JP4596843B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

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

  The electrophotographic photosensitive member is required to have sensitivity, electrical characteristics, and optical characteristics according to the electrophotographic process applied thereto. In addition, electrical and / or mechanical external forces such as charging, exposure (image exposure), development with toner, transfer to a transfer material such as paper, and cleaning of residual toner are directly applied to the surface of the electrophotographic photosensitive member. Therefore, the electrophotographic photosensitive member is also required to have durability against these external forces. Specifically, durability against surface scratches and wear due to rubbing, surface degradation due to charging, such as durability against transfer efficiency and slippage deterioration, and deterioration of electrical characteristics such as sensitivity reduction and potential reduction Durability is required.

  As an electrophotographic photosensitive member, an electrophotographic photosensitive member using an organic material as a photoconductive substance (a charge generating substance or a charge transporting substance), so-called an organic electrophotographic photosensitive member, is widely used because of its low cost and high productivity. is doing. Organic electrophotographic photoreceptors include a charge generation layer containing a charge generation material such as a photoconductive dye or a photoconductive pigment and a charge transport containing a charge transport material such as a photoconductive polymer or a photoconductive low molecular weight compound. An electrophotographic photoreceptor having a photosensitive layer formed by laminating layers, that is, a so-called laminated photosensitive layer, is the mainstream.

  Further, as an organic electrophotographic photosensitive member, a surface layer (layer located on the outermost surface of the electrophotographic photosensitive member) in which a layer in which a photoconductive substance is molecularly dispersed in a binder resin is provided is common. . The mechanical strength of the surface of such an electrophotographic photosensitive member (electrical external force and / or durability against mechanical external force) depends on the mechanical strength of the binder resin in the surface layer.

  The mechanical strength of the surface of a conventional electrophotographic photoreceptor is not sufficient to meet the recent demand for higher image quality and longer life. This is because if the surface layer of the electrophotographic photosensitive member is formed with a composition aiming at high sensitivity in order to achieve high image quality, the contact member (charging) The surface of the electrophotographic photosensitive member is scratched or worn due to the rubbing of a member, a developing member, a transfer member, a cleaning member, or the like. On the other hand, in order to achieve a long life, it is aimed for scratch resistance and wear resistance. This is because when the surface layer of the electrophotographic photosensitive member is formed with a composition, the sensitivity is lowered or the residual potential is increased, so that the electrophotographic characteristics cannot be satisfied. In addition, when scratches or abrasion occurs on the surface of the electrophotographic photosensitive member, the roughness of the surface increases, and the capacity of the electrophotographic photosensitive member changes within a minute range, so that the sensitivity uniformity decreases.

  In order to solve these problems, a technique using a specific curable resin as a binder resin of a charge transport layer serving as a surface layer has been disclosed (for example, see Patent Document 1). Further, a technique is disclosed in which a cured film obtained by curing a monomer having a carbon-carbon double bond using heat or light energy is used as a surface layer of an electrophotographic photoreceptor (for example, Patent Document 2 or 3).

  However, the electrophotographic photoreceptors disclosed in these documents have room for improvement from the viewpoint of achieving both sensitivity and surface mechanical strength.

Incidentally, “hardness” is one measure for knowing the degree of mechanical deterioration of the surface of the electrophotographic photosensitive member, and attempts have been made to quantify it quantitatively. Examples thereof include a scratch hardness test, a pencil hardness test, and a Vickers hardness test. The hardness indicated by these tests is quantitatively quantified from the amount of deformation of the surface layer of the electrophotographic photosensitive member.

  However, according to these tests, even an electrophotographic photosensitive member having a high surface hardness is more likely to be scratched or worn than an electrophotographic photosensitive member having a low surface hardness. There was a case where I was lost. That is, the surface hardness indicated by the scratch hardness test, the pencil hardness test, the Vickers hardness test, and the like and the mechanical strength of the surface of the electrophotographic photosensitive member are not necessarily correlated. The deformation includes plastic deformation and elastic deformation, and it is impossible to capture the hardness only by the total deformation amount without considering this.

Japanese Patent Laid-Open No. 02-127652 JP 05-216249 A Japanese Patent Laid-Open No. 07-072640

  The present invention has been made in order to solve the above-mentioned problems. An electrophotographic photosensitive member that maintains high sensitivity and is less likely to cause scratches or wear on the surface even after repeated use, and the electrophotography. It is an object of the present invention to provide a process cartridge and an electrophotographic apparatus having a photoreceptor.

  As a result of intensive studies, the present inventors have found that an electrophotographic photosensitive member having a universal hardness value and an elastic deformation rate of the surface of the electrophotographic photosensitive member within a specific range can solve the above-described problems. The present invention has been completed.

That is, the present invention is as follows.
(1) In an electrophotographic photosensitive member having a support and a photosensitive layer provided on the support,
Universal hardness value of the surface of the electrophotographic photoreceptor measured using a Vickers square pyramid diamond indenter with a facing angle of 136 ° under conditions of 25 ° C./50% RH, final load 6 mN and holding time 0.1 seconds. (HU) is 160~200N / mm ^2, and,
The elastic deformation rate of the surface of the electrophotographic photosensitive member measured using a Vickers square pyramid diamond indenter with a face angle of 136 ° under conditions of a final load of 6 mN and a holding time of 0.1 second in a 25 ° C./50% RH environment. 50-65%,
The electrophotographic photosensitive member is irradiated with an electron beam so that the irradiation dose is 0.5 to 20 Mrad on the coating film of the surface layer coating solution containing a hole transporting compound having a chain polymerizable functional group , and thereafter electrons temperature of the coating film is heated so that 80 to 140 ° C., and wherein the Rukoto that having a surface layer having a three-dimensional matrix formed by formed by polymerizing a hole-transporting compound Photoconductor.
(2) The electrophotographic photosensitive member according to (1), wherein the hole transporting compound having a chain polymerizable functional group is a hole transporting compound having two or more chain polymerizable functional groups.
(3) The hole transporting compound having the chain polymerizable functional group is a hole transporting compound having at least one of an acryloyloxy group and a methacryloyloxy group as the chain polymerizable functional group (1) or The electrophotographic photosensitive member according to (2) .
(4 ) An electrophotographic photosensitive member according to any one of (1) to ( 3 ) and at least one means selected from the group consisting of a charging means, a developing means, a transfer means and a cleaning means are integrally supported. A process cartridge which is detachable from the electrophotographic apparatus main body.
( 5 ) An electrophotographic apparatus comprising the electrophotographic photosensitive member according to any one of (1) to ( 3 ), a charging unit, an exposing unit, a developing unit, and a transferring unit.

  According to the present invention, there are provided an electrophotographic photosensitive member that maintains high sensitivity even when used repeatedly, and that hardly causes scratches or abrasion on the surface, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. Can be provided.

  Hereinafter, the present invention will be described in detail.

As described above, the electrophotographic photosensitive member of the present invention has a universal hardness value (HU) of 150 to 220 N / mm ² and an elastic deformation rate of 50 to 65% in a 25 ° C./50% RH environment on the surface. Is. In particular, the universal hardness value (HU) is more preferably 160 to 200 N / mm ² .

If the universal hardness value (HU) is too large, or if the elastic deformation rate is too small, the elastic force on the surface of the electrophotographic photosensitive member is insufficient, so that the electrophotographic photosensitive member and the charging member, cleaning member, etc. The paper powder or toner sandwiched between the contact members rubs the surface of the electrophotographic photosensitive member, so that the surface of the electrophotographic photosensitive member is likely to be scratched, and wear is also likely to occur. In addition, if the universal hardness value (HU) is too large, even if the elastic deformation rate is high, the amount of elastic deformation becomes small. As a result, a large pressure is applied to the local area of the surface of the electrophotographic photosensitive member, so that the electron Deep scratches are likely to occur on the surface of the photoconductor. In other words, an electrophotographic photosensitive member having a large surface hardness (including not only the universal hardness value (HU) but also a hardness derived from a scratch hardness test, a pencil hardness test, a Vickers hardness test, etc.) is not necessarily preferable. is there.

  Even if the universal hardness value (HU) is in the above range, if the elastic deformation rate is too large, the amount of plastic deformation also increases. Therefore, the electrophotographic photosensitive member and a contact member such as a charging member or a cleaning member The paper powder or toner sandwiched between the two rubs the surface of the electrophotographic photosensitive member, so that fine scratches are likely to occur on the surface of the electrophotographic photosensitive member, and wear is also likely to occur.

  Further, even if the universal hardness value (HU) is in the above range, if the elastic deformation rate is too small, the amount of plastic deformation becomes relatively large, so that fine scratches are likely to occur on the surface of the electrophotographic photosensitive member. In addition, wear tends to occur. This becomes particularly noticeable when the elastic deformation rate is not only too small but also the universal hardness value (HU) is too small.

  In the present invention, the universal hardness value (HU) and elastic deformation rate of the surface of the electrophotographic photosensitive member are measured using a microhardness measuring apparatus Fischerscope H100V (Fischer) in an environment of 25 ° C./50% RH. It is the value. This Fischerscope H100V has an indenter in contact with the object to be measured (the surface of the electrophotographic photosensitive member), continuously applies a load to the indenter, and directly reads the indentation depth under the load to obtain continuous hardness. Device.

  In the present invention, a Vickers quadrangular pyramid diamond indenter with a face angle of 136 ° is used as the indenter, and the final load applied to the indenter (final load) is 6 mN, and the final load of 6 mN is maintained on the indenter. The time (holding time) to perform was 0.1 second. The measurement points were 273 points.

An outline of an output chart of the Fischer scope H100V (Fischer) is shown in FIG. FIG. 2 shows an example of an output chart of the Fischer scope H100V (Fischer) when the electrophotographic photosensitive member of the present invention is used as a measurement object. 1 and 2, the vertical axis represents the load F (mN) applied to the indenter, and the horizontal axis represents the indentation depth h (μm). FIG. 1 shows the results when the load applied to the indenter is increased stepwise to maximize the load (A → B) and then decreased gradually (B → C). FIG. 2 shows the results when the load applied to the indenter is increased stepwise to finally make the load 6 mN, and then the load is decreased stepwise.

The universal hardness value (HU) can be obtained by the following equation from the indentation depth of the indenter when a final load of 6 mN is applied to the indenter. In the following formula, HU means universal hardness (HU), F _f means the final load, S _f means the surface area of the indented portion when the final load is applied, h _f means the indentation depth of the indenter when the final load is applied.

  The elastic deformation rate is the amount of work (energy) performed by the indenter with respect to the measurement target (electrophotographic photosensitive member surface), that is, the energy due to the increase or decrease of the load with respect to the indenter measurement target (electrophotographic photosensitive member surface). It can be obtained from the change of. Specifically, a value (We / Wt) obtained by dividing the elastic deformation work We by the total work Wt is the elastic deformation rate. The total work Wt is the area of the region surrounded by A-B-D-A in FIG. 1, and the elastic deformation work We is the area of the region surrounded by C-B-D-C in FIG. It is.

  Hereinafter, the electrophotographic photosensitive member of the present invention will be described in detail including its manufacturing method.

  In order to obtain an electrophotographic photosensitive member having a surface universal hardness value (HU) and elastic deformation rate within the above ranges, the surface layer of the electrophotographic photosensitive member is formed of a hole transporting compound having a chain polymerizable functional group. It is particularly effective to form the polymer by polymerizing and crosslinking a hole transporting compound having two or more chain polymerizable functional groups (in the same molecule). The surface layer of the electrophotographic photosensitive member means a layer located on the outermost surface of the electrophotographic photosensitive member, in other words, a layer that is located farthest from the support.

  First, a method for forming a surface layer using a hole transporting compound having a chain polymerizable functional group will be described more specifically.

  The surface layer is coated with a hole transporting compound having a chain polymerizable functional group and a solvent, and if necessary, a surface layer coating solution further containing a binder resin, and the hole transport having the chain polymerizable functional group is applied. By polymerizing (and crosslinking) the functional compound, the applied surface layer coating liquid can be cured.

  When applying the surface layer coating solution, for example, a coating method such as a dip coating method (dip coating method), a spray coating method, a curtain coating method, or a spin coating method can be used. Among these coating methods, the dip coating method and the spray coating method are preferable from the viewpoints of efficiency and productivity.

  Examples of a method for polymerizing (and crosslinking) a hole transporting compound having a chain polymerizable functional group include a method using heat, light such as visible light and ultraviolet light, and radiation such as electron beam and γ ray. If necessary, the surface layer coating solution may contain a polymerization initiator.

  In addition, as a method for polymerizing (and crosslinking) a hole transporting compound having a chain polymerizable functional group, a method using radiation such as an electron beam or γ-ray, particularly an electron beam is preferable. This is because polymerization by radiation does not particularly require a polymerization initiator. By polymerizing (and cross-linking) a hole transporting compound having a chain polymerizable functional group without using a polymerization initiator, a surface layer of a very high purity three-dimensional matrix can be formed, and good electrons can be formed. An electrophotographic photoreceptor showing photographic characteristics can be obtained. Further, polymerization with an electron beam among radiations causes very little damage to the electrophotographic photosensitive member due to irradiation, and can exhibit good electrophotographic characteristics.

  A hole transporting compound having a chain polymerizable functional group is polymerized (and crosslinked) by irradiation with an electron beam to obtain an electrophotographic photosensitive member of the present invention having a universal hardness value (HU) and an elastic deformation rate in the above ranges. For this, it is important to consider the irradiation conditions of the electron beam.

  When irradiating an electron beam, it can carry out using accelerators, such as a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type. The acceleration voltage is preferably 250 kV or less, and more preferably 150 kV or less. The irradiation dose is preferably in the range of 0.1 to 100 Mrad, and more preferably in the range of 0.5 to 20 Mrad. If the acceleration voltage or irradiation dose is too large, the electrical characteristics of the electrophotographic photosensitive member may deteriorate. If the irradiation dose is too small, the polymerization (and crosslinking) of the hole transporting compound having a chain polymerizable functional group may be insufficient, and the surface layer coating solution may be insufficiently cured.

  In order to accelerate the curing of the coating solution for the surface layer, an object to be irradiated (electron beam is irradiated during polymerization (and crosslinking) of a hole transporting compound having a chain polymerizable functional group by electron beam. It is preferable to heat the one). The timing of heating may be at any stage before, during or after the electron beam irradiation, but the irradiated object is kept at a constant temperature while the radical of the hole transporting compound having a chain polymerizable functional group is present. It is preferable that Since the material of the electrophotographic photosensitive member may be deteriorated when the heating temperature is too high, the heating is preferably performed so that the temperature of the irradiated body is 140 ° C. or lower, and is 110 ° C. or lower. More preferably. On the other hand, if the heating temperature is too low, the effect obtained by heating becomes poor. Therefore, the heating is preferably performed so that the temperature of the irradiated object is 50 ° C. or higher, and is 80 ° C. or higher. More preferably. The heating time is preferably 5 to 30 minutes, and more preferably 10 to 30 minutes. If the heating time is too short, the effect obtained by heating becomes poor.

  The atmosphere at the time of electron beam irradiation and heating of the irradiated object may be any of the atmosphere, an inert gas such as nitrogen or helium, or a vacuum, but can suppress radical deactivation due to oxygen. In that respect, in an inert gas or vacuum is preferable.

  The thickness of the surface layer of the electrophotographic photoreceptor is preferably 30 μm or less, more preferably 20 μm or less, more preferably 10 μm or less, and more preferably 7 μm or less from the viewpoint of electrophotographic characteristics. More preferably. On the other hand, from the viewpoint of durability of the electrophotographic photosensitive member, it is preferably 0.5 μm or more, and more preferably 1 μm or more.

  In the present invention, the “hole transportable compound having a chain polymerizable functional group” refers to a compound in which the chain polymerizable functional group is chemically bonded to a part of the molecule of the hole transportable compound.

Chain polymerization refers to the former form of polymerization reaction when the polymer formation reaction is largely divided into chain polymerization and sequential polymerization. Specifically, the reaction form mainly passes through intermediates such as radicals or ions. It means unsaturated polymerization, ring-opening polymerization or isomerization polymerization in which the reaction proceeds.

  The chain polymerizable functional group means a functional group capable of the above reaction form. Examples of unsaturated polymerizable functional groups and ring-opening polymerizable functional groups having a wide range of applications will be shown below.

  Unsaturated polymerization is a reaction in which unsaturated groups such as C═C, C≡C, C═O, C═N, C≡N, and the like are polymerized by radicals or ions, among which C═C Is the main. Specific examples of the unsaturated polymerizable functional group are shown below.

In the above formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or the like. Here, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

  Ring-opening polymerization is a reaction in which unstable cyclic structures such as carbocycles, oxo rings, and nitrogen heterocycles open and repeat polymerization to form chain polymers, and ions are active species. Most of them act as Specific examples of the ring-opening polymerizable functional group are shown below.

In the above formula, R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or the like. Here, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

  Among the chain polymerizable functional groups exemplified above, chain polymerizable functional groups having a structure represented by the following formulas (1) to (3) are preferable.

In formula (1), E ¹¹ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkoxy group, or a cyano group , A nitro group, —COOR ¹¹ , or —CONR ¹² R ¹³ . W ¹¹ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, —COO—, —O—, —OO—, —S—, or CONR ¹⁴ —. R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. The subscript X indicates 0 or 1. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a thiophenyl group, and a furyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, and a thienyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Examples of the alkylene group include a methylene group, an ethylene group, and a butylene group. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

  Examples of the substituent that each of the above groups may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkyl groups such as methyl group, ethyl group, propyl group and butyl group, and phenyl group. Aryl groups such as naphthyl group, anthryl group, pyrenyl group, aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, Examples thereof include aryloxy groups such as phenoxy group and naphthoxy group, nitro group, cyano group, and hydroxyl group.

In formula (2), R ²¹ and R ²² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. The subscript Y represents an integer of 1 to 10. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

  Examples of the substituent that each of the above groups may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkyl groups such as methyl group, ethyl group, propyl group and butyl group, and phenyl group. Aryl groups such as naphthyl group, anthryl group, pyrenyl group, aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, Examples thereof include aryloxy groups such as phenoxy group and naphthoxy group.

In formula (3), R ³¹ and R ³² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. The subscript Z represents an integer of 0 to 10. Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

  Examples of the substituent that each of the above groups may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkyl groups such as methyl group, ethyl group, propyl group and butyl group, and phenyl group. Aryl groups such as naphthyl group, anthryl group, pyrenyl group, aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, Examples thereof include aryloxy groups such as phenoxy group and naphthoxy group.

  Among the chain polymerizable functional groups having the structures represented by the above formulas (1) to (3), the chain polymerizable functional groups having the structures represented by the following formulas (P-1) to (P-11) are more preferable. .

  Among the chain polymerizable functional groups having a structure represented by the above formulas (P-1) to (P-11), a chain polymerizable functional group having a structure represented by the above formula (P-1), that is, an acryloyloxy group, A chain polymerizable functional group having a structure represented by the above formula (P-2), that is, a methacryloyloxy group is even more preferable.

  In the present invention, among the hole transporting compounds having the chain polymerizable functional group, a hole transporting compound having two or more chain polymerizable functional groups (in the same molecule) is preferable. Specific examples of the hole transporting compound having two or more chain polymerizable functional groups are shown below.

In the formula ^{(4), P 41, P} 42 each independently represent a chain polymerizable functional group. R ⁴¹ represents a divalent group. A ⁴¹ represents a hole transporting group. The subscripts a, b, and d each independently represent an integer of 0 or more. However, a + b × d is 2 or more. In addition, when a is 2 or more, a number of ^{P 41} may be the same or different and when b is 2 or more, the number b _{^{[R 41 - (P 42)}} d] are identical Or may be different. When d is 2 or more, the d P ^{42 s} may be the same or different.

Examples in which (P ⁴¹ ) _a and [R ^41- (P ⁴² ) _d ] _b in the above formula (4) are all replaced with hydrogen atoms are oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triarylamines Derivatives (such as triphenylamine), 9- (p-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, thiazole derivatives, triazole derivatives Phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, N-phenylcarbazole derivatives, and the like. Among these (in which (P ⁴¹ ) _a and [R ^41- (P ⁴² ) _d ] _b in the above formula (4) are all replaced with hydrogen atoms), those having a structure represented by the following formula (5) Is preferred.

In the above formula (5), R ⁵¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. Ar ⁵¹ and Ar ⁵² each independently represent a substituted or unsubstituted aryl group. R ⁵¹ , Ar ⁵¹ , Ar ⁵² may be directly bonded to N (nitrogen atom), an alkylene group (methyl group, ethyl group, propylene group, etc.), a hetero atom (oxygen atom, sulfur atom, etc.) or — You may couple | bond with N (nitrogen atom) through CH = CH-. Here, as an alkyl group, a C1-C10 thing is preferable and a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned. As the aryl group, phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, thiophenyl group, furyl group, pyridyl group, quinolyl group, benzoquinolyl group, galvazolyl group, phenothiazinyl group, benzofuryl group, benzothiophenyl group, A dibenzofuryl group, a dibenzothiophenyl group, etc. are mentioned. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, and a thienyl group. Incidentally, R ⁵¹ in the formula (5) is preferably a substituted or unsubstituted aryl group.

  Examples of the substituent that each of the above groups may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkyl groups such as methyl group, ethyl group, propyl group and butyl group, and phenyl group. Aryl groups such as naphthyl group, anthryl group, pyrenyl group, aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, Aryloxy groups such as phenoxy group and naphthoxy group, substituted amino groups such as dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, di (p-tolyl) amino group, styryl group, naphthylvinyl group, etc. Aryl vinyl group, nitro group, cyano group, hydroxyl group and the like.

As the divalent group of R ^{41 in} the above formula (4), a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, —CR ⁴¹¹ ═CR ⁴¹² — (R ⁴¹¹ , R ⁴¹² are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.), —CO—, —SO—, —SO ₂ —, an oxygen atom, a sulfur atom, etc. Are combined. Among these, a divalent group having a structure represented by the following formula (6) is preferable, and a divalent group having a structure represented by the following formula (7) is more preferable.

In the above formula (6), X ^{61 to} X ⁶³ are each independently a substituted or unsubstituted alkylene group, — (CR ⁶¹ = CR ⁶² ) _n6 — (R ⁶¹ , R ⁶² are each independently a hydrogen atom , A substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, the subscript n6 represents an integer of 1 or more (preferably 5 or less), -CO-, -SO- , —SO ₂ —, an oxygen atom, or a sulfur atom. Ar ⁶¹ and Ar ⁶² each independently represent a substituted or unsubstituted arylene group. The subscripts p6, q6, r6, s6, and t6 each independently represent an integer of 0 or more (preferably 10 or less, more preferably 5 or less). However, all of p6, q6, r6, s6, and t6 are not 0. Here, as an alkylene group, a C1-C20, especially 1-10 thing is preferable, and a methylene group, ethylene group, a propylene group, etc. are mentioned. The arylene group is a divalent divalent benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. The group of is mentioned. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a thiophenyl group.

  Examples of the substituent that each of the above groups may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkyl groups such as methyl group, ethyl group, propyl group and butyl group, and phenyl group. Aryl groups such as naphthyl group, anthryl group, pyrenyl group, aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, Aryloxy groups such as phenoxy group and naphthoxy group, substituted amino groups such as dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, di (p-tolyl) amino group, styryl group, naphthylvinyl group, etc. Aryl vinyl group, nitro group, cyano group, hydroxyl group and the like.

In formula (7), X ⁷¹ and X ⁷² are each independently a substituted or unsubstituted alkylene group, — (CR ⁷¹ = CR ⁷² ) _n7 — (R ⁷¹ and R ⁷² are each independently a hydrogen atom, Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and the subscript n7 represents an integer of 1 or more (preferably 5 or less), —CO— or oxygen Indicates an atom. Ar ⁷¹ represents a substituted or unsubstituted arylene group. The subscripts p7, q7, and r7 each independently represent an integer of 0 or more (preferably 10 or less, more preferably 5 or less). However, all of p7, q7, and r7 are not 0. Here, as an alkylene group, a C1-C20, especially 1-10 thing is preferable, and a methylene group, ethylene group, a propylene group, etc. are mentioned. The arylene group is a divalent divalent benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. The group of is mentioned. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a thiophenyl group.

  Examples of the substituent that each of the above groups may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkyl groups such as methyl group, ethyl group, propyl group and butyl group, and phenyl group. Aryl groups such as naphthyl group, anthryl group, pyrenyl group, aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group, thienyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group, Aryloxy groups such as phenoxy group and naphthoxy group, substituted amino groups such as dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, di (p-tolyl) amino group, styryl group, naphthylvinyl group, etc. Aryl vinyl group, nitro group, cyano group, hydroxyl group and the like.

  Below, the suitable example (compound example) of the hole transportable compound which has two or more chain polymerizable functional groups is given.

  Next, the electrophotographic photoreceptor of the present invention will be described in more detail including layers other than the surface layer.

  As described above, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a support and a photosensitive layer provided on the support.

  The photosensitive layer is separated into a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material even if it is a single layer type photosensitive layer containing the charge transporting material and the charge generating material in the same layer. A laminated type (functional separation type) photosensitive layer may be used, but a laminated type photosensitive layer is preferred from the viewpoint of electrophotographic characteristics. The laminated photosensitive layer has a normal layer type photosensitive layer laminated in the order of the charge generation layer and the charge transport layer from the support side, and a reverse layer type photosensitive layer laminated in the order of the charge transport layer and the charge generation layer from the support side. However, a normal photosensitive layer is preferred from the viewpoint of electrophotographic characteristics. Further, the charge generation layer may have a laminated structure, and the charge transport layer may have a laminated structure.

  FIG. 3 shows an example of the layer structure of the electrophotographic photosensitive member of the present invention.

  In the electrophotographic photosensitive member having the layer structure shown in FIG. 3A, a layer (charge generation layer) 341 containing a charge generation material on a support 31 and a layer containing a charge transport material (first charge transport) Layer) 342 is provided in order, and a layer (second charge transport layer) 35 formed by polymerizing a hole transporting compound having a chain polymerizable functional group is provided thereon as a surface layer. ing.

  In the electrophotographic photosensitive member having the layer structure shown in FIG. 3B, a layer 34 containing a charge generating substance and a charge transporting substance is provided on a support 31, and a surface layer is further provided thereon. As described above, a layer 35 formed by polymerizing a hole transporting compound having a chain polymerizable functional group is provided.

  In addition, the electrophotographic photosensitive member having a layer structure shown in FIG. 3C is provided with a layer (charge generation layer) 341 containing a charge generation material on a support 31 and a surface layer thereon. A layer 35 formed by polymerizing a hole transporting compound having a chain polymerizable functional group is directly provided.

Further, as shown in FIGS. 3D to 3I, between the support 31 and a layer (charge generation layer) 341 containing a charge generation material or a layer 34 containing a charge generation material and a charge transport material. Further, an intermediate layer (also referred to as “undercoat layer”) 33 having a barrier function or an adhesive function, a conductive layer 32 for the purpose of preventing interference fringes, or the like may be provided.

  In addition, the universal hardness value (HU) and elastic deformation rate of the surface of the electrophotographic photosensitive member may be in the above ranges regardless of the layer configuration. In the case of forming a layer formed by polymerizing a hole transporting compound having a chain polymerizable functional group, among the layer configurations shown in FIGS. 3 (a) to 3 (i), FIG. , (G) is preferable.

  As the support, any material may be used as long as it exhibits conductivity (conductive support), and any material that does not affect the measurement of the surface hardness of the electrophotographic photosensitive member. For example, aluminum, copper, A support made of a metal (made of alloy) such as chromium, nickel, zinc, and stainless steel can be used. Moreover, the said metal support body and plastic support body which have a layer in which aluminum, an aluminum alloy, an indium oxide tin oxide alloy etc. were formed into a film by vacuum deposition can also be used. In addition, a support in which conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles are impregnated into plastic or paper together with an appropriate binder resin, or a plastic support having a conductive binder resin, etc. Can also be used. Examples of the shape of the support include a cylindrical shape and a belt shape, and a cylindrical shape is preferable.

  The surface of the support may be subjected to cutting treatment, roughening treatment, alumite treatment, etc. for the purpose of preventing interference fringes due to scattering of laser light or the like.

  As described above, between the support and the photosensitive layer (charge generation layer, charge transport layer) or an intermediate layer described later, for the purpose of preventing interference fringes due to scattering of laser light or the like and covering the scratches on the support An electrically conductive layer may be provided.

  The conductive layer can be formed by dispersing conductive particles such as carbon black, metal particles, and metal oxide particles in a binder resin.

  The thickness of the conductive layer is preferably 1 to 40 μm, and more preferably 2 to 20 μm.

  Further, as described above, an intermediate layer having a barrier function or an adhesive function may be provided between the support or the conductive layer and the photosensitive layer (charge generation layer, charge transport layer). The intermediate layer is formed for the purpose of improving the adhesion of the photosensitive layer, improving the coating property, improving the charge injection property from the support, and protecting the photosensitive layer from electrical breakdown.

  The intermediate layer is made of materials such as polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide, N-methoxymethylated 6 nylon, copolymer nylon, glue and gelatin. Can be formed.

  The film thickness of the intermediate layer is preferably 0.1 to 2 μm.

Examples of the charge generating material used in the electrophotographic photosensitive member of the present invention include selenium-tellurium, pyrylium, thiapyrylium dyes, various central metals, and various crystal systems (α, β, γ, ε, X type, etc.). Phthalocyanine pigments, anthanthrone pigments, dibenzpyrenequinone pigments, pyrantron pigments, azo pigments such as monoazo, disazo, trisazo, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanine pigments, Examples thereof include amorphous silicon (described in JP-A No. 54-143645). These charge generation materials may be used alone or in combination of two or more.

  As the charge transport material used in the electrophotographic photoreceptor of the present invention, in addition to the hole transport compound having the chain polymerizable functional group, for example, a heterocyclic ring such as poly-N-vinylcarbazole and polystyrylanthracene, Polymer compounds having condensed polycyclic aromatics, heterocyclic compounds such as pyrazoline, imidazole, oxazole, triazole, carbazole, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, Examples include phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, hydrazone derivatives, and the like.

  When the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer, the charge generation layer is coated with a coating solution for a charge generation layer obtained by dispersing a charge generation material together with a binder resin and a solvent, and dried. Can be formed. Examples of the dispersion method include a method using a homogenizer, an ultrasonic disperser, a ball mill, a vibrating ball mill, a sand mill, a roll mill, an attritor, a liquid collision type high-speed disperser, and the like. The ratio between the charge generating material and the binder resin is preferably in the range of 1: 0.3 to 1: 4 (mass ratio). Alternatively, the charge generation material can be formed alone by a vapor deposition method or the like to form a charge generation layer.

  The thickness of the charge generation layer is preferably 5 μm or less, and more preferably 0.1 to 2 μm.

  When the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer, a charge transport layer, particularly a charge transport layer that is not a surface layer of an electrophotographic photosensitive member, is obtained by dissolving a charge transport material and a binder resin in a solvent. It can form by apply | coating the coating liquid for charge transport layers, and drying. In addition, among the above charge transport materials, those having film formability alone can be formed as a charge transport layer by itself without using a binder resin. The ratio between the charge transport material and the binder resin is preferably in the range of 2: 8 to 10: 0 (mass ratio), and more preferably in the range of 3: 7 to 10: 0 (mass ratio). If the amount of the charge transporting material is too small, the charge transporting ability is lowered, and the sensitivity may be lowered or the residual potential may be raised.

  The film thickness of the charge transport layer, particularly the charge transport layer that is not the surface layer of the electrophotographic photosensitive member, is preferably 1 to 50 μm, more preferably 1 to 30 μm, and more preferably 3 to 30 μm. More preferably, it is ˜20 μm.

  When the charge transport material and the charge generation material are contained in the same layer, the layer is coated with a coating solution for the layer obtained by dispersing the charge generation material and the charge transport material together with a binder resin and a solvent. It can be formed by drying.

  Examples of the binder resin used in the photosensitive layer (charge transport layer, charge generation layer) include vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylate ester, methacrylate ester, vinylidene fluoride, and trifluoroethylene. Polymer or copolymer, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polycarbonate resin, polyarylate resin, polyester resin, polysulfone resin, polyphenylene oxide resin, polyurethane resin, cellulose Resins, phenol resins, melamine resins, silicon resins, epoxy resins, and the like can be given. These can be used singly or in combination of two or more as a mixture or copolymer.

  FIG. 4 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 4, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is rotationally driven in a direction of an arrow about a shaft 2 at a predetermined peripheral speed.

  The surface of the electrophotographic photosensitive member 1 that is rotationally driven is uniformly charged to a predetermined positive or negative potential by a charging unit (primary charging unit: charging roller or the like) 3, and then subjected to slit exposure, laser beam scanning exposure, or the like. Exposure light (image exposure light) 4 output from exposure means (not shown) is received. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the surface of the electrophotographic photosensitive member 1.

  The electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is developed with toner contained in the developer of the developing means 5 to become a toner image. Next, the toner image formed and supported on the surface of the electrophotographic photoreceptor 1 is transferred from a transfer material supply means (not shown) to the electrophotographic photoreceptor 1 and the transfer means by a transfer bias from a transfer means (transfer roller or the like) 6. 6 (contact portion) is sequentially transferred onto a transfer material (paper or the like) P taken out and fed in synchronization with the rotation of the electrophotographic photosensitive member 1.

  The transfer material P that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member 1 and introduced into the fixing means 8 to receive the image fixing, and is printed out as an image formed product (print, copy). Is done.

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by a cleaning means (cleaning blade or the like) 7 to remove the developer (toner) remaining after transfer, and further from a pre-exposure means (not shown). After being subjected to charge removal processing by pre-exposure light (not shown), it is repeatedly used for image formation. As shown in FIG. 4, when the charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.

  Among the above-described components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6 and the cleaning unit 7, a plurality of components are housed in a container and integrally combined as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. In FIG. 4, the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5 and the cleaning unit 7 are integrally supported to form a cartridge, and the electrophotographic apparatus is used by using a guide unit 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is detachable from the main body.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to these. In the examples, “part” means “part by mass”. Examples 7 to 13, 15 and 18 are reference examples.

  (Example 1)

The surface of an aluminum cylinder having a diameter of 30 mm and a length of 357.5 mm was subjected to honing treatment and subjected to ultrasonic cleaning as a support.

  Next, 5 parts of N-methoxymethylated 6 nylon was dissolved in 95 parts of methanol to prepare an intermediate layer coating solution.

  This intermediate layer coating solution was dip coated on the support and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.6 μm.

Next, the Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction is 9.0 °, 14.2
3 parts of oxytitanium phthalocyanine crystal (charge generation material) having strong peaks at °, 23.9 ° and 27.1 °, 3 parts of polyvinyl butyral resin (trade name: ESREC BM2, manufactured by Sekisui Chemical Co., Ltd.), and After 35 parts of cyclohexanone was dispersed in a sand mill using glass beads having a diameter of 1 mm for 2 hours, 60 parts of ethyl acetate was added thereto to prepare a charge generation layer coating solution.

  This charge generation layer coating solution was dip-coated on the intermediate layer and dried at 50 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm.

  Next, 60 parts of a hole transporting compound having a structure represented by the following formula (E-1) was dissolved in a mixed solvent of 30 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating solution for a charge transport layer. .

  This charge transport layer coating solution was dip coated on the charge generation layer.

  Next, the charge transport layer coating solution applied on the charge generation layer is irradiated with an electron beam in an atmosphere having an oxygen concentration of 10 ppm under the conditions of an acceleration voltage of 150 kV and an irradiation dose of 4 Mrad. Heat treatment was performed for 10 minutes under the condition that the temperature of the body (= electron beam irradiated body) was 100 ° C., and a charge transport layer having a thickness of 15 μm was formed.

  In this way, an electrophotographic photosensitive member for measuring surface physical properties (for universal hardness value (HU) / elastic deformation rate measurement) of Example 1 was produced.

  Further, another electrophotographic photosensitive member was produced in the same manner as described above, and this was used as an electrophotographic photosensitive member for actual machine testing of Example 1.

Measurement of universal hardness value (HU) and elastic deformation rate After leaving an electrophotographic photosensitive member for measuring surface physical properties in a 25 ° C./50% RH environment for 24 hours, the above Fischer scope H100V manufactured by Fischer was used. As described above, the universal hardness value (HU) and elastic deformation rate were measured. Table 1 shows the measurement results of universal hardness value (HU) and elastic deformation rate.

-Actual machine test In an environment of normal temperature and normal humidity (23 ° C / 50% RH), an electrophotographic photosensitive member for actual machine test was mounted on a copying machine GP40 manufactured by Canon Inc., and an initial output image was evaluated. Next, a 40,000 sheet passing durability test was performed, and the amount of abrasion of the electrophotographic photosensitive member after the evaluation of the output image and the durability test was measured. An eddy current film thickness meter PERMASCOPE TYPE E111 (manufactured by Fischer) was used for measurement of the amount of scraping. The durability test was performed in an intermittent mode in which the print was stopped once for each print. Table 1 shows the evaluation results of the actual machine test.

(Example 2)
In Example 1, an electrophotographic photoreceptor for measuring surface physical properties and an actual machine test were carried out in the same manner as in Example 1 except that the irradiation dose for irradiating the coating solution for charge transport layer with an electron beam was changed from 4 Mrad to 8 Mrad. An electrophotographic photosensitive member was prepared, and in the same manner as in Example 1, measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

(Example 3)
In Example 1, an electrophotographic photoreceptor for measuring surface physical properties and an actual machine test were carried out in the same manner as in Example 1 except that the irradiation dose when irradiating the coating solution for charge transport layer with an electron beam was changed from 4 Mrad to 20 Mrad. An electrophotographic photosensitive member was prepared, and in the same manner as in Example 1, measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

Example 4
In the same manner as in Example 1, an intermediate layer and a charge generation layer were formed on the support.
Next, 10 parts of a styryl compound having a structure represented by the following formula (E-2) and a polycarbonate resin having a repeating structural unit represented by the following formula (E-3) (viscosity average molecular weight (Mv): 20000) 10 parts were dissolved in a mixed solvent of 50 parts of monochlorobenzene / 30 parts of dichloromethane to prepare a coating solution for the first charge transport layer.

  This first charge transport layer coating solution was dip-coated on the charge generation layer and dried at 120 ° C. for 1 hour to form a first charge transport layer having a thickness of 20 μm.

Next, 60 parts of the hole transporting compound having the structure represented by the above formula (E-1) is dissolved in a mixed solvent of 50 parts of monochlorobenzene / 50 parts of dichloromethane to obtain a coating solution for the second charge transporting layer. Prepared.
The coating solution for the second charge transport layer was spray-coated on the first charge transport layer.

Next, the second charge transport layer coating solution coated on the first charge transport layer is irradiated with an electron beam under the conditions of an acceleration voltage of 150 kV and an irradiation dose of 4 Mrad in an atmosphere having an oxygen concentration of 10 ppm. Under the condition that the temperature of the electrophotographic photosensitive member (= electron beam irradiated body) was 100 ° C., a heat treatment was performed for 10 minutes to form a second charge transport layer having a thickness of 5 μm.
Thus, an electrophotographic photosensitive member for measuring surface physical properties of Example 4 was produced.

Further, another electrophotographic photosensitive member was produced in the same manner as described above, and this was used as an electrophotographic photosensitive member for actual machine testing of Example 4.
For the electrophotographic photosensitive member for measuring the surface physical properties of Example 4, the universal hardness value (HU) and the elastic deformation rate were measured in the same manner as in Example 1, and the electrophotographic for actual machine test of Example 4 was performed. The photoconductor was tested in the same manner as in Example 1. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

(Example 5)
In Example 4, an electrophotographic photosensitive member for measuring surface physical properties was obtained in the same manner as in Example 4 except that the irradiation dose when irradiating the coating solution for the second charge transport layer with an electron beam was changed from 4 Mrad to 8 Mrad. An electrophotographic photosensitive member for an actual machine test was produced, and the universal hardness value (HU) and the elastic deformation rate were measured and the actual machine test was performed in the same manner as in Example 4. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

(Example 6)
In Example 4, an electrophotographic photosensitive member for measuring surface physical properties was obtained in the same manner as in Example 4 except that the irradiation dose when irradiating the coating solution for the second charge transport layer with an electron beam was changed from 4 Mrad to 20 Mrad. An electrophotographic photosensitive member for an actual machine test was produced, and the universal hardness value (HU) and the elastic deformation rate were measured and the actual machine test was performed in the same manner as in Example 4. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

(Example 7)
In Example 1, the hole transporting compound used for the charge transporting layer was changed from the hole transporting compound having the structure represented by the above formula (E-1) to the positive compound having the structure represented by the following formula (E-4). An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing an actual machine were prepared in the same manner as in Example 1 except that the compound was changed to a hole-transporting compound. Measurement of hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

(Example 8)
In Example 2, the hole transporting compound used for the charge transporting layer was changed from the hole transporting compound having the structure represented by the above formula (E-1) to the positive compound having the structure represented by the above formula (E-4). An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing an actual machine were prepared in the same manner as in Example 2 except that the compound was changed to a hole-transporting compound. Measurement of hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

Example 9
In Example 3, the hole transporting compound used in the charge transporting layer was changed from the hole transporting compound having the structure represented by the above formula (E-1) to the positive compound having the structure represented by the above formula (E-4). An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing an actual machine were prepared in the same manner as in Example 3 except that the compound was changed to a hole-transporting compound. Measurement of hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

(Example 10)
In Example 1, the hole transporting compound used for the charge transporting layer was changed from the hole transporting compound having the structure represented by the above formula (E-1) to the positive compound having the structure represented by the following formula (E-5). An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing an actual machine were prepared in the same manner as in Example 1 except that the compound was changed to a hole-transporting compound. Measurement of hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

(Example 11)
In Example 1, the hole transporting compound used for the charge transporting layer was changed from the hole transporting compound having the structure represented by the above formula (E-1) to the positive compound having the structure represented by the following formula (E-6). An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing an actual machine were prepared in the same manner as in Example 1 except that the compound was changed to a hole-transporting compound. Measurement of hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

Example 12
In Example 1, the hole transporting compound used for the charge transporting layer was changed from the hole transporting compound having the structure represented by the above formula (E-1) to the positive compound having the structure represented by the following formula (E-7). An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing an actual machine were prepared in the same manner as in Example 1 except that the compound was changed to a hole-transporting compound. Measurement of hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

(Example 13)
In Example 7, the electrophotographic photosensitive member for surface property measurement and the electrophotographic photosensitive member for actual machine test were used in the same manner as in Example 7 except that the coating solution for charge transport layer was changed to the one prepared as follows. Further, in the same manner as in Example 7, the universal hardness value (HU) and the elastic deformation rate were measured, and the actual machine test was performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

  That is, 40 parts of a hole transporting compound having a structure represented by the above formula (E-4) and 20 parts of a hole transporting compound having a structure represented by the following formula (E-8) were mixed with monochlorobenzene 50. Part / dichloromethane in a mixed solvent of 50 parts to prepare a charge transport layer coating solution of Example 13.

(Example 14)
In Example 1, except that the coating solution for charge transport layer was changed to the one prepared as follows, an electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing an actual machine were the same as in Example 1. Further, in the same manner as in Example 1, the universal hardness value (HU) and the elastic deformation rate were measured, and the actual machine test was performed. Table 1 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

  That is, first, 5 parts of polytetrafluoroethylene resin particles (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) and 50 parts of monochlorobenzene were dispersed in a sand mill apparatus using glass beads. To this, 60 parts of a hole transporting compound having a structure represented by the above formula (E-1) and 50 parts of dichloromethane are added, and a hole transporting compound having a structure represented by the above formula (E-1) is obtained. After dissolution, 30 parts of dichloromethane was further added to prepare a charge transport layer coating solution of Example 14.

(Example 15)
In Example 4, after irradiating the coating solution for the second charge transport layer with an electron beam, the “condition for the temperature of the electrophotographic photosensitive member to be 100 ° C.” when performing the heat treatment is “the temperature of the electrophotographic photosensitive member is An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for actual machine testing were prepared in the same manner as in Example 4 except that the conditions were changed to “70 ° C.”. Measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 2 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Example 16)
In Example 4, after irradiating the coating solution for the second charge transport layer with an electron beam, the “condition for the temperature of the electrophotographic photosensitive member to be 100 ° C.” when performing the heat treatment is “the temperature of the electrophotographic photosensitive member is An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing an actual machine were prepared in the same manner as in Example 4 except that the conditions were changed to “80 ° C.”. Measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 2 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Example 17)
In Example 4, after irradiating the coating solution for the second charge transport layer with an electron beam, the “condition for the temperature of the electrophotographic photosensitive member to be 100 ° C.” when performing the heat treatment is “the temperature of the electrophotographic photosensitive member is An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for actual machine testing were prepared in the same manner as in Example 4 except that the conditions were changed to “110 ° C.”. Measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 2 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Example 18)
In Example 4, after irradiating the coating solution for the second charge transport layer with an electron beam, the “condition for the temperature of the electrophotographic photosensitive member to be 100 ° C.” when performing the heat treatment is “the temperature of the electrophotographic photosensitive member is An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing a real machine were prepared in the same manner as in Example 4 except that the conditions were changed to “120 ° C.”. Measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 2 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Example 19)
In Example 14, the surface physical property measurement was performed in the same manner as in Example 14 except that the amount of polytetrafluoroethylene resin particles used in preparing the charge transport layer coating solution was changed from 5 parts to 10 parts. The electrophotographic photosensitive member and the electrophotographic photosensitive member for the actual machine test were produced, and the universal hardness value (HU) and the elastic deformation rate were measured and the actual machine test was performed in the same manner as in Example 14. Table 2 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Example 20)
In Example 6, “the condition that the temperature of the electrophotographic photosensitive member becomes 100 ° C.” when performing the heat treatment after irradiating the coating solution for the second charge transport layer with the electron beam is “the temperature of the electrophotographic photosensitive member is An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for actual machine testing were prepared in the same manner as in Example 6 except that the conditions were changed to “140 ° C.”. Measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 2 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Example 21)
In Example 4, the coating solution for the second charge transport layer was changed to the one prepared as follows, and the coating of the coating solution for the second charge transport layer onto the first charge transport layer was immersed from the spray coating. An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for testing a real machine were prepared in the same manner as in Example 4 except that the coating was changed to coating. Measurement of (HU) and elastic deformation rate and actual machine test were conducted. Table 2 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

  That is, first, 20 parts of polytetrafluoroethylene resin particles (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) and 50 parts of ethanol were dispersed in a sand mill apparatus using glass beads. To this, 60 parts of a hole transporting compound having a structure represented by the following formula (E-9) and 50 parts of butyl alcohol are added, and a hole transporting compound having a structure represented by the above formula (E-9) Then, 20 parts of ethanol was further added to prepare a coating solution for the second charge transport layer of Example 21.

(Example 22)
In Example 21, an electrophotographic photosensitive member for measuring surface physical properties was obtained in the same manner as in Example 21 except that the irradiation dose when irradiating the coating solution for the second charge transport layer with the electron beam was changed from 4 Mrad to 1.5 Mrad. The electrophotographic photosensitive member for the body and the actual machine test was produced, and in the same manner as in Example 21, the measurement of the universal hardness value (HU) and the elastic deformation rate and the actual machine test were performed. Table 2 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Comparative Example 1)
In Example 1, an electrophotographic photoreceptor for measuring surface physical properties and an electron for actual machine test were used in the same manner as in Example 1 except that the heat treatment after irradiating the charge transport layer coating solution with an electron beam was not performed. A photographic photoconductor was prepared, and the universal hardness value (HU) and elastic deformation rate were measured and tested in the same manner as in Example 1. Table 3 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Comparative Example 2)
In Example 2, an electrophotographic photosensitive member for surface physical property measurement and an electron for actual device testing were conducted in the same manner as in Example 2 except that the heat treatment after irradiating the electron transport beam to the charge transport layer coating solution was not performed. A photographic photoconductor was prepared, and in the same manner as in Example 2, measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 3 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Comparative Example 3)
In Example 9, an electrophotographic photosensitive member for surface property measurement and an electron for actual device testing were performed in the same manner as in Example 9 except that the heat treatment after irradiating the charge transport layer coating solution with an electron beam was not performed. A photographic photoconductor was prepared, and in the same manner as in Example 9, measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 3 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Comparative Example 4)
In the same manner as in Example 1, an intermediate layer and a charge generation layer were formed on the support.
Next, 10 parts of a styryl compound having a structure represented by the above formula (E-2) and a polycarbonate resin having a repeating structural unit represented by the above formula (E-3) (viscosity average molecular weight (Mv): 20000) 10 parts was dissolved in a mixed solvent of 50 parts monochlorobenzene / 30 parts dichloromethane to prepare a charge transport layer coating solution.

This charge transport layer coating solution was dip coated on the charge generation layer and dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 30 μm.
In this way, an electrophotographic photosensitive member for measuring surface physical properties of Comparative Example 4 was produced.

Further, another electrophotographic photosensitive member was produced in the same manner as described above, and this was used as an electrophotographic photosensitive member for actual machine test of Comparative Example 4.
For the electrophotographic photosensitive member for measuring the surface physical properties of Comparative Example 4, the universal hardness value (HU) and the elastic deformation rate were measured in the same manner as in Example 1, and the electrophotographic for actual machine test of Comparative Example 4 was performed. The photoconductor was tested in the same manner as in Example 1. Table 3 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Comparative Example 5)
In the same manner as in Example 1, an intermediate layer, a charge generation layer, and a charge transport layer were formed on the support.
Next, 100 parts of antimony-containing tin oxide fine particles having an average particle size of 0.02 μm (trade name: T-1, manufactured by Mitsubishi Materials Corporation), (3,3,3-trifluoropropyl) trimethoxysilane (Shin-Etsu Chemical) (Made by Co., Ltd.) 30 parts and a 95% ethanol-5% aqueous solution 300 parts mixed solution was dispersed in a milling device for 1 hour, the dispersed solution was filtered, washed with ethanol, dried, and 120 ° C. The surface of the antimony-containing tin oxide fine particles was treated by heating for 1 hour.

  Next, 25 parts of a curable acrylic monomer (photopolymerizable monomer) having a structure represented by the following formula (E-10), 5 parts of 2,2-dimethoxy-2-phenylacetophenone (photopolymerization initiator), the surface 50 parts of antimony-containing tin oxide fine particles after treatment and 300 parts of ethanol were dispersed in a sand mill for 96 hours, and then polytetrafluoroethylene resin particles (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) ) 20 parts were added, and further dispersed for 8 hours in a sand mill device to prepare a coating solution for a protective layer.

This protective layer coating solution is dip-coated on the charge transport layer, dried at 50 ° C. for 10 minutes, and then irradiated with ultraviolet light having a light intensity of 1000 mW / cm ² for 30 seconds with a metal halide lamp, resulting in a film thickness of 3 μm. A protective layer was formed.

In this way, an electrophotographic photosensitive member for measuring surface physical properties of Comparative Example 5 was produced.
Further, another electrophotographic photosensitive member was produced in exactly the same manner as described above, and this was used as an electrophotographic photosensitive member for actual machine test of Comparative Example 5.

  For the electrophotographic photosensitive member for measuring the surface physical properties of Comparative Example 5, the universal hardness value (HU) and the elastic deformation rate were measured in the same manner as in Example 1, and the electrophotographic for actual machine test of Comparative Example 5 was performed. The photoconductor was tested in the same manner as in Example 1. Table 3 shows the measurement results of the universal hardness value (HU) and elastic deformation rate, and the evaluation results of the actual machine test.

(Comparative Example 6)
In the same manner as in Example 4, an intermediate layer, a charge generation layer, and a first charge transport layer were formed on the support.
Next, 10 parts of a polycarbonate resin having a repeating structural unit represented by the above formula (E-3) (viscosity average molecular weight (Mv): 20000) is dissolved in a mixed solvent of 100 parts monochlorobenzene / 60 parts dichloromethane, 1 part of hydrophobic silica particles was mixed and dispersed to prepare a coating solution for a protective layer.

This protective layer coating solution was spray-coated on the first charge transport layer and dried at 110 ° C. for 60 minutes to form a protective layer having a thickness of 1.0 μm.
In this way, an electrophotographic photosensitive member for measuring surface physical properties of Comparative Example 6 was produced.
Further, another electrophotographic photosensitive member was produced in exactly the same manner as described above, and this was used as an electrophotographic photosensitive member for actual machine test of Comparative Example 6.

  For the electrophotographic photosensitive member for measuring surface physical properties of Comparative Example 6, the universal hardness value (HU) and the elastic deformation rate were measured in the same manner as in Example 1, and the electrophotographic for actual machine test of Comparative Example 6 was performed. The photoconductor was tested in the same manner as in Example 1. Table 3 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Comparative Example 7)
In the same manner as in Example 6, an intermediate layer, a charge generation layer, and a first charge transport layer were formed on the support.
Next, 30 parts of a hole transporting compound having a structure represented by the above formula (E-1) and 10 parts of a hole transporting compound having a structure represented by the following formula (E-11) were mixed with monochlorobenzene. A second charge transport layer coating solution was prepared by dissolving in 50 parts of a mixed solvent of 50 parts of dichloromethane.

The coating solution for the second charge transport layer was spray-coated on the first charge transport layer.
Next, the coating solution for the second charge transport layer applied on the first charge transport layer is irradiated with an electron beam under the conditions of an acceleration voltage of 150 kV and an irradiation dose of 20 Mrad in an atmosphere having an oxygen concentration of 10 ppm. Under the condition that the temperature of the electrophotographic photosensitive member (= electron beam irradiated body) was 100 ° C., heat treatment was performed for 10 minutes to form a second charge transport layer having a thickness of 2 μm.
In this way, an electrophotographic photosensitive member for surface property measurement of Comparative Example 7 was produced.

Further, another electrophotographic photosensitive member was produced in the same manner as described above, and this was used as an electrophotographic photosensitive member for actual machine test of Comparative Example 7.
For the electrophotographic photosensitive member for measuring the surface physical properties of Comparative Example 7, the universal hardness value (HU) and the elastic deformation rate were measured in the same manner as in Example 1, and the electrophotographic for actual machine test of Comparative Example 7 was performed. The photoconductor was tested in the same manner as in Example 1. Table 3 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

(Comparative Example 8)
In Comparative Example 7, the amount of the formula (E-11) used when preparing the second charge transport layer coating solution was changed from 10 parts to 15 parts, and the second charge transport layer coating solution was changed to an electron. The irradiation condition when irradiating the beam is changed from 20 Mrad to 1.5 Mrad, and after irradiating the electron beam, the “condition that the temperature of the electrophotographic photosensitive member becomes 100 ° C.” is set to “electrophotographic photosensitive” An electrophotographic photosensitive member for measuring surface physical properties and an electrophotographic photosensitive member for actual machine testing were prepared in the same manner as in Comparative Example 7 except that the condition was changed to “conditions at which the body temperature would be 80 ° C.”. In the same manner as above, measurement of universal hardness value (HU) and elastic deformation rate and actual machine test were performed. Table 3 shows the measurement results of the universal hardness value (HU) and the elastic deformation rate, and the evaluation results of the actual machine test.

From the above results, the following can be said.
The electrophotographic photosensitive member of Comparative Example 1 having a surface universal hardness value (HU) of less than 150 N / mm ² even when the surface elastic deformation rate is in the range of 50 to 65% is the electrophotographic example. Compared to the photoreceptor, the amount of surface abrasion after the paper passing durability test is very large.
Even if the surface universal hardness value (HU) is in the range of 150 to 220 N / mm ² , the electrophotographic photosensitive member of Comparative Example 2 having a surface elastic deformation rate of less than 50% is the electrophotographic example of Example. Compared to the photoconductor, the amount of scraping on the surface after the paper passing durability test is large, and the surface is scratched during the paper passing durability test, and deeper scratches are also generated.

Even when the elastic deformation rate of the surface is in the range of 50 to 65%, the electrophotographic photosensitive member of Comparative Example 3 having a surface universal hardness value (HU) exceeding 220 N / mm ² is the surface during the paper passing durability test. Scratches will occur.
Even if the surface universal hardness value (HU) is in the range of 150 to 220 N / mm ² , the electrophotographic photosensitive member of Comparative Example 4 having an elastic deformation rate of less than 50% is the electrophotographic example of the example. Compared to the photoconductor, the amount of scraping on the surface after the paper passing durability test is very large, and the output image is fogged during the paper passing durability test.

Even if the surface universal hardness value (HU) is in the range of 150 to 220 N / mm ² , the electrophotographic photosensitive member of Comparative Example 8 in which the elastic deformation rate of the surface exceeds 65% is in the paper-passing durability test ( After), the surface is scratched.
The electrophotographic photosensitive members of Comparative Examples 5 to 7 whose surface universal hardness value (HU) is not in the range of 150 to 220 N / mm ² and whose elastic deformation rate is not in the range of 50 to 65% There is a problem with at least one of scratching and shaving.

The electrophotographic photoreceptors of Examples 1 to 20 in which the universal hardness value (HU) of the surface is in the range of 150 to 220 N / mm ² and the elastic deformation rate of the surface is in the range of 50 to 65% are compared. Compared to the electrophotographic photoreceptors of Examples 1 to 8, good results were obtained for both surface scratching and abrasion, and the surface universal hardness value (HU) was in the range of 160 to 200 N / mm ² . The electrophotographic photoreceptors of Examples 1 to 6, 14, 16, 17 and 19 to 22 in FIG. 6 are better after the paper passing durability test than the electrophotographic photoreceptors of Examples 7 to 13, 15 and 18. An output image can be obtained.

It is a figure which shows the outline of the output chart of Fischer scope H100V (made by Fischer). It is a figure which shows an example of the output chart of Fischer scope H100V (made by Fischer) when the electrophotographic photosensitive member of this invention is made into a measuring object. It is a figure which shows the example of a layer structure of the electrophotographic photoreceptor of this invention. 1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention.

Claims (5)

In an electrophotographic photosensitive member having a support and a photosensitive layer provided on the support,
Universal hardness value of the surface of the electrophotographic photosensitive member measured using a Vickers square pyramid diamond indenter with a face angle of 136 ° under conditions of 25 ° C./50% RH and a final load of 6 mN and a holding time of 0.1 second. (HU) is 160~200N / mm ^2, and,
The elastic deformation rate of the surface of the electrophotographic photosensitive member measured using a Vickers square pyramid diamond indenter with a facing angle of 136 ° under the conditions of a final load of 6 mN and a holding time of 0.1 second in a 25 ° C./50% RH environment. 50-65%,
The electrophotographic photoreceptor is irradiated with an electron beam so that the irradiation dose is 0.5 to 20 Mrad on the coating film of the surface layer coating solution containing a hole transporting compound having a chain polymerizable functional group , and then electrons temperature of the coating film is heated so that 80 to 140 ° C., and wherein the Rukoto that having a surface layer having a three-dimensional matrix formed by formed by polymerizing a hole-transporting compound Photoconductor.   The electrophotographic photoreceptor according to claim 1, wherein the hole transporting compound having a chain polymerizable functional group is a hole transporting compound having two or more chain polymerizable functional groups.   The hole transporting compound having the chain polymerizable functional group is a hole transporting compound having at least one of an acryloyloxy group and a methacryloyloxy group as the chain polymerizable functional group. Electrophotographic photoreceptor. An electrophotographic apparatus main body integrally supporting the electrophotographic photosensitive member according to any one of claims 1 to 3 and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means. A process cartridge that is detachable. The electrophotographic photosensitive member according to any one of claims 1 to 3, a charging means, an exposure means, the electrophotographic apparatus, characterized in that it comprises a developing means and transfer means.

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