya Butyl D, Kaya Hexa YD-E85, Perkadox 12-XL25, Perkadox 12-EB20, Trigonox 22-N70, Trigonox 22-70E, Trigonox DT50, Trigonox 423-C70, Kayaester CND-C70, Kayaester CND-W50, Trigonox 23-C70, Trigonox 23-W5 N, Trigonox 257-C70, Kayaester P-70, Kayaester TMPO-70, Trigonox 121, Kayaester O, Kayaester HTP-65W, Kayaester AN, Trigonox42, Trigonox F-C50, Kayabutyl B, Kayacarboxyl EH- C70, Kaya-Carbon EH-W60, Kaya-Carbon I-20, Kaya-Carbon BIC-75, Trigonox 117, Kayalen 6-70 (manufactured by Kayaku Akzo), Luperox LP (same: 64 ° C.), Ruperox 610 (same: 37 ° C. ), Lupelox 188 (same: 38 ° C), Lupelox 844 (same: 44 ° C), Lupelox 259 (same: 46 ° C), Lupelox 10 (same: 48 ° C), Lupelox 701 (same: 53 ° C), Lupelox 11 ( Same: 58 ℃) Rox 26 (same: 77 ° C), Lupelox 80 (same: 82 ° C), Lupelox 7 (same: 102 ° C), Lupelox 270 (same: 102 ° C), Lupelox P (same: 104 ° C), Lupelox 546 (same: 46 ° C), Lupelox 554 (same: 55 ° C), Lupelox 575 (same: 75 ° C), Lupelox TANPO (same: 96 ° C), Lupelox 555 (same: 100 ° C), Lupelox 570 (same: 96 ° C), Lupelox TAP (same as above: 100 ° C.), Luperox TBIC (same as above: 99 ° C.), Luperlocks TBEC (same as above: 100 ° C.), Luperlocks JW (same as above: 100 ° C.), Lupelox TAIC (same as above: 96 ° C.), Lupelox TAEC (same as 99) ° C), Luperox DC (same as 117 ° C), Luperox 101 (same as 120 ° C) Lupelox F (same as 116 ° C), Lupelox DI (same as 129 ° C), Lupelox 130 (same as 131 ° C), Lupelox 220 (same as 107 ° C), Lupelox 230 (same as 109 ° C), Lupelox 233 (same as above) : 114 ° C.), Ruperox 531 (same as 93 ° C.) (above, manufactured by Arkema Yoshitomi).

  The thermal radical initiator is preferably contained in an amount of 0.001% by mass to 10% by mass with respect to the reactive compound in the composition, more preferably 0.01% by mass to 5% by mass. It is more desirable to contain 1 mass% or more and 3 mass% or less.

Moreover, when forming charge transport layer 2B-2 by photocuring, a well-known thing is used as a photoinitiator. Examples of the photo radical initiator include an intramolecular open type and a hydrogen abstraction type.
Examples of the intramolecular open type include benzyl ketal, alkylphenone, aminoalkylphenone, phosphine oxide, titanocene, and oxime.
Specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one is mentioned as the benzyl ketal system. Examples of alkylphenones include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl] -2. -Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane- Examples include 1-one, acetophenone, and 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone. Examples of aminoalkylphenones include p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1 -Butanone and the like. Examples of the phosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Examples of the titanocene include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Examples of oximes include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (0-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-, 1- (0-acetyloxime) and the like.

Examples of the hydrogen abstraction type include benzophenone series, thioxanthone series, benzyl series, and Michler ketone series.
Specifically, examples of the benzophenone series include 2-benzoylbenzoic acid, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl 4′-methyldiphenyl sulfide, p, p′-bisdiethylaminobenzophenone, and the like. It is done. Examples of the thioxanthone series include 2,4-diethylthioxanthen-9-one, 2-chlorothioxanthone, and 2-isopropylthioxanthone. Examples of the benzyl type include benzyl, (±) -camphorquinone, p-anisyl and the like.

  The photo radical initiator is preferably contained in an amount of 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, based on the reactive compound in the composition. It is more desirable to contain 1 mass% or more and 3 mass% or less.

  In addition, the composition used for forming the charge transport layer 2B-2 is added with a phenol resin, for the purpose of effectively suppressing oxidation by the discharge generated gas by adding the discharge generated gas so as not to adsorb too much. You may add other thermosetting resins, such as a melamine resin and a benzoguanamine resin.

Further, the composition used for forming the charge transport layer 2B-2 further includes a coupling agent, a hard coat for the purpose of adjusting the film formability, flexibility, lubricity, and adhesiveness of the film. An agent and a fluorine-containing compound may be added. Specifically, various silane coupling agents and commercially available silicone hard coat agents are used as these additives.
As the silane coupling agent, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane and the like are used.

Commercially available hard coat agents include KP-85, X-40-9740, X-8239 (manufactured by Shin-Etsu Silicone), AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Etc.) are used.
Further, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (hepta) for imparting water repellency and the like. Fluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyl Fluorine-containing compounds such as triethoxysilane may be added.
Although the silane coupling agent is used in an arbitrary amount, the amount of the fluorine-containing compound should be 0.25 times or less in terms of mass ratio with respect to the compound not containing fluorine from the viewpoint of the film formability of the crosslinked film. Is desirable.

The composition used to form the charge transport layer 2B-2 includes discharge gas resistance, mechanical strength, scratch resistance, torque reduction, wear amount control, pot life extension, etc. of the charge transport layer 2B-2, A thermoplastic resin may be added for the purpose of particle dispersibility and viscosity control.
Polyvinyl butyral resin, polyvinyl formal resin, polyvinyl acetal resin such as partially acetalized polyvinyl acetal resin in which a part of butyral is modified with formal, acetoacetal, or the like (for example, Sleksui Chemical Co., Ltd., ESREC B, K, etc.), polyamide resin, cellulosic -Resin, polyvinyl phenol resin and the like. In particular, polyvinyl acetal resin and polyvinyl phenol resin are desirable in terms of electrical characteristics. The resin preferably has a weight average molecular weight of 2,000 to 100,000, and more preferably 5,000 to 50,000. If the molecular weight of the resin is less than 2,000, the effect due to the addition of the resin tends to be insufficient, and if it exceeds 100,000, the solubility is reduced and the addition amount is limited. It tends to cause defects. The amount of the resin added is preferably 1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 30% by mass or less, and further preferably 5% by mass or more and 20% by mass or less. If the addition amount of the resin is less than 1% by mass, the effect of the addition of the resin tends to be insufficient. If the addition amount exceeds 40% by mass, the temperature is high under high humidity (for example, 28 ° C., 85% RH). Image blur is likely to occur.

An antioxidant is added to the composition used for forming the charge transport layer 2B-2 for the purpose of preventing deterioration due to an oxidizing gas such as ozone generated in the charging device of the charge transport layer 2B-2. Is desirable. When the mechanical strength of the surface of the photoconductor is increased and the photoconductor has a long life, the photoconductor is in contact with the oxidizing gas for a long time, and therefore, stronger oxidation resistance is required than before.
Antioxidants are preferably hindered phenols or hindered amines, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants. , Etc., may be used. The addition amount of the antioxidant is preferably 20% by mass or less, and more preferably 10% by mass or less.
Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, N, N′-hexamethylene bis (3,5-di). -T-butyl-4-hydroxyhydrocinnamide, 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,5-di-t-amylhydroquinone, 2-t-butyl-6- (3-butyl-2-hydro Xyl-5-methylbenzyl) -4-methylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), and the like.

Furthermore, various particles may be added to the composition used for forming the charge transport layer 2B-2 for the purpose of lowering the residual potential of the charge transport layer 2B-2 or improving the strength.
An example of the particles is silicon-containing particles. The silicon-containing particles are particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone particles. The colloidal silica used as the silicon-containing particles is obtained by dispersing silica having an average particle diameter of 1 nm or more and 100 nm or less, preferably 10 nm or more and 30 nm or less in an organic solvent such as an acidic or alkaline aqueous dispersion, alcohol, ketone, or ester. A commercially available product may be used. The solid content of colloidal silica in the charge transport layer 2B-2 is not particularly limited, but the total solid content of the charge transport layer 2B-2 is determined from the viewpoint of film forming properties, electrical characteristics, and strength. As a reference, it is used in the range of 0.1 to 50% by mass, desirably 0.1 to 30% by mass.
The silicone particles used as the silicon-containing particles are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and those commercially available are generally used. These silicone particles are spherical, and the average particle size is desirably 1 nm or more and 500 nm or less, and more desirably 10 nm or more and 100 nm or less. Silicone particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain more sufficient properties is low, the electron does not hinder the crosslinking reaction. The surface properties of the photographic photoreceptor are improved. In other words, it is improved in lubricity and water repellency on the surface of the electrophotographic photosensitive member in a state of being taken in without a variation in a strong cross-linked structure, and has good wear resistance and contamination resistance adhesion over a long period of time. Maintained.
The content of the silicone particles in the charge transport layer 2B-2 is desirably 0.1% by mass or more and 30% by mass or less, more desirably 0.5% by mass based on the total amount of the total solid content of the charge transport layer 2B-2. It is 10 mass% or less.

Other particles include fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, and vinylidene fluoride, as shown in the 8th Polymer Materials Forum Lecture Proceedings p89. As shown, particles made of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO ₂ —TiO ₂ , ZnO Examples thereof include semiconductive metal oxides such as —TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. For the same purpose, an oil such as silicone oil may be added. Silicone oils include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane; amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, mercapto-modified poly Reactive silicone oils such as siloxane and phenol-modified polysiloxane; cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; 1,3,5- Trimethyl-1.3.5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclo Cyclic methylphenylcyclosiloxanes such as tetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane; cyclic phenylcyclosiloxanes such as hexaphenylcyclotrisiloxane Fluorine-containing cyclosiloxanes such as (3,3,3-trifluoropropyl) methylcyclotrisiloxane; hydrosilyl group-containing cyclosiloxanes such as methylhydrosiloxane mixtures, pentamethylcyclopentasiloxane, and phenylhydrocyclosiloxane; penta And vinyl group-containing cyclosiloxanes such as vinylpentamethylcyclopentasiloxane.

  Moreover, you may add a metal, a metal oxide, carbon black, etc. to the composition used in order to form charge transport layer 2B-2. Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, or those obtained by depositing these metals on the surface of plastic particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. . These may be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion. The average particle diameter of the conductive particles is preferably 0.3 μm or less, particularly preferably 0.1 μm or less, from the viewpoint of the transparency of the charge transport layer 2B-2.

The composition used to form the charge transport layer 2B-2 is preferably prepared as a coating solution for forming the charge transport layer 2B-2, and this coating solution may be solventless or necessary. Aromatic hydrocarbons such as toluene, xylene and chlorobenzene; alcohols such as methanol, ethanol, propanol, butanol, cyclopentanol and cyclohexanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran, diethyl Ethers such as ether, diisopropyl ether and dioxane; solvents such as esters such as ethyl acetate, npropyl acetate, nbutyl acetate and ethyl lactate may be contained.
Such solvents are used singly or in combination of two or more, and preferably have a boiling point of 100 degrees or less.
Moreover, you may contain a polymerization inhibitor in order to improve the storage stability of the coating liquid for charge transport layer 2B-2 formation. Known polymerization inhibitors are used. The hindered phenol type or hindered amine type listed as specific examples of the above-mentioned antioxidant is advantageous because it functions also as a polymerization inhibitor.

A coating liquid for forming a charge transport layer 2B-2 containing a composition used for forming the charge transport layer 2B-2 is formed on the charge transport layer 2B-1 by a blade coating method, a wire bar coating method, or a spray coating method. Applied to the surface to be coated (in the first embodiment shown in FIG. 1, the surface of the charge transport layer 2B-1) by a usual method such as dip coating, bead coating, air knife coating, curtain coating, etc. If necessary, for example, a polymerized or cured film is obtained by heating (polymerization) by heating at a temperature of 100 ° C. or more and 170 ° C. or less. As a result, a charge transport layer 2B-2 (corresponding to the layer (Oc1) of the present embodiment in the first mode) made of this polymerized or cured film is obtained.
In addition, the oxygen concentration during curing of the coating liquid for forming the charge transport layer 2B-2 is desirably 1% or less, more desirably 1000 ppm or less, and further desirably 500 ppm or less.

  The coating liquid for forming the charge transport layer 2B-2 is used for, for example, an antistatic film such as a fluorescent coloring paint, a glass surface, a plastic surface, etc., in addition to the use as a photoreceptor. When this coating solution is used, a film having excellent adhesion to the lower layer is formed, and performance deterioration due to repeated use over a long period is suppressed.

-Charge transport layer 2B (corresponding to the layer (Oc2) of the present embodiment in the second mode)
The charge transport layer 2B may have the same configuration as that of the charge transport layer 2B-2 in the first embodiment. As a composition for forming the charge transport layer 2B and a method for forming the composition, the charge transport layer 2B-2 is used. Is the same as

-Single-layer type photosensitive layer 6 (corresponding to the layer (Oc3) of the present embodiment in the third mode)-
As described above, the example of the function separation type is described as the electrophotographic photosensitive member. However, the content of the charge generation material in the single-layer type photosensitive layer 6 (charge generation / charge transport layer) shown in FIG. It is about 85% by mass or less, desirably 20% by mass or more and 50% by mass or less. In addition, the content of the charge transport material is desirably 5% by mass or more and 50% by mass or less.
The formation method of the single-layer type photosensitive layer 6 (charge generation / charge transport layer) is the same as the formation method of the charge generation layer 2A and the charge transport layer 2B-2. The film thickness of the single-layer type photosensitive layer (charge generation / charge transport layer) 6 is preferably about 5 μm to 50 μm, and more preferably 10 μm to 40 μm.

  Moreover, in the said embodiment, although the outermost surface layer which consists of a polymerization of the composition containing the said charge transport material (A) or a cured film demonstrated the form which is a charge transport layer or a photosensitive layer, a charge transport layer or When a protective layer is provided as the outermost surface layer on the photosensitive layer, the protective layer may be constituted by a polymerized or cured film of a composition containing the charge transporting material (A).

[Image forming apparatus / process cartridge]
FIG. 4 is a schematic configuration diagram illustrating the image forming apparatus according to the present embodiment. An image forming apparatus 100 shown in FIG. 4 includes a process cartridge 300 including an electrophotographic photosensitive member 7, an exposure device (electrostatic latent image forming unit) 9, a transfer device (transfer unit) 40, and an intermediate transfer member 50. . In the image forming apparatus 100, the exposure device 9 is disposed at a position where the electrophotographic photosensitive member 7 is exposed from the opening of the process cartridge 300, and the transfer device 40 is interposed between the electrophotographic photosensitive member 7 via the intermediate transfer member 50. The intermediate transfer member 50 is partly in contact with the electrophotographic photosensitive member 7.

  A process cartridge 300 in FIG. 4 integrally supports an electrophotographic photosensitive member 7, a charging device (charging means) 8, a developing device (developing means) 11, and a cleaning device 13 in a housing. The cleaning device 13 has a cleaning blade (cleaning member) 131, and the cleaning blade 131 is disposed so as to contact the surface of the electrophotographic photoreceptor 7.

  In FIG. 4, the cleaning device 13 includes a fibrous member 132 (roll shape) for supplying the lubricant 14 to the surface of the photoreceptor 7, and a fibrous member 133 (flat brush shape) that assists cleaning. Although the example used is shown, these are used as needed.

  As the charging device 8, for example, a contact type charger using a conductive or semiconductive charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube or the like is used. Further, a non-contact type roller charger, a known charger such as a scorotron charger using a corona discharge or a corotron charger may be used.

  Although not shown, a photosensitive member heating member for increasing the temperature of the electrophotographic photosensitive member 7 and reducing the relative temperature is provided around the electrophotographic photosensitive member 7 for the purpose of improving the stability of the image. Also good.

  Examples of the exposure apparatus 9 include optical system devices that expose the surface of the photoconductor 7 with light such as semiconductor laser light, LED light, and liquid crystal shutter light in a desired image-like manner. The wavelength of the light source is in the spectral sensitivity region of the photoreceptor. As the wavelength of the semiconductor laser, near infrared having an oscillation wavelength near 780 nm is the mainstream. However, the present invention is not limited to this wavelength, and an oscillation wavelength laser in the 600 nm range or a laser having an oscillation wavelength in the vicinity of 400 nm to 450 nm as a blue laser may be used. For color image formation, a surface-emitting laser light source capable of multi-beam output is also effective.

  As the developing device 11, for example, a general developing device that performs development by bringing a magnetic or non-magnetic one-component developer or a two-component developer into contact or non-contact may be used. The developing device is not particularly limited as long as it has the functions described above, and is selected according to the purpose. For example, a known developing device having a function of attaching the one-component developer or the two-component developer to the photoreceptor 7 using a brush, a roller, or the like can be used. Among these, those using a developing roller holding the developer on the surface are desirable.

Hereinafter, the toner used in the developing device 11 will be described.
The developer may be a one-component developer made of toner, or a two-component developer containing toner and carrier.

  The toner includes, for example, toner particles containing a binder resin, a colorant, and, if necessary, other additives such as a release agent, and external additives as necessary.

  The toner particles have an average shape factor (shape factor = (ML2 / A) × (π / 4) × 100), which is the number average of shape factors, where ML represents the maximum length of the particles, and A represents the projected area of the particles. Is preferably from 100 to 150, more preferably from 105 to 145, and even more preferably from 110 to 140. Further, the toner preferably has a volume average particle diameter of 3 μm or more and 12 μm or less, more preferably 3.5 μm or more and 10 μm or less, and further preferably 4 μm or more and 9 μm or less.

  The toner particles are not particularly limited by the production method, and for example, a kneading and pulverizing method in which a binder resin, a colorant and a release agent, and a charge control agent and the like are added, if necessary, are kneaded, pulverized, and classified; A method of changing the shape of the particles obtained by the kneading and pulverization method by mechanical impact force or thermal energy; the polymerization monomer of the binder resin is emulsion-polymerized, the formed dispersion, the colorant and the release agent Emulsion polymerization aggregation method to obtain a toner particle by mixing a mold agent and, if necessary, a dispersion of a charge control agent, and agglomerating and heat-fusing; a polymerizable monomer for obtaining a binder resin, and coloring Suspension polymerization method in which a solution of an agent, a release agent and, if necessary, a charge control agent is suspended in an aqueous solvent for polymerization; a binder resin, a colorant and a release agent, and if necessary, a charge control agent Toner particles produced by a solution suspension method in which a solution such as a liquid is suspended in an aqueous solvent and granulated There will be used.

  Further, a known method such as a production method in which the toner particles obtained by the above method are used as a core, and agglomerated particles are further adhered and heated and fused to give a core-shell structure is used. The toner production method is preferably a suspension polymerization method, an emulsion polymerization aggregation method, or a dissolution suspension method in which an aqueous solvent is used from the viewpoint of shape control and particle size distribution control, and an emulsion polymerization aggregation method is particularly desirable.

  The toner is produced by mixing the toner particles and the external additive with a Henschel mixer or a V blender. Further, when the toner particles are produced by a wet method, they may be externally added by a wet method.

  When the toner is used as a two-component developer, the mixing ratio with the carrier is set at a known ratio. In addition, there is no restriction | limiting in particular as a carrier, For example, what carried out resin coating to the surface of a magnetic particle as a carrier is mentioned suitably.

  As the transfer device 40, for example, a contact transfer charger using a belt, a roller, a film, a rubber blade, etc., or a known transfer charger such as a scorotron transfer charger using a corona discharge or a corotron transfer charger. Can be mentioned.

  As the intermediate transfer member 50, a belt-like member (intermediate transfer belt) made of polyimide, polyamideimide, polycarbonate, polyarylate, polyester, rubber or the like having semiconductivity is used. Further, as the form of the intermediate transfer member 50, a drum-like one is used in addition to the belt shape.

  In addition to the above-described devices, the image forming apparatus 100 may include, for example, a light neutralizing device that performs light neutralization on the photoconductor 7.

FIG. 5 is a schematic cross-sectional view showing an image forming apparatus 120 according to another embodiment.
An image forming apparatus 120 shown in FIG. 5 is a tandem color image forming apparatus equipped with four process cartridges 300.
In the image forming apparatus 120, four process cartridges 300 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member is used for one color. The image forming apparatus 120 has the same configuration as that of the image forming apparatus 100 except that it is a tandem system.

  The image forming apparatus according to the present embodiment is not limited to the above configuration, and other well-known image forming apparatuses may be applied.

  In the present embodiment described above, the form in which the polymerized or cured film of the composition containing the charge transporting material (A) of the present embodiment is applied as the outermost surface layer of the electrophotographic photoreceptor has been described. The polymerized or cured film containing the charge transport material (A) of the present embodiment is not limited to this. The polymerized or cured film containing the charge transporting material (A) of this embodiment is applied to, for example, an organic electroluminescence (electroluminescence, EL) element, a memory element, a wavelength conversion element, and the like. Since the polymerized or cured film according to the present embodiment is considered to form a polymerized or cured film without impairing the charge transportability, the morphologic due to Joule heat as seen in the conventional charge transportable film. There is no change, and the film has excellent film-forming properties when laminated. As a result, it is useful for the above applications.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
<Synthesis Example 1>
—Synthesis of Charge Transfer Agent I-15 of the Present Invention—
In a 500 ml three-necked flask, 68.3 g of 4,4′-bis (2-methoxycarbonylethyl) diphenylamine, 46.4 g of 4-iodoxylene, 30.4 g of potassium carbonate, 1.5 g of copper sulfate pentahydrate, 50 ml of n-tridecane Was added, and the system was stirred for 20 hours while heating at 220 ° C. while flowing nitrogen. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 20 g of sodium sulfate was added and stirred for 10 minutes, and then sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 65.1 g of I-15a (yield 73%).

  To a 3 L three-necked flask, 59.4 g of I-15a and 450 ml of tetrahydrofuran were added, and an aqueous solution in which 11.7 g of sodium hydroxide was dissolved in 450 ml of water was added thereto, followed by stirring at 60 ° C. for 3 hours. Thereafter, the reaction solution was added dropwise to 1 L of water / 60 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. Further, 50 ml of an acetone / water mixed solvent (volume ratio 40/60) was added to this solid and stirred in a suspended state, and then collected by suction filtration and vacuum-dried for 10 hours to obtain 46.2 g of I-15b. (Yield 83%).

To a 500 ml three-necked flask, 29.2 g of I-15b, 23.5 g of 4-chloromethylstyrene, 21.3 g of potassium carbonate, 0.17 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide) were added. The mixture was flowed and stirred at 75 ° C. for 3 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 36.4 g of the charge transfer agent I-15 of the present invention (yield 80%). .
FIG. 7 shows the IR spectrum of the obtained compound (I) -15.

<Synthesis Example 2>
—Synthesis of Charge Transfer Agent I-43 of the Present Invention—
In a 500 ml three-necked flask, 68.3 g of 4,4′-bis (2-methoxycarbonylethyl) diphenylamine, 43.4 g of 4,4′-diiodo 3,3′-dimethyl-1,1′-biphenyl, 30.4 g of potassium carbonate, Copper sulfate pentahydrate (1.5 g) and n-tridecane (50 ml) were added, and the system was stirred for 20 hours while heating at 220 ° C. with nitrogen flow. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 56.0 g of I-43a (yield 65%).

  43.1 g of I-43a and 350 ml of tetrahydrofuran were added to a 3 L three-necked flask, and an aqueous solution in which 8.8 g of sodium hydroxide was dissolved in 350 ml of water was added thereto, followed by stirring for 5 hours while heating to 60 ° C. Thereafter, the reaction solution was added dropwise to 1 L of water / 40 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. The solid was further added with 50 ml of an acetone / water mixed solvent (volume ratio 40/60), stirred in a suspended state, collected by suction filtration, and vacuum-dried for 10 hours to obtain 36.6 g of I-43b. (Yield 91%).

To a 500 ml three-necked flask, 28.2 g of I-43b, 23.5 g of 4-chloromethylstyrene, 21.3 g of potassium carbonate, 0.09 g of nitrobenzene, and 175 ml of DMF (N, N-dimethylformamide) were added. The mixture was flowed and stirred at 75 ° C. for 5 hours. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 37.8 g of the charge transfer agent I-43 of the present invention (yield 85%). .
An IR spectrum of the obtained compound (I) -43 is shown in FIG.

[Example 1]
(Preparation of electrophotographic photoreceptor)
-Production of undercoat layer 4-
Zinc oxide: (average particle diameter 70 nm: manufactured by Teica Co., Ltd .: specific surface area value 15 m ² / g) 100 parts by mass is stirred and mixed with 500 parts by mass of toluene, and silane coupling agent (KBM503: manufactured by Shin-Etsu Chemical Co., Ltd.) 1.3 parts by mass Part was added and stirred for 2 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 3 hours to obtain zinc oxide surface-treated with a silane coupling agent. 110 parts by mass of surface-treated zinc oxide was stirred and mixed with 500 parts by mass of tetrahydrofuran, a solution prepared by dissolving 0.6 parts by mass of alizarin in 50 parts by mass of tetrahydrofuran was added, and the mixture was stirred at 50 ° C. for 5 hours. . Then, the zinc oxide to which alizarin was imparted by filtration under reduced pressure was filtered off, and further dried at 60 ° C. under reduced pressure to obtain zinc oxide to which alizarin was imparted.

  Zinc oxide provided with this alizarin: 60 parts by mass, curing agent (blocked isocyanate Sumijoule 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.): 13.5 parts by mass, butyral resin (ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.) ): 15 parts by mass of 38 parts by mass of methyl ethyl ketone mixed with 85 parts by mass of methyl ethyl ketone: 25 parts by mass of methyl ethyl ketone were mixed, and dispersion was performed for 2 hours with a sand mill using glass beads having a diameter of 1 mmφ. Got. Dioctyltin dilaurate: 0.005 parts by mass and silicone resin particles (Tospearl 145, manufactured by GE Toshiba Silicone): 40 parts by mass were added as catalysts to the obtained dispersion to obtain a coating liquid for forming an undercoat layer. . This coating solution was applied onto an aluminum substrate by a dip coating method, followed by drying and curing at 170 ° C. for 40 minutes to obtain an undercoat layer having a thickness of 20 μm.

-Production of charge generation layer 2A-
Bragg angles (2θ ± 0.2 °) of X-ray diffraction spectrum using Cukα characteristic X-ray as a charge generating material are at least 7.3 °, 16.0 °, 24.9 °, 28.0 ° 15 parts by mass of hydroxygallium phthalocyanine (CGM-1) having a diffraction peak at 10 parts by mass, vinyl chloride / vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unicar) as binder resin, and 200 parts by mass of n-butyl acetate The mixture of parts was dispersed for 4 hours in a sand mill using glass beads having a diameter of 1 mmφ. To the obtained dispersion, 175 parts by mass of n-butyl acetate and 180 parts by mass of methyl ethyl ketone were added and stirred to obtain a coating solution for forming a charge generation layer. This charge generation layer forming coating solution was dip coated on the undercoat layer and dried at room temperature (25 ° C.) to form a charge generation layer having a thickness of 0.2 μm.

-Preparation of charge transport layer 2B-1-
A coating liquid for forming the charge transport layer 2B-1 having the following composition was prepared.
(Charge transport agent)
N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine (CTM-1): 45 parts by mass (resin)
Bisphenol Z polycarbonate resin (hereinafter referred to as “PCZ500”, viscosity average molecular weight: 50,000): 55 parts by mass (solvent)
Chlorbenzene: 800 parts by mass This coating solution was applied onto the charge generation layer and dried at 130 ° C. for 45 minutes to form a charge transport layer 2B-1 having a thickness of 20 μm.

-Preparation of charge transport layer 2B-2-
A coating solution for forming a charge transport layer 2B-2 having the following composition was prepared.
(Charge transport agent)
Charge transport material synthesized in Synthesis Example 1 ((I) -15): 100 parts by mass (initiator)
V-601 (Wako Pure Chemical Industries, Ltd.): 2 parts by mass (solvent)
Tetrahydrofuran (THF) / toluene mixed solvent (mass ratio 60/40): 150 parts by mass This coating solution is applied onto the charge transport layer 2B-1 and heated at 150 ° C. for 40 minutes in an atmosphere having an oxygen concentration of about 100 ppm. A protective layer of 7 μm was formed.
An electrophotographic photoreceptor was obtained by the method as described above. This photoreceptor is referred to as a photoreceptor 1.

[Examples 2 to 22, Comparative Examples 1 and 2]
(Preparation of electrophotographic photoreceptor)
An electrophotographic photosensitive member was obtained in the same manner as in Example 1 except that the charge transport material in the coating liquid for forming the charge transport layer 2B-2 in Example 1 was changed as shown in Table 5. This photoreceptor is referred to as photoreceptors 2 to 22 and comparative photoreceptors 1 and 2.

[Photoconductor running evaluation 1]
The electrophotographic photosensitive members produced in Examples 1 to 22 and Comparative Examples 1 and 2 are mounted on DocuCenter Color 400CP (manufactured by Fuji Xerox Co., Ltd.), and are subjected to normal environment (20 ° C., 50% RH) in FIG. The image evaluation pattern shown in A) was output. Then, after continuously outputting 30000 black solid patterns, an image evaluation pattern was output again. The amount of light was adjusted using a filter depending on the sensitivity of the charge generation material.

<Image stability>
The image evaluation patterns output before and after the running evaluation 1 were compared, and the deterioration degree of the image quality was visually evaluated as shown below. A ++ indicates the best characteristics.
A ++: Best (deterioration is hardly seen in all output image patterns)
A +: Change is confirmed in the enlarged image in a part of the plurality of output image patterns. A: Good (change is not visually confirmed, but change is confirmed in the enlarged image)
B: Image quality degradation can be confirmed, but acceptable level C: Image quality degradation has occurred, causing a problem

<Electrical property stability>
Before and after the execution of the photoconductor running evaluation 1, each photoconductor was negatively charged with a scorotron charger with a grid applied voltage of −700 V in a normal environment (20 ° C., 50% RH), and then charged. Using a semiconductor laser of 780 nm as the photoreceptor, flash exposure was performed with a light amount of 10 mJ / m ² . The potential (V) on the surface of the photoconductor after 10 seconds after the exposure was measured, and this value was taken as the value of the residual potential. In any photoreceptor, the residual potential showed a negative value. For each photoreceptor, a value of (residual potential before running evaluation 1) − (residual potential after running evaluation 1) was calculated to evaluate the electrical property stability. A ++ indicates the best characteristics.
A ++: Less than 10V A +: 10V or more and less than 20V A: 20V or more and less than 30V B: 30V or more and less than 50V C: 50V or more

<Mechanical strength>
The degree of occurrence of scratches on the surface of the photoreceptor after performing the photoreceptor evaluation 1 was judged visually. A + indicates the best characteristics.
A +: Scratches are not confirmed even by microscopic observation.
A: Although scratches are not visually confirmed, small scratches are confirmed by microscopic observation.
B: Scratches are partially generated.
C: Scratches are generated on the entire surface.

[Photoconductor running evaluation 2]
The electrophotographic photoconductors produced in Examples 1 to 22 and Comparative Examples 1 and 2 were mounted on DocuCenter Color 400CP (manufactured by Fuji Xerox Co., Ltd.). The image evaluation pattern shown in (A) was output as [Evaluation image 1]. Subsequently, after continuously outputting 10,000 black solid patterns, an image evaluation pattern was output [evaluation image 2]. After being left for 24 hours in a low-temperature and low-humidity (20 ° C., 30% RH) environment, an image evaluation pattern was output [evaluation image 3]. Next, 5000 black solid patterns were output in a high humidity (28 ° C., 60% RH) environment, and then an image evaluation pattern was output [evaluation image 4]. After being left for 24 hours in a high humidity (28 ° C., 60% RH) environment, an image evaluation pattern was output [Evaluation Image 5]. Again, the temperature was returned to a low-temperature and low-humidity (20 ° C., 30% RH) environment, and 20000 black solid patterns were output, and an image evaluation pattern was output [evaluation image 6].

<Ghost evaluation>
[Evaluation image 3] and [Evaluation image 5] were compared with [Evaluation image 2] and [Evaluation image 4], respectively, and the degree of deterioration in image quality was visually evaluated. A ++ indicates the best characteristics.
A +: Good state as shown in FIG. 6A A: Good state as shown in FIG. 6A, but slightly occurring B: State slightly conspicuous as shown in FIG. 6B C: FIG. State that can be clearly confirmed as in 6 (C)

[Examples 23 to 37]
(Preparation of electrophotographic photoreceptor)
Except that the charge generation material in the charge generation layer 2A in Example 1, the charge transfer agent of the charge transport layer 2B-1, the components of the charge transport layer 2B-2 and the type of coating solvent are changed as shown in Table 6. In the same manner as in Example 1, an electrophotographic photosensitive member was obtained. This photoreceptor is referred to as photoreceptors 23 to 37.
The photoreceptors 23 to 37 were evaluated in the same manner as in Example 1. The results are shown in Table 6. The compounds in the table are as follows.

CGM-2: titanyl phthalocyanine CTM-2: the following compound

CTM-3: The following compounds

Monomer-1: A-DCP (bifunctional acrylate monomer manufactured by Shin-Nakamura Chemical Co., Ltd.)
Monomer 2: A-DPH (6 functional acrylate monomer manufactured by Shin-Nakamura Chemical Co., Ltd.)
Monomer 3: BPE-200 (bifunctional methacrylate monomer manufactured by Shin-Nakamura Chemical Co., Ltd.)
(Initiator)
V-40: Wako Pure Chemical Industries initiator (thermal radical generator)
VE-073: Wako Pure Chemical Industries initiator (thermal radical generator)
OTazo-15: Initiator (thermal radical generator) manufactured by Otsuka Chemical Co., Ltd.
Perhexyl O: NOF initiator (thermal radical generator)
(resin)
Eclek B BX-L: Polyvinyl butyral resin made by Sekisui Chemical

DESCRIPTION OF SYMBOLS 1 ... Base | substrate, 2 ... Photosensitive layer, 2A ... Charge generation layer, 2B, 2B-1, 2B-2 ... Charge transport layer, 4 ... Undercoat layer, 6 ... Function-integrated type photosensitive layer, 7 ... Electrophotographic photoreceptor , 8 ... charging device, 9 ... exposure device, 11 ... developing device, 13 ... cleaning device, 14 ... lubricant, 40 ... transfer device, 50 ... intermediate transfer member, 100, 120 ... image forming device, 131 ... cleaning blade, 132, 133 ... fibrous member, 300 ... process cartridge

Claims (11)

At least a conductive substrate and a photosensitive layer provided on the conductive substrate;
An electrophotographic photoreceptor, wherein the outermost surface layer is a layer made of a polymerized or cured film of a composition containing one or more charge transport materials (A) represented by the following general formula (I).

(In general formula (I), F represents a charge transporting skeleton. D represents a group represented by the following general formula (III). M represents an integer of 1 to 8.)

(In General Formula (III), L represents —C (═O) —, —N (R) —, —S—, or —C (═O) —, and —O—, —N (R) —). Or a divalent linking group containing one or more groups selected from the group consisting of a combination of -S-, R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. 2. The electrophotographic photosensitive member according to claim 1, wherein the charge transport material (A) represented by the general formula (I) is a charge transport material represented by the following general formula (II).


(In the general formula (II), Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group. Ar ⁵ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group. D is synonymous with D in formula (I), c1 to c5 each represents an integer of 0 to 2, and the sum of c1 to c5 is an integer of 1 to 8. k is 0 or 1 .)   The electrophotographic photoreceptor according to claim 1, wherein L in the general formula (III) is a divalent linking group containing —C (═O) —O—. The electrophotographic photosensitive member according to any one of claims 1 to 3, wherein the general formula (III) is a compound represented by the following general formula (IV).


(In general formula (IV), p represents an integer of 0 or more and 4 or less.)   The electrophotographic photoreceptor according to claim 1, wherein m in the general formula (I) represents an integer of 2 or more and 6 or less.   The electrophotographic photosensitive member according to claim 5, wherein m in the general formula (I) represents an integer of 3 or more and 6 or less.   The electrophotographic photosensitive member according to claim 6, wherein m in the general formula (I) represents an integer of 4 or more and 6 or less.   The said outermost surface layer is a layer which consists of a film | membrane which superposed | polymerized or hardened | cured the composition containing the said charge transport material (A) with a heat | fever, light, or an electron beam. The electrophotographic photosensitive member according to Item. At least the electrophotographic photoreceptor according to any one of claims 1 to 8,
A process cartridge that is detachable from the image forming apparatus. The electrophotographic photosensitive member according to any one of claims 1 to 8,
A charging device for charging the electrophotographic photosensitive member;
A latent image forming apparatus for forming an electrostatic latent image on the surface of the charged electrophotographic photosensitive member;
A developing device for developing the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with a developer containing toner to form a toner image;
A transfer device for transferring a toner image formed on the surface of the electrophotographic photosensitive member to a recording medium;
An image forming apparatus. A step of applying a coating liquid comprising a composition containing the charge transport material (A) represented by the general formula (I) to a surface to be coated to form a coating film;
And a step of heating the coating film under conditions of 100 ° C. or more and 170 ° C. or less to polymerize or cure to obtain an outermost surface layer.