JP2008291011A - Polymerizable compound, electrophotographic photoreceptor using the polymerizable compound, image forming method using the electrophotographic photoreceptor, image forming device and process cartridge for image forming device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable compound having good polymerizing property and charge transport property, excellent in film forming property and compatibility and forming a high density crosslinked film, and to provide an electrophotographic photoreceptor excellent in abrasion resistance, having good electric properties, low in image defects and causing no afterimage. <P>SOLUTION: A polymerizable compound represented by general formula (1) is provided, and an electrophotographic photoreceptor having, on the surface thereof, at least a cured covering composition obtained by polymerizing the polymerizable compound as the following component A is provided. (Wherein, Ar<SB>1</SB>and Ar<SB>2</SB>are each an alkyl, aralkyl or aryl group or a heterocycle, and may bond to form a cyclic structure A<SB>1</SB>; Ar<SB>3</SB>to Ar<SB>5</SB>are a divalent arylene group or a hetero aromatic ring; R<SB>1</SB>is an alkylene, arylene or oxyalkylene group; X<SB>1</SB>is O or S; Z is a polymerizable group; n1 is 1 or 2; n2 and n3 are 0 or 1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel polysynthetic compound, and the polymerizable compound has both polymerizability and charge transport function (hole transportability), and can form a thermoplastic resin or a cross-linked cured resin by polymerization. In addition, since the obtained resin exhibits a charge transport function, it is useful as a stable semiconductor film forming material for an organic electrophotographic photosensitive member. The present invention also relates to a highly wear-resistant organic electrophotographic photosensitive member having a printing durability of 2 million or more continuously in terms of a photosensitive member having a diameter of 100 mm, and further to chargeability, sensitivity, residual potential. The present invention relates to a highly durable and highly reliable electrophotographic photosensitive member that is excellent in electrical characteristics such as storage properties and that maintains high image quality with few image defects, and is also less susceptible to image defects such as white spots. It is about. The present invention also relates to a highly durable organic electrophotographic photosensitive member having a wide correspondence range to a writing light source wavelength that can be applied to a blue-violet laser writing light source. The present invention also relates to an image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus using a long-life, high-performance photoconductor.

  In recent years, organic photoreceptors (OPC) have been widely used in copying machines, facsimile machines, laser printers, and composite machines in place of inorganic photoreceptors because of their good performance and various advantages. This is because, for example, (1) optical characteristics such as the light absorption wavelength range and the amount of absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, and (3) material selection range (4) Ease of manufacturing, (5) Low cost, (6) Non-toxicity, and the like. On the other hand, the diameter of the photoconductor has recently been reduced due to the downsizing of the image forming apparatus, and the high speed of the machine and the maintenance-free movement have been added to increase the durability of the photoconductor. From this point of view, organophotoreceptors are generally soft because the charge transport layer is mainly composed of a low molecular charge transport material and an inert polymer. There is a drawback that wear is likely to occur due to a mechanical load. In addition, due to the demand for higher image quality, the cleaning blade is required to increase its rubber hardness and contact pressure for the purpose of improving the cleaning property as the particle size of the toner particles is reduced. This also promotes wear of the photoreceptor. It is a factor. Such abrasion of the photoreceptor deteriorates electrical characteristics such as sensitivity deterioration and chargeability, and causes abnormal images such as image density reduction and background stains. Further, scratches where wear is locally generated cause streak-like stain images due to poor cleaning. Therefore, the wear resistance has been improved.

(1) A material using a curable binder for the charge transport layer (for example, see Patent Document 1).
(2) Using a polymer type charge transport material (for example, see Patent Document 2)
(3) An inorganic filler dispersed in a charge transport layer (see, for example, Patent Document 3)
(4) A polyfunctional acrylate monomer cured product (for example, see Patent Document 4).
(5) Provided with a charge transport layer formed using a coating liquid comprising a monomer having a carbon-carbon double bond, a charge transport material having a carbon-carbon double bond, and a binder resin (for example, Patent Document 5. See Patent Document 49.)
(6) A compound in which a compound obtained by curing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule is contained (for example, see Patent Documents 6 and 7).

  Although these improvements have improved wear resistance compared to conventional products, new problems have arisen. Conventional photoconductors are refaced due to wear even if foreign matter adheres to or scratches on the surface, and image defects are not dragged indefinitely. However, photoconductors with improved wear resistance once have strong foreign matter on the surface. When sticking or scratches occur, the state remains indefinitely and continues to produce image defects. Thus, there is a problem that image defects are likely to occur. Particularly in recent years, due to the demand for higher image quality and energy saving, the particle size of the toner is small and the softening temperature is low. In order to ensure its fluidity, it is common to add inorganic fine particles such as silica to the toner. It is getting to be. In some cases, the silica particles may pierce the OPC surface during the development process, and a wax component of toner or the like is deposited on the periphery of the silica particles, making it impossible to develop, resulting in the occurrence of white spot image defects.

  In addition, with the conventionally known four hundred and ten kinds of radical polymerizable monomers described in Patent Document 7, it is possible to achieve both high wear resistance at a high level and electrical characteristics with small residual potential generation. I could not. The cause is considered to be insufficient crosslinkability. For that purpose, it is necessary to increase the content ratio of the radical polymerizable group, and it is necessary to polyfunctionalize the radical polymerizable group or reduce the molecular weight of the charge transporting structure. There is a limit to lowering the molecular weight of the expressed structure, and this is not a practical method. On the other hand, polyfunctionalization of the radical polymerizable group is effective for increasing the content ratio, but the charge transportability after curing is deteriorated. The cause of this is not clear, but it is presumed that the molecular movement of the charge transporting structure is restricted by cross-linking at several points, so that the range of free movement is reduced and the hopping mobility of the charge is reduced. The Thus, at present, no sufficiently satisfactory radical polysynthetic monomer has yet been obtained.

  In recent years, due to the demand for higher image quality and energy saving, the particle size of the toner is small and the softening temperature is low. In order to ensure its fluidity, it is preferable to add inorganic fine particles such as silica to the toner. It is getting done. In some cases, the silica particles may pierce the OPC surface during the development process, and a wax component of toner or the like is deposited on the periphery of the silica particles, making it impossible to develop, resulting in the occurrence of white spot image defects. In addition, along with further higher image quality and higher durability in recent years, it is necessary to make wear resistance and residual potential accumulation compatible at a higher level.

  In recent years, electrophotographic apparatuses are increasingly required to be smaller, faster, and higher in image quality. However, in such an electrophotographic apparatus that forms an image at a high density in order to achieve high image quality at a high speed cycle, there are many cases in which image deterioration called “afterimage” or “ghost” is accompanied as a side effect. However, the current situation is that high speed and high image quality as required are not achieved.

Here, the afterimage phenomenon will be described.
In an electrophotographic apparatus that forms an image by an electrophotographic method, for example, when a halftone image is printed next to an image with clear contrast shown in FIG. There are cases in which an image pattern printed before a halftone image appears in the image. This schematic diagram is shown in FIG. Such image deterioration is referred to as “positive afterimage” or “positive ghost”. In particular, in high-quality full-color electrophotographic apparatuses, it is necessary to suppress this image deterioration. On the contrary, image degradation in which the image pattern printed before this is identified with a low density in the halftone image area is called “negative afterimage” or “negative ghost”, and this image degradation is similarly suppressed. There is a need to. This schematic diagram is shown in FIG.

  There are several mechanisms for the afterimage phenomenon, and one of them can be interpreted as being caused by fluctuations in the surface potential of the photoreceptor (see, for example, Patent Document 8). For this explanation, FIG. 13 schematically shows changes in the photoreceptor surface potential in each step after latent image formation, development, and transfer.

  In this case, when the latent image shown in FIG. 13A is formed, the surface of the photosensitive member is uniformly charged to −700 V, and then the image information is exposed (the arrow indicates the exposed portion). The potential of the exposed portion is approximately 0V. Then, at the time of development in FIG. 13B, the toner is attached to the surface of the photoconductor and developed according to the potential difference between the development potential and the surface of the photoconductor. Next, at the time of transfer, the print paper side is charged positively to transfer the toner image from the photoconductor to the print paper. As shown in FIG. 13C, when the reverse bias is applied to the photosensitive member by the transfer unit, the surface potential of the photosensitive member after the transfer is entirely changed in the positive direction, and the potential of the exposed portion exceeds 0V. Eventually, the polarity is reversed and becomes a positive potential (+10 V in the figure).

  If this phenomenon is repeated, even if the surface of the photoconductor is uniformly negatively charged before the image is exposed by the charging means, the portion of the photoconductor surface that has become close to the positive side has a positive charge potential. It will be close. As a result, the difference in development potential is greater in the portion that has shifted in the positive direction than in the other portions, so that apparent sensitization occurs and a dark toner image is formed. This portion is identified as a positive afterimage.

  As shown in Patent Document 9, for example, an afterimage is generated even in a method of processing the density of an image with or without dots (in a binary manner), such as a printing method widely used in an ink jet printer. The beam spot for writing the dot shape has a slight illuminance distribution. For this reason, if the beam spot is irradiated to the part where the charging potential has shifted to the plus side, the contour of the dot that can be developed will be widened by the offset of the surface potential to the low potential side, resulting in an increase in the dot diameter. End up.

  The dot image that has become unnecessarily large is felt dark when viewed as a whole image, and this is also an image in which a positive afterimage is identified. In this case, for example, the degree of afterimage is felt stronger as the image is output at a higher resolution of 1200 dpi than 600 dpi. Therefore, when the resolution of an electrophotographic apparatus that forms an image by an electrophotographic method is increased, the degree of seriousness of this problem Becomes larger.

  It is understood that the cause of the fluctuation of the photoreceptor surface potential is mainly the accumulation of space charges inside the photosensitive layer (see, for example, Patent Document 10). Therefore, in order to eliminate the occurrence of the afterimage, a means for preventing the accumulation of space charge is required.

The prior art for afterimage prevention is described below.
(1) Improvement of photoconductor surface layer Patent Document 11 proposes that the photoconductor surface layer contains a polyarylate resin and the dielectric constant is regulated to 2.3 or more. As a proposal similar to this, it has been proposed to contain an azo pigment in the photosensitive layer and a polyarylate resin in the surface layer of the photosensitive member (see, for example, Patent Document 12). According to the patent document, the polyarylate resin has high crystallinity and is presumed to orient the charge transport material to some extent due to its properties. By combining the orientation and a specific charge generation material (azo pigment), the injection is performed. It is believed that the interface barrier is lowered, resulting in a reduction in photomemory.

  In addition, in an electrophotographic apparatus having an intermediate transfer member, it has been proposed to include a bisphenol-type polycarbonate in the surface layer of an electrophotographic photosensitive member having a multilayer structure having a charge generation layer containing a phthalocyanine compound (for example, (See Patent Document 13). Although the explanation of the mechanism for the effect is not found, the effect is confirmed by the examples. The effect seems to be due to the selected material.

  In addition, in an electrophotographic apparatus having an intermediate transfer member, it has been proposed to include a charge transport material made of a polymer in the surface layer of an electrophotographic photosensitive member having a multilayer structure having a charge generation layer containing a phthalocyanine compound. (For example, refer to Patent Document 14). Although the explanation of the mechanism for the effect is not found, the effect is confirmed by the examples. The effect seems to be due to the selected material.

  Further, in the electrophotographic apparatus having the intermediate transfer member, the electrophotographic photosensitive member having a multilayer structure having a charge generation layer containing a phthalocyanine compound may be any one of an insulating material and a semiconductive material including at least a resistance adjusting material. Providing a surface protective layer has been proposed (see, for example, Patent Document 15). Although the explanation of the mechanism for the effect is not found, the effect is confirmed by the examples. The effect seems to be due to the selected material.

Further, it is disclosed that injection of reverse polarity charges from the surface layer side can be prevented by using a copolymer polycarbonate of bisphenol A and a specific arylene group for the surface layer of the photoreceptor such as a charge transport layer (for example, patents). Reference 16).
In addition, it has been proposed that the surface layer contains surface-treated metal oxide particles, an alcohol-soluble resin, and an alcohol-soluble charge transport material (see, for example, Patent Document 17). In this patent document, as a binder resin for the surface layer, a thermoplastic resin is inadequate in strength, so that it is inappropriate, and a solvent that dissolves the resin during coating is a solvent that easily dissolves the resin. Therefore, it has been pointed out that a method of dissolving the photosensitive layer cannot be adopted. The explanation of the mechanism for the effect is unclear, but it is interpreted from the description in the examples that the generation of a ghost image can be prevented by using an alcohol-soluble charge transport material as a combination of these materials.

  In addition, in an electrophotographic photoreceptor having a photosensitive layer and a protective layer, it has been proposed that the protective layer contains at least one of an alkali metal element or an alkaline earth metal element (see, for example, Patent Document 18). By containing these elements in the protective layer, it is interpreted as a means for imparting ionic conductivity and achieving both durability and accumulation elimination of residual potential. In this patent document, it is pointed out that although the residual potential can be lowered by including a charge transport material in the protective layer, there is a problem that the wear amount increases with respect to durability.

(2) Improvement of photosensitive layer In Patent Document 19, the charge transport material contained in the electrophotographic photoreceptor contains at least one selected from a chlorogallium phthalocyanine compound and a hydroxygallium phthalocyanine compound, and hydrazone is used as the charge transport material. It has been proposed to contain at least one specific compound having a skeleton. The patent document proposes that there is always a more preferable combination between the charge generating material that transfers charges and the charge transport material, and if these are preferable combinations, the transfer memory and the photo memory can be improved. Although it is difficult at present to predict the law regarding the compatibility of these combinations, the above combinations are considered appropriate.

  In addition, in an electrophotographic apparatus that irradiates a photoreceptor with a short-wavelength semiconductor laser beam having a wavelength of 380 to 500 nm, it has been proposed that the photosensitive layer contains an azo pigment (for example, see Patent Document 20). Although no explanation of the mechanism for the effect can be found, the examples confirm that many of the azo pigments have a smaller photomemory than the α-type titanyl phthalocyanine.

  In addition, in an electrophotographic photosensitive member containing a charge generation material and a charge transport material, the charge transport material has a calculated polarizability value of more than 70% by structure optimization calculation using semi-empirical molecular orbital calculation using PM3 parameters. A substance having a large and dipole moment value smaller than 1.8D and a compound having a wavelength of 50% transmittance on the longer wavelength side than the wavelength of 50% transmittance of the charge transport material. Has been proposed (see, for example, Patent Document 21). It is considered that the latter compound improves the photomemory property because it absorbs extra light irradiated to the photoreceptor.

(3) Improvement of the charge transport layer In Patent Document 22, in the multilayer photoreceptor, the charge generation layer contains oxytitanium phthalocyanine, the charge transport layer contains two or more kinds of charge transport materials, and individual charge transport materials. It has been proposed to define the oxidation potential difference of 0.04V or less. Although the explanation of the mechanism for the effect is unclear, it is possible to smoothly hop the charge carriers between the charge transport materials by matching the energy level of the charge transport material, and to reduce the trapping of the charge transport material, thereby transferring the charge transport material. It is considered that the afterimage is prevented because the absolute amount of electrons excited by the reverse polarity charging by the means becomes small.

In addition, in an electrophotographic photoreceptor mounted in a back exposure type high-speed electrophotographic process (the time from the exposure means to the development means is about 10 to 150 msec), the charge mobility of the charge transport layer is expressed by the electric field strength of 2 × 10 ^6. It has been proposed to specify 1 × 10 ⁻⁶ cm ² / V · sec or more under the condition of V / cm (see, for example, Patent Document 23). When the dynamic sensitivity of the photoreceptor is slow, latent image formation is not completed before development, and it has been pointed out that repeated use increases afterimages. The above measures ensure dynamic sensitivity characteristics and prevent afterimage formation. Means to do this have been proposed.

  In addition, in an electrophotographic apparatus having an intermediate transfer member, a triphenylamine compound and N, N, N ′, N′— are used as a charge transport layer of an electrophotographic photosensitive member having a multilayer structure having a charge generation layer containing a phthalocyanine compound. It has been proposed to include a charge transport material selected from tetraphenylbenzidine compounds (see, for example, Patent Document 24). Although the explanation of the mechanism for the effect is not found, the effect is confirmed by the examples. The effect seems to be due to the selected material.

(4) Improvement of charge generation layer In Patent Document 25, the film thickness of the charge generation layer is increased to 0.25 μm or more, or the content of the charge generation material in the charge generation layer is increased to 50% by weight or more. There has been proposed a means for increasing the charge trapping of this layer and, as a result, making the ghost inconspicuous.
In addition, it has been proposed that a triarylamine compound having a xylyl group is contained in a charge generation layer in an electrophotographic photoreceptor having a laminated structure (see, for example, Patent Document 26). According to the patent document, it is described that a carrier transport barrier is formed at the interface between the charge generation layer and the charge transport layer, and charges are trapped therein. Since the trap carriers reduce the space electric field in the charge generation layer, the potential of the halftone image portion does not drop, and an afterimage occurs at this portion. Thus, by mixing a charge transport agent (triarylamine compound having a xylyl group) in the charge generation layer, the generated carriers are quickly injected into the charge transport agent and moved to the charge transport layer. As a result, accumulation of trapping carriers can be prevented and the occurrence of afterimages is improved.

  Further, in an electrophotographic photosensitive member having at least a photosensitive layer and a surface protective layer in this order on a conductive support, the diffraction angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction is 9 as a charge generating substance in the photosensitive layer. It has been proposed to contain oxytitanium phthalocyanine having strong peaks at .5 °, 24.1 ° and 27.3 ° (see, for example, Patent Document 27). Although the explanation of the mechanism for the effect is not found, the effect is confirmed by the examples. The effect seems to be due to the selected material.

The charge generation layer is composed of hydroxygallium phthalocyanine, a binder resin, an acetalized portion, an acetyl group portion, and a hydroxyl portion. The butyralization degree is 62 mol% or more, and the weight average molecular weight (Mw) is 2. It has been proposed to contain a butyral resin having 0 × 10 ⁵ or more and a number average molecular weight of 5.0 × 10 ⁴ or more (for example, see Patent Document 28). The effect of the butyral resin having the above specific composition (for example, the influence of the number of hydroxyl groups, etc.) is estimated to reduce the amount of residual photocarriers in the photosensitive layer and improve the afterimage.

(5) Matching rules between charge generation layer and charge transport layer In Patent Document 29, regarding the electrophotographic photoreceptor having a laminated structure, the charge generation layer contains a specific azo pigment, and the charge transport layer has a fluorene skeleton. It has been proposed to contain a charge transport material. The explanation of the mechanism for the effect is not found, but the effect of suppressing light fatigue is confirmed by the examples. The effect seems to be due to the selected material.
Further, in a negative-type photosensitive member exhibiting high gamma characteristics, a laminated structure in which a charge generation layer containing a phthalocyanine compound and a P-type charge transport layer are provided on a conductive support, and the P-type charge transport layer includes It has been proposed to use a material selected from the group consisting of an inorganic P-type semiconductor, t-Se fine powder, and a charge transporting polymer (for example, see Patent Document 30). This patent document is characterized in that a hole transporting molecule is not included in the P-type charge transporting layer, thereby preventing the hole transporting molecule from diffusing into the charge generating layer. Thus, it is described that the trapping by the phthalocyanine pigment is suppressed and the afterimage is reduced.

(6) Improvement of undercoat layer In Patent Document 31, it is proposed to provide an undercoat layer prepared using a silane coupling agent and an inorganic pigment as an electrophotographic photosensitive member. As a result, the charge that should flow out to the support (base) side is smoothly discharged, and as a result, no afterimage is generated.
In addition, regarding a photoreceptor having an undercoat layer (intermediate layer), it is proposed that the undercoat layer contains a specific polyamic acid or polyamic acid ester structure, a polyimide resin having a specific structure, and a resin having a cyanoethyl group. (See, for example, Patent Document 32). The explanation of the mechanism for the effect is not found, but the effect of suppressing light fatigue is confirmed by the examples. The effect seems to be due to the selected material.

  In addition, it has been introduced that a crosslinkable resin having a small variation in resistance value due to a change in external humidity has been used for the undercoat layer (intermediate layer) (see, for example, Patent Document 33). In this patent document, as a proposal for reducing afterimage generation, an example in which polycyclic quinone, perylene and the like are contained in the undercoat layer (Patent Document 34), an example using a metallocene compound, an electron-withdrawing compound, and a melamine resin (Patent Document) 35) An example using metal oxide fine particles and a silane coupling agent (Patent Document 28), an example using metal oxide fine particles surface-treated with a silane coupling agent (Patent Document 36), etc. It is shown.

  In the case of a high-sensitivity type electrophotographic photosensitive member using oxytitanium phthalocyanine as a charge generation layer, charge separation is performed in an electrophotographic process in which charging and exposure are repeated because the high number of excited molecules and generated carriers is large because of high sensitivity. It has been pointed out that excited species, electrons, holes, and the like that do not cause oxidization easily remain in the photoreceptor. On the other hand, Patent Document 33 proposes that the constituent material of the undercoat layer includes a polyamide resin and a zirconium compound, or a polyamide resin and a diketone compound such as zirconium alkoxide and acetylacetone. Similarly, it has been proposed to use a cellulose resin as the resin for the undercoat layer and to contain a zirconium compound or zirconium alkoxide and a diketone compound (see, for example, Patent Document 37).

  In addition, in an electrophotographic photoreceptor containing an undercoat layer, a charge generation material, and a charge transport material, the charge transport material is a calculated value of polarizability by structure optimization calculation using semi-empirical molecular orbital calculation using PM3 parameters. Is a substance having a calculated value of dipole moment of less than 1.8D or a specific arylamine compound, and titanium oxide particles coated with an organosilicon compound on the undercoat layer and having a specific structure It has been proposed to contain a polyamide having a diamine component as a constituent component (see, for example, Patent Document 38). In this patent document, improvement of the photomemory characteristics has been confirmed by providing an undercoat layer, but it is considered that this mechanism is to make it easier for missed carriers in the photosensitive layer to escape by providing an undercoat layer. Yes.

In addition, in the laminated type photoconductor having the undercoat layer (intermediate layer), the volume resistivity of the undercoat layer is set to 10 ¹⁰ to 10 ¹² Ωcm, the film thickness of the charge transport layer is set to 18 μm or less, and the charge eliminating means is omitted. Has been proposed (see, for example, Patent Document 39). By eliminating static elimination means (static elimination light), photo-fatigue of the photoconductor is prevented and the resistance of the undercoat layer is regulated, so that charge injection from the support to the photoconductor is controlled, thereby accumulating space charge. It is interpreted as preventing.

(7) Blending of additive In Patent Document 3, in an electrophotographic apparatus having an intermediate transfer member, at least a hindered phenol structure is formed on the surface layer of the electrophotographic photoreceptor having a multilayer structure having a charge generation layer containing a phthalocyanine compound. It has been proposed to contain units. Although the explanation of the mechanism for the effect is not found, the effect is confirmed by the examples. The effect seems to be due to the selected material.
In addition, it has been proposed to contain a dithiobenzyl compound in a charge generation layer using a phthalocyanine pigment (see, for example, Patent Document 40). The explanation of the mechanism for the effect is omitted, but in the embodiment, the accumulation of the photo memory and the improvement of the positive ghost are shown.

(8) Device for electrophotographic process In Patent Document 41, it is proposed that a photoconductor is charged with a polarity opposite to that of normal charging (plus) and used under a certain condition. In the case of a photoreceptor having a highly sensitive charge transport layer, there are many photoinduced charge carriers generated by exposure. Photoinduced charge carriers generate the same number of electrons as holes injected into the charge transport layer. However, if the electrons do not quickly escape to the support, electrons remain in the charge generation layer, resulting in an afterimage. Therefore, by intentionally performing positive charging, electrons are injected from the support and the electron trap is held inside the charge generation layer. When the photosensitive member is exposed in this state, it is interpreted that the difference between the electron traps of the exposed portion and the non-exposed portion is small, and the ghost image becomes inconspicuous.
In addition, means for applying a direct current in which an alternating current is superimposed on the support side of the photosensitive member has been proposed (see, for example, Patent Document 42). It is interpreted as a means that the electrons trapped in the charge generation layer are emitted by applying a reverse bias to the support side. It is described that the aim of superimposing alternating current is to increase the amount of current and promote the reverse charge bias effect.

  In addition, an electrophotographic photosensitive member having a charge generation layer containing a phthalocyanine compound is subjected to a charge other than the main charge, followed by a photostatic charge, and the main charge is first performed. Image formation can be performed in a state in which the space charge in the photosensitive member is released and extinguished by performing main charging from the time when the body part enters a position facing the main charging means, It has been proposed that the occurrence of afterimages at the initial stage of image formation can be suppressed (see, for example, Patent Document 43).

  In addition, it has been proposed to provide a control means for controlling the transfer current from the transfer means flowing into the photoreceptor to a constant level for an electrophotographic photoreceptor having a multilayer structure having a charge generation layer containing a phthalocyanine compound. (For example, see Patent Document 44). According to this patent document, the occurrence of afterimages depends on the transfer current, and when the transfer current increases, negative afterimages appear strongly. This is because holes are injected into the non-exposed area (non-image area) of the photoreceptor during transfer, and the holes are trapped at the substrate-side interface of the charge generation layer or charge transport layer, and the next charge It is estimated that the dark decay increases (apparently sensitization) when released during the process, and a negative afterimage occurs. Therefore, if the transfer current value is controlled to be constant, the charge injected to the photoreceptor can be controlled to be constant, and as a result, afterimages can be suppressed.

In addition, means for defining a writing light wavelength or a neutralizing light wavelength from an action spectrum of a pre-charging optical memory ratio with respect to sensitivity has been proposed (for example, see Patent Document 45).
In addition, by exposing the electrophotographic photosensitive member having a charge generation layer containing a phthalocyanine compound to a non-exposed portion by performing exposure before transfer, the charged potential of the non-exposed portion is reduced to 1/3 before the exposure. It is disclosed that an afterimage can be suppressed with (see, for example, Patent Document 46). Although the explanation of the mechanism for the effect is not described in detail, if the exposure is performed before the transfer, the gap difference between the exposed portion potential and the non-exposed portion potential becomes small, so that it is considered that the afterimage cannot be identified.

  Further, regarding an electrophotographic apparatus using an electrophotographic photosensitive member having a photosensitive layer and a protective layer containing a photocurable resin (acrylic resin), it has been proposed to provide a humidity sensor near the surface of the electrophotographic photosensitive member ( For example, see Patent Document 47). The humidity sensor controls the current value of the AC component applied to the charging member. This patent document describes a mechanism relating to image blurring and image blur reduction due to the installation of a humidity sensor, but omits a description of the mechanism relating to the effect of reducing photomemory. However, in the embodiment, it has been confirmed that the photo memory is reduced by installing the humidity sensor.

Further, as a measure for preventing the ghost image output of the S-shaped photoconductor, the half time of the photoconductor charging potential due to the exposure calculated from the xerographic TOF method is the time from the exposure unit to the development unit of the electrophotographic apparatus (hereinafter referred to as the following). For the sake of simplicity, it has been proposed that this be defined as 1/10 or less of “exposure-development time” (see, for example, Patent Document 48).
Further, as described in the section of improving the undercoat layer, Patent Document 32 proposes a method for preventing light fatigue of the photosensitive member by omitting the charge removal means (charge removal light).

  In Patent Document 9, the time T from charging to exposure, the charging potential on the surface of the photoconductor is VH, the dark decaying potential is V1 until 10T after charging, and after charging and image exposure, charging is performed again. It has been proposed to satisfy the relationship of | (V1−V2) / VH | <0.020, where V2 is the dark decay potential until 10T later. As an actual means, in the embodiment, it is shown that the dark decay time is shortened by increasing the process speed or the charging potential is reduced.

Regarding the prevention of afterimage generation, we tried to apply the above-mentioned conventional technology, but the results are not sufficient for application to electrophotographic photoreceptors and electrophotographic apparatuses that are highly durable, high-speed, and oriented for high-quality printing. It was all over. In other words, the current state of the art is not yet solved by the conventional technology.
JP 56-48637 A JP-A 64-1728 JP-A-4-281461 Japanese Patent No. 3262488 Japanese Patent No. 3194392 JP 2000-66425 A JP 2004-221959 A Japanese Patent Laid-Open No. 11-133825 JP 2002-123067 A JP-A-10-177261 JP-A-10-115946 JP-A-11-184135 Japanese Patent Laid-Open No. 10-177263 JP-A-10-177264 Japanese Patent Laid-Open No. 10-177269 JP 2000-147803 A JP 2001-235889 A JP 2002-6528 A JP 2000-75521 A JP 2000-105478 A JP 2001-305762 A Japanese Patent Application Laid-Open No. 7-92701 JP-A-8-152721 Japanese Patent Laid-Open No. 10-177262 JP-A-6-313972 JP-A-10-69104 JP-A-10-186696 JP 2002-107972 A JP 7-43920 A Japanese Patent Laid-Open No. 9-211876 JP-A-8-22136. JP-A-11-184127 JP 2000-112162 A Japanese Patent Application Laid-Open No. 8-14639 Japanese Patent Laid-Open No. 10-73942 JP 9-258469 A JP 2001-51438 A JP 2001-305763 A JP 2002-107983 A JP 2000-292946 A JP 7-13374 A JP 7-44065 A JP-A-10-123802 Japanese Patent Laid-Open No. 10-123855 JP 2000-231246 A JP-A-10-123856 Japanese Patent Laid-Open No. 10-246997 JP 2001-117244 A Japanese Patent No. 3164426

  The object of the present invention is to have good polymerizability and charge transport property, excellent film formability and compatibility with other monomers, and can form a high-density cross-linked film. It is intended to provide a polymerizable compound that sometimes exhibits excellent charge transporting properties, and further has excellent wear resistance and electrical characteristics and less image defects due to white spots and the like, resulting in afterimages. It is an object of the present invention to provide a long-life electrophotographic photosensitive member that does not occur. Another object of the present invention is to provide an image forming method, an image forming apparatus, and a process cartridge for an image forming apparatus that use a long-life photoconductor with few white spot image defects and realize high image quality over a long period of time.

（式中、Ａｒ₁、Ａｒ₂は置換基を有していても良いアルキル基、アラルキル基、アリール基、ヘテロ環の何れかを表し、Ａｒ₁とＡｒ₂は結合して環状構造Ａ₁を形成しても良い。Ａｒ₃、Ａｒ₄、Ａｒ₅は置換基を有していても良い２価のアリーレン基またはヘテロ芳香環を表す。Ｒ₁はアルキレン基、アリーレン基またはオキサアルキレン基を表す。Ｘ₁は酸素原子または硫黄原子を表す。Ｚは重合性基を表す。ｎ１は１または２を表し、ｎ２、ｎ３は０または１を表す。） As a result of intensive studies, the present inventors have found that the above object can be achieved by the following (1) to (21).
(1) A polymerizable compound represented by the following general formula (1).

(In the formula, Ar ₁ and Ar ₂ represent any of an optionally substituted alkyl group, aralkyl group, aryl group, and heterocyclic ring, and Ar ₁ and Ar ₂ are bonded to form a cyclic structure A ₁ . Ar ₃ , Ar ₄ , and Ar ₅ each represent a divalent arylene group or heteroaromatic ring that may have a substituent, and R ₁ represents an alkylene group, an arylene group, or an oxaalkylene group. X ₁ represents an oxygen atom or a sulfur atom, Z represents a polymerizable group, n1 represents 1 or 2, and n2 and n3 represent 0 or 1.)

（式中、Ａｒ₁、Ａｒ₂は置換基を有していても良いアルキル基、アラルキル基、アリール基、ヘテロ環の何れかを表す。Ｒ₁はアルキレン基、アリーレン基またはオキサアルキレン基を表す。Ｒ₂、Ｒ₃、Ｒ₄は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｘ₁は酸素原子または硫黄原子を表す。Ｚは重合性基を表す。ｎ２、ｎ３は０または１を表す。ｍ１〜ｍ３は１〜４の整数を表す。） (2) The polymerizable compound according to (1), wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, Ar ₁ and Ar _{2 each} represent an optionally substituted alkyl group, aralkyl group, aryl group or heterocyclic ring. R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R ₂ , R ₃ , and R _{4 each} represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, an aryl group, or a halogen atom, and X ₁ represents an oxygen atom or a sulfur atom. Z represents a polymerizable group, n2 and n3 represent 0 or 1. m1 to m3 represent an integer of 1 to 4.)

（式中、Ｒ₁はアルキレン基、アリーレン基またはオキサアルキレン基を表す。Ｒ₂〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。Ｘ₁は酸素原子または硫黄原子を表す。ｎ２、ｎ３は０または１を表す。ｍ１〜ｍ３は１〜４の整数を表す。ｐ１、ｐ２は１〜５の整数を表す。） (3) The polymerizable compound according to (2), wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

(In the formula, R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R _{2 to} R ₆ are any one of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, X ₁ represents an oxygen atom or a sulfur atom, n2 and n3 represent 0 or 1, m1 to m3 represent an integer of 1 to 4, and p1 P2 represents an integer of 1 to 5.)

（式中、Ｒ₈は、炭素数２〜５のアルキレン基を表し、Ｒ₅〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。ｐ１、ｐ２は１〜５の整数を表す・BR>B） (4) The polymerizable compound according to (3), wherein the compound represented by the general formula (3) is a compound represented by the following general formula (4).

(In the formula, R ₈ represents an alkylene group having 2 to 5 carbon atoms, and R _{5 to} R ₆ are any of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group, an aryl group, and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, and p1 and p2 represent an integer of 1 to 5 (BR> B).

（式中、Ｒ₅〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。ｐ１、ｐ２は１〜５の整数を表す。） (5) The polymerizable compound according to (3), wherein the compound represented by the general formula (3) is a compound represented by the following general formula (5).

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.)

（式中、Ｒ₅〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。ｐ１、ｐ２は１〜５の整数を表す。） (6) The polymerizable compound according to (3), wherein the compound represented by the general formula (3) is a compound represented by the following general formula (6).

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.)

(7) An electrophotographic photoreceptor having a cured coating composition on the surface, the cured coating composition obtained by polymerizing at least the following component A on the surface.
Component A: A cured coating composition on the surface of a polymerizable compound (8) in which a polymerizable group and a substituted amino group not containing a polymerizable group are bonded with a compound in which three or more aromatic rings or heteroaromatic rings are linked. An electrophotographic photoreceptor comprising a cured coating composition obtained by polymerizing at least a mixture of the following components A and B on the surface.
Component A: Polymerizable compound in which a polymerizable group and a substituted amino group not containing a polymerizable group are bonded with a compound in which three or more aromatic rings or heteroaromatic rings are linked Component B: a polymerizable group in the molecule In an electrophotographic photosensitive member having a cured coating composition on the surface of three or more polymerizable monomers (9), a cured coating composition obtained by polymerizing at least a mixture of the following component A, component B and component C on the surface An electrophotographic photosensitive member comprising:
Component A: Polymerizable compound in which a polymerizable group and a substituted amino group not containing a polymerizable group are bonded with a compound in which three or more aromatic rings or heteroaromatic rings are linked Component B: a polymerizable group in the molecule Three or more polymerizable monomer components C: photopolymerization initiator

（式中、Ａｒ₁、Ａｒ₂は置換基を有していても良いアルキル基、アラルキル基、アリール基、ヘテロ環の何れかを表し、Ａｒ₁とＡｒ₂は結合して環状構造Ａ₁を形成しても良い。Ａｒ₃、Ａｒ₄、Ａｒ₅は置換基を有していても良い２価のアリーレン基またはヘテロ芳香環を表す。Ｒ₁はアルキレン基、アリーレン基またはオキサアルキレン基を表す。Ｘ₁は酸素原子または硫黄原子を表す。Ｚは重合性基を表す。ｎ１は１または２を表し、ｎ２、ｎ３は０または１を表す。） (10) The electrophotographic photosensitive member according to any one of (7) to (9), wherein the component A is a polymerizable compound represented by the following general formula (1).

(In the formula, Ar ₁ and Ar ₂ represent any of an optionally substituted alkyl group, aralkyl group, aryl group, and heterocyclic ring, and Ar ₁ and Ar ₂ are bonded to form a cyclic structure A ₁ . Ar ₃ , Ar ₄ , and Ar ₅ each represent a divalent arylene group or heteroaromatic ring that may have a substituent, and R ₁ represents an alkylene group, an arylene group, or an oxaalkylene group. X ₁ represents an oxygen atom or a sulfur atom, Z represents a polymerizable group, n1 represents 1 or 2, and n2 and n3 represent 0 or 1.)

（式中、Ａｒ₁、Ａｒ₂は置換基を有していても良いアルキル基、アラルキル基、アリール基、ヘテロ環の何れかを表す。Ｒ₁はアルキレン基、アリーレン基またはオキサアルキレン基を表す。Ｒ₂、Ｒ₃、Ｒ₄は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｘ₁は酸素原子または硫黄原子を表す。Ｚは重合性基を表す。ｎ２、ｎ３は０または１を表す。ｍ１〜ｍ３は１〜４の整数を表す。） (11) The electrophotographic photosensitive member according to any one of (7) to (9), wherein the component A is a polymerizable compound represented by the following general formula (2).

(In the formula, Ar ₁ and Ar _{2 each} represent an optionally substituted alkyl group, aralkyl group, aryl group or heterocyclic ring. R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R ₂ , R ₃ , and R _{4 each} represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, an aryl group, or a halogen atom, and X ₁ represents an oxygen atom or a sulfur atom. Z represents a polymerizable group, n2 and n3 represent 0 or 1. m1 to m3 represent an integer of 1 to 4.)

（式中、Ｒ₁はアルキレン基、アリーレン基またはオキサアルキレン基を表す。Ｒ₂〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。Ｘ₁は酸素原子または硫黄原子を表す。ｎ２、ｎ３は０または１を表す。ｍ１〜ｍ３は１〜４の整数を表す。ｐ１、ｐ２は１〜５の整数を表す。） (12) The electrophotographic photosensitive member according to any one of (7) to (9), wherein the component A is a polymerizable compound represented by the following general formula (3).

(In the formula, R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R _{2 to} R ₆ are any one of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, X ₁ represents an oxygen atom or a sulfur atom, n2 and n3 represent 0 or 1, m1 to m3 represent an integer of 1 to 4, and p1 P2 represents an integer of 1 to 5.)

（式中、Ｒ₈は、炭素数２〜５のアルキレン基を表し、Ｒ₅〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。ｐ１、ｐ２は１〜５の整数を表す。） (13) The electrophotographic photosensitive member according to any one of (7) to (9), wherein the component A is a polymerizable compound represented by the following general formula (4).

(In the formula, R ₈ represents an alkylene group having 2 to 5 carbon atoms, and R _{5 to} R ₆ are any of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group, an aryl group, and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, and p1 and p2 represent an integer of 1 to 5.)

（式中、Ｒ₅〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。ｐ１、ｐ２は１〜５の整数を表す。） (14) The electrophotographic photosensitive member according to any one of (7) to (9), wherein the component A is a polymerizable compound represented by the following general formula (5).

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.)

（式中、Ｒ₅〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。ｐ１、ｐ２は１〜５の整数を表す。） (15) The electrophotographic photosensitive member according to any one of (7) to (9), wherein the component A is a polymerizable compound represented by the following general formula (6).

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.)

(16) The electrophotographic photosensitive member according to any one of (7) to (11), wherein the polymerizable group of component A and / or component B is an acryloyloxy group and / or a methacryloyloxy group. .
(17) In the electrophotographic photosensitive member in which at least a charge generation layer, a charge transport layer, and a crosslinkable charge transport layer are sequentially laminated on a conductive support, the crosslinkable charge transport layer is any one of (7) to (16) An electrophotographic photoreceptor comprising the cured coating composition according to claim 1.
(18) The electrophotographic photosensitive member as described in (17) above, wherein the cross-linked charge transport layer is insoluble in an organic solvent.

(19) An image forming method, wherein at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to any one of (7) to (18).
(20) In the image forming apparatus comprising at least a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit, the electrophotographic photosensitive member according to any one of (7) to (18). An image forming apparatus comprising:
(21) At least one selected from the group consisting of the electrophotographic photosensitive member according to any one of (7) to (18), a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a neutralizing unit. A process cartridge for an image forming apparatus, characterized in that the process cartridge is detachable from an image forming apparatus main body.

  According to the present invention, an electrophotographic photosensitive member having good wear resistance and electrical characteristics can be obtained by providing an electrophotographic photosensitive member provided with a surface layer of a cured coating composition obtained by radical polymerization of at least the component A. Therefore, it is possible to provide a long-life photosensitive member with few image defects due to white spots. This is because the three aromatic rings or heteroaromatic rings in the component A of the present invention have better pi-electron conjugation than the comparative compound biphenyl, and as a result, the charge transfer is also excellent, so that good electrophotographic characteristics are obtained. It is thought that it was obtained. Further, by having three or more aromatic rings or heteroaromatic rings such as a terphenyl group, it is considered that a stronger polymerized film can be obtained, and as a result, the wear resistance is also excellent. Furthermore, by having a cured coating composition obtained by radical polymerization of the component A and the component B on the surface, an electrophotography having excellent charge mobility with low residual potential while having excellent wear resistance, which has not been achieved conventionally. An electrophotographic photosensitive member having a cured coating composition on the surface obtained by radical polymerization of the component A, component B, and component C can be provided. Can be easily manufactured in a short time, and therefore can be provided to the market at a low cost. Moreover, the polymerizable compound of the present invention has a very good afterimage evaluation. Therefore, by using this photoreceptor, it is possible to provide an image forming method, an image forming apparatus, and a process cartridge for an image forming apparatus that realize high image quality over a long period of time.

In addition, the polymerizable compound represented by the general formula (4), the general formula (5), and the general formula (6) useful as the component A has a terphenyl structure and is difficult to crystallize. When the cured coating composition obtained by polymerizing the component A or the mixture of the component A and the component B or the mixture of the component A, the component B and the component C is formed on the surface, the component A is hardly crystallized. Thus, an electrophotographic photosensitive member having a cured coating composition that is easy to smooth and excellent in homogeneity can be produced.
In addition, when the polymerizable compound represented by the general formula (4) is used, it is presumed that the crosslinking reaction of the cured coating composition is likely to proceed, but a photoconductor that has both excellent wear resistance and charge transfer characteristics. Can be provided.

  In addition, by using these photoconductors, it is possible to provide an image forming apparatus and an image forming apparatus process cartridge that realize high image quality over a long period of time with few abnormal images due to poor cleaning.

Hereinafter, the present invention will be described in detail.
The present invention is based on an electrophotographic photosensitive member having a cured film obtained by polymerizing a specific polymerizable compound on the surface, an image forming method using the photosensitive member, an image forming apparatus, and a process cartridge for the image forming apparatus. Yes. The polymerizable compound referred to here has both a structure exhibiting a charge transporting function and a polymerizable structure, and a cured film obtained by polymerization functions as a charge transporting film.

  As a result of studying a new polymerizable compound capable of achieving both high-density polymerizability and charge transportability, the present inventors have found that a polymerizable group and a substituted amino group containing no polymerizable group have three or more aromatic rings. Alternatively, the present invention has found that a film cured using a polymerizable compound bonded with a compound having a heteroaromatic ring linked is effective in achieving both high-density polymerization and good charge transportability. . The reason for this effect is not clear, but by connecting three or more polymerizable groups and a substituted amino group not containing a polymerizable group with an aromatic ring or a heteroaromatic ring, the pi-conjugated system is expanded and the charge transport property is improved. I think it is to improve. Although the cause is unknown, it has been found that an afterimage can be suppressed by using a charge transport material spreading in a pi-conjugated system. Thus, the use of a polymerizable compound in which three or more aromatic rings or heteroaromatic rings are connected to a polymerizable group and a substituted amino group that does not contain a polymerizable group can suppress the afterimage.

  In addition, when a conventional polyfunctional charge transporting monomer is used, there is a problem that distortion at the time of curing increases, cracks such as cracks occur, and a problem that insufficient curability occurs despite the polyfunctionality. In the curing of the specific polymerizable compound of the present invention, a uniform and smooth film that is sufficiently crosslinked and cured without generation of cracks or the like is obtained, and functions as a good photoreceptor surface layer. In addition, the formation of a high-density charge-transporting cured film enables the film strength to be sufficiently high and prevents external additives in extremely hard toner such as silica fine particles from sticking to the photoreceptor. In addition, image defects such as white spots can be reduced.

  In addition, a high-density crosslinked cured film can be realized by using the polymerizable compound of component A. More preferably, component A is mixed with a polymerizable monomer having three or more polymerizable groups as component B in the molecule. Various conventionally known methods can be applied to initiate polymerization, and a photoconductor having a high crosslink density and excellent mechanical strength can be obtained by adding a photopolymerization initiator and curing it by light irradiation in a short time.

Next, each component will be described.
Regarding a polymerizable compound in which a polymerizable group and a substituted amino group not containing a polymerizable group are bonded with a compound in which three or more aromatic rings or heteroaromatic rings are linked:
Any conventionally known group can be applied as the polymerizable group. For example, vinyl group, allyl group, acryloyloxy group, methacryloyloxy group, acryloylthio group, acrylamide group, epoxy group and the like. In particular, an acryloyloxy group or a methacryloyloxy group is preferable from the viewpoint of polymerization characteristics. By using an acryloyloxy group or a methacryloyloxy group, it is possible to produce a smooth film sufficiently cured in a short time.

  The substituted amino group that does not contain a polymerizable group is not particularly limited as long as it is a secondary amino group that does not contain the vinyl group, allyl group, acryloyloxy group, methacryloyloxy group, acrylamide group, or the like. . Specific examples of the secondary amino group include dimethylamine, diethylamine, dibenzylamine, bis (4-methylbenzyl) amine, diphenylamine, di-p-tolylamine, bis (2-thienyl) amine, bis (2- Furyl) amine and the like.

  The charge transporting compound having the secondary amino group as a substituent is a compound having a property of transporting charges generated by light reception in the photosensitive layer by hopping conduction or the like, and those that transport holes are particularly preferable. Specific examples of the hole transport material include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethanes. Derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, etc., other known materials such as bisstilbene derivatives, enamine derivatives and the like can be mentioned.

（式中、Ａｒ₁、Ａｒ₂は置換基を有していても良いアルキル基、アラルキル基、アリール基、ヘテロ環の何れかを表し、Ａｒ₁とＡｒ₂は結合して環状構造Ａ₁を形成しても良い。Ａｒ₃、Ａｒ₄、Ａｒ₅は置換基を有していても良い２価のアリーレン基またはヘテロ芳香環を表す。Ｒ₁はアルキレン基、アリーレン基またはオキサアルキレン基を表す。Ｘ₁は酸素原子または硫黄原子を表す。Ｚは重合性基を表す。ｎ１は１または２を表し、ｎ２、ｎ３は０または１を表す。） As the polymerizable compound of component A described above, a polymerizable compound represented by the following general formula (1) is preferable, and a compound represented by the following general formula (2) is more preferable. Furthermore, what is represented by the following general formula (3) is particularly preferable. This compound is mentioned as a preferable material that can be well adapted to a blue-violet laser writing light source.

(In the formula, Ar ₁ and Ar ₂ represent any of an optionally substituted alkyl group, aralkyl group, aryl group, and heterocyclic ring, and Ar ₁ and Ar ₂ are bonded to form a cyclic structure A ₁ . Ar ₃ , Ar ₄ , and Ar ₅ each represent a divalent arylene group or heteroaromatic ring that may have a substituent, and R ₁ represents an alkylene group, an arylene group, or an oxaalkylene group. X ₁ represents an oxygen atom or a sulfur atom, Z represents a polymerizable group, n1 represents 1 or 2, and n2 and n3 represent 0 or 1.)

In the general formula (1), specific examples of the alkyl group of Ar ₁ and Ar ₂ include a methyl group, an ethyl group, an isopropyl group, and a 2-ethylhexyl group. Specific examples of the aralkyl group include benzyl group, 4-methylbenzyl group, 2-phenethyl group, 2-naphthylmethyl group and the like. Specific examples of the aryl group include phenyl, o-tolyl, p-tolyl, α-naphthyl, β-naphthyl, 4-biphenyl, pyrenyl, 2-fluorenyl, 9,9-dimethyl-2. -A fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrycenyl group is mentioned. Specific examples of the heterocyclic ring include 2-furyl group, 2-thienyl group, 5-methyl-2-thienyl group, 2-pyridyl group, 4-phenyl-2-pyridyl group and the like. Ar ₁ and Ar ₂ may combine to form a cyclic structure A _1, and specific examples thereof include the following exemplary compounds (A-01) to (A-13). Specific examples of the arylene group for Ar ₃ , Ar ₄ , and Ar ₅ include 1,2-phenylene, 1,4-phenylene, 2,6-naphthylene, and the like. Specific examples of the divalent heteroaromatic ring include 2,5-thienylene and 3,4-thienylene. Specific examples of the alkylene group for R ₁ include a methylene group, a 1,2-ethylene group, a 1,1-cyclohexene group, and a 2,2-propylene group. Specific examples of the arylene group can include the above-described arylene groups, and specific examples of the oxaalkylene group include 3-oxapentane-1,5-diyl group, 4-oxaheptane-1,7-diyl group, 3 , 6-Dioxaoctane-1,8-diyl group, 1,4-dimethyl-3-oxapentane-1,5-diyl group, 3,6,9-trioxaundecane-1,11-diyl group be able to. X ₁ is an oxygen atom or a sulfur atom. Specific examples of Z include vinyl group, allyl group, acryloyloxy group, methacryloyloxy group, acrylamide group, epoxy group and the like.

（式中、Ａｒ₁、Ａｒ₂は置換基を有していても良いアルキル基、アラルキル基、アリール基、ヘテロ環の何れかを表す。Ｒ₁はアルキレン基、アリーレン基またはオキサアルキレン基を表す。Ｒ₂、Ｒ₃、Ｒ₄は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｘ₁は酸素原子または硫黄原子を表す。Ｚは重合性基を表す。ｎ２、ｎ３は０または１を表す。ｍ１〜ｍ３は１〜４の整数を表す。）

(In the formula, Ar ₁ and Ar _{2 each} represent an optionally substituted alkyl group, aralkyl group, aryl group or heterocyclic ring. R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R ₂ , R ₃ , and R _{4 each} represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, an aryl group, or a halogen atom, and X ₁ represents an oxygen atom or a sulfur atom. Z represents a polymerizable group, n2 and n3 represent 0 or 1. m1 to m3 represent an integer of 1 to 4.)

Specific examples of Ar ₁ and Ar ₂ in the general formula (2) include the above-described alkyl group, the above-described aralkyl group, the above-described aryl group, and the above-described heterocycle. Specific examples of R1 include the aforementioned alkylene group, the aforementioned arylene group, and the aforementioned oxaalkylene group. Specific examples of R _{2 to} R ₄ include a hydrogen atom, an alkoxy group such as the aforementioned alkyl group, methoxy group, ethoxy group, and 2-ethylhexyloxy group, and a halogen atom such as the aforementioned aryl group, chlorine atom, and bromine atom. Can do. A specific example of X ₁ is an oxygen atom or a sulfur atom. Specific examples of Z include a vinyl group, an allyl group, an acryloyloxy group, a methacryloyloxy group, an acrylamide group, and an epoxy group.

（式中、Ｒ₁はアルキレン基、アリーレン基またはオキサアルキレン基を表す。Ｒ₂〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。Ｘ₁は酸素原子または硫黄原子を表す。ｎ２、ｎ３は０または１を表す。ｍ１〜ｍ３は１〜４の整数を表す。ｐ１、ｐ２は１〜５の整数を表す。）

(In the formula, R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R _{2 to} R ₆ are any one of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, X ₁ represents an oxygen atom or a sulfur atom, n2 and n3 represent 0 or 1, m1 to m3 represent an integer of 1 to 4, and p1 P2 represents an integer of 1 to 5.)

In the general formula (3), specific examples of R ₁ include the aforementioned alkylene group, the aforementioned arylene group, and the aforementioned oxaalkylene group. Specific examples of R _{2 to} R ₆ include a hydrogen atom, the aforementioned alkyl group, the aforementioned alkoxy group, the aforementioned aryl group, and the aforementioned halogen atom. Specific examples of R ₇ include a hydrogen atom or a methyl group. Specific examples of X ₁ include an oxygen atom or a sulfur atom.

In addition, the polymerizable compound represented by the general formula (4), the general formula (5), or the general formula (6) has a terphenyl structure and is difficult to crystallize. When a cured coating composition obtained by polymerizing the mixture of component A and component B or the mixture of component A, component B and component C is formed on the surface, component A is difficult to crystallize and is easily smooth and homogeneous. An electrophotographic photoreceptor having a cured coating composition having excellent properties formed on the surface can be produced.
In addition, when the polymerizable compound represented by the general formula (4) is used, it is presumed that the crosslinking reaction of the cured coating composition is likely to proceed, but a photoconductor that has both excellent wear resistance and charge transfer characteristics. Can be provided.

（式中、Ｒ₈は、炭素数２〜５のアルキレン基を表し、Ｒ₅〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。ｐ１、ｐ２は１〜５の整数を表す。）

(In the formula, R ₈ represents an alkylene group having 2 to 5 carbon atoms, and R _{5 to} R ₆ are any of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group, an aryl group, and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, and p1 and p2 represent an integer of 1 to 5.)

（式中、Ｒ₅〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。ｐ１、ｐ２は１〜５の整数を表す。）

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.)

（式中、Ｒ₅〜Ｒ₆は水素原子、置換基を有していても良いアルキル基、アルコキシ基、アリール基、ハロゲン原子の何れかを表す。Ｒ₇は水素原子、またはメチル基を表す。ｐ１、ｐ２は１〜５の整数を表す。）

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.)

In the general formula (4), specific examples of R ₈ represent ethylene, propylene, butylene and pentanylene groups. Specific examples of R _{5 to} R ₆ include a hydrogen atom, the aforementioned alkyl group, the aforementioned alkoxy group, the aforementioned aryl group, and the aforementioned halogen atom. Among them, a hydrogen atom and an alkyl group are particularly preferable, and a methyl group is most preferable as the alkyl group. Specific examples of R ₇ include a hydrogen atom or a methyl group.
Specific examples of R _{5 to} R ₆ and specific examples of R _{7 in} the general formula (5) and the general formula (6) are the same as those in the general formula (4).

Specific examples of the polymerizable compound used in the present invention are listed below, but these specific examples do not present the present invention in a restrictive manner, nor are they disclosed with the intention of limiting the present invention.

The polymerizable compound represented by the general formulas (1) to (6) is a novel substance. For example, the polymerizable group can be easily synthesized by the following production method.
(Synthesis of hydroxy compounds)

  The step of obtaining the compound (C-2) from the compound (C-1) shown above is a step of obtaining a hydroxy compound by demethylation, and the hydroxy compound can be synthesized by using a conventionally known method. That is, a method using an acid such as concentrated hydrochloric acid, hydrobromic acid, hydroiodic acid, trifluoroacetic acid, pyridine hydrochloride, magnesium iodide etherate, aluminum chloride, aluminum bromide, boron trichloride, boron tribromide Alternatively, a method using a base such as potassium hydroxide, Grignard reagent, sodium-butanol, lithium-biphenyl, lithium iodide-collidine, lithium diphenyl phosphide-THF, sodium thiolate-DMF, or an organometallic reagent is available. Among these methods, the method using boron tribromide and sodium thiolate-DMF is particularly effective, but the synthesis method for obtaining the hydroxy compound which is an intermediate of the present invention is limited to these methods. is not.

上記に示す化合物（Ｃ−２）より化合物（Ｃ−３）を得る工程は、アクリル化、あるいはメタクリル化工程であり、従来のエステル化と同様にして合成できる。すなわち、アルコール誘導体にアクリル酸、あるいはメタクリル酸、またはこれらカルボン酸のエステル化合物、酸ハロゲン化物、酸無水物を作用させる。例えば、ヒドロキシ化合物とアクリル酸とをｐ−トルエンスルフォン酸等のエステル化触媒と共に有機溶媒中で脱水しながら加熱撹拌することで合成できる。また、ヒドロキシ化合物とアクリル酸クロリドとを有機溶媒中アルカリ存在下で反応させることでも容易に合成できる。この時用いられるアルカリとしては、例えば水酸化ナトリウムや水酸化カリウム等のアルカリ、またはその水溶液、トリエチルアミン、ピリジン等のアミン系塩基を使用することができる。反応に用いられる有機溶媒としては、トルエン等の炭化水素系溶媒やテトラヒドロフラン等のエーテル系溶媒や酢酸エチル等のエステル系溶媒、メチルエチルケトン等のケトン系溶媒、クロロホルム等のハロゲン系溶媒等が使用できる。 (Synthesis of acrylic or methacrylic compounds)

The step of obtaining the compound (C-3) from the compound (C-2) shown above is an acrylation or methacrylation step, and can be synthesized in the same manner as conventional esterification. That is, acrylic acid, methacrylic acid, ester compounds of these carboxylic acids, acid halides, and acid anhydrides are allowed to act on alcohol derivatives. For example, it can be synthesized by heating and stirring a hydroxy compound and acrylic acid together with an esterification catalyst such as p-toluenesulfonic acid while dehydrating in an organic solvent. It can also be easily synthesized by reacting a hydroxy compound and acrylic acid chloride in an organic solvent in the presence of an alkali. Examples of the alkali used at this time include alkalis such as sodium hydroxide and potassium hydroxide, aqueous solutions thereof, and amine bases such as triethylamine and pyridine. As the organic solvent used in the reaction, a hydrocarbon solvent such as toluene, an ether solvent such as tetrahydrofuran, an ester solvent such as ethyl acetate, a ketone solvent such as methyl ethyl ketone, a halogen solvent such as chloroform, and the like can be used.

(Synthesis of a polysynthesized compound in which three or more aromatic rings or heteroaromatic rings are connected to a polymerizable group and a substituted amino group not containing a polymerizable group)
In the polymerizable compound of the present invention, three or more aromatic rings or heteroaromatic rings are connected to a polymerizable group and a substituted amino group not containing the polymerizable group. As a method for synthesizing this site, it is possible to easily synthesize by using Suzuki coupling using aryl halide and aryl boride, Stille coupling using aryl halide and aryl tin, etc. Preferably, Suzuki coupling is used. The synthetic route may be either method A or method B. Moreover, there is no restriction | limiting in the aryl halide used for reaction, and an aryl boride.

  In the Suzuki coupling, the reaction proceeds satisfactorily by using a palladium catalyst. As a palladium catalyst, it is effective to use a method in which a ligand is added to palladium chloride, palladium acetate, palladium carbon, or a reagent in which a ligand is incorporated in advance, such as tetra (triphenylphosphino) palladium. is there. As the ligand used at this time, a phosphorus-based ligand is effective, and examples thereof include tri (t-butyl) phosphine.

  The reaction requires a base, carbonates such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate, metal hydroxides such as barium hydroxide, sodium hydroxide and potassium hydroxide, potassium t-butoxide, sodium t- Metal alkoxides such as butoxide, lithium t-butoxide, potassium 2-methyl-2-butoxide, sodium 2-methyl-2-butoxide, sodium methoxide, sodium ethoxide, potassium ethoxide, potassium methoxide, tripotassium phosphate, etc. Is used.

For polymerizable monomers having 3 or more polymerizable groups in the molecule:
Examples of polymerizable monomers having three or more polymerizable groups in the molecule include hole transport structures such as triarylamine, hydrazone, pyrazoline, and carbazole, such as condensed polycyclic quinones, diphenoquinones, cyano groups, and nitro groups. A monomer that does not have an electron transport structure such as an electron-withdrawing aromatic ring and has three or more radically polymerizable functional groups. The radical polymerizable functional group may be any group as long as it has a carbon-carbon double bond and can be radically polymerized. Examples of these radical polymerizable functional groups include 1-substituted ethylene functional groups and 1,1-substituted ethylene functional groups shown below.

Examples of the 1-substituted ethylene functional group include functional groups represented by the following formulas.
CH ₂ = CH-X _1- (Formula 1)
(In the formula, X ₁ represents an arylene group such as a phenylene group or a naphthylene group which may have a substituent, an alkenylene group which may have a substituent, a carbonyl group, a carbonyloxy group, or —CON. (R ₁₇ ) — group (R ₁₇ represents an alkyl group such as hydrogen, methyl group or ethyl group, an aralkyl group such as benzyl group, naphthylmethyl group or phenethyl group, or an aryl group such as phenyl group or naphthyl group.) Or a sulfide group.)
Specific examples of these substituents include vinyl group, styryl group, 2-methyl-1,3-butadienyl group, vinylcarbonyl group, acryloyloxy group, acryloylamide group, vinylthioether group and the like.

Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following formulas.
CH ₂ = C (Y) -X _2- (Formula 2)
(In the formula, Y is an aryl group such as an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a phenyl group which may have a substituent, or a naphthyl group. Group, halogen atom, cyano group, nitro group, alkoxy group such as methoxy group or ethoxy group, -COOR ₁₈ group (R ₁₈ is an alkyl such as hydrogen atom, optionally substituted methyl group, ethyl group) Group, an aralkyl group such as benzyl which may have a substituent and a phenethyl group, an aryl group such as a phenyl group and a naphthyl group which may have a substituent, or -CONR ₁₉ R ₂₀ (R ₁₉ and R ₂₀ is a hydrogen atom, which may have a substituent an alkyl group such as methyl group and ethyl group, which may have a substituent group benzyl group, naphthylmethyl group or an aralkyl group such as a phenethyl group, or location, A phenyl group which may have a group, an aryl group such as a naphthyl group, which may be the same or different from each other.) Further, X ₂ above (identical substituents and X ₁ of formula 1) and Represents a single bond or an alkylene group, provided that at least one of Y and X ₂ is an oxycarbonyl group, a cyano group, an alkenylene group, and an aromatic ring.)
Specific examples of these substituents include an α-acryloyloxy chloride group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, an α-cyanophenylene group, and a methacryloylamino group.

Examples of the substituent that X ₁ , X ₂ , and Y may have include, for example, an alkyl group such as a halogen atom, a nitro group, a cyano group, a methyl group, and an ethyl group, and an alkoxy group such as a methoxy group and an ethoxy group. Groups, aryloxy groups such as phenoxy groups, aryl groups such as phenyl groups and naphthyl groups, aralkyl groups such as benzyl groups and phenethyl groups, and the like. Among these radical polymerizable functional groups, acryloyloxy group and methacryloyloxy group are particularly useful, and a compound having three or more acryloyloxy groups is, for example, a compound having three or more hydroxyl groups in the molecule and an acrylic group. It can be obtained by using an acid (salt), an acrylic acid halide, or an acrylic ester to cause an ester reaction or a transesterification reaction. A compound having three or more methacryloyloxy groups can be obtained in the same manner. Further, the radical polymerizable functional groups in the monomer having three or more radical polymerizable functional groups may be the same or different.

  Examples of the radical polymerizable monomer having three or more radical polymerizable groups in the molecule include the following, but are not limited to these compounds. That is, examples of the radical polymerizable monomer used in the present invention include trimethylolpropane triacrylate (hereinafter abbreviated as TMPTA), trimethylolpropane trimethacrylate, trimethylolpropane alkylene-modified triacrylate, and trimethylolpropane ethyleneoxy-modified. Triacrylate (hereinafter abbreviated as EO modification), trimethylolpropylenepropyleneoxy modified (hereinafter abbreviated as PO modification) triacrylate, trimethylolpropanecaprolactone modified triacrylate, trimethylolpropane alkylene modified trimethacrylate, pentaerythritol triacrylate Pentaerythritol tetraacrylate (hereinafter abbreviated as PETTA), glycerol triacrylate, Serol epichlorohydrin modified (hereinafter ECH modified) triacrylate, glycerol EO modified triacrylate, glycerol PO modified triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA), Dipentaerythritol caprolactone-modified hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkylated dipentaerythritol pentaacrylate, alkylated dipentaerythritol tetraacrylate, alkylated dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (hereinafter abbreviated as DTMPTA) ), Pentaerythritol ethoxytetraacrylate, phosphoric acid EO-modified tria Relate, 2,2,5,5, - such as tetrahydroxy methyl cyclopentanone tetraacrylate and the like. These may be used alone or in combination of two or more.

  In addition, as a polymerizable monomer having three or more polymerizable groups in the molecule used in the present invention, the ratio of molecular weight to the number of functional groups in the monomer in order to form a dense crosslink in the cured coating composition (Molecular weight / functional group number) is preferably 250 or less. Further, when this ratio is larger than 250, the cured coating composition layer is soft and wear resistance is somewhat lowered. Therefore, among the monomers exemplified above, monomers having a modifying group such as EO, PO, caprolactone, etc. It is not preferable to use a compound having a long modifying group alone. Moreover, the component ratio of the radically polymerizable monomer having 3 or more radically polymerizable groups in the molecule is 20 to 80% by weight, more preferably 30 to 70% by weight with respect to the total amount of the cured coating composition. , Depending on the proportion of radically polymerizable monomer having 3 or more radically polymerizable groups in the molecule in the solid content of the coating liquid. When the monomer component is less than 20% by weight, the three-dimensional cross-linking density of the cured coating composition is small, and a drastic improvement in wear resistance is not achieved as compared with the case of using a conventional thermoplastic binder resin. On the other hand, if it exceeds 80% by weight, the content of the charge transporting compound is lowered, and the electrical characteristics are deteriorated. The electrical properties and abrasion resistance required differ depending on the process used, and the film thickness of the cured coating composition of this photoconductor also varies accordingly. A range of 30 to 70% by weight is most preferred.

About photopolymerization initiator:
Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Acetophenone-based or ketal-based photopolymerization initiators such as methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether Benzoin ether photopolymerization initiators such as benzoin isopropyl ether, benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, 1 Benzophenone photopolymerization initiators such as 1,4-benzoylbenzene, thioxanthone photopolymerization such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Examples of the initiator and other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenyl ether. Xylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10- Examples include phenanthrene, acridine compounds, triazine compounds, imidazole compounds. Moreover, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples thereof include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′-dimethylaminobenzophenone, and the like. These polymerization initiators may be used alone or in combination of two or more. The preferred content of the polymerization initiator is 0.5 to 40 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total content having radical polymerizability.

Next, a method for forming a cured coating composition will be described.
The cured coating composition used in the present invention is prepared after preparing a coating solution containing at least component A, components A and B, or components A, B and C, and coating the coating solution on the surface of the photoreceptor. It is formed by radical polymerization. In the case of component A, B, and C, it forms by performing light irradiation according to the absorption wavelength of a photoinitiator, and making it polymerize.

  When the polymerizable monomer is a liquid, the coating liquid can be applied by dissolving other components in the liquid, but it is diluted with a solvent as required. Solvents used at this time include alcohols such as methanol, ethanol, 2-propanol and butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran, dioxane and propyl. Examples include ethers such as ether, halogens such as dichloromethane, dichloroethane, trichloroethane, and chlorobenzene, aromatics such as benzene, toluene, and xylene, and cellosolves such as methyl cellosolve, ethyl cellosolve, and cellosolve acetate. These solvents may be used alone or in combination of two or more. The dilution ratio with the solvent varies depending on the solubility of the composition, the coating method, and the target film thickness, and is arbitrary. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.

  Component A is important for imparting the charge transport performance of the cured coating composition, and this component is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, based on the cured coating composition. If this component is less than 20% by weight, the charge transport performance cannot be sufficiently maintained, and deterioration of electrical characteristics such as a decrease in sensitivity and an increase in residual potential appear after repeated use. On the other hand, if it exceeds 80% by weight, the content of Component B is lowered, the crosslink density is lowered, and the intended characteristics are hardly exhibited.

  In addition to Component A, Component B, and Component C, the coating liquid is monofunctional or bifunctional for the purpose of imparting functions such as viscosity adjustment during coating, stress relaxation of the cured coating composition, low surface energy, and reduction of friction coefficient. These radical polymerizable monomers and radical polymerizable oligomers can be used in combination. Known radical polymerizable monomers and oligomers can be used. Examples of the monofunctional radical monomer include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, and cyclohexyl acrylate. , Isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, and the like. Examples of the bifunctional radical polymerizable monomer include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1, Examples include 6-hexanediol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate bisphenol A-EO modified diacrylate, bisphenol F-EO modified diacrylate, neopentyl glycol diacrylate, and the like. Examples of the functional monomer include those substituted with a fluorine atom such as octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluoroisononylethyl acrylate, No. 60503, JP-B-6-45770, siloxane repeating units: 20-70 acryloyl polydimethylsiloxane ethyl, methacryloyl polydimethylsiloxane ethyl, acryloyl polydimethylsiloxane propyl, acryloyl polydimethylsiloxane butyl, diacryloyl polydimethylsiloxane Examples thereof include vinyl monomers having a polysiloxane group such as diethyl, acrylates and methacrylates. Examples of the radical polymerizable oligomer include epoxy acrylate, urethane acrylate, and polyester acrylate oligomers. However, when a large amount of monofunctional and bifunctional radically polymerizable monomers and radically polymerizable oligomers are contained, the three-dimensional cross-linking density of the cured coating composition is substantially reduced, leading to deterioration of properties. For this reason, the content of these monomers and oligomers is limited to 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of Component A.

  Furthermore, the coating liquid can contain additives such as various plasticizers (for the purpose of stress relaxation and adhesion improvement), leveling agents, and low molecular charge transport materials having no radical reactivity, as necessary. As these additives, known additives can be used, and as plasticizers, those used in general resins such as dibutyl phthalate and dioctyl phthalate can be used, and the amount used is the total solid content of the coating liquid. To 20 wt% or less, more preferably 10 wt% or less. As leveling agents, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the side chain can be used, and the amount used is based on the total solid content of the coating liquid. 3% by weight or less is appropriate.

After applying the coating liquid, a drying step is optionally inserted, and curing is performed by light irradiation or the like. For UV irradiation, UV light sources such as high-pressure mercury lamps and metal halide lamps that emit light mainly in ultraviolet light can be used, but a visible light source can also be selected according to the absorption wavelength of radically polymerizable substances and photopolymerization initiators. It is. Irradiation light amount is 50 mW / cm ² or more, preferably 2000 mW / cm ² or less, it takes time for the curing reaction is less than 50 mW / cm ^2. When it is higher than 2000 mW / cm ^2, the progress of the reaction becomes uneven, and local wrinkles are generated on the surface of the cured coating composition, many unreacted residues, reaction termination ends, and the like are generated. In addition, internal stress increases due to rapid crosslinking, which causes cracks and film peeling. Moreover, nitrogen substitution may be performed at the time of light irradiation to prevent polymerization inhibition by oxygen, or continuous light irradiation may be performed, or irradiation may be intermittently performed in a plurality of times. Electron beam irradiation can also be used as a similar means of light irradiation. However, those using light energy are preferred because of easy reaction rate control and simplicity of the apparatus.

The greater the amount of light irradiation, the higher the gel fraction of the cured coating composition and the more insoluble and infusible state. In order to achieve the object of the present invention, the gel fraction is preferably 95% or more. Therefore, in the present invention, being insoluble in an organic solvent means a gel fraction of 95% or more. The gel fraction can be observed by immersing the cured coating composition in a highly soluble organic solvent such as tetrahydrofuran for 5 days and measuring the weight loss.
Gel fraction (%)
= 100 × (weight of cured coating composition after immersion drying / initial weight of cured coating composition)

In order to form a cured coating composition having a gel fraction of 95% or more, it is desirable to irradiate an integrated irradiation energy of 10 J / cm ² or more, and more preferably to cure to a gel fraction of 97% or more. By increasing the gel fraction, it is possible to further prevent the sticking of silica or the like. In this case, it is desirable to irradiate the integrated irradiation energy of 20 J / cm ² or more.

  After curing by light irradiation, annealing is performed at 80 ° C. to 150 ° C., and it is used as an electrophotographic photosensitive member. The annealing time is preferably 1 minute to 60 minutes.

Next, the configuration of the electrophotographic photosensitive member will be described.
The electrophotographic photoreceptor of the present invention has the above-mentioned cured coating composition on the surface, and there is no limitation on the structure thereof, but the general formulas (1) to (3) listed as preferred radical polymerizable monomers of Component A It is preferable that the compound is formed on the surface of a negatively charged organic photoreceptor because of its hole transportability. As a typical structure of the negatively charged organic photoreceptor, a charge generation layer and a charge transport layer are sequentially laminated on a conductive support, and the cured coating composition can be applied to the charge transport layer. However, in this case, since the film thickness of the charge transport layer is restricted depending on the curing conditions, a photoconductor structure in which a crosslinkable charge transport layer is further laminated on the charge transport layer is formed, and the cured coating composition is formed on the crosslinkable charge transport layer. Is most preferably applied.

Next, the layer structure of the electrophotographic photosensitive member of the present invention will be described with reference to FIGS. 1 to 5 are sectional views of the electrophotographic photosensitive member.
In the embodiment shown in FIG. 1, a photosensitive layer (33) mainly composed of a charge generation material and a charge transport material is provided on a conductive support (31). The cured coating composition is applied to the photosensitive layer (33).
In the embodiment shown in FIG. 2, a charge generation layer (35) mainly composed of a charge generation material and a charge transport layer (37) mainly composed of a charge transport material are formed on a conductive support (31). The photosensitive layer is laminated. The cured coating composition is applied to the charge transport layer (37).
In the embodiment shown in FIG. 3, a photosensitive layer (33) mainly composed of a charge generation material and a charge transport material is provided on a conductive support (31), and a protective layer (cross-linked charge) is further formed on the surface of the photosensitive layer. A transport layer (39) is provided. The cured coating composition is applied to the protective layer (39).
In the embodiment shown in FIG. 4, on a conductive support (31), a charge generation layer (35) mainly composed of a charge generation material, and then a charge transport layer (37) mainly composed of a charge transport material; Are laminated as a photosensitive layer, and a protective layer (39) is further provided on the charge transport layer. The cured coating composition is applied to the protective layer (39).
In the embodiment shown in FIG. 5, a charge transport layer (37) containing a charge transport material as a main component and then a charge generation layer (35) containing a charge generation material as a main component are formed on a conductive support (31). The photosensitive layer is laminated, and a protective layer (39) is provided on the charge generation layer. The cured coating composition is applied to the protective layer (39).

In the present invention, the configuration shown in FIG. 4 is preferable as described above.
Examples of the conductive support (31) include those having a volume resistance of 10 ¹⁰ Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation Metal oxide such as indium is deposited or sputtered to form film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. After conversion, a tube that has been subjected to surface treatment such as cutting, superfinishing, or polishing can be used. In addition, an endless nickel belt and an endless stainless steel belt disclosed in JP-A-52-36016 can also be used as the conductive support (31). In addition, the conductive support dispersed in a suitable binder resin and coated on the support can also be used as the conductive support (31) of the present invention.

  Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide powder such as conductive tin oxide and ITO. Can be mentioned. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Furthermore, a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, polytetrafluoroethylene fluororesin on a suitable cylindrical substrate. Those provided with a conductive layer can be used favorably as the conductive support (31) of the present invention.

  The charge generation layer (35) is a layer mainly composed of a charge generation material having a charge generation function, and a binder resin can be used in combination as necessary. As the charge generation material, inorganic materials and organic materials can be used. Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms, phosphorus atoms, or the like are preferably used. On the other hand, a known material can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having carbazole skeleton, azo pigments having triphenylamine skeleton, azo pigments having diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having a fluorenone skeleton, azo pigments having an oxadiazole skeleton, azo pigments having a bis-stilbene skeleton, azo pigments having a distyryl oxadiazole skeleton, azo pigments having a distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, Goido based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  The binder resin used as necessary for the charge generation layer (35) is polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-. Examples thereof include vinyl carbazole and polyacrylamide. These binder resins can be used alone or as a mixture of two or more. In addition to the binder resin described above as a binder resin for the charge generation layer, a polymer charge transport material having a charge transport function, such as an arylamine skeleton, benzidine skeleton, hydrazone skeleton, carbazole skeleton, stilbene skeleton, pyrazoline skeleton, etc. Polymer materials such as polycarbonate, polyester, polyurethane, polyether, polysiloxane, and acrylic resin, polymer materials having a polysilane skeleton, and the like can be used.

  Specific examples of the former include JP-A-01-001728, JP-A-01-009964, JP-A-01-013061, JP-A-01-019049, JP-A-01-241559, Japanese Unexamined Patent Publication Nos. 04-011627, 04-175337, 04-183719, 04-2225014, 04-230767, 04-320420, 05 -232727, JP-A 05-310904, JP-A 06-234836, JP-A 06-234837, JP-A 06-234838, JP-A 06-234839, JP-A 06-234840. No. 1, JP-A 06-234841, JP-A 06-239049, Japanese Unexamined Patent Publication Nos. 06-236050, 06-236051, 06-295077, 07-0756374, 08-176293, 08-208820, 08 No. -21640, JP 08-253568, JP 08-269183, JP 09-062019, JP 09-043883, JP 09-71642, JP 09-87376. JP-A 09-104746, JP-A 09-110974, JP-A 09-110976, JP-A 09-157378, JP-A 09-221544, JP-A 09-227669. JP 09-235367 A, JP 09-241369 A Charge transporting polymer materials described in JP 09-268226 A, JP 09-272735 A, JP 09-302084 A, JP 09-302085 A, JP 09-328539 A, etc. Can be mentioned. Specific examples of the latter include polysilylene polymers described in, for example, JP-A No. 63-285552, JP-A No. 05-19497, JP-A No. 05-70595, JP-A No. 10-73944, and the like. Illustrated.

  The charge generation layer (35) may contain a low molecular charge transport material. Low molecular charge transport materials that can be used in combination with the charge generation layer (35) include hole transport materials and electron transport materials. Examples of the electron transporting material include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and diphenoquinone derivatives. These electron transport materials can be used alone or as a mixture of two or more.

  Examples of the hole transporting material include the electron donating materials shown below and are used favorably. As hole transport materials, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triaryls Other known materials such as methane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and the like can be given. These hole transport materials can be used alone or as a mixture of two or more.

  Methods for forming the charge generation layer (35) include a vacuum thin film preparation method and a casting method from a solution dispersion system. As the former method, a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-described inorganic materials and organic materials can be satisfactorily formed. In addition, in order to provide a charge generation layer by the casting method described later, if necessary, the inorganic or organic charge generation material together with a binder resin, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclohexane. It can be formed by dispersing with a ball mill, attritor, sand mill, bead mill, etc. using a solvent such as pentanone, anisole, xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, etc. Further, a leveling agent such as dimethyl silicone oil or methyl phenyl silicone oil can be added as necessary. The application can be performed by dip coating, spray coating, bead coating, ring coating, or the like. The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, more preferably 0.05 to 2 μm.

  The charge transport layer (37) is a layer having a charge transport function. A charge transport material having a charge transport function and a binder resin are dissolved or dispersed in an appropriate solvent, and this is coated on the charge generation layer (35) and dried. To form. As the charge transport material, the electron transport material, hole transport material and polymer charge transport material described in the charge generation layer (35) can be used. As described above, the use of the polymer charge transport material can reduce the solubility of the lower layer when the cross-linked charge transport layer is applied, and is particularly useful.

  As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin And thermoplastic or thermosetting resins such as phenol resins and alkyd resins. The amount of the charge transport material is appropriately 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. However, when a polymer charge transport material is used, it can be used alone or in combination with a binder resin. As the solvent used for coating the charge transport layer, the same solvent as that used for the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin well is suitable. These solvents may be used alone or in combination of two or more. The charge transport layer can be formed by the same coating method as that for the charge generation layer (35).

  If necessary, a plasticizer and a leveling agent can be added. As a plasticizer that can be used in combination with the charge transport layer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is based on 100 parts by weight of the binder resin. About 0 to 30 parts by weight is appropriate. Leveling agents that can be used in combination with the charge transport layer include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. The amount used is a binder resin. About 0 to 1 part by weight is appropriate for 100 parts by weight. The thickness of the charge transport layer is suitably about 5 to 40 μm, more preferably about 10 to 30 μm. On the charge transport layer thus formed, the above-described curable coating liquid is applied, and if necessary, dried, and then a curing reaction is initiated by the external energy of light irradiation to form a crosslinkable charge transport layer. The

  In the photoreceptor of the present invention, an intermediate layer is provided between the charge transport layer and the cross-linked charge transport layer for the purpose of suppressing charge transport layer component mixing into the cross-linked charge transport layer or improving adhesion between the two layers. It is possible. For this reason, as the intermediate layer, those which are insoluble or hardly soluble in the cross-linked charge transport layer coating solution are suitable, and generally a binder resin is used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a generally used coating method is employed as described above. The thickness of the intermediate layer is preferably about 0.05 to 2 μm.

  In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support (31) and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential. These undercoat layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, the undercoat layer of the present invention is vacuum-treated with anodized alumina, organic substances such as polyparaxylylene (parylene), and inorganic substances such as silica, tin oxide, titanium oxide, ITO, and ceria. Those provided by the thin film preparation method can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is preferably 0 to 5 μm.

  Further, in the present invention, in order to improve environmental resistance, in particular, for the purpose of preventing a decrease in sensitivity and an increase in residual potential, a cross-linked charge transport layer, a charge transport layer, a charge generation layer, an undercoat layer, an intermediate layer An antioxidant can be added to each layer. Antioxidants that can be used in the present invention include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4 -Ethyl-6-tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 1, 1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- 4-hide Xylbenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3 ′) -T-Butylphenyl) butyric acid] phenolic compounds, tocopherols and other phenolic compounds, N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p- Phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N, N'-di-isopropyl-p-phenylenediamine, N, N'-dimethyl-N, N'-di-t-butyl- Paraphenylenediamine compounds such as p-phenylenediamine, 2,5-di-t-octylhydroquinone, 2,6-didodecyl high Hydroquinone compounds such as droquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- (2-octadecenyl) -5-methylhydroquinone, dilauryl-3,3 Organic sulfur compounds such as' -thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate, triphenylphosphine, tri (nonylphenyl) phosphine, tri Examples thereof include organic phosphorus compounds such as (dinonylphenyl) phosphine, tricresylphosphine, and tri (2,4-dibutylphenoxy) phosphine. These compounds are known as antioxidants such as rubbers, plastics, oils and fats, and commercially available products can be easily obtained. The addition amount of the antioxidant in the present invention is 0.01 to 10% by weight based on the total weight of the layer to be added.

  The film thickness of the crosslinked charge transport layer (39) of the present invention is 1 μm or more and 30 μm or less, preferably 1 μm or more and 10 μm or less, more preferably 3 μm or more and 10 μm or less. When it is thicker than 30 μm, cracks and film peeling are likely to occur, and radical polymerization due to photocleavage of the photoinitiator hardly occurs in the deep part, so that it becomes difficult to form a film having a high crosslinking density. On the other hand, the radical polymerization reaction is susceptible to oxygen inhibition, that is, the surface in contact with the air is liable to become non-uniform or non-uniform due to the influence of radical trapping by oxygen. This effect is noticeable when the surface layer is 1 μm or less, and the cross-linked charge transport layer having a thickness of less than this thickness is liable to cause a decrease in wear resistance or uneven wear. In addition, mixing of the lower layer charge transport layer component occurs during the application of the crosslinkable charge transport layer. If the coating thickness of the crosslinkable charge transport layer is thin, contaminants spread throughout the layer, which inhibits the curing reaction and lowers the crosslink density. For these reasons, the crosslinked charge transport layer of the present invention can form a high-density crosslinked body with a film thickness of 1 μm or more, thereby preventing white spots. In addition, a decrease in film thickness due to wear in repeated use tends to cause local chargeability and sensitivity fluctuations, and it is desirable that the film thickness of the cross-linked charge transport layer be 3 μm or more from the viewpoint of extending the life.

When the electrophotographic photosensitive member has the structure shown in FIG. 1, the photosensitive layer (35) is a layer mainly composed of a charge generating substance and a charge transporting substance, and further uses the polymerizable compound and binder resin of the present invention in combination. Can do. The charge generating material, charge transporting material, and binder resin described above are suitable. The film thickness of the photosensitive layer (35) is suitably about 5 to 40 μm, more preferably about 10 to 30 μm. An antioxidant may be added to the photosensitive layer, and specific examples thereof are those described above.
In the case of the configuration shown in FIG. 3, the photosensitive layer (33) is a layer mainly composed of a charge generation material and a charge transport material, and may further contain a binder resin or an antioxidant. Specific examples thereof include those described above. As the cross-linked charge transport layer (39) provided on the photosensitive layer, those described above can be applied.

  Next, the image forming method and the image forming apparatus of the present invention will be described in detail with reference to the drawings. The image forming method and the image forming apparatus of the present invention use a photoreceptor having a cured coating composition on the surface, which has very high wear resistance and scratch resistance and hardly causes cracks and film peeling. An image forming method and an image forming apparatus comprising processes of charging, image exposure, and development, and then transferring the toner image onto an image carrier (transfer paper), fixing, and cleaning the surface of the photoreceptor. In some cases, an image forming method or the like in which an electrostatic latent image is directly transferred to a transfer member and developed does not necessarily have the above-described process arranged on a photosensitive member.

  FIG. 6 is a schematic diagram illustrating an example of an image forming apparatus. A charging charger (3) is used as a means for charging the photoconductor on average. As the charging means, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, or the like is used, and a known system can be used. In particular, the configuration of the present invention is particularly effective when a charging unit such as a contact charging method or a non-contact proximity arrangement charging method is used in which the photosensitive composition is decomposed by proximity discharge from the charging unit. The contact charging method referred to here is a charging method in which a charging roller, a charging brush, a charging blade, or the like is in direct contact with the photosensitive member. On the other hand, the proximity charging method is, for example, a type in which the charging roller is arranged in a non-contact state so as to have a gap of 200 μm or less between the surface of the photoreceptor and the charging means. If this gap is too large, the charging tends to become unstable, and if it is too small, the surface of the charging member may be contaminated when toner remaining on the photoreceptor exists. is there. Accordingly, the gap is suitably 10 to 200 μm, more preferably 10 to 100 μm.

  Next, the image exposure unit (5) is used to form an electrostatic latent image on the uniformly charged photoreceptor (1). As the light source, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

  Next, the developing unit (6) is used to visualize the electrostatic latent image formed on the photoreceptor (1). Development methods include a one-component development method using a dry toner, a two-component development method, and a wet development method using a wet toner. When the photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.

Next, a transfer charger (10) is used to transfer the toner image visualized on the photoconductor onto the transfer body (9). In addition, a pre-transfer charger (7) may be used for better transfer. As these transfer means, a transfer charger, an electrostatic transfer method using a bias roller, a mechanical transfer method such as an adhesive transfer method and a pressure transfer method, and a magnetic transfer method can be used. As the electrostatic transfer method, the charging means can be used.
Next, a separation charger (11) and a separation claw (12) are used as means for separating the transfer body (9) from the photoreceptor (1). As other separation means, electrostatic adsorption induction separation, side end belt separation, tip grip conveyance, curvature separation, and the like are used. As the separation charger (11), the charging means can be used.

Next, a fur brush (14) and a cleaning blade (15) are used to clean the toner remaining on the photoreceptor after transfer. Further, a pre-cleaning charger (13) may be used in order to perform cleaning more efficiently. As other cleaning means, there are a web system, a magnet brush system, and the like, but a single system or a plurality of systems may be used together.
Next, a neutralizing unit is used for the purpose of removing the latent image on the photoconductor as necessary. As the charge removal means, a charge removal lamp (2) and a charge removal charger are used, and the exposure light source and the charging means can be used respectively. In addition, known processes can be used for reading, feeding, fixing, paper discharge and the like that are not close to the photoconductor.

  The present invention is an image forming method and an image forming apparatus using the electrophotographic photoreceptor according to the present invention for such image forming means. This image forming means may be fixedly incorporated in a copying apparatus, facsimile, or printer, but may be incorporated in these apparatuses in the form of a process cartridge and detachable. An example of the process cartridge is shown in FIG. The image forming apparatus and BR> p process cartridge includes a photoconductor (101), in addition to a charging unit (102), a developing unit (104), a transfer unit (106), a cleaning unit (107), and a charge eliminating unit ( And an apparatus (part) that is detachable from the main body of the image forming apparatus. Referring to the image forming process by the apparatus illustrated in FIG. 7, the surface of the photoreceptor (101) is exposed by charging by the charging means (102) and exposure by the exposure means (103) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed, and the electrostatic latent image is developed with toner by the developing means (104). The toner development is transferred to the transfer body (105) by the transfer means (106), and printed. Out. Next, the surface of the photoconductor after the image transfer is cleaned by a cleaning unit (107), and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again. The present invention is a laminate type photoconductor having a cross-linked charge transport layer on its surface that has very high wear resistance and scratch resistance and is unlikely to cause cracks or film peeling, and at least one of charging, developing, transferring, cleaning, and neutralizing means. The present invention provides a process cartridge for an image forming apparatus in which the two are integrated. As is apparent from the above description, the electrophotographic photosensitive member of the present invention is not only used in electrophotographic copying machines, but also in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making. Can also be used widely.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. Note that “parts” used in the examples all represent parts by weight.

<Synthesis of Component A used in the present invention>
<Example 1>
Synthesis of Exemplary Compound (B-07) Synthesis of Compound (D-2)

  Into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 15.00 g of the compound represented by (D-1) and 100 ml of THF are placed, and stirred while cooling with a refrigerant in an argon gas stream. 25 ml of n-butyllithium solution (2.6 M, hexane solution) was added dropwise with care so that the internal temperature does not exceed -70 ° C. After completion of dropping, stirring is continued for 1.5 hours at the same temperature. A solution of 13.32 g of trimethoxyborane and 5 ml of THF was added dropwise with care so that the internal temperature does not exceed -70 ° C. After completion of dropping, stirring was continued for 2 hours, and then the temperature was raised to room temperature. Add 100 ml of 3N hydrochloric acid in small portions. The mixture was further stirred at room temperature for 1.5 hours. Transfer the reaction mixture to a separatory funnel and extract the organic components with ethyl acetate. Further, the organic layer was washed with water twice. The organic layer was separated, dried over magnesium sulfate and concentrated under reduced pressure. The precipitated crystals were washed with stirring with n-hexane. The obtained crude crystals were recrystallized with a mixed solvent of cyclohexane / toluene. 6.27 g, yield 46.4%. m. p. = 250 ° C or higher.

攪拌子、温度計、冷却管をつけた反応容器に、（Ｄ−２）６．１６ｇ、４−ブロモ−４’−メトキシビフェニル３．６２ｇ、カリウム−ｔ−ブトキシド３．２７ｇ、酢酸パラジウム０．１１９ｇ、キシレン１００ｍｌを入れ、アルゴンガス気流下、室温で攪拌。トリ−ｔ−ブチルフォスフフィン０．２ｍｌを添加し、１００℃で加熱攪拌。２時間後反応を停止し、室温まで冷却。少量のシリカゲルを通して不溶成分を除去。濾液を減圧濃縮。析出した結晶を２−メトキシエタノールで再結晶。４．０８ｇ、収率６５．１％。 Synthesis of compound (D-3)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube, (D-2) 6.16 g, 4-bromo-4′-methoxybiphenyl 3.62 g, potassium t-butoxide 3.27 g, palladium acetate 0. 119 g and xylene 100 ml were added and stirred at room temperature under an argon gas stream. Add 0.2 ml of tri-t-butylphosphine and stir at 100 ° C. The reaction was stopped after 2 hours and cooled to room temperature. Remove insoluble components through a small amount of silica gel. Concentrate the filtrate under reduced pressure. The precipitated crystals are recrystallized from 2-methoxyethanol. 4.08 g, yield 65.1%.

攪拌子、温度計をつけた反応容器に、化合物（Ｄ−３）３．９９ｇ、塩化メチレン９０ｍｌを加え、アルゴンガス気流下、冷媒で冷却攪拌。三臭化ホウ素の塩化メチレン溶液１０ｍｌを滴下し、更に同温度で２時間反応を行ない、更に室温まで昇温して２時間反応を行った。その後、反応液を氷水に注ぎ込み、酢酸エチルで抽出した。有機層を水洗した後、分離し、硫酸マグネシウムで乾燥後、減圧濃縮。残渣をシリカゲルカラムクロマトグラフィーで精製。３．２７ｇ、収量８４．５％。 Synthesis of compound (D-4)

To a reaction vessel equipped with a stirrer and a thermometer, 3.99 g of compound (D-3) and 90 ml of methylene chloride were added, and the mixture was cooled and stirred with a refrigerant in an argon gas stream. 10 ml of a boron tribromide methylene chloride solution was added dropwise, the reaction was further carried out at the same temperature for 2 hours, and the temperature was further raised to room temperature for 2 hours. Thereafter, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, separated, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography. 3.27 g, yield 84.5%.

攪拌子、温度計、冷却管をつけた反応容器に、化合物（Ｄ−４）３．２１ｇ、炭酸エチレン１２．７２ｇ、炭酸カリウム０．３ｇ、キシレン５０ｍｌを入れ、１３０℃で加熱攪拌。１．５時間後、反応を停止。反応液を分液ロートに移し、有機層を３回水洗。有機層を分離し、硫酸マグネシウムで乾燥後、減圧濃縮。析出した結晶をシリカゲルカラムクロマトグラフィーで精製。２．９１ｇ、収率８２．４％。 Synthesis of compound (D-5)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube, 3.21 g of compound (D-4), 12.72 g of ethylene carbonate, 0.3 g of potassium carbonate, and 50 ml of xylene were placed, and the mixture was heated and stirred at 130 ° C. The reaction was stopped after 1.5 hours. The reaction solution was transferred to a separatory funnel, and the organic layer was washed with water three times. The organic layer was separated, dried over magnesium sulfate, and concentrated under reduced pressure. The precipitated crystals are purified by silica gel column chromatography. 2.91 g, yield 82.4%.

攪拌子、温度計、冷却管をつけた反応容器に、化合物（Ｄ−５）２．８２ｇ、Ｎ，Ｎ’−ジアセチルアミド５０ｍｌを入れ、アルゴンガス気流下、室温で攪拌。３−クロロプロピオニルクロリド０．８８ｇ、Ｎ，Ｎ−ジメチルアセトアミド２．０ｍｌの溶液を滴下。５分後、トリエチルアミン２３．５ｇを投入し、６０℃で過熱攪拌。１時間後反応を停止。反応液をイオン交換水２００ｍｌに注ぎ込む。次いで酢酸エチル１００ｍｌを加えて室温で攪拌。分液ロートに移し、有機層を４回水洗。分離した有機層を硫酸マグネシウムで乾燥後、減圧濃縮。析出した粗結晶をシリカゲルカラムクロマトグラフィーで精製。得た結晶をｎ−ヘキサン、メタノールで１回ずつ洗浄。２．５５ｇ、収率８１．３％。ｍ．ｐ．＝１３３．０〜１３４．０℃。ＩＲスペクトルを図８に示す。 Synthesis of exemplary compound (B-07)

2.82 g of compound (D-5) and 50 ml of N, N′-diacetylamide were placed in a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, and stirred at room temperature under an argon gas stream. A solution of 0.88 g of 3-chloropropionyl chloride and 2.0 ml of N, N-dimethylacetamide was added dropwise. After 5 minutes, 23.5 g of triethylamine was added, and the mixture was heated and stirred at 60 ° C. The reaction was stopped after 1 hour. The reaction solution is poured into 200 ml of ion exchange water. Next, 100 ml of ethyl acetate was added and stirred at room temperature. Transfer to separatory funnel and wash organic layer 4 times with water. The separated organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The precipitated crude crystals are purified by silica gel column chromatography. The obtained crystals were washed once with n-hexane and methanol. 2.55 g, yield 81.3%. m. p. = 133.0-134.0 ° C. The IR spectrum is shown in FIG.

攪拌子、温度計をつけた反応容器に、化合物（Ｄ−４）３．８８ｇ、トリエチルアミン１．３６ｇ、ＴＨＦ５０ｍｌを入れ、室温で攪拌下、アクリロイルクロリド１．０ｍｌ、ＴＨＦ２．０ｍｌの溶液を滴下。２時間後攪拌を停止し、イオン交換水３００ｍｌへ注ぎ込む。酢酸エチル１００ｍｌを加えて室温で攪拌。分液ロートに移し、有機層を３回水洗。分離した有機層を硫酸マグネシウムで乾燥後、減圧濃縮。得た粗結晶をシリカゲルカラムクロマトグラフィーで精製。更にシクロヘキサンで再結晶。３．３６ｇ。収率７７．１％。ｍ．ｐ．＝１６９．５〜１７０．５℃。ＩＲスペクトルを図９に示す。 <Example 2>
Synthesis of exemplary compound (B-08)

A reaction vessel equipped with a stirrer and a thermometer was charged with 3.88 g of compound (D-4), 1.36 g of triethylamine and 50 ml of THF, and a solution of 1.0 ml of acryloyl chloride and 2.0 ml of THF was added dropwise at room temperature. Stirring is stopped after 2 hours and poured into 300 ml of ion-exchanged water. Add 100 ml of ethyl acetate and stir at room temperature. Transfer to separatory funnel and wash organic layer 3 times with water. The separated organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude crystals were purified by silica gel column chromatography. Recrystallize with cyclohexane. 3.36 g. Yield 77.1%. m. p. = 169.5-170.5 <0> C. The IR spectrum is shown in FIG.

攪拌子、温度計、冷却管をつけた反応容器に、化合物（Ｄ−６）２６．４５ｇ、クロロホルム２００ｍｌを入れ、室温で攪拌しながらＮ−ブロモコハク酸イミド１５．６２ｇを１．５時間かけて投入。投入後、１時間同温で攪拌。反応液を水に注ぎ込み、塩化メチレンでした。有機層を水洗した後、分離し、硫酸マグネシウムで乾燥後、減圧濃縮。粗結晶を２−プロパノールと酢酸エチルの混合溶媒で再結晶。３０．３６ｇ、収率９１．０％。ｍ．ｐ．＝１２６．０〜１２７．０℃。
<Example 3>
Synthesis of Exemplary Compound (B-12) Synthesis of Compound (D-7)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube, 26.45 g of Compound (D-6) and 200 ml of chloroform were placed, and 15.62 g of N-bromosuccinimide was added over 1.5 hours while stirring at room temperature. Input. Stir at the same temperature for 1 hour after charging. The reaction was poured into water and was methylene chloride. The organic layer was washed with water, separated, dried over magnesium sulfate, and concentrated under reduced pressure. The crude crystals were recrystallized with a mixed solvent of 2-propanol and ethyl acetate. 30.36 g, yield 91.0%. m. p. = 126.0-127.0 ° C.

攪拌子、温度計、冷却管をつけた反応容器に、（Ｄ−７）９．７８ｇ、４−メトキシ−４’−ビフェニルボロン酸８．５６ｇ、カリウム−ｔ−ブトキシド５．１９ｇ、酢酸パラジウム０．０６８ｇ、キシレン１５０ｍｌを入れ、アルゴンガス気流下、室温で攪拌。トリ−ｔ−ブチルフォスフフィン０．４ｍｌを添加し、１２０℃で加熱攪拌。１時間後反応を停止し、室温まで冷却。少量のシリカゲルを通して不溶成分を除去。濾液を減圧濃縮。析出した結晶をｎ−ヘキサンで洗浄。１０．３２ｇ、収率８３．０％。
Synthesis of compound (D-8)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, (D-7) 9.78 g, 4-methoxy-4′-biphenylboronic acid 8.56 g, potassium t-butoxide 5.19 g, palladium acetate 0 0.068 g and xylene 150 ml were added and stirred at room temperature under a stream of argon gas. Add 0.4 ml of tri-t-butylphosphine and stir at 120 ° C. The reaction was stopped after 1 hour and cooled to room temperature. Remove insoluble components through a small amount of silica gel. Concentrate the filtrate under reduced pressure. The precipitated crystals were washed with n-hexane. 10.32 g, yield 83.0%.

攪拌子、温度計をつけた反応容器に、化合物（Ｄ−８）９．９５ｇ、塩化メチレン１８０ｍｌを加え、アルゴンガス気流下、冷媒で冷却攪拌。三臭化ホウ素の塩化メチレン溶液２５ｍｌを滴下し、更に同温度で１時間反応を行ない、更に室温まで昇温して１．５時間反応を行った。その後、反応液を氷水（５００ｍｌ）に注ぎ込み、酢酸エチルで抽出した。有機層を水洗した後、分離し、硫酸マグネシウムで乾燥後、減圧濃縮。残渣をシリカゲルカラムクロマトグラフィーで精製。９．２６ｇ、収量９５．９％。
Synthesis of compound (D-9)

To a reaction vessel equipped with a stirrer and a thermometer, 9.95 g of compound (D-8) and 180 ml of methylene chloride were added, and the mixture was cooled and stirred with a refrigerant in an argon gas stream. 25 ml of a methylene chloride solution of boron tribromide was added dropwise, and the reaction was further carried out at the same temperature for 1 hour, and further the temperature was raised to room temperature and the reaction was carried out for 1.5 hours. Thereafter, the reaction solution was poured into ice water (500 ml) and extracted with ethyl acetate. The organic layer was washed with water, separated, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography. 9.26 g, yield 95.9%.

攪拌子、温度計、冷却管をつけた反応容器に、化合物（Ｄ−９）９．０９ｇ、炭酸エチレン３４．１５ｇ、炭酸カリウム０．１４ｇ、キシレン１００ｍｌを入れ、１３０℃で加熱攪拌。２時間後、反応を停止。反応液を分液ロートに移し、有機層を３回水洗。有機層を分離し、硫酸マグネシウムで乾燥後、減圧濃縮。析出した結晶をシリカゲルカラムクロマトグラフィーで精製。得た結晶をメタノールで攪拌洗浄。８．０２ｇ、収率８０．６％。
Synthesis of compound (D-10)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube, 9.09 g of compound (D-9), 34.15 g of ethylene carbonate, 0.14 g of potassium carbonate, and 100 ml of xylene were added, and the mixture was heated and stirred at 130 ° C. The reaction was stopped after 2 hours. The reaction solution was transferred to a separatory funnel, and the organic layer was washed with water three times. The organic layer was separated, dried over magnesium sulfate, and concentrated under reduced pressure. The precipitated crystals are purified by silica gel column chromatography. The obtained crystal was stirred and washed with methanol. 8.02 g, yield 80.6%.

攪拌子、温度計、冷却管をつけた反応容器に、化合物（Ｄ−１０）７．５３ｇ、Ｎ，Ｎ’−ジアセチルアミド５０ｍｌを入れ、アルゴンガス気流下、室温で攪拌。３−クロロプロピオニルクロリド２．２３ｇ、Ｎ，Ｎ−ジメチルアセトアミド２．０ｍｌの溶液を滴下。５分後、トリエチルアミン５９．３４ｇを投入し、６０℃で過熱攪拌。３時間後反応を停止。反応液をイオン交換水３００ｍｌに注ぎ込む。次いで酢酸エチル１００ｍｌを加えて室温で攪拌。分液ロートに移し、有機層を３回水洗。分離した有機層を硫酸マグネシウムで乾燥後、減圧濃縮。析出した粗結晶をシリカゲルカラムクロマトグラフィーで精製。得た結晶をｎ−ヘキサン、メタノールで１回ずつ洗浄。５．３８ｇ、収率６４．６％。ｍ．ｐ．＝１２３．０〜１２４．５℃。ＩＲスペクトルを図１４に示す。 Synthesis of exemplary compound (B-12)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 7.53 g of compound (D-10) and 50 ml of N, N′-diacetylamide were added and stirred at room temperature under an argon gas stream. A solution of 2.23 g of 3-chloropropionyl chloride and 2.0 ml of N, N-dimethylacetamide was added dropwise. After 5 minutes, 59.34 g of triethylamine was added, and the mixture was heated and stirred at 60 ° C. The reaction was stopped after 3 hours. The reaction solution is poured into 300 ml of ion exchange water. Next, 100 ml of ethyl acetate was added and stirred at room temperature. Transfer to separatory funnel and wash organic layer 3 times with water. The separated organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The precipitated crude crystals are purified by silica gel column chromatography. The obtained crystals were washed once with n-hexane and methanol. 5.38 g, yield 64.6%. m. p. = 123.0-124.5 ° C. The IR spectrum is shown in FIG.

攪拌子、温度計、冷却管をつけた反応容器に４−ビフェニル酢酸１１．２１ｇを酢酸５８ｍｌを入れ、８０℃に加熱しながら、ヨウ素６．０３ｇ、過ヨウ素酸２．４１ｇを加え、更に、濃硫酸０．１７ｍｌを加えて、４時間撹拌。その後、室温に戻し、水１００ｍｌに注ぎ込み、析出した素結晶をろ過し、亜硫酸ソーダ水溶液で洗浄し、さらに水で洗浄し、最後にメタノールで洗浄して、4’−ヨード−４−ビフェニル酢酸１０．３８ｇを得た。
これをエタノール５０ｍｌに溶解させ、濃硫酸０．５ｍｌを加えて、７５℃で２時間撹拌した後、濃縮し、水１００ｍｌに注ぎ込んだ。析出した素結晶をろ別し、水洗後、メタノールで再結晶し、４’−ヨード−４−ビフェニル酢酸エチルエステル９．１ｇを得た。ｍ．ｐ．＝８０．５〜８０．８℃。
得られた４’−ヨード−４−ビフェニル酢酸エチルエステル９．０ｇをテトラヒドロフラン１１０ｍｌに溶解し、水素化ホウ素ナトリウム２．５２ｇを加え、６６℃でメタノール１６．５ｇをゆっくり滴下した。その後、６７℃で７時間撹拌。希塩酸を加えた後、酢酸エチルで抽出し、水洗後、濃縮して粗収物を得た。これをメタノールで再結晶し、２−（４’−ヨードビフェニル−４−イル）エタノール６．０８ｇを得た。ｍ．ｐ．＝１６９．５〜１７１．０℃。 <Example 4>
Synthesis of Exemplary Compound (B-25) Synthesis of 2- (4′-iodobiphenyl-4-yl) ethanol

Into a reaction vessel equipped with a stirrer, a thermometer, and a condenser tube, 11.21 g of 4-biphenylacetic acid was added with 58 ml of acetic acid, and while heating to 80 ° C., 6.03 g of iodine and 2.41 g of periodic acid were added. Add 0.17 ml of concentrated sulfuric acid and stir for 4 hours. Thereafter, the temperature is returned to room temperature, poured into 100 ml of water, the precipitated elementary crystals are filtered, washed with an aqueous solution of sodium sulfite, further washed with water, and finally washed with methanol to give 4'-iodo-4-biphenylacetic acid 10 .38 g was obtained.
This was dissolved in 50 ml of ethanol, added with 0.5 ml of concentrated sulfuric acid, stirred at 75 ° C. for 2 hours, concentrated, and poured into 100 ml of water. The precipitated elementary crystals were separated by filtration, washed with water, and recrystallized with methanol to obtain 9.1 g of 4′-iodo-4-biphenylacetic acid ethyl ester. m. p. = 80.5-80.8 ° C.
9.0 g of the obtained 4′-iodo-4-biphenylacetic acid ethyl ester was dissolved in 110 ml of tetrahydrofuran, 2.52 g of sodium borohydride was added, and 16.5 g of methanol was slowly added dropwise at 66 ° C. Then, it stirred at 67 degreeC for 7 hours. After adding diluted hydrochloric acid, the mixture was extracted with ethyl acetate, washed with water, and concentrated to obtain a crude product. This was recrystallized from methanol to obtain 6.08 g of 2- (4′-iodobiphenyl-4-yl) ethanol. m. p. = 169.5-171.0 ° C.

攪拌子、温度計、冷却管をつけた反応容器に、（Ｄ−２）７．３ｇ、２−（４’−ヨードビフェニル−４−イル）エタノール８．４ｇ、トルエン１００ｍｌ、エタノール５０ｍｌ、２Ｍ炭酸カリウム水溶液１００ｍｌを入れ、アルゴンガス気流下、室温で攪拌。テトラキストリフェニルホスフィンパラジウム（０）価錯体０．５３ｇを添加し、７０℃で加熱攪拌。８時間後反応を停止し、室温まで冷却。トルエンで抽出し、抽出液を水洗した後に濃縮して、粗収物を得た。エタノールとメタノールの混合溶媒で再結晶。８．２ｇ、収率７５．９％。ｍ．ｐ．＝１７６．５〜１７７．０℃。ＩＲスペクトルを図１５に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ／ｚ値は４７０であり、分子式から計算される分子量４６９．６３にプロトンの１を加えた値と一致した。 Synthesis of (D-11)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, (D-2) 7.3 g, 2- (4′-iodobiphenyl-4-yl) ethanol 8.4 g, toluene 100 ml, ethanol 50 ml, 2M carbonic acid Add 100 ml of aqueous potassium solution and stir at room temperature under an argon gas stream. Add 0.53 g of tetrakistriphenylphosphinepalladium (0) -valent complex and stir at 70 ° C. with heating. The reaction was stopped after 8 hours and cooled to room temperature. Extraction was performed with toluene, and the extract was washed with water and concentrated to obtain a crude product. Recrystallize with a mixed solvent of ethanol and methanol. 8.2 g, yield 75.9%. m. p. = 176.5-177.0 <0> C. The IR spectrum is shown in FIG. The m / z value measured in the positive mode after ionization by the atmospheric pressure chemical ionization method was 470, which coincided with the value obtained by adding 1 of proton to the molecular weight of 469.63 calculated from the molecular formula.

攪拌子、温度計、冷却管をつけた反応容器に、化合物（Ｄ−１１）７．２ｇ、Ｎ，Ｎ’−ジアセチルアミド８０ｍｌを入れ、アルゴンガス気流下、室温で攪拌。３−クロロプロピオニルクロリド３．９ｇを滴下。２時間後、トリエチルアミン８．６ｍｌを投入し、６０℃で過熱攪拌。４時間後反応を停止。反応液をイオン交換水３００ｍｌに注ぎ込む。次いで酢酸エチル１００ｍｌを加えて室温で攪拌。分液ロートに移し、有機層を３回水洗。分離した有機層を硫酸マグネシウムで乾燥後、減圧濃縮。得られた粗収物をシリカゲルカラムクロマトグラフィーで精製。無色のアモルファス体として得られた。６．８ｇ、収率８５．０％。ＩＲスペクトルを図１６に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ／ｚ値は５２４であり、分子式から計算される分子量５２３．２５にプロトンの１を加えた値と一致した。 Synthesis of exemplary compound (B-25)

In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 7.2 g of compound (D-11) and 80 ml of N, N′-diacetylamide were added and stirred at room temperature under a stream of argon gas. 3.9 g of 3-chloropropionyl chloride was added dropwise. After 2 hours, 8.6 ml of triethylamine was added, and the mixture was heated and stirred at 60 ° C. The reaction was stopped after 4 hours. The reaction solution is poured into 300 ml of ion exchange water. Next, 100 ml of ethyl acetate was added and stirred at room temperature. Transfer to separatory funnel and wash organic layer 3 times with water. The separated organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography. It was obtained as a colorless amorphous body. 6.8 g, yield 85.0%. The IR spectrum is shown in FIG. The m / z value measured in the positive mode by ionization by the atmospheric pressure chemical ionization method was 524, which coincided with the value obtained by adding 1 of proton to the molecular weight 523.25 calculated from the molecular formula.

攪拌子、温度計、冷却管をつけた反応容器に、５−フェニル−１−ペンタノール２５ｇ、酢酸１２０ｍｌを入れ、濃硫酸０．５ｍｌを加えて６５℃で２時間撹拌。その後、ヨウ素、１７．３６ｇ、過ヨウ素酸６．９３ｇを加え、７０℃で５時間撹拌。室温に戻し、水４００ｍｌに注ぎ込み、得られた油層を亜硫酸水溶液で洗浄し、さらに水洗した後、乾燥させて、酢酸５−（４−ヨードフェニル）−１−ペンチルエステル４８．６ｇを得た。この物は、一部酢酸５−（２−ヨードフェニル）−１−ペンチルエステルを混入していたが、次工程ではそのまま使用した。
得られた酢酸５−（４−ヨードフェニル）−１−ペンチルエステル２８．４６ｇをエタノール１０５ｍｌに溶解させ、さらに水酸化ナトリウム６．７４ｇを水７６ｍｌに溶解させた水溶液を加えて６５℃で１時間撹拌した。室温に戻し、水４００ｍｌに注ぎ込み、塩酸で中和した後、油層を水洗して目的物の５−（４−ヨードフェニル）−１−ペンタノール２３．１１ｇを得た。この物は、一部５−（２−ヨードフェニル）−１−ペンタノールを混入していたが、次工程ではそのまま使用した。 <Example 5>
Synthesis of Exemplary Compound (B-44) Synthesis of 5- (4-iodophenyl) -1-pentanol

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 25 g of 5-phenyl-1-pentanol and 120 ml of acetic acid were added, 0.5 ml of concentrated sulfuric acid was added, and the mixture was stirred at 65 ° C. for 2 hours. Then, iodine, 17.36 g, and periodic acid 6.93 g were added and stirred at 70 ° C. for 5 hours. The temperature was returned to room temperature, poured into 400 ml of water, and the obtained oil layer was washed with an aqueous solution of sulfurous acid, further washed with water and then dried to obtain 48.6 g of acetic acid 5- (4-iodophenyl) -1-pentyl ester. This product was partially mixed with acetic acid 5- (2-iodophenyl) -1-pentyl ester, but was used as it was in the next step.
28.46 g of the acetic acid 5- (4-iodophenyl) -1-pentyl ester thus obtained was dissolved in 105 ml of ethanol, and an aqueous solution in which 6.74 g of sodium hydroxide was dissolved in 76 ml of water was added, and the mixture was stirred at 65 ° C. for 1 hour. Stir. After returning to room temperature and pouring into 400 ml of water and neutralizing with hydrochloric acid, the oil layer was washed with water to obtain 23.11 g of the desired 5- (4-iodophenyl) -1-pentanol. This product was partially mixed with 5- (2-iodophenyl) -1-pentanol, but was used as it was in the next step.

攪拌子、温度計、冷却管をつけた反応容器に、（Ｄ−１２）５．０ｇ、５−（４−ヨードフェニル）−１−ペンタノール３．７ｇ、トルエン１００ｍｌ、エタノール５０ｍｌ、２Ｍ炭酸カリウム水溶液１００ｍｌを入れ、アルゴンガス気流下、室温で攪拌。テトラキストリフェニルホスフィンパラジウム（０）価錯体０．３ｇを添加し、７０℃で加熱攪拌。８時間後反応を停止し、室温まで冷却。トルエンで抽出し、抽出液を水洗した後に濃縮して、粗収物を得た。得られた粗収物をシリカゲルカラムクロマトグラフィーで精製。さらにヘキサンと酢酸エチルの混合溶媒で再結晶。４．１ｇ、収率６３．１％。ｍ．ｐ．＝１３８．０〜１３８．５℃。ＩＲスペクトルを図１７に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ/ｚ値は５１２であり、分子式から計算される分子量５１１．７１にプロトンの1を加えた値と一致した。 Synthesis of (D-13)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, (D-12) 5.0 g, 5- (4-iodophenyl) -1-pentanol 3.7 g, toluene 100 ml, ethanol 50 ml, 2M potassium carbonate Add 100 ml of aqueous solution and stir at room temperature under a stream of argon gas. Add 0.3 g of tetrakistriphenylphosphine palladium (0) -valent complex and stir with heating at 70 ° C. The reaction was stopped after 8 hours and cooled to room temperature. Extraction was performed with toluene, and the extract was washed with water and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography. Recrystallize in a mixed solvent of hexane and ethyl acetate. 4.1 g, yield 63.1%. m. p. = 138.0-138.5 ° C. The IR spectrum is shown in FIG. The m / z value measured in the positive mode and ionized by the atmospheric pressure chemical ionization method was 512, which coincided with the value obtained by adding 1 of proton to the molecular weight 511.71 calculated from the molecular formula.

攪拌子、温度計、冷却管をつけた反応容器に、化合物（Ｄ−１３）４．１ｇ、Ｎ，Ｎ’−ジアセチルアミド１００ｍｌを入れ、アルゴンガス気流下、室温で攪拌。３−クロロプロピオニルクロリド１．５ｇを滴下。２時間後、トリエチルアミン５．０ｍｌを投入し、６０℃で過熱攪拌。４時間後反応を停止。反応液をイオン交換水３００ｍｌに注ぎ込む。次いで酢酸エチル１００ｍｌを加えて室温で攪拌。分液ロートに移し、有機層を３回水洗。分離した有機層を硫酸マグネシウムで乾燥後、減圧濃縮。得られた粗収物をシリカゲルカラムクロマトグラフィーで精製。その後、エタノールで再結晶。２．７ｇ、収率６０．２％。ｍ．ｐ．＝９８．５〜９９．０℃。ＩＲスペクトルを図１８に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ／ｚ値は５６６であり、分子式から計算される分子量５６５．３０にプロトンの１を加えた値と一致した。 Synthesis of exemplary compound (B-44)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 4.1 g of compound (D-13) and 100 ml of N, N′-diacetylamide were added and stirred at room temperature under a stream of argon gas. Add dropwise 1.5 g of 3-chloropropionyl chloride. After 2 hours, 5.0 ml of triethylamine was added, and the mixture was heated and stirred at 60 ° C. The reaction was stopped after 4 hours. The reaction solution is poured into 300 ml of ion exchange water. Next, 100 ml of ethyl acetate was added and stirred at room temperature. Transfer to separatory funnel and wash organic layer 3 times with water. The separated organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography. Then recrystallize with ethanol. 2.7 g, yield 60.2%. m. p. = 98.5-99.0 ° C. The IR spectrum is shown in FIG. The m / z value measured in the positive mode and ionized by the atmospheric pressure chemical ionization method was 566, which coincided with the value obtained by adding 1 of proton to the molecular weight 565.30 calculated from the molecular formula.

攪拌子、温度計、冷却管をつけた反応容器に、３−ブロモフェニルボロン酸２５．８ｇ、１，８−ジアミノナフタレン２０．５３ｇ、トルエン６００ｍｌを入れ、１時間加熱還流した。室温に戻し、反応液を濃縮して、シリカゲルによるカラムクロマトグラフィーで精製し、３−ブロモ−１−（２，３−ジヒドロ−１Ｈ−ナフト［１，８−ｄｅ］−１，３，２−ジアザボリニル）ベンゼン３５．０３ｇを得た。
攪拌子、温度計、冷却管をつけた反応容器に、３−ブロモ−１−（２，３−ジヒドロ−１Ｈ−ナフト［１，８−ｄｅ］−１，３，２−ジアザボリニル）ベンゼン３．８５ｇ、４−メトキシフェニルボロン酸２．３５ｇ、トルエン３０ｍｌ、エタノール１５ｍｌ、２Ｍ炭酸カリウム水溶液３０ｍｌ、テトラキストリフェニルホスフィンパラジウム（０）価錯体０．２７ｇを入れ、７０℃で６時間撹拌した。反応液をトルエンで抽出し、水洗した後、濃縮して粗収物を得た。これを、テトラヒドロフラン１６ｍｌに溶解させ、硫酸０．８ｇ、水３ｇを加えて室温で３時間撹拌した。生成物をエーテルで抽出し、乾燥させて（４’−メトキシビフェニル−３−イル）ボロン酸３．５ｇを得た。 <Example 6>
Synthesis of Exemplified Compound (B-47) Synthesis of (4′-methoxybiphenyl-3-yl) boronic acid

Into a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 25.8 g of 3-bromophenylboronic acid, 20.53 g of 1,8-diaminonaphthalene, and 600 ml of toluene were placed and heated under reflux for 1 hour. After returning to room temperature, the reaction solution was concentrated and purified by column chromatography on silica gel to obtain 3-bromo-1- (2,3-dihydro-1H-naphtho [1,8-de] -1,3,2- 35.03 g of diazaborinyl) benzene was obtained.
In a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, 3-bromo-1- (2,3-dihydro-1H-naphtho [1,8-de] -1,3,2-diazaborinyl) benzene; 85 g, 2.35 g of 4-methoxyphenylboronic acid, 30 ml of toluene, 15 ml of ethanol, 30 ml of 2M aqueous potassium carbonate solution and 0.27 g of tetrakistriphenylphosphine palladium (0) -valent complex were added and stirred at 70 ° C. for 6 hours. The reaction solution was extracted with toluene, washed with water, and concentrated to obtain a crude product. This was dissolved in 16 ml of tetrahydrofuran, 0.8 g of sulfuric acid and 3 g of water were added, and the mixture was stirred at room temperature for 3 hours. The product was extracted with ether and dried to give 3.5 g of (4′-methoxybiphenyl-3-yl) boronic acid.

攪拌子、温度計、冷却管をつけた反応容器に、（Ｄ−１）３．１４ｇ、（４’−メトキシビフェニル−３−イル）ボロン酸３．０ｇ、トルエン５０ｍｌ、エタノール２５ｍｌ、２Ｍ炭酸カリウム水溶液５０ｍｌを入れ、アルゴンガス気流下、室温で攪拌。テトラキストリフェニルホスフィンパラジウム（０）価錯体０．２ｇを添加し、７０℃で加熱攪拌。８時間後反応を停止し、室温まで冷却。トルエンで抽出し、抽出液を水洗した後に濃縮して、粗収物を得た。得られた粗収物をシリカゲルカラムクロマトグラフィーで精製。無色のアモルファス体として得られた。４．０ｇ、収率９８．８％。ＩＲスペクトルを図１９に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ/ｚ値は４５６であり、分子式から計算される分子量４５５．６０にプロトンの1を加えた値と一致した。 Synthesis of (D-14)

In a reaction vessel equipped with a stirrer, thermometer and condenser, (D-1) 3.14 g, (4'-methoxybiphenyl-3-yl) boronic acid 3.0 g, toluene 50 ml, ethanol 25 ml, 2M potassium carbonate Add 50 ml of aqueous solution and stir at room temperature under a stream of argon gas. Add 0.2 g of tetrakistriphenylphosphine palladium (0) -valent complex and stir with heating at 70 ° C. The reaction was stopped after 8 hours and cooled to room temperature. Extraction was performed with toluene, and the extract was washed with water and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography. It was obtained as a colorless amorphous body. 4.0 g, yield 98.8%. The IR spectrum is shown in FIG. The m / z value measured by positive mode and ionized by the atmospheric pressure chemical ionization method was 456, which coincided with the value obtained by adding 1 of proton to the molecular weight 455.60 calculated from the molecular formula.

攪拌子、温度計をつけた反応容器に、化合物（Ｄ−１４）３．０ｇ、塩化メチレン１２ｍｌを加え、アルゴンガス気流下、冷媒で冷却攪拌。一規定の三臭化ホウ素の塩化メチレン溶液４．４ｍｌを滴下し、更に同温度で１時間反応を行ない、更に室温まで昇温して１．５時間反応を行った。その後、反応液を氷水（１００ｍｌ）に注ぎ込み、酢酸エチルで抽出した。有機層を水洗した後、分離し、硫酸マグネシウムで乾燥後、減圧濃縮。残渣をシリカゲルカラムクロマトグラフィーで精製。２．４ｇ、収量８２．８％。ＩＲスペクトルを図２０に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ／ｚ値は４４２であり、分子式から計算される分子量４４１．５６にプロトンの１を加えた値と一致した。 Synthesis of (D-15)

To a reaction vessel equipped with a stirrer and a thermometer, 3.0 g of compound (D-14) and 12 ml of methylene chloride were added, and the mixture was cooled and stirred with a refrigerant in an argon gas stream. 4.4 ml of a methylene chloride solution of 1N boron tribromide was added dropwise, and the reaction was further carried out at the same temperature for 1 hour. Thereafter, the reaction solution was poured into ice water (100 ml) and extracted with ethyl acetate. The organic layer was washed with water, separated, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography. 2.4 g, yield 82.8%. The IR spectrum is shown in FIG. The m / z value measured by positive mode and ionized by the atmospheric pressure chemical ionization method was 442, which coincided with the value obtained by adding 1 of proton to the molecular weight 441.56 calculated from the molecular formula.

攪拌子、温度計、冷却管をつけた反応容器に、化合物（Ｄ−１５）２．０ｇ、Ｎ，Ｎ’−ジアセチルアミド１７ｍｌを入れ、アルゴンガス気流下、室温で攪拌。３−クロロプロピオニルクロリド０．９ｇを滴下。２時間後、トリエチルアミン８．５ｍｌを投入し、６０℃で過熱攪拌。４時間後反応を停止。反応液をイオン交換水３００ｍｌに注ぎ込む。次いで酢酸エチル５０ｍｌを加えて室温で攪拌。分液ロートに移し、有機層を３回水洗。分離した有機層を硫酸マグネシウムで乾燥後、減圧濃縮。得られた粗収物をシリカゲルカラムクロマトグラフィーで精製。無色のアモルファス体として得られた。１．８ｇ、収率７８．２％。ＩＲスペクトルを図２１に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ／ｚ値は４９６であり、分子式から計算される分子量４９５．６２にプロトンの１を加えた値と一致した。 Synthesis of exemplary compound (B-47)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 2.0 g of compound (D-15) and 17 ml of N, N′-diacetylamide were added and stirred at room temperature under a stream of argon gas. 0.9 g of 3-chloropropionyl chloride was added dropwise. Two hours later, 8.5 ml of triethylamine was added, and the mixture was heated and stirred at 60 ° C. The reaction was stopped after 4 hours. The reaction solution is poured into 300 ml of ion exchange water. Next, 50 ml of ethyl acetate was added and stirred at room temperature. Transfer to separatory funnel and wash organic layer 3 times with water. The separated organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography. It was obtained as a colorless amorphous body. 1.8 g, yield 78.2%. The IR spectrum is shown in FIG. The ionization was performed by the atmospheric pressure chemical ionization method, and the m / z value measured in the positive mode was 496, which coincided with the value obtained by adding 1 of proton to the molecular weight of 495.62 calculated from the molecular formula.

攪拌子、温度計、冷却管をつけた反応容器に、２−ブロモフェニルボロン酸２４．５ｇ、１，８−ジアミノナフタレン１９．４９ｇ、トルエン６００ｍｌを入れ、２時間加熱還流した。室温に戻し、反応液を濃縮して、シリカゲルによるカラムクロマトグラフィーで精製し、２−ブロモ−１−（２，３−ジヒドロ−１Ｈ−ナフト［１，８−ｄｅ］−１，３，２−ジアザボリニル）ベンゼン３７．７８ｇを得た。
攪拌子、温度計、冷却管をつけた反応容器に、２−ブロモ−１−（２，３−ジヒドロ−１Ｈ−ナフト［１，８−ｄｅ］−１，３，２−ジアザボリニル）ベンゼン６．７２ｇ、４−メトキシフェニルボロン酸３．４８ｇ、フッ化セシウム６．９５ｇ、パラジウム（II）アセテート０．０９３ｇ、テトラヒドロフラン６５ｍｌを入れ、さらに、トリ−ｔｅｒｔ−ブチルホスフィン０．４５ｍｌと水１３ｍｌを加え、６０℃で１０時間撹拌した。反応液を酢酸エチルで抽出し、水洗した後、濃縮してシリカゲルによるカラムクロマトグラフィーで精製し、中間体５．４９ｇを得た。これを、テトラヒドロフラン５０ｍｌに溶解させ、硫酸７．４ｇ、水２８．４ｇを加えて室温で３７時間撹拌した。生成物をエーテルで抽出し、濃縮してシリカゲルによるカラムクロマトグラフィーで精製し（４’−メトキシビフェニル−２−イル）ボロン酸５．０ｇを得た。 <Example 7>
Synthesis of Exemplary Compound (B-48) Synthesis of (4′-methoxybiphenyl-2-yl) boronic acid

24.5 g of 2-bromophenylboronic acid, 19.49 g of 1,8-diaminonaphthalene, and 600 ml of toluene were placed in a reaction vessel equipped with a stirrer, a thermometer, and a condenser, and heated under reflux for 2 hours. After returning to room temperature, the reaction solution is concentrated and purified by column chromatography on silica gel to give 2-bromo-1- (2,3-dihydro-1H-naphtho [1,8-de] -1,3,2- 37.78 g of diazaborinyl) benzene was obtained.
2-bromo-1- (2,3-dihydro-1H-naphtho [1,8-de] -1,3,2-diazaborinyl) benzene in a reaction vessel equipped with a stirrer, thermometer, and condenser. 72 g, 3.48 g of 4-methoxyphenylboronic acid, 6.95 g of cesium fluoride, 0.093 g of palladium (II) acetate, 65 ml of tetrahydrofuran, 0.45 ml of tri-tert-butylphosphine and 13 ml of water were added, Stir at 60 ° C. for 10 hours. The reaction solution was extracted with ethyl acetate, washed with water, concentrated and purified by silica gel column chromatography to obtain 5.49 g of an intermediate. This was dissolved in 50 ml of tetrahydrofuran, 7.4 g of sulfuric acid and 28.4 g of water were added, and the mixture was stirred at room temperature for 37 hours. The product was extracted with ether, concentrated and purified by silica gel column chromatography to obtain 5.0 g of (4′-methoxybiphenyl-2-yl) boronic acid.

攪拌子、温度計、冷却管をつけた反応容器に、（Ｄ−１）７．０ｇ、（４’−メトキシビフェニル−２−イル）ボロン酸６．７ｇ、トルエン１００ｍｌ、エタノール５０ｍｌ、２Ｍ炭酸カリウム水溶液１００ｍｌを入れ、アルゴンガス気流下、室温で攪拌。テトラキストリフェニルホスフィンパラジウム（０）価錯体０．４６ｇを添加し、７０℃で加熱攪拌。８時間後反応を停止し、室温まで冷却。トルエンで抽出し、抽出液を水洗した後に濃縮して、粗収物を得た。得られた粗収物をシリカゲルカラムクロマトグラフィーで精製。無色のアモルファス体として得られた。８．１ｇ、収率８９．３％。ＩＲスペクトルを図２２に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ／ｚ値は４５６であり、分子式から計算される分子量４５５．６０にプロトンの１を加えた値と一致した。 Synthesis of (D-16)

In a reaction vessel equipped with a stirrer, a thermometer and a condenser, (D-1) 7.0 g, (4′-methoxybiphenyl-2-yl) boronic acid 6.7 g, toluene 100 ml, ethanol 50 ml, 2M potassium carbonate Add 100 ml of aqueous solution and stir at room temperature under a stream of argon gas. Add 0.46 g of tetrakistriphenylphosphine palladium (0) -valent complex, and heat and stir at 70 ° C. The reaction was stopped after 8 hours and cooled to room temperature. Extraction was performed with toluene, and the extract was washed with water and concentrated to obtain a crude product. The obtained crude product was purified by silica gel column chromatography. It was obtained as a colorless amorphous body. 8.1 g, yield 89.3%. The IR spectrum is shown in FIG. The m / z value measured by positive mode and ionized by the atmospheric pressure chemical ionization method was 456, which coincided with the value obtained by adding 1 of proton to the molecular weight 455.60 calculated from the molecular formula.

攪拌子、温度計をつけた反応容器に、化合物（Ｄ−１７）７．１ｇ、塩化メチレン２９ｍｌを加え、アルゴンガス気流下、冷媒で冷却攪拌。一規定の三臭化ホウ素の塩化メチレン溶液１０．４ｍｌを滴下し、更に同温度で１時間反応を行ない、更に室温まで昇温して１．５時間反応を行った。その後、反応液を氷水（２００ｍｌ）に注ぎ込み、酢酸エチルで抽出した。有機層を水洗した後、分離し、硫酸マグネシウムで乾燥後、減圧濃縮。残渣をシリカゲルカラムクロマトグラフィーで精製。６．５ｇ、収量９４．３％。ＩＲスペクトルを図２３に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ／ｚ値は４４２であり、分子式から計算される分子量４４１．５６にプロトンの１を加えた値と一致した。 Synthesis of (D-17)

In a reaction vessel equipped with a stirrer and a thermometer, 7.1 g of compound (D-17) and 29 ml of methylene chloride were added, and the mixture was cooled and stirred with a refrigerant in an argon gas stream. 10.4 ml of a methylene chloride solution of 1N boron tribromide was added dropwise, the reaction was further carried out at the same temperature for 1 hour, the temperature was further raised to room temperature, and the reaction was carried out for 1.5 hours. Thereafter, the reaction solution was poured into ice water (200 ml) and extracted with ethyl acetate. The organic layer was washed with water, separated, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography. 6.5 g, yield 94.3%. The IR spectrum is shown in FIG. The m / z value measured by positive mode and ionized by the atmospheric pressure chemical ionization method was 442, which coincided with the value obtained by adding 1 of proton to the molecular weight 441.56 calculated from the molecular formula.

攪拌子、温度計、冷却管をつけた反応容器に、化合物（Ｄ−１７）５．３ｇ、Ｎ，Ｎ’−ジアセチルアミド４５ｍｌを入れ、アルゴンガス気流下、室温で攪拌。３−クロロプロピオニルクロリド２．４ｇを滴下。２時間後、トリエチルアミン１１．４ｍｌを投入し、６０℃で過熱攪拌。４時間後反応を停止。反応液をイオン交換水３００ｍｌに注ぎ込む。次いで酢酸エチル１５０ｍｌを加えて室温で攪拌。分液ロートに移し、有機層を３回水洗。分離した有機層を硫酸マグネシウムで乾燥後、減圧濃縮。得られた粗収物をシリカゲルカラムクロマトグラフィーで精製。無色のアモルファス体として得られた。４．５ｇ、収率７５．６％。ＩＲスペクトルを図２４に示す。大気圧化学イオン化法によりイオン化し、ポジティブモードで測定したｍ／ｚ値は４９６であり、分子式から計算される分子量４９５．６２にプロトンの１を加えた値と一致した。 Synthesis of exemplary compound (B-48)

In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 5.3 g of compound (D-17) and 45 ml of N, N′-diacetylamide were stirred at room temperature under an argon gas stream. 2.4 g of 3-chloropropionyl chloride is added dropwise. Two hours later, 11.4 ml of triethylamine was added, and the mixture was heated and stirred at 60 ° C. The reaction was stopped after 4 hours. The reaction solution is poured into 300 ml of ion exchange water. Next, 150 ml of ethyl acetate was added and stirred at room temperature. Transfer to separatory funnel and wash organic layer 3 times with water. The separated organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography. It was obtained as a colorless amorphous body. 4.5 g, yield 75.6%. The IR spectrum is shown in FIG. The ionization was performed by the atmospheric pressure chemical ionization method, and the m / z value measured in the positive mode was 496, which coincided with the value obtained by adding 1 of proton to the molecular weight of 495.62 calculated from the molecular formula.

<Example 8>
By coating and drying an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution in the following order on a φ30 mm aluminum cylinder in sequence, an undercoat layer of 3.5 μm A 0.2 μm charge generation layer and an 18 μm charge transport layer were formed. On this charge transport layer, a coating solution for a crosslinkable charge transport layer having the following composition was spray-coated and naturally dried for 20 minutes, and then a metal halide lamp: 160 W / cm, irradiation distance: 110 mm, irradiation intensity: 750 mW / cm ^2. , Irradiation time: The coating film was cured by light irradiation under the condition of 240 seconds. Furthermore, drying was performed at 130 ° C. for 20 minutes, and a 5.0 μm cross-linked charge transport layer was provided to obtain an electrophotographic photoreceptor of the present invention.

ポリビニルブチラール（ＵＣＣ製ＸＹＨＬ） ０．５部
シクロヘキサノン ２００部
メチルエチルケトン ８０部 [Coating liquid for undercoat layer]
Alkyd resin (Beckosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals) 6 parts Melamine resin (Super Becamine G-821-60, manufactured by Dainippon Ink and Chemicals) 4 parts Titanium oxide 40 parts Methyl ethyl ketone 50 parts [for charge generation layer (Coating fluid)
Bisazo pigment represented by the following formula (F-1) 2.5 parts

Polyvinyl butyral (UCC XYHL) 0.5 part Cyclohexanone 200 parts Methyl ethyl ketone 80 parts

テトラヒドロフラン １００部
１％シリコーンオイルのテトラヒドロフラン溶液
（信越化学工業製ＫＦ５０−１００ＣＳ） ０．２部 [Coating liquid for charge transport layer]
Bisphenol Z polycarbonate (Teijin Chemicals Panlite TS-2050) 10 parts Low molecular charge transport material represented by the following formula (F-2) 7 parts

Tetrahydrofuran 100 parts 1% silicone oil in tetrahydrofuran (Shin-Etsu Chemical KF50-100CS) 0.2 part

[Coating liquid for cross-linked charge transport layer]
Component A: Exemplified Compound (B-07) 10 parts Component B: Trimethylolpropane triacrylate
(Nippon Kayaku KAYARAD TMPTA, molecular weight: 296,
3 functional groups, molecular weight / number of functional groups = 99) 10 parts Component C: 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184 manufactured by Ciba Specialty Chemicals) 1 part Solvent: 100 parts tetrahydrofuran

<Example 9>
Electrophotographic photosensitivity in the same manner except that component A of the coating solution for a crosslinkable charge transport layer of Example 8 is replaced with a 1: 1 mixture of the exemplified compound (B-07) and the exemplified compound (B-08). The body was made.
<Example 10>
An electrophotographic photosensitive member was produced in the same manner except that the component A of the coating liquid for a crosslinkable charge transport layer of Example 8 was replaced with the exemplified compound (B-08).
<Examples 11 to 15>
An electrophotographic photosensitive member was produced in the same manner except that the thickness of the cross-linked charge transport layer in Example 10 was changed to the thickness shown in Table 1.

<Comparative Example 1>
An electrophotographic photosensitive member was produced in the same manner except that component A of the coating solution for a crosslinkable charge transport layer in Example 8 was replaced with the following compound (the compound described in G-01, Japanese Patent No. 3164426).

<Comparative example 2>
An electrophotographic photosensitive member was produced in the same manner except that component A of the coating solution for a crosslinked charge transport layer in Example 8 was replaced with the following compound (the compound described in G-02, Japanese Patent No. 3164426).

<Comparative Example 3>
An electrophotographic photosensitive member was produced in the same manner except that component A of the coating solution for a crosslinkable charge transport layer in Example 8 was replaced with the following compound (G-03, compound described in JP-A No. 2002-040686). did.

<Comparative Example 4>
An electrophotographic photosensitive member was produced in the same manner except that component A of the coating solution for a crosslinkable charge transport layer in Example 8 was replaced with the following compound (G-04, compound described in Japanese Patent No. 3286704).

  With respect to the electrophotographic photoreceptors of Examples 8 to 15 and Comparative Examples 1 to 4 produced as described above, the appearance was visually observed to determine the presence or absence of cracks and film peeling. Moreover, the gel fraction of each crosslinkable charge transport layer was determined. The gel fraction was determined by applying a crosslinked charge transport layer coating solution directly onto an aluminum support in the same manner as in each Example and Comparative Example, and irradiating and drying the membrane under the same conditions in a tetrahydrofuran solution at 25 ° C. It was immersed for 5 days and determined from the weight residual ratio of the gel. The results are shown in Table 1.

  Next, a paper passing test of 50,000 sheets of A4 size was carried out using the photoreceptors prepared in the same manner as in Examples 8 to 15 and Comparative Examples 1 to 4 and toner containing a silica external additive. First, the photosensitive member was mounted on a process cartridge for an electrophotographic apparatus, and the initial dark portion potential was set to −700 V with a Ricoh imagio Neo 270 remodeling machine using a 655 nm semiconductor laser as an image exposure light source. Then, measure the total film thickness after the initial and 50,000 copies, calculate the amount of wear from the difference, observe the image after 50,000 copies, and the number of white spots per unit area from the solid image area I counted. Further, in order to check the residual potential accumulation property, the initial portion and the exposure portion potential (VL) after 50,000 copies were measured. The results are shown in Table 2.

  As shown in Table 2, the electrophotographic photosensitive member of the present invention is more excellent in wear resistance among organic photoconductors having excellent wear resistance, while enabling image output with few defects. Yes. In particular, white spots caused by the sticking of silica hardly occur, and the image has sufficient image stability even when used for a long time. It is clear that the primary factor of these is due to the specific component A used in the present invention in comparison with the comparative example, and the surface has a cured coating composition obtained by radical polymerization of the component A of the present invention. This indicates that the electrophotographic photosensitive member has excellent characteristics. In particular, the combination of the component A and the component B of the present invention is smooth and extremely excellent in wear resistance, has a low residual charge accumulation property, and has a low durability such as white spots as shown in the examples. To give. The examples also show that a cured coating composition of the composition photocured in the presence of a photoinitiator is effective. In addition, the cross-linked charge transport layer has a good thickness in the range of 1 to 10 μm, and with 1 μm, there is almost no margin for the amount of wear after copying 50,000 sheets. When exceeding, since the fall of a gel fraction is seen and the residual potential accumulation property is getting worse, it has shown that the range of 1-10 micrometers shown above is preferable. In the curing conditions of the examples, the gel fraction data was judged to be substantially insoluble in organic solvents, and it was shown that excellent abrasion resistance and image stability were achieved under those conditions. Yes.

<Examples 16 to 22>
An electrophotographic photosensitive member was produced in the same manner except that the component A of the coating liquid for a crosslinkable charge transport layer in Example 8 was replaced with the exemplified compounds shown in Table 3 below. The film thickness of the cross-linked charge transport layer was all 5.0 μm. Surface observation and gel fraction were also carried out in the same manner as in Example 8. The results are shown in Table 3. Further, a paper passing test similar to that in Example 8 was carried out using these photoreceptors and toner containing silica external additive. The results are shown in Table 4. From the results shown in Tables 3 and 4, it is clear that the product of the present invention exhibits excellent characteristics as in the above-described Examples.
Further, when Example Compound B-25 of Example 21 was used, the smoothness was particularly excellent in surface observation.

表３、表４から明らかなように、本発明の重合性化合物を用いた感光体は、何れも良好な特性を示した。

As is clear from Tables 3 and 4, the photoreceptors using the polymerizable compound of the present invention exhibited good characteristics.

<Example 23>
An undercoat layer coating solution and a photosensitive layer coating solution having the following composition are sequentially applied onto an aluminum cylinder having a diameter of 30 mm, and dried to obtain an undercoat layer having a thickness of 3.5 μm and a thickness of 15 μm. A photosensitive layer was formed.
[Coating liquid for undercoat layer]
Alkyd resin (Dainippon Ink Chemical Co., Ltd .: Beccosol 1307-60-EL) 6 parts Melamine resin (Dainippon Ink Chemical Co., Ltd .: Super Becamine G-821-60) 4 parts Titanium oxide (Ishihara Sangyo) : Type C CR-50) 40 parts Methyl ethyl ketone 50 parts

下記式（Ｆ−４）で表わされる電子輸送物質 １８部

下記式（Ｆ−５）で表わされる電子輸送物質 ２部

ビスフェノールＺポリカーボネート
（帝人化成株式会社製：パンライトＴＳ−２０５０） ５０部
テトラヒドロフラン ５００部 [Coating solution for photosensitive layer]
X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc .: FastogenBlue8120B) 2 parts 30 parts of a hole transport material represented by the following formula (F-3)

18 parts of an electron transport material represented by the following formula (F-4)

2 parts of an electron transport material represented by the following formula (F-5)

Bisphenol Z polycarbonate (manufactured by Teijin Chemicals Ltd .: Panlite TS-2050) 50 parts Tetrahydrofuran 500 parts

Next, a coating solution for a crosslinkable charge transport layer having the following composition is spray-coated on the obtained photosensitive layer, and after natural drying for 20 minutes, a metal halide lamp: 160 W / cm, irradiation distance: 110 mm, irradiation intensity: It was cured by light irradiation under the conditions of 750 mW / cm ² and irradiation time: 240 seconds. Furthermore, it dried at 130 degreeC for 20 minute (s), and formed the 5.0 micrometer-thick bridge | crosslinking type charge transport layer.
[Coating liquid for cross-linked charge transport layer]
Component A: Exemplified compound (B-07) 10 parts Component B: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD TMPTA, molecular weight = 296,
Functional group number = trifunctional, molecular weight / functional group number = 99) 10 parts Component C: 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals: Irgacure 184) 1 part Solvent: THF 124 parts

<Examples 24-31>
An electrophotographic photosensitive member was produced in the same manner except that the component A of the coating solution for a crosslinked charge transport layer in Example 23 was replaced with the exemplified compounds shown in Table 5. The film thickness of the cross-linked charge transport layer was all 5.0 μm.
<Comparative Examples 5-8>
An electrophotographic photosensitive member was produced in the same manner except that the component A in the coating solution for a crosslinked charge transport layer in Example 23 was replaced with the compounds shown in Table 5. The film thickness of the cross-linked charge transport layer was all 5.0 μm.

  With respect to the electrophotographic photoreceptors of Examples 23 to 31 and Comparative Examples 5 to 8 produced as described above, the appearance was visually observed to determine the presence or absence of cracks and film peeling. Further, the gel fraction of each cross-linked charge transport layer was determined in the same manner as in Example 8. The results are shown in Table 5. Further, the characteristics of the obtained electrophotographic photoreceptor were measured by the same method as in Example 8. The results are shown in Table 6.

表５、表６の結果から明らかなように、本発明の重合性化合物を用いた感光体は、何れも良好な特性を示した。

As is clear from the results in Tables 5 and 6, the photoreceptors using the polymerizable compound of the present invention all showed good characteristics.

<Example 32>
An electrophotographic photosensitive member was produced in the same manner except that Component B of the coating solution for a crosslinkable charge transport layer in Example 8 was not added. The film thickness of the crosslinkable charge transport layer was 5.0 μm. The external appearance of the photoconductor produced as described above was observed visually, and there was no crack or film peeling. Further, the gel fraction of the crosslinkable charge transport layer was determined in the same manner as in Example 8. As a result, the gel fraction was 93%.

<Example 33>
An electrophotographic photosensitive member was produced in the same manner except that Component C of the coating solution for a crosslinkable charge transport layer in Example 8 was not added. The film thickness of the crosslinkable charge transport layer was 5.0 μm. The external appearance of the photoconductor produced as described above was observed visually, and there was no crack or film peeling. Further, the gel fraction of the crosslinkable charge transport layer was determined in the same manner as in Example 8. As a result, the gel fraction was 95%.

<Example 34>
An electrophotographic photosensitive member was prepared in the same manner except that Component B and Component C of the coating solution for a crosslinked charge transport layer in Example 8 were not added. The film thickness of the crosslinkable charge transport layer was 5.0 μm. The external appearance of the photoconductor produced as described above was observed visually, and there was no crack or film peeling. Further, the gel fraction of the crosslinkable charge transport layer was determined in the same manner as in Example 8. As a result, the gel fraction was 89%. When the tetrahydrofuran in which the cross-linked charge transport layer was immersed in order to determine the gel fraction was analyzed by liquid chromatography mass spectrometry, the molecular ion peak m / Z = 539 of the exemplified compound (B-07) was confirmed.

  Next, using the photoreceptors of Examples 32 to 34 and the toner with silica external additive, the same paper passing test as in Example 8, measurement of the amount of film thickness reduction, from the solid image area per unit area of white spots Number. In order to check the residual potential accumulation property, the exposure portion potential (VL) at the initial stage and after copying 50,000 sheets was measured. The results are shown in Table 7.

  As is apparent from the results in Table 7, it can be seen that the polymerizable compound of the present invention has good electrophotographic characteristics even without Component B or Component C. Even if an uncured product of component A remained, there was no problem in image stability and electrical characteristics.

<Example 35>
On the aluminum sheet, an undercoat layer coating solution and a photosensitive layer coating solution having the following composition are sequentially applied and dried to form an undercoat layer having a thickness of 3.5 μm and a photosensitive layer having a thickness of 15 μm. Formed.
[Coating liquid for undercoat layer]
Alkyd resin (Dainippon Ink Chemical Co., Ltd .: Beccosol 1307-60-EL) 6 parts Melamine resin (Dainippon Ink Chemical Co., Ltd .: Super Becamine G-821-60) 4 parts Titanium oxide (Ishihara Sangyo) : Type C CR-50) 40 parts Methyl ethyl ketone 50 parts [Coating solution for photosensitive layer]
X-type metal-free phthalocyanine (manufactured by Dainippon Ink & Chemicals, Inc .: FastogenBlue8120B) 2 parts Exemplary compound (B-07) 30 parts Electron transport material represented by (F-4) 18 parts Electron transport represented by (F-5) Substance 2 parts Bisphenol Z polycarbonate (manufactured by Teijin Chemicals Ltd .: Panlite TS-2050) 50 parts THF 500 parts

Next, the obtained photoreceptor was cured by light irradiation under the conditions of a metal halide lamp: 160 W / cm, irradiation distance: 110 mm, irradiation intensity: 750 mW / cm ² , and irradiation time: 240 seconds. Further, it was dried at 130 ° C. for 20 minutes.
Next, the photoreceptor of Example 35 was charged to +700 V by a corona discharge of +6 kV in a dark place using a commercially available electrostatic copying paper test apparatus [EPA-8200 type manufactured by Kawaguchi Electric Mfg. Co., Ltd.] Tungsten lamp light is irradiated so that the illuminance on the surface of the photoreceptor is 4.5 lux, the time (seconds) until the potential becomes 1/2 is obtained, and the half exposure amount E1 / 2 (lux · sec) is calculated. Calculated. Further, the residual potential (V) after 30 seconds of exposure was determined. As a result, the half-exposure amount was 1.0 lux · sec, and the residual potential was 110 V, showing excellent characteristics.

<Comparative Example 9>
A photoconductor was prepared by the same way as that of Example 35 except that the exemplified compound (B-07) in the working solution for photosensitive layer in Example 35 was changed to a comparative compound (G-01). The obtained photoreceptor was evaluated in the same manner as in Example 35. As a result, the half-exposure amount was 2.7 lux · sec and the residual potential was 159 V, which was a bad characteristic as compared with the product of the present invention.

<Examples 36 to 43, Comparative Examples 10 to 14>
After the electrophotographic photoreceptors obtained in Examples 8 and 16 to 22 and Comparative Examples 1 to 4 were mounted, the image exposure light source was remodeled to 655 nm, and the LED irradiation mechanism serving as a static eliminating means was further remodeled. The test was carried out on a modified electrophotographic apparatus (image Neo Neo 270, manufactured by Ricoh Co., Ltd.) and printed on a total of 20,000 sheets of mixed images of rectangular patches and characters with an image density of 5%. The toner and developer used were exclusive for imgio Neo 270. As the charging means of the electrophotographic apparatus, a charging roller disposed in proximity to the electrophotographic photosensitive member was used. Also, using an external power source, the voltage applied to the charging roller was selected as an AC component with a peak-to-peak voltage of 2 kV and a frequency of 1.3 kHz. For the DC component, a bias was set so that the charged potential of the photosensitive member at the start of the test was −700 V, and the test was performed under this charging condition until the end of the test. The developing bias was −500V. The test environment was 24 ° C./54% RH.
At the end of the test, afterimage evaluation and other image quality were evaluated.
The afterimage evaluation was determined by visual evaluation of the output image and divided into the following five stages.
5: Afterimage is not observed at all and is good.
4: Very little afterimage is observed, but good for practical use.
3: Although a slight afterimage is observed, it is substantially good.
2: A slight afterimage is observed, but there is substantially no problem.
1: An afterimage is observed, which causes a problem.
Table 8 shows the results of the image quality.

  As is apparent from the results in Table 8, it can be seen that the polymerizable compound of the present invention has a very good afterimage evaluation. In all of the output images of Comparative Examples 10 to 13, since unevenness is observed in the halftone image, it is determined that the photoconductor is inappropriate for increasing the speed of the apparatus.

<Examples 44 to 46>
An electrophotographic photosensitive member was produced in the same manner except that the component A of the coating solution for a crosslinkable charge transport layer in Example 8 was replaced with the exemplified compounds shown in Table 9 below. The film thickness of the cross-linked charge transport layer was all 5.0 μm. Surface observation and gel fraction were also performed in the same manner as in Example 8. The results are shown in Table 9. Further, a paper passing test similar to that in Example 8 was carried out using these photoreceptors and toner containing silica external additive. The results are shown in Table 10.

これらの結果より、本願発明品は前述の実施例と同様、優れた特性を示すことが明らかである。
また、実施例４４、４５、４６の表面観察では、平滑性に特に優れていた。また、これらは、中でも摩耗量が少なく露光部電位も低く、優れた特性を示した。

From these results, it is clear that the product of the present invention exhibits excellent characteristics as in the above-described examples.
Moreover, in the surface observation of Examples 44, 45, and 46, the smoothness was particularly excellent. In addition, among them, the wear amount was small and the exposed portion potential was low, and excellent characteristics were exhibited.

An example of a layer structure of the electrophotographic photosensitive member in the present invention. Another example of the layer structure of the electrophotographic photosensitive member in the present invention. Another example of the layer structure of the electrophotographic photosensitive member in the present invention. Another example of the layer structure of the electrophotographic photosensitive member in the present invention. Another example of the layer structure of the electrophotographic photosensitive member in the present invention. 1 is a schematic diagram illustrating an example of an image forming apparatus according to the present invention. FIG. 2 is a schematic diagram illustrating an example of a process cartridge for an image forming apparatus according to the present invention. IR spectrum of exemplary compound (B-07). IR spectrum of exemplary compound (B-08). An example figure of an image pattern. The schematic diagram of a positive afterimage. The schematic diagram of a negative afterimage. FIG. 3 is a diagram for explaining a potential state during each process on the surface of the photosensitive drum in the electrophotographic photosensitive member. IR spectrum of exemplary compound (B-12). (D-11) IR spectrum of the compound. IR spectrum of exemplary compound (B-25). (D-13) IR spectrum of the compound. IR spectrum of exemplary compound (B-44). (D-14) IR spectrum of the compound. (D-15) IR spectrum of the compound. IR spectrum of exemplary compound (B-47). (D-16) IR spectrum of the compound. (D-17) IR spectrum of the compound. IR spectrum of exemplary compound (B-48).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1: Photoconductor 2: Static elimination lamp 3: Charger charger 5: Image exposure part 6: Developing unit 7: Charger before transfer 8: Registration roller 9: Transfer paper 10: Transfer charger 11: Separation charger 12: Separation claw 13: Before cleaning Charger 14: Fur brush 15: Cleaning blade 31: Conductive support 33: Photosensitive layer 35: Charge generation layer 37: Charge transport layer 39: Cross-linked charge transport layer 101: Photosensitive drum 102: Charging device 103: Exposure 104: Development Device 105: Transfer body 106: Transfer device 107: Cleaning blade

Claims (21)

A polymerizable compound represented by the following general formula (1):

(In the formula, Ar ₁ and Ar ₂ represent any of an optionally substituted alkyl group, aralkyl group, aryl group, and heterocyclic ring, and Ar ₁ and Ar ₂ are bonded to form a cyclic structure A ₁ . Ar ₃ , Ar ₄ , and Ar ₅ each represent a divalent arylene group or heteroaromatic ring that may have a substituent, and R ₁ represents an alkylene group, an arylene group, or an oxaalkylene group. X ₁ represents an oxygen atom or a sulfur atom, Z represents a polymerizable group, n1 represents 1 or 2, and n2 and n3 represent 0 or 1.) The polymerizable compound according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, Ar ₁ and Ar _{2 each} represent an optionally substituted alkyl group, aralkyl group, aryl group or heterocyclic ring. R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R ₂ , R ₃ , and R _{4 each} represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, an aryl group, or a halogen atom, and X ₁ represents an oxygen atom or a sulfur atom. Z represents a polymerizable group, n2 and n3 represent 0 or 1. m1 to m3 represent an integer of 1 to 4.) The polymerizable compound according to claim 2, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

(In the formula, R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R _{2 to} R ₆ are any one of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, X ₁ represents an oxygen atom or a sulfur atom, n2 and n3 represent 0 or 1, m1 to m3 represent an integer of 1 to 4, and p1 P2 represents an integer of 1 to 5.) The polymerizable compound according to claim 3, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (4).

(In the formula, R ₈ represents an alkylene group having 2 to 5 carbon atoms, and R _{5 to} R ₆ are any of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group, an aryl group, and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, and p1 and p2 represent an integer of 1 to 5.) The polymerizable compound according to claim 3, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (5).

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.) The polymerizable compound according to claim 3, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (6).

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.) An electrophotographic photosensitive member having a cured coating composition on the surface, the surface having a cured coating composition obtained by polymerizing at least the following component A:
Component A: A polymerizable compound in which a polymerizable group and a substituted amino group not containing a polymerizable group are bonded with a compound in which three or more aromatic rings or heteroaromatic rings are linked. An electrophotographic photoreceptor having a cured coating composition on the surface, the surface comprising a cured coating composition obtained by polymerizing at least a mixture of the following components A and B.
Component A: Polymerizable compound in which a polymerizable group and a substituted amino group not containing a polymerizable group are bonded with a compound in which three or more aromatic rings or heteroaromatic rings are linked Component B: a polymerizable group in the molecule Three or more polymerizable monomers An electrophotographic photosensitive member having a cured coating composition on the surface, the surface comprising a cured coating composition obtained by polymerizing at least a mixture of the following components A, B and C: .
Component A: Polymerizable compound in which a polymerizable group and a substituted amino group not containing a polymerizable group are bonded with a compound in which three or more aromatic rings or heteroaromatic rings are linked Component B: a polymerizable group in the molecule Three or more polymerizable monomer components C: photopolymerization initiator The electrophotographic photosensitive member according to claim 7, wherein the component A is a polymerizable compound represented by the following general formula (1).

(In the formula, Ar ₁ and Ar ₂ represent any of an optionally substituted alkyl group, aralkyl group, aryl group, and heterocyclic ring, and Ar ₁ and Ar ₂ are bonded to form a cyclic structure A ₁ . Ar ₃ , Ar ₄ , and Ar ₅ each represent a divalent arylene group or heteroaromatic ring that may have a substituent, and R ₁ represents an alkylene group, an arylene group, or an oxaalkylene group. X ₁ represents an oxygen atom or a sulfur atom, Z represents a polymerizable group, n1 represents 1 or 2, and n2 and n3 represent 0 or 1.) The electrophotographic photosensitive member according to claim 7, wherein the component A is a polymerizable compound represented by the following general formula (2).

(In the formula, Ar ₁ and Ar _{2 each} represent an optionally substituted alkyl group, aralkyl group, aryl group or heterocyclic ring. R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R ₂ , R ₃ , and R _{4 each} represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, an aryl group, or a halogen atom, and X ₁ represents an oxygen atom or a sulfur atom. Z represents a polymerizable group, n2 and n3 represent 0 or 1. m1 to m3 represent an integer of 1 to 4.) The electrophotographic photosensitive member according to claim 7, wherein the component A is a polymerizable compound represented by the following general formula (3).

(In the formula, R ₁ represents an alkylene group, an arylene group or an oxaalkylene group. R _{2 to} R ₆ are any one of a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, X ₁ represents an oxygen atom or a sulfur atom, n2 and n3 represent 0 or 1, m1 to m3 represent an integer of 1 to 4, and p1 P2 represents an integer of 1 to 5.) The electrophotographic photosensitive member according to claim 7, wherein the component A is a polymerizable compound represented by the following general formula (4).

(In the formula, R ₈ represents an alkylene group having 2 to 5 carbon atoms, and R _{5 to} R ₆ are any of a hydrogen atom, an alkyl group optionally having a substituent, an alkoxy group, an aryl group, and a halogen atom. R ₇ represents a hydrogen atom or a methyl group, and p1 and p2 represent an integer of 1 to 5.) The electrophotographic photosensitive member according to claim 7, wherein the component A is a polymerizable compound represented by the following general formula (5).

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.) The electrophotographic photosensitive member according to claim 7, wherein the component A is a polymerizable compound represented by the following general formula (6).

(Wherein R _{5 to} R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a halogen atom. R ₇ represents a hydrogen atom or a methyl group. P1 and p2 represent an integer of 1 to 5.)   The electrophotographic photosensitive member according to claim 7, wherein the polymerizable group of component A and / or component B is an acryloyloxy group and / or a methacryloyloxy group.   17. The cured coating according to claim 7, wherein at least a charge generation layer, a charge transport layer, and a crosslinked charge transport layer are sequentially laminated on a conductive support, wherein the crosslinked charge transport layer is a cured coating according to claim 7. An electrophotographic photoreceptor comprising the composition.   The electrophotographic photosensitive member according to claim 17, wherein the crosslinkable charge transport layer is insoluble in an organic solvent.   19. An image forming method, wherein at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to claim 7.   An image forming apparatus comprising at least a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit, comprising the electrophotographic photosensitive member according to any one of claims 7 to 18. Image forming apparatus.   An electrophotographic photosensitive member according to any one of claims 7 to 18, and at least one means selected from the group consisting of a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a static elimination means. A process cartridge for an image forming apparatus, wherein the process cartridge is removable from the main body of the image forming apparatus.

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