JP2006178005A - Image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming apparatus achieving all of high speed, high image quality and prolonged life at a high level and in a well-balanced manner. <P>SOLUTION: The image forming apparatus comprises: an electrophotographic photoreceptor having a conductive support body and a photosensitive layer formed on the conductive support; a charging device for charging the electrophotographic photoreceptor; an exposure device for forming an electrostatic latent image by exposing the charged electrophotographic photoreceptor; a developing device for forming a toner image by developing the electrostatic latent image with toner; and a transfer device for transferring the toner image to a transfer medium, wherein the photosensitive layer has a charge transporting outermost surface layer containing a resin having a crosslinked structure on a side remotest from the conductive support. The image forming apparatus further comprises a contact member having a continuous surface configured so that a fibrous material is substantially continuously contained, wherein the contact member is disposed so that the continuous surface abuts on the outermost surface layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an image forming apparatus.

  A so-called xerographic image forming apparatus includes an electrophotographic photosensitive member (hereinafter sometimes referred to as “photosensitive member”), a charging device, an exposure device, a developing device, and a transfer device, and forms an image by an electrophotographic process using them. I do.

  In recent years, in the field of xerographic image forming apparatuses (electrophotographic apparatuses), there are increasing demands for speeding up of image forming processes, higher image quality, and longer life. In particular, when speeding up, image quality and life are often impaired. More specifically, when the image forming process is speeded up, the electrophotographic photosensitive member used for image writing is subjected to stress due to sliding with a charging member of a contact charging device or a cleaning member of a cleaning device. In many cases, wear causes image quality defects.

  In order to suppress such scratches and wear, the electrophotographic photosensitive member uses a resin having high mechanical strength, and further extends its life. For example, a photoreceptor having a cross-linked surface layer has been proposed (see, for example, Patent Documents 1 to 3).

Japanese Patent No. 3264218 JP 2003-186214 A JP 2003-43815 A

  However, the photoconductors described in Patent Documents 1 to 3 tend to cause image quality defects when used over a long period of time, although scratches and wear on the surface thereof are suppressed by improving mechanical strength. There was room for further improvement in terms of image quality.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an image forming apparatus that can achieve all of high speed, high image quality, and long life in a high level with a good balance.

  In order to solve the above problems, an image forming apparatus of the present invention includes an electrophotographic photosensitive member having a conductive support and a photosensitive layer formed on the conductive support, a charging unit for charging the electrophotographic photosensitive member, An exposure unit that exposes the electrophotographic photosensitive member to form an electrostatic latent image, a developing unit that develops the electrostatic latent image with toner to form a toner image, and a transfer unit that transfers the toner image to a transfer medium. In the image forming apparatus, the photosensitive layer has a charge transporting outermost layer containing a resin having a crosslinked structure on the side far from the conductive support, and the image forming apparatus substantially includes a fibrous substance. A contact member having a continuous surface that is continuously included, and the contact member is arranged such that the continuous surface can come into contact with the outermost surface layer.

  Here, the “continuous surface configured to include the fibrous substance substantially continuously” means a surface formed by overlapping or entanglement of the fibrous substance, and is distinguished from the brush. Further, a substance other than a void or a fibrous substance may be present between the fibrous substances.

  According to the image forming apparatus of the present invention, with the above-described configuration, it is possible to achieve high speed, high image quality, and long life in a balanced manner at a high level. The reason why such an effect is obtained by the present invention is not necessarily clear, but the present inventors infer as follows.

  In other words, a more uniform rubbing can be achieved by contacting a continuous surface comprising a fibrous substance substantially continuously with the outermost surface layer containing a resin having a crosslinked structure with excellent mechanical strength. This makes it possible to sufficiently remove contaminants such as discharge products remaining on the surface of the photosensitive member, and suppresses local wear on the surface of the photosensitive member for an extremely long time even when repeatedly rubbed. It is considered possible. In addition, the increase in deposits and poor cleaning due to wear on the surface of the photoconductor can be suppressed over a long period of time, and all of high speed, high image quality and long life can be achieved at a high level in a balanced manner. it is conceivable that.

  Further, according to the image forming apparatus of the present invention, it is possible to achieve further higher image quality. For example, in recent years, in order to meet the demand for higher image quality, the toner has been reduced in particle size, made uniform in particle size distribution, and spheroidized. Development of manufactured toners, so-called chemical toners, has been actively conducted. However, in the image forming apparatus having the conventional photoconductor, a cleaning failure such as residual toner slipping between the photoconductor and the cleaning member easily occurs due to damage of the cleaning member. The image quality could not be fully demonstrated. On the other hand, in the case of the image forming apparatus of the present invention, since the residual toner can be removed by the contact member, cleaning defects can be sufficiently reduced even when combined with chemical toner. Therefore, by combining the image forming apparatus of the present invention and the chemical toner, it is possible to realize further higher image quality (for example, photographic image quality).

  Conventionally, when a high-strength outermost surface layer having a crosslinked structure is formed, there is a problem that information of the previous cycle is likely to remain in the next cycle, and so-called ghost is easily generated. As a method for reducing such a ghost, a method of irradiating erase light for erasing information of the previous cycle is conventionally known. However, the installation of such a device leads to an increase in cost. In contrast, in the case of the image forming apparatus of the present invention, the combination of the photoconductor and the contact member surprisingly provides a sufficient ghost suppression effect and also suppresses image quality defects other than the ghost described above. Because it is possible to achieve high image quality, it can be said to be extremely excellent in cost performance. The mechanism by which the ghost suppression effect is achieved is not necessarily clear, but the present inventor has inferred as follows. That is, it is considered that a kind of phenomenon similar to triboelectric charging occurs by rubbing the outermost surface layer with a fibrous substance, and this causes uniform residual charge on the surface of the photoreceptor.

  In the image forming apparatus of the present invention, it is preferable that the shape of the contact member is a roller shape, a blade shape, or a belt shape.

  With such a shape, the continuous surface of the contact member can be brought into more uniform contact with the outermost surface layer of the photoreceptor.

  The image forming apparatus of the present invention further includes a cleaning unit that removes toner remaining on the electrophotographic photosensitive member after the transfer of the toner image, and the cleaning unit includes a cleaning blade, a cleaning brush, and a cleaning magnetic brush. It is preferable to have at least one selected from the group.

  In the image forming apparatus according to the present invention, the photoconductor is provided with the outermost surface layer, so that the wear of the photoconductor can be sufficiently suppressed even when the cleaning unit is used. Cleaning failure such as residual toner slipping between the photoreceptor and the cleaning member due to damage or the like can be suppressed by the contact member. Therefore, according to the image forming apparatus, it is possible to effectively use the cleaning unit and maintain high image quality over a long period of time.

  In the image forming apparatus of the present invention, it is preferable that the resin having a crosslinked structure is a siloxane resin. As a result, the heat resistance and mechanical strength of the photoreceptor surface are further improved, and high image quality can be maintained for a longer period of time.

  In the image forming apparatus of the present invention, it is preferable that the outermost surface layer further contains a charge transport material. The charge transport material may be incorporated into the crosslinked structure as a structural unit having charge transport ability by reacting with the resin or reacting with the compound constituting the resin. As a result, it is possible to improve the electrical characteristics of the photoreceptor, and to achieve higher image quality more reliably.

  The outermost surface layer includes a phenol derivative having a methylol group and a charge transport material having at least one selected from a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group. A derivative-containing layer is preferred.

  By providing the photoreceptor with the phenol derivative-containing layer, both wear resistance and electrical characteristics can be compatible at a higher level, and the combination of the photoreceptor and the contact member can increase the speed, improve the image quality, and It is possible to achieve all of the longer life at a higher level.

Furthermore, it is preferable that the charge transport material contains a compound represented by the following general formula (I) or a derivative thereof.
F- [D-Si (R ¹ ) _(3-a) Q _a ] _b (I)
In formula (I), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or A substituted or unsubstituted aryl group, Q is a hydrolyzable group, a is an integer of 1 to 3, and b is an integer of 1 to 4.

In addition, the charge transport material preferably contains a compound represented by the following general formula (II) or a derivative thereof.
F-[(X ¹ ) _n1 R ² —ZH] _n2 (II)
In the formula (II), F represents an organic group derived from a compound having a hole transporting ability, X ¹ represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z represents an oxygen atom, a sulfur atom, N or In COO, n1 represents 0 or 1, and n2 represents an integer of 1 to 4. In (II), ZH represents a hydroxyl group, a thiol group, an amino group, or a carboxyl group.

Furthermore, it is preferable that the charge transport material contains a compound represented by the following general formula (III) or a derivative thereof.
^{_{F - [(X 2) n3}} - (R 3) n4 - (Z) n5 G] n6 (III)
In formula (III), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ³ represents an alkylene group, Z represents an oxygen atom, a sulfur atom, NH or COO, G represents an epoxy group, n3, n4 and n5 each independently represents 0 or 1, and n6 represents an integer of 2 to 4.

式（ＩＶ）中、Ｆは正孔輸送性を有するｎ７価の有機基を、Ｔは２価の基を、Ｙは酸素原子又は硫黄原子を、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は１価の有機基を、Ｒ^７は１価の有機基を、ｍ１は０又は１を、ｎ７は１〜４の整数を、それぞれ示す。但し、Ｒ^６とＲ^７は互いに結合してＹをヘテロ原子とする複素環を形成してもよい。 Moreover, it is preferable to contain the compound shown by the following general formula (IV), or its derivative (s) as said charge transport material.

In formula (IV), F is an n7-valent organic group having hole transportability, T is a divalent group, Y is an oxygen atom or sulfur atom, and R ⁴ , R ⁵ and R ⁶ are independently A hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m1 represents 0 or 1, and n7 represents an integer of 1 to 4. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom.

式（V）中、Ｆは正孔輸送性を有するｎ８価の有機基を、Ｔは２価の基を、Ｒ^８は１価の有機基を、ｍ２は０又は１を、ｎ８は１〜４の整数を、それぞれ示す。 Furthermore, it is preferable that the charge transport material contains a compound represented by the following general formula (V) or a derivative thereof.

In formula (V), F is an n8 valent organic group having hole transporting property, T is a divalent group, R ⁸ is a monovalent organic group, m2 is 0 or 1, and n8 is 1 to 1. An integer of 4 is shown respectively.

式（VＩ）中、Ａｒ^１、Ａｒ^２、Ａｒ^３及びＡｒ^４はそれぞれ独立に置換又は未置換のアリール基を、Ａｒ^５は置換若しくは未置換のアリール基又はアリーレン基を、ｋは０又は１を、それぞれ示す。但し、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ａｒ^４及びＡｒ^５のうち１〜４個は、上記式（Ｉ）、上記式（ＩＩ）、上記式（ＩＩＩ）、上記式（ＩV）又は上記式（V）で示される化合物における、−［Ｄ−Ｓｉ（Ｒ^１）_{（３−ａ）}Ｑ_ａ］、−［（Ｘ^１）_ｎ１Ｒ^２−ＺＨ］、−［（Ｘ^２）_ｎ３−（Ｒ^３）_ｎ４−（Ｚ）_ｎ５Ｇ］、下記式（ＩV−１）で示される構造単位、又は下記式（V−１）で示される構造単位で表される部位と結合するための結合手を有する。

Further, the organic group F having a hole transporting property in the above formula (I), the above formula (II), the above formula (III), the above formula (IV) or the above formula (V) is represented by the following general formula (VI). It is preferred to have the structure shown.

In formula (VI), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or arylene group, and k is 0 or 1 Are shown respectively. However, ^{1 to 4 of} Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are the above formula (I), the above formula (II), the above formula (III), the above formula (IV) or the above formula. in the compound represented by _{^{(V), - [D-}} Si (R 1) (3-a) Q a], - [(X 1) n1 R 2 -ZH], - [(X 2) n3 - (R ³ ) _n4- (Z) _n5G ], a structural unit represented by the following formula (IV-1), or a bond for binding to a site represented by the structural unit represented by the following formula (V-1) Have.

  The image forming apparatus of the present invention containing the compound represented by the above formula (I), (II), (III), (IV) or (V) or a derivative thereof as a charge transport material in the outermost surface layer has an abrasion resistance. In addition, both the electrical characteristics and the electrical characteristics can be achieved at a higher level, and the combination of the photoconductor and the contact member can achieve higher speed, higher image quality, and longer life at a higher level. It becomes possible.

  In the image forming apparatus of the present invention, it is preferable that the outermost surface layer further contains an antioxidant. As a result, it is possible to suppress degradation of the photoreceptor due to ozone, oxidizing gas, light, or heat generated in the image forming apparatus, and it becomes easier to remove contaminants from the photoreceptor surface by the contact member.

  Moreover, it is preferable that the outermost surface layer further contains a resin soluble in an alcohol-based or ketone-based solvent. By containing such a resin, it becomes easy to control the film characteristics when producing a photoreceptor, and to extend the pot life of the coating solution for forming the outermost surface layer and improve the adhesion to the lower layer. The image forming apparatus of the present invention can be made excellent in productivity.

  Moreover, it is preferable that the said outermost surface layer further contains electroconductive fine particles. Thereby, the tolerance with respect to abrasion, a damage | wound, etc. further improves, and high image quality can be maintained over a long term by the combination with the said contact member.

  The outermost layer preferably further contains fluorine atom-containing resin particles. As a result, wear resistance and adherence to contaminants are improved, and high image quality can be maintained over a longer period by combination with the contact member.

  Further, the image forming apparatus of the present invention preferably further comprises a lubricant supply means for supplying a lubricant to the surface of the electrophotographic photosensitive member. As a result, it is possible to suppress wear and scratches on the photosensitive member, and it is possible to maintain higher image quality for a longer period by combining with the contact member.

  The present invention also provides the above image forming apparatus for forming an image using toner having an average shape factor of 100 to 150 and an average particle diameter of 3 to 12 μm. As described above, since the residual toner can be removed by the contact member, cleaning failure can be sufficiently reduced even when combined with the toner having the average shape factor and the average particle diameter. Therefore, by combining the image forming apparatus of the present invention and the above toner, it is possible to realize further higher image quality (for example, photographic image quality).

  According to the present invention, it is possible to provide an image forming apparatus that can achieve all of high speed, high image quality, and long life in a balanced manner at a high level.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 1 is a schematic diagram showing a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 100 shown in FIG. 1 includes a process cartridge 20 including an electrophotographic photosensitive member 1, an exposure device 30, a transfer device 40, and an intermediate transfer member 50 in an image forming apparatus main body (not shown). . In the image forming apparatus 100, the exposure device 30 is disposed at a position where the electrophotographic photosensitive member 1 can be exposed from the opening of the process cartridge 20. The intermediate transfer member 50 is disposed such that a part of the intermediate transfer member 50 can come into contact with the electrophotographic photosensitive member 1.

  The process cartridge 20 is obtained by integrating a charging device 21, a developing device 25, a cleaning device 27, and a contact member 29 together with an electrophotographic photosensitive member 1 by a mounting rail in a case. The case is provided with an opening for exposure.

  First, the contact member 29 will be described.

(Contact member)
FIG. 2 is an explanatory view showing a preferred embodiment of the contact member according to this embodiment. FIG. 3 is a schematic cross-sectional view of the contact member taken along the line III-III shown in FIG. In FIG. 3, the photosensitive member with which the contact member abuts together with the contact member is shown.

  As shown in FIGS. 2 and 3, the contact member 29 has a roller shape, and includes a rod-shaped support portion 50, an elastic portion 52 formed on the outer peripheral surface of the support portion 50, and an outer peripheral surface of the elastic portion 52. And an abutting portion 54 provided. As shown in FIG. 3, the contact member 29 is disposed so that the continuous surface 51 of the contact portion 54 contacts the surface of the photoreceptor 1. Further, the contact member 29 shown in FIG. 3 is configured such that when the photoreceptor 1 is rotated in the direction of arrow B by a drive motor (not shown), the continuous surface 51 of the contact portion 54 rubs the surface of the photoreceptor 1. Rotate in the direction of arrow A. In FIG. 3, illustration of a support for supporting the contact member for disposing the contact member 29 in this way is omitted.

  The support part 50 is a columnar rod-shaped member. The material in particular of the support part 50 is not restrict | limited, For example, materials, such as a metal or resin, are mentioned.

  Examples of the elastic member constituting the elastic portion 52 include urethane foam and rubber. The elastic part may be formed by winding the above-mentioned member formed in a sheet shape around the support part, or a coating liquid capable of forming a layer made of the above-mentioned member by drying or reaction is formed on the outer periphery of the support part. You may form by apply | coating to.

  The abutting portion 54 may be any one having a continuous surface configured to include a fibrous substance substantially continuously. For example, a knitted fabric, a nonwoven fabric, a woven fabric, a resin foam containing a fibrous substance, or the like. Is provided on the outer peripheral surface of the support portion 52 with a substantially uniform film thickness. In this embodiment, it is preferable that the contact part is comprised from the nonwoven fabric. By adopting non-woven fabric, it is difficult for the non-woven fabric to produce lint derived from fibrous materials, that it can reduce re-contamination due to once-contaminated contaminants, and does not use binders such as binder resins. The cleaning of the surface of the photoreceptor can be further promoted by such advantages.

  The fibrous material is not particularly limited as long as it has an elongated shape, but the fiber diameter is preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 5 μm or less.

  Furthermore, in this embodiment, it is particularly preferable to use ultrafine fibers. Here, in general, an ultrafine fiber refers to a fiber of approximately 0.5 to 0.2 d, and a fiber of 0.2 d or less is referred to as a superfine fiber, but in the present invention, a superfine fiber is also included in the ultrafine fiber. And In addition, d is denier, and when the weight of a 9000 m fiber is 1 g, it is called 1d (denier). Therefore, when the fiber diameter of the ultrafine fiber is expressed in units of microns, it is about 1 to 5 μm, and the fiber diameter of the ultrafine fiber is about 1 μm or less.

  In the present embodiment, it is particularly preferable to use a nonwoven fabric composed of such ultrafine fibers. In this case, the fibrous material can be more uniformly brought into contact with the surface of the electrophotographic photosensitive member. As a result, it is possible to more effectively remove contaminants such as discharge reactants present on the surface of the photoconductor while suppressing the occurrence of local wear on the surface of the photoconductor.

  Non-woven fabrics composed of extra fine fibers that can be obtained commercially include Toray's “Tracy” and “Exseine” (above, trade name, 60% polyester, 40% polyurethane, approximately 0.2d, manufactured by Toray Industries, Inc.) ), "Zabina Minimax", "Clausen" (above, manufactured by Kanebo, trade name, polyester, nylon, approximately 0.3d), "Miemie" (produced by Mitsubishi Rayon, trade name, acrylic 45%, polyester 52% , Polyurethane 3%, 0.2d), Teijin's Microstar (polyester, nylon, 0.2d), and the like.

  Examples of the material of the fibrous material include natural fibers such as cotton, silk, and paper, and synthetic fibers such as polyester, polyurethane, rayon, cellulose, polyamide, polyamideimide, and activated carbon fiber. The material of the fibrous material is preferably selected to have sufficient mechanical strength so as to suppress wear due to rubbing with the electrophotographic photosensitive member, and is optimal depending on the composition of the surface layer of the photosensitive member. It is preferable to select one appropriately.

As shown in FIG. 3, the contact member 29 may be disposed so that the continuous surface 51 of the contact portion 54 contacts the surface of the photoreceptor 1, but the surface between the contact portion and the photoreceptor. It is preferable to press against the photoreceptor so that the pressure is ² to 30 g / cm ² , particularly 3 to 25 g / cm ² . By making the surface pressure in the range of ² to 30 g / cm ² , it is possible to more effectively remove contaminants such as discharge reactants existing on the surface of the photoconductor while suppressing the wear of the surface of the photoconductor and the fibrous material. Can do.

  In FIG. 3, although the above-described load is applied by the weight of the contact member, the method of pressing the contact member is not limited to this.

  The abutment portion 54 can contain or supply a lubricant such as silicone oil as necessary.

  The width L1 of the contact portion 54 is preferably a length that can cover the entire length of the photoreceptor. However, when a plurality of contact members are provided, L1 does not necessarily have to be the entire length of the photoreceptor.

  Since the contact member 29 has a roller shape, the area of the continuous surface 51 that can come into contact with the photosensitive member can be increased. Thereby, high image quality can be maintained over a longer period.

  FIG. 4 is an explanatory view showing another preferred embodiment of the contact member according to the present invention. FIG. 5 is a schematic cross-sectional view of the contact member in the VV line direction shown in FIG. FIG. 5 shows a photosensitive member with which the contact member abuts together with the contact member.

  The contact member 129 shown in FIGS. 4 and 5 includes a support portion 56 made of a plate material having an L-shaped cross section, an elastic portion 52 provided on the support portion so as to cover one side of the support portion 56, And a contact portion 54 provided on the elastic portion 52. As shown in FIG. 5, the contact member 129 is disposed so that the continuous surface 51 of the contact portion 54 contacts the surface of the photoreceptor 1, and the photoreceptor 1 is moved to the arrow B by a drive motor (not shown). , The continuous surface 51 of the contact portion 54 rubs the surface of the photoreceptor 1. In FIG. 5, illustration of a support for supporting the contact member for arranging the contact member 129 in this way is omitted.

  The material in particular of the support part 56 is not restrict | limited, For example, materials, such as a metal or resin, are mentioned.

  The shape of the support portion 56 is a plate material having an L-shaped cross section in consideration of attachment to the image forming apparatus, but is not limited thereto.

  Examples of the elastic portion 52 include those formed from the above-described elastic members, and more specifically, those in which a sheet of foamed urethane, rubber, or the like is bonded onto the support portion 56.

  As a member of the contact part 54, the thing similar to what is used for said contact member 29 can be used. Also in this embodiment, it is preferable to use a non-woven fabric made of ultrafine fibers as a member of the contact portion 54. This makes it possible to more effectively remove contaminants such as discharge reactants present on the surface of the photoconductor while suppressing local wear on the surface of the photoconductor.

Also in the contact member 129 shown in FIGS. 4 and 5, the contact pressure between the contact portion 54 and the photoreceptor 1 is ² to 30 g / cm ² , particularly 3 to 25 g / cm ^2. Preferably it is. By making the surface pressure in the range of ² to 30 g / cm ² , it is possible to more effectively remove contaminants such as discharge reactants existing on the surface of the photoconductor while suppressing the wear of the surface of the photoconductor and the fibrous material. Can do.

  The width L2 of the contact portion 54 is preferably a length that can cover the entire length of the photoreceptor. However, when a plurality of contact members are provided, L2 does not necessarily have to be the entire length of the photoreceptor.

  FIG. 6 is an explanatory view showing another preferred embodiment of the contact member according to the present invention. FIG. 7 is a schematic cross-sectional view of the contact member in the VII-VII line direction shown in FIG. In FIG. 7, the photosensitive member with which the contact member abuts together with the contact member is shown.

  The contact member 229 shown in FIGS. 6 and 7 includes a supply roll 60 that supplies the belt-like contact member 55, a take-up roll 58 that winds the supplied contact member, and extends between these rolls. The pressing member 62 is configured to press the contact member 55 to be pressed with a predetermined pressure to bring the continuous surface 51 of the contact member into contact with the photosensitive member. In addition, the pressing roll 62 includes a support portion 50 and an elastic portion 52 provided on the outer periphery of the support portion 50. As shown in FIG. 7, the contact member 229 is arranged so that the contact member 55 contacts the surface of the photoreceptor 1, and the photoreceptor 1 is rotated in the direction of arrow B by a drive motor (not shown). Then, the continuous surface 51 of the contact member 55 rubs the surface of the photoreceptor 1. In FIG. 5, illustration of a support for supporting the contact member for arranging the contact member 229 in this way is omitted.

As the support part 50 and the elastic part 52 constituting the pressing roll 62, the same ones as those constituting the contact member 29 described above can be adopted. Also in the contact member 229, the pressing force of the pressing roll 62 can be adjusted so that the surface pressure between the contact member 55 and the photoreceptor 1 is ² to 30 g / cm ² , particularly 3 to 25 g / cm ^2. preferable. By making the surface pressure in the range of ² to 30 g / cm ² , it is possible to more effectively remove contaminants such as discharge reactants existing on the surface of the photoreceptor while suppressing the abrasion of the surface of the photoreceptor and the fibrous material. Can do.

  The abutting member 55 only needs to have a continuous surface configured to contain a fibrous substance substantially continuously. For example, a knitted fabric, a nonwoven fabric and a woven fabric formed in a belt shape, and a fiber Examples thereof include a resin sheet containing a particulate material. Moreover, about a fibrous substance, the thing similar to the said fibrous substance is employable. Also in this embodiment, it is preferable to use a non-woven fabric composed of ultrafine fibers as the contact member 54. This makes it possible to more effectively remove contaminants such as discharge reactants present on the surface of the photoconductor while suppressing local wear on the surface of the photoconductor.

  As the supply roll 60 and the take-up roll 58, those generally used for supplying and winding a belt-like member can be adopted. Further, according to the contact member of the present embodiment, by driving the supply roll 60 and the take-up roll 58, a new surface of the continuous surface 51 of the contact member 55 can be brought into contact with the photosensitive member, and contaminants can be removed. It is possible to prevent the removal performance from deteriorating, and to reliably prevent recontamination due to the contaminant once taken into the contact member, and to obtain high image quality over a long period of time.

  In the present embodiment, it is preferable to wind the contact member 55 at a speed of 0.1 to 3.0 cm while the photosensitive member 1 is rotated 1000 times.

  The width L3 of the contact member 55 is preferably a length that can cover the entire length of the photoreceptor. However, when a plurality of contact members are provided, L3 does not necessarily have to be the entire length of the photoreceptor.

  Next, the electrophotographic photoreceptor 1 provided in the image forming apparatus 100 of the present embodiment will be described.

(Electrophotographic photoreceptor)
FIG. 8 is a schematic cross-sectional view showing a preferred embodiment of the electrophotographic photosensitive member 1 according to this embodiment. As shown in FIG. 1, the electrophotographic photosensitive member 1 includes a conductive support 2 and a photosensitive layer 3. The photosensitive layer 3 has a structure in which an undercoat layer 4, a charge generation layer 5, and a charge transport layer 6 are laminated in this order on a conductive support 2. In the electrophotographic photosensitive member 1 shown in FIG. 1, the charge transport layer 6 is the outermost surface layer.

  9 to 12 are schematic sectional views showing other preferred embodiments of the electrophotographic photosensitive member according to the present invention. The electrophotographic photosensitive member shown in FIGS. 9 and 10 includes the photosensitive layer 3 in which the functions are separated into the charge generating layer 5 and the charge transporting layer 6 as in the electrophotographic photosensitive member shown in FIG. 11 and 12 contain the charge generation material and the charge transport material in the same layer (single-layer type photosensitive layer 8).

  The electrophotographic photoreceptor 1 shown in FIG. 9 has a structure in which an undercoat layer 4, a charge generation layer 5, a charge transport layer 6 and a protective layer 7 are sequentially laminated on a conductive support 2. The electrophotographic photoreceptor 1 shown in FIG. 10 has a structure in which an undercoat layer 4, a charge transport layer 6, a charge generation layer 5, and a protective layer 7 are sequentially laminated on a conductive support 2. In the electrophotographic photoreceptor 1 shown in FIGS. 9 and 10, the protective layer 7 is the outermost surface layer. In addition, the electrophotographic photoreceptor 1 shown in FIG. 11 has a structure in which an undercoat layer 4 and a single-layer type photosensitive layer 8 are sequentially laminated on a conductive support 2. It is the outermost surface layer. The electrophotographic photoreceptor 1 shown in FIG. 12 has a structure in which an undercoat layer 4, a single-layer type photosensitive layer 8, and a protective layer 7 are sequentially laminated on a conductive support 2. Is the outermost surface layer. In the electrophotographic photoreceptor 1, the undercoat layer 4 is not necessarily provided.

  Hereinafter, each element will be described based on the electrophotographic photosensitive member 1 shown in FIG.

  Examples of the conductive support 2 include a metal plate, a metal drum, and a metal belt formed using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Etc. Examples of the conductive support 2 include a paper, a plastic film, a belt, and the like on which a conductive polymer, a conductive compound such as indium oxide, or a metal or alloy such as aluminum, palladium, or gold is applied, evaporated, or laminated.

  When the photosensitive member 1 is used in a laser printer, the laser oscillation wavelength is preferably 350 nm to 850 nm, and the shorter wavelength is preferable because the resolution is excellent. The surface of the conductive support 2 is preferably roughened to a center line average roughness Ra of 0.04 μm to 0.5 μm in order to prevent interference fringes generated when laser light is irradiated. If Ra is less than 0.04 μm, it tends to be close to a mirror surface, so that the effect of preventing interference tends not to be obtained. On the other hand, if Ra exceeds 0.5 μm, the image quality tends to be rough even if a film is formed. . Further, when non-interfering light is used for the light source, it is not particularly necessary to roughen the interference fringes, and it is possible to prevent the occurrence of defects due to the irregularities on the surface of the conductive support 2, which is suitable for longer life.

  As a roughening method, a wet honing process in which an abrasive is suspended in water and sprayed on a support, a centerless grinding process in which a support is pressed against a rotating grindstone, and grinding is continuously performed, an anode Examples thereof include an oxidation treatment or a method of forming a layer containing organic or inorganic semiconductive fine particles.

  Anodizing treatment is to form an oxide film on an aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the porous anodic oxide film as it is after the treatment is chemically active, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the anodic oxide film is treated with pressurized steam or boiling water (a metal salt such as nickel may be added), blocked by volume expansion due to micropore hydration reaction, and converted into a more stable hydrated oxide. It is preferable to perform a hole treatment.

  The thickness of the anodized film is preferably 0.3 to 15 μm. When the film thickness is less than 0.3 μm, the barrier property against implantation is poor and the effect tends to be insufficient. On the other hand, if it exceeds 15 μm, the residual potential tends to increase due to repeated use.

  Further, the conductive support 2 may be subjected to treatment with an acidic treatment liquid or boehmite treatment. The treatment with the acidic treatment liquid is carried out as follows using an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10 to 11% by mass, chromic acid is in the range of 3 to 5% by mass, and hydrofluoric acid is in the range of 0.5 to 2% by mass. The concentration of these acids is preferably in the range of 13.5 to 18% by mass. The processing temperature is 42 to 48 ° C., but by keeping the processing temperature high, a thicker film can be formed faster. The film thickness is preferably 0.3 to 15 μm. When the film thickness is less than 0.3 μm, the barrier property against implantation is poor and the effect tends to be insufficient. On the other hand, if it exceeds 15 μm, the residual potential tends to increase due to repeated use.

  The boehmite treatment can be performed by immersing the conductive support 2 in pure water at 90 to 100 ° C. for 5 to 60 minutes, or by contacting it with heated steam at 90 to 120 ° C. for 5 to 60 minutes. The film thickness is preferably 0.1 to 5 μm. This may be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate, etc. Good.

  In the case of forming a layer containing organic or inorganic semiconductive fine particles, organic or inorganic semiconductive fine particles include perylene pigments, bisbenzimidazole perylene pigments, polycyclic rings described in JP-A-47-30330. Organic pigments such as quinone pigments, indigo pigments, quinacridone pigments, organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as cyano group, nitro group, nitroso group, halogen atom, zinc oxide, oxidation Examples include inorganic pigments such as titanium and aluminum oxide. Among these pigments, zinc oxide and titanium oxide are preferable because they have high charge transport ability and are effective for thickening.

  The surface of these pigments may be surface treated with an organic titanium compound such as a titanate coupling agent, an aluminum chelate compound, an aluminum coupling agent or the like for the purpose of improving dispersibility or adjusting the energy level. In particular, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxy It is preferable to treat with a silane coupling agent such as cyclohexyltrimethoxysilane.

  When there are too many organic or inorganic semiconductive fine particles, the strength of the layer is lowered and a coating film defect is caused. Therefore, it is preferably used at 95% by mass or less, more preferably 90% by mass or less.

  As a method for mixing / dispersing the organic or inorganic semiconductive fine particles, a method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent, but as an organic solvent, a fixed metal compound or resin is dissolved, and no gelation or aggregation occurs when organic / inorganic semiconductive fine particles are mixed / dispersed. Anything is acceptable.

  Examples of the organic solvent include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. Ordinary organic solvents such as chloroform, chlorobenzene and toluene can be used alone or in admixture of two or more.

  The undercoat layer 4 is configured to contain an organometallic compound and a binder resin. As organometallic compounds, zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organotitanium compounds such as titanate coupling agents, aluminum chelate compounds, aluminum coupling agents In addition to organoaluminum compounds such as antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, And aluminum zirconium alkoxide compounds. . As the organometallic compound, an organic zirconium compound, an organic titanyl compound, and an organoaluminum compound are particularly preferably used since they have low residual potential and good electrophotographic characteristics.

  As binder resin, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenol resin , Vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, polyacrylic acid, and other known binder resins can be used. These mixing ratios can be appropriately set as necessary.

  The undercoat layer 4 includes vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxy. Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, Silane coupling agents such as β-3,4-epoxycyclohexyltrimethoxysilane can also be included.

  In the undercoat layer 4, an electron transport pigment can also be mixed / dispersed. Examples of the electron transport pigment include organic pigments such as perylene pigment, bisbenzimidazole perylene pigment, polycyclic quinone pigment, indigo pigment, and quinacridone pigment described in JP-A-47-30330, cyano group, nitro group, Examples thereof include organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as nitroso groups and halogen atoms, and inorganic pigments such as zinc oxide and titanium oxide. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments, zinc oxide, and titanium oxide are preferably used because of their high electron mobility.

  Further, the surface of these pigments may be surface-treated with the above coupling agent, binder resin or the like for the purpose of controlling dispersibility and charge transport property. If the amount of the electron transporting pigment is too large, the strength of the undercoat layer is lowered and a coating film defect is caused.

  The undercoat layer 4 is configured using a coating solution for forming an undercoat layer containing the above constituent materials.

  As a method for mixing / dispersing the coating solution for forming the undercoat layer, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent. The organic solvent dissolves a periodical metal compound and a binder resin, and does not cause gelation or aggregation when an electron transporting pigment is mixed / dispersed. I just need it.

  Examples of the organic solvent include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. Ordinary organic solvents such as chloroform, chlorobenzene and toluene. These can be used individually by 1 type or in mixture of 2 or more types.

  The coating method used when providing the undercoat layer 4 is a normal method such as a blade coating method, a Mayer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method. Can be used.

  After coating, the coating film is dried to obtain an undercoat layer. Usually, the drying is performed at a temperature at which the solvent can be evaporated and a film can be formed. In particular, the conductive support 2 that has been subjected to the acidic solution treatment and the boehmite treatment is preferably formed with the undercoat layer 4 because its defect concealing power tends to be insufficient.

  The thickness of the undercoat layer 4 is preferably 0.1 to 30 μm, more preferably 0.2 to 25 μm.

  The charge generation layer 5 includes a charge generation material or includes a charge generation material and a binder resin.

  Charge generation materials include azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, organic pigments such as perylene pigments, pyrrolopyrrole pigments, and phthalocyanine pigments, and inorganic pigments such as trigonal selenium and zinc oxide. All known ones can be used. As the charge generation material, an inorganic pigment is preferable when a light source with an exposure wavelength of 380 nm to 500 nm is used, and a metal and a metal-free phthalocyanine pigment are preferable when a light source with an exposure wavelength of 700 nm to 800 nm is used. Among them, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472 and special Dichlorotin phthalocyanine disclosed in Kaihei 5-140473 or titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 is particularly preferable.

  As the charge generation material, Bragg angles (2θ ± 0.2 °) with respect to CuKα characteristic X-rays of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25 Hydroxygallium phthalocyanine having diffraction peaks at .1 ° and 28.3 °, titanyl phthalocyanine having a strong diffraction peak at 27.2 ° with a Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray, CuKα characteristic X Also preferred are chlorogallium phthalocyanines with strong diffraction peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° of the Bragg angle to the line (2θ ± 0.2 °).

  The binder resin can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polymers such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin. Insulating resins such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be mentioned, but are not limited thereto. These binder resins can be used individually by 1 type or in mixture of 2 or more types.

  The charge generation layer 5 is formed by vapor deposition using the charge generation material, or using a charge generation layer forming coating solution containing the charge generation material and a binder resin.

  In the charge generation layer forming coating solution, the mixing ratio (mass ratio) of the charge generation material and the binder resin is preferably 10: 1 to 1:10. Further, as a method for dispersing them, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. At this time, a condition that the crystal type does not change due to dispersion is required. Incidentally, it has been confirmed that the crystal form is not changed before dispersion in any of the above dispersion methods.

  Further, in this dispersion, it is effective that the particles have a particle size of preferably 0.5 μm or less, more preferably 0.3 μm or less, and still more preferably 0.15 μm or less.

  Moreover, as a solvent used for these dispersions, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, Examples include ordinary organic solvents such as tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene. These can be used individually by 1 type or in mixture of 2 or more types.

  In addition, as a coating method used when the charge generation layer 5 is provided, a normal method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Can be used.

  The film thickness of the charge generation layer 5 is preferably 0.1 to 5 μm, more preferably 0.2 to 2.0 μm.

  The charge transport layer 6 includes a charge transport material and a binder resin, or a polymer charge transport material.

  Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds , Electron transport compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include pore transporting compounds. These charge transport materials can be used singly or in combination of two or more, but are not limited thereto.

  Moreover, as a charge transport material, the compound shown by the following general formula (a-1), (a-2) or (a-3) from a mobility viewpoint is preferable.

In the above formula (a-1), R ³⁴ represents a hydrogen atom or a methyl group, and k10 represents 1 or 2. Ar ⁶ and Ar ⁷ represent a substituted or unsubstituted aryl group, and the substituent is a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. A substituted amino group substituted with an alkyl group can be mentioned.

Here, in said formula (a-2), R ^<35> and R ^<35 '> respectively independently represent a hydrogen atom, a halogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, R ^<36> , R ³⁶ ′, R ³⁷ and R ³⁷ ′ are each independently a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group substituted with an alkyl group having 1 to 2 carbon atoms, A substituted or unsubstituted aryl group, —C (R ³⁸ ) ═C (R ³⁹ ) (R ⁴⁰ ), or —CH═CH—CH═C (Ar) ₂ , R ³⁸ , R ³⁹ and R ⁴⁰ are Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group. m3 and m4 each independently represent an integer of 0-2.

Here, in the formula (a-3), R ⁴¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH. -CH = C (Ar) ₂ is shown. Ar represents a substituted or unsubstituted aryl group. R ⁴² , R ⁴² ′, R ⁴³ , and R ⁴³ ′ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl having 1 to 2 carbon atoms. An amino group substituted with a group, or a substituted or unsubstituted aryl group is shown.

  As the binder resin, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, Vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polysilane, Polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used individually by 1 type or in mixture of 2 or more types. The blending ratio (mass ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  A polymer charge transport material can also be used alone. As the polymer charge transport material, known materials having charge transport properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. The polymer charge transport material alone can be used as the charge transport layer, but it may be formed by mixing with the binder resin.

  The charge transport layer 6 is configured using a charge transport layer forming coating solution containing the above-described constituent materials. Solvents used in the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride. Examples include ordinary organic solvents such as aliphatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether, and linear ethers. These can be used individually by 1 type or in mixture of 2 or more types. Moreover, a well-known method can be used as a dispersion | distribution method of said each constituent material.

  Coating methods for applying the charge transport layer forming coating solution onto the charge generation layer 5 include blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain A usual method such as a coating method can be used.

  The film thickness of the charge transport layer 6 is preferably 5 to 50 μm, more preferably 10 to 30 μm.

  In the photosensitive layer 3, additives such as an antioxidant, a light stabilizer, and a heat stabilizer are added for the purpose of preventing deterioration of the photoreceptor due to ozone, an oxidizing gas, or light or heat generated in the image forming apparatus. Can be added. Examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds.

  Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine. In addition, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use.

Examples of the electron acceptor include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, Examples include chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, and phthalic acid. Of these, benzene derivatives having an electron-withdrawing substituent such as fluorenone, quinone, Cl, CN, and NO ₂ are particularly preferable.

  The protective layer 7 is configured to contain a resin having a crosslinked structure. Such a resin may be any resin that can form a crosslinked structure, and various materials can be used. Phenol resins, urethane resins, melamine resins, curable acrylic resins, siloxane resins, and the like are preferable. Among these, a siloxane resin is particularly preferable.

  In addition, in order to give the protective layer resistance to abrasion, scratches, etc., conductive fine particles are dispersed, lubricating fine particles such as fluorine atom-containing resin and acrylic resin are dispersed, or a hard coat such as silicone or acrylic. Agents can be used. The protective layer preferably contains a charge transport material in order to improve its electrical characteristics. In addition, as a charge transport material, what was mentioned as a constituent material of the said charge transport layer can be used, for example.

As the charge transport material, compounds represented by the following general formulas (I) to (V) or derivatives thereof are particularly preferable because of excellent strength and stability.

F- [D-Si (R ¹ ) _(3-a) Q _a ] _b (I)
In formula (I), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group ( The number of carbon atoms is preferably 1-15, more preferably 1-10, or a substituted or unsubstituted aryl group (carbon number is preferably 6-20, more preferably 6-15), and Q is a hydrolyzable group. A represents an integer of 1 to 3, and b represents an integer of 1 to 4.

In addition, as the divalent group D having flexibility, specifically, a site of F for imparting photoelectric characteristics, a substituted silicon group contributing to the construction of a three-dimensional inorganic glassy network, It is a divalent group that plays a role in linking. In addition, D represents an organic group structure that imparts moderate flexibility to the portion of the inorganic glassy network that is hard but brittle, and plays a role of improving mechanical toughness as a film. Specific examples _{D, -C α H 2α -,} - C β H 2β-2 -, - C γ H 2γ-4 - 2 divalent hydrocarbon group (here represented by, alpha is 1 to 15 Represents an integer, β represents an integer of 2 to 15, and γ represents an integer of 3 to 15), —COO—, —S—, —O—, —CH ₂ —C ₆ H ₄ —, —N═. CH—, — (C ₆ H ₄ ) — (C ₆ H ₄ ) —, and a characteristic group having a structure in which these characteristic groups are arbitrarily combined, and further, the constituent atoms of these characteristic groups are substituted with other substituents. And the like. The hydrolyzable group Q is preferably an alkoxy group, more preferably an alkoxy group having 1 to 15 carbon atoms.

F-[(X ¹ ) _n1 R ² —ZH] _n2 (II)
In the above formula (II), F represents an organic group derived from a compound having a hole transporting ability, X represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z represents an oxygen atom or a sulfur atom. , N or COO, m1 represents 0 or 1, and m2 represents an integer of 1 to 4. In (II), ZH represents a hydroxyl group, a thiol group, an amino group, or a carboxyl group.

^{_{F - [(X 2) n3}} - (R 3) n4 - (Z) n5 G] n6 (III)
In the above formula (II), F is an organic group derived from a compound having a hole transporting ability, X ² is an oxygen atom or a sulfur atom, R ³ is an alkylene group (the number of carbon atoms is preferably 1 to 15, preferably 1). 10 is more preferable), Z represents an oxygen atom, sulfur atom, NH or COO, G represents an epoxy group, n3, n4 and n5 each independently represents 0 or 1, and n6 represents an integer of 1 to 4. .

ここで、式（ＩＶ）中、Ｆは正孔輸送性を有するｎ７価の有機基を、Ｔは２価の基を、Ｙは酸素原子又は硫黄原子を、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は１価の有機基を、Ｒ^７は１価の有機基を、ｍ１は０又は１を、ｎ７は１〜４の整数を、それぞれ示す。但し、Ｒ^６とＲ^７は互いに結合してＹをヘテロ原子とする複素環を形成してもよい。

Here, in formula (IV), F is an n7-valent organic group having hole transportability, T is a divalent group, Y is an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ⁶ are Each independently represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m 1 represents 0 or 1, and n ⁷ represents an integer of 1 to 4. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom.

ここで、式（V）中、Ｆは正孔輸送性を有するｎ８価の有機基を、Ｔは２価の基を、Ｒ^８は１価の有機基を、ｍ２は０又は１を、ｎ８は１〜４の整数を、それぞれ示す。

Here, in the formula (V), F is an n8 valent organic group having a hole transport property, T is a divalent group, R ⁸ is a monovalent organic group, m2 is 0 or 1, n8 Represents an integer of 1 to 4, respectively.

  In the present embodiment, the protective layer 7 includes a phenol derivative having a methylol group, and a charge transport material having at least one selected from a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group. It is preferable to contain.

  Examples of the phenol derivative having a methylol group include monomers of monomethylolphenols, dimethylolphenols or trimethylolphenols, mixtures thereof, oligomers thereof, or mixtures of these monomers and oligomers. Such phenol derivatives having a methylol group include resorcin, bisphenol, etc., substituted phenols containing one hydroxyl group such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, and two hydroxyl groups such as catechol, resorcinol, hydroquinone, etc. It is obtained by reacting a compound having a phenol structure, such as substituted phenols, bisphenol A, bisphenol Z, and the like having a phenol structure with formaldehyde, paraformaldehyde, etc. in the presence of an acid catalyst or an alkali catalyst, Generally what is marketed as a phenol resin can also be used. In the present specification, a relatively large molecule having about 2 to 20 repeating molecular structural units is referred to as an oligomer, and a molecule smaller than that is referred to as a monomer.

As the acid catalyst, sulfuric acid, paratoluenesulfonic acid, phosphoric acid and the like are used. Further, as the alkali catalyst, hydroxides or amine catalysts of alkali metals and alkaline earth metals such as NaOH, KOH, Ca (OH) ₂ and Ba (OH) ₂ are used.

  Examples of the amine catalyst include, but are not limited to, ammonia, hexamethylenetetramine, trimethylamine, triethylamine, and triethanolamine. When a basic catalyst is used, the carrier is remarkably trapped by the remaining catalyst, and the electrophotographic characteristics tend to be deteriorated. Therefore, it is preferable to inactivate or remove by neutralizing with an acid or contacting with an adsorbent such as silica gel or an ion exchange resin.

  Moreover, as a phenol derivative which has a methylol group, a phenol resin is preferable and a resol type phenol resin is more preferable.

  Examples of the charge transport material having at least one selected from a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group include compounds represented by the general formulas (I) to (V) or derivatives thereof. Preferably there is.

  As the organic group F derived from the compound having a hole transporting ability in the compound represented by the general formula (I), (II), (III), (IV) or (V), the following general formula (VI) The compound shown by these is preferable.

Here, in formula (VI), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group, Ar ⁵ is a substituted or unsubstituted aryl group or arylene group, and k is 0 or 1 is shown respectively. However, 1-4 of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are compounds represented by the above general formula (I), (II), (III), (IV) or (V) _{^{in, - [D-Si (R}} 1) (3-a) Q a], - [(X 1) n1 R 2 -ZH], - [(X 2) n3 - (R 3) n4 - (Z) _n5 G], a structural unit represented by the following formula (IV-1), or a bond for binding to a site represented by the structural unit represented by the following formula (V-1).

Specific examples of the substituted or unsubstituted aryl group represented by Ar ^{1 to} Ar ⁴ in the compound represented by the general formula (VI) include aryl represented by the following formulas (VI-1) to (VI-7): Groups are preferred.

  As Ar in the aryl group represented by the above formula (VI-7), an aryl group represented by the following formula (VI-8) or (VI-9) is preferable.

  In addition, as Z in the aryl group represented by the formula (VI-7), a divalent group represented by the following formula (VI-10) or (VI-17) is preferable.

Here, in the formula (VI-1) ~ (VI -17), R 16 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms A substituted or unsubstituted phenyl group, or an aralkyl group having 7 to 10 carbon atoms, R ^{17 to} R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom. An alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted or unsubstituted with them, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, m and s are each independently 0; Or 1, q and r each independently represent an integer of 1 to 10, and t each independently represents an integer of 1 to 3.

In the above formulas (VI-1) to (VI-7), X represents-[D-Si (R ¹ ) _(3-a) Q _a in the compounds represented by the above formulas (I) to (V). _{^{], - [(X 1)}} n1 R 2 -ZH], - [(X 2) n3 - (R 3) n4 - (Z) n5 G], structural units represented by the formula (IV-1), or It has a bond for binding to the site represented by the structural unit represented by the above formula (V-1).

  In the above formulas (VI-16) to (VI-17), W represents a divalent group represented by the following formulas (VI-18) to (VI-26). In formula (VI-25), u represents an integer of 0 to 3.

Further, the specific structure of Ar ⁵ in the general formula (VI) is as follows. When k = 0, the structure of m = 1 in the specific structure of Ar ^{1 to} Ar ^{4 and} when Ar = 1, the structure of Ar 5 ^The structure of m = 0 in the specific structure of ^{1 to} Ar ⁴ is given.

Specific examples of the compound represented by the general formula (I) include the following compounds (F-1) to (F-61). In addition, the following compounds (F-1) to (F-61) are combinations of Ar ^{1 to} Ar ⁵ and k of the compound represented by the general formula (VI) as shown in the following table, and an alkoxysilyl group. (S) is the specific one shown in the table below.

  Specific examples of the compound represented by the general formula (II) include the following compounds (II-1) to (II-26). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (III) include the following compounds (III-1) to (III-47). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (IV) include the following compounds (IV-1) to (IV-40). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (V) include the following compounds (V-1) to (V-13). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

In addition, a compound represented by the following general formula (VII) can be added to the protective layer 7 in order to control various physical properties such as strength and film resistance of the protective layer 7.
Si (R ⁵⁰ ) _(4-c) Q _c (VII)

In the above formula (VII), R ⁵⁰ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and c represents an integer of 1 to 4.

  Specific examples of the compound represented by the general formula (VII) include the following silane coupling agents. Examples of silane coupling agents include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl L) Triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H , 1H, 2H, 2H-perfluorodecyltriethoxysilane, trifunctional alkoxysilanes such as 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (c = 3); dimethyldimethoxysilane, diphenyldimethoxysilane, methyl And bifunctional alkoxysilanes such as phenyldimethoxysilane (c = 2); monofunctional alkoxysilanes such as trimethylmethoxysilane (c = 1), and the like. Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and monofunctional and bifunctional alkoxysilanes are preferable for improving the flexibility and film formability.

  In addition, a silicon-based hard coat agent produced mainly from these coupling agents can also be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Etc.) can be used.

In order to increase the strength of the protective layer 7, it is also preferable to use a compound having two or more silicon atoms as shown in the general formula (VIII).
B- (Si (R ⁵¹ ) _(3-d) Q _d ) ₂ (VIII)

In the above formula (VIII), B represents a divalent organic group, R ³¹ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and a represents an integer of 1 to 3. Show. More specific examples of the compound represented by the general formula (VIII) include the following compounds (VIII-1) to (VIII-16).

  Further, a resin soluble in an alcohol solvent or a ketone solvent may be added for controlling the film characteristics and extending the liquid life. Examples of such resins include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal, acetoacetal, or the like (for example, ESREC B, K manufactured by Sekisui Chemical Co., Ltd.). Etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics.

  Various resins can be added for the purposes of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like. Particularly in the case of a siloxane resin, it is preferable to add a resin that dissolves in alcohol. Examples of resins soluble in alcohol solvents include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal or acetoacetal (for example, manufactured by Sekisui Chemical Co., Ltd.). ESREC B, K, etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics.

  The molecular weight of the resin is preferably 2000-100000, more preferably 5000-50000. If the molecular weight is less than 2000, the desired effect tends not to be obtained. If the molecular weight is more than 100000, the solubility tends to be low and the addition amount is limited, or the film formation tends to be poor during coating. The addition amount is preferably 1 to 40%, more preferably 1 to 30%, and most preferably 5 to 20%. If the amount is less than 1%, it is difficult to obtain a desired effect. If the amount is more than 40%, image blurring under high temperature and high humidity tends to occur. These resins may be used alone or in combination.

  Further, for the purpose of extending the pot life and controlling the film properties, it is preferable to contain a cyclic compound having a repeating structural unit represented by the following general formula (IX) or a derivative thereof.

In the above formula (IX), A ¹ and A ² each independently represent a monovalent organic group.

  Examples of the cyclic compound having the repeating structural unit represented by the general formula (IX) include commercially available cyclic siloxanes. Specifically, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5-trimethyl-1,3,5- Triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7 , 9-pentaphenylcyclopentasiloxane and other cyclic methylphenylcyclosiloxanes, hexaphenylcyclotrisiloxane and other cyclic phenylcyclosiloxanes, and 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane and other fluorine Atom-containing cyclosiloxanes, methylhydrosiloxa Mixture, pentamethylcyclopentasiloxane, mention may be made of phenyl hydrosilyl group-containing cyclosiloxanes of hydrocyclosiloxane like, cyclic siloxanes and vinyl group-containing cyclosiloxanes such as penta vinyl pentamethylcyclopentasiloxane like. These cyclic siloxane compounds may be used alone or in combination of two or more.

  Furthermore, various fine particles can be added to control the antifouling substance adhesion, lubricity, hardness and the like on the surface of the electrophotographic photosensitive member. They can be used alone or in combination of two or more.

  Examples of the fine particles include silicon atom-containing fine particles or fluorine atom-containing resin particles. The silicon atom-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon atom-containing fine particles preferably has an average particle diameter of 1 to 100 nm, more preferably 10 to 30 nm, in an acidic or alkaline aqueous dispersion, or an organic solvent such as alcohol, ketone or ester. What was chosen from what was disperse | distributed and generally marketed can be used. The solid content of colloidal silica in the protective layer 7 is not particularly limited, but preferably 0.1 to 0.1 based on the total solid content of the protective layer 7 in terms of film formability, electrical characteristics, and strength. It is used in the range of 50% by mass, more preferably in the range of 0.1-30% by mass.

  The silicone fine particles used as the silicon atom-containing fine particles are spherical and preferably have an average particle size of 1 to 500 nm, more preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles. A commercially available product can be used.

  Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain sufficient characteristics is low, the electron does not hinder the crosslinking reaction, The surface properties of the photographic photoreceptor can be improved. In other words, it is possible to improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and to maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles in the protective layer 7 is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.5 to 10% by mass based on the total solid content of the protective layer 7. .

  Fluorine atom-containing resin particles include fluorine-based fine particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Materials Forum Lecture Proceedings p89. And fine particles made of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group.

Other fine particles include ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—. Examples thereof include semiconductive metal oxides such as TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO.

  For the same purpose, an oil such as silicone oil can be added. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Examples include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes. These may be added in advance to the protective layer-forming coating solution, or may be impregnated under reduced pressure or increased pressure after producing the photoreceptor.

  In addition, additives such as plasticizers, surface modifiers, antioxidants, and photodegradation inhibitors can also be used. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons. An antioxidant having a hindered phenol, hindered amine, thioether, or phosphite partial structure can be added to the protective layer 7, which is effective in improving the potential stability and image quality when the environment changes.

  Examples of the antioxidant include the following compounds. For example, hindered phenols include “Sumilizer BHT-R”, “Sumilizer MDP-S”, “Sumilizer BBM-S”, “Sumizer WX-R”, “Sumizer NW”, “Sumizer BP-76”, “ Sumilizer BP-101 "," Sumilizer GA-80 "," Sumilizer GM "," Sumilizer GS "or more manufactured by Sumitomo Chemical Co., Ltd.," IRGANOX1010 "," IRGANOX1035 "," IRGANOX1076 "," IRGANOX1098 "," IRGANOX1098 "," 114 " ”,“ IRGANOX1222 ”,“ IRGANOX1330 ”,“ IRGANOX1425WL ”,“ IRGANOX1 20L "," IRGANOX 245 "," IRGANOX 259 "," IRGANOX 3114 "," IRGANOX 3790 "," IRGANOX 5057 "," IRGANOX 565 "or more, manufactured by Ciba Specialty Chemicals," ADK STAB AO-20 "," ADK STAB AO-30 "," ADEKA STAB " "AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", "ADK STAB AO-330" or more manufactured by Asahi Denka. Examples of hindered amines include “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”. ”,“ Mark LA68 ”,“ Mark LA63 ”,“ Smilizer TPS ”,“ Smilizer TP-D ”for thioethers,“ Mark 2112 ”,“ Mark PEP 8 ”,“ Mark PEP ”for phosphites -24G "," Mark PEP.36 "," Mark 329K "," Mark HP.10 ", and hindered phenols and hindered amine antioxidants are particularly preferable. Furthermore, these may be modified with a substituent such as an alkoxysilyl group capable of undergoing a crosslinking reaction with the material forming the crosslinked film.

  The protective layer 7 includes polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin An insulating resin such as a resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, or polyvinyl pyrrolidone resin may be contained. In this case, the insulating resin can be added at a desired ratio, and thereby, adhesion to the charge transport layer 6, coating film defects due to heat shrinkage and repellency, and the like can be suppressed.

  The protective layer 7 is formed using a coating liquid for forming a protective layer containing the above-described constituent materials.

  It is preferable to add or use a catalyst when forming the protective layer forming coating solution or the protective layer forming coating solution. Such catalysts include inorganic acids such as hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, potassium hydroxide, hydroxide Examples include alkali catalysts such as sodium, calcium hydroxide, ammonia, triethylamine.

Furthermore, a solid catalyst insoluble in the system as shown below can also be used. Amberlite 15, Amberlite 200C, Amberlist 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co.); Levacit SPC-108, Levacit SPC-118 (manufactured by Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (Above, manufactured by Sumitomo Chemical Co., Ltd.); cation exchange resins such as Nafion-H (manufactured by DuPont); shades such as Amberlite IRA-400, Amberlite IRA-45 (above, manufactured by Rohm and Haas) ion exchange _{resins; Zr (O 3 PCH 2 CH} 2 SO 3 H) 2, Th (O 3 Cobalt tungstate; polyorganosiloxanes containing protonic acid group of the polyorganosiloxane having a sulfonic acid group; CH ₂ CH ₂ COOH) groups containing protonic acid group of ₂ such as inorganic solids are bonded to the surface Heteropolyacids such as phosphomolybdic acid; isopolyacids such as niobic acid, tantalum acid, molybdic acid; monometallic oxides such as silica gel, alumina, chromia, zirconia, CaO, MgO; silica-alumina, silica-magnesia, silica- Complex metal oxides such as zirconia and zeolites; clay minerals such as acid clay, activated clay, montmorillonite and kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; metal phosphates such as zirconia phosphate and lanthanum phosphate _{; LiNO 3, Mn (NO 3} ) 2 and the like of a metal nitrate; silica An inorganic solid in which a group containing an amino group such as a solid obtained by reacting aminopropyltriethoxysilane on the surface is bonded to the surface; a polyorganosiloxane containing an amino group such as an amino-modified silicone resin; Can be mentioned.

  Further, when preparing a coating solution for forming a protective layer, it is preferable to use a solid catalyst that is insoluble in a photofunctional compound, a reaction product, water, a solvent, etc., because the stability of the coating solution tends to be improved. . The solid catalyst insoluble in the system is not particularly limited as long as the catalyst component is insoluble in a material for forming a resin having a crosslinked structure, other additives, water, a solvent and the like. Although the usage-amount of these solid catalysts is not restrict | limited in particular, 0.1-100 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group. Further, as described above, these solid catalysts are insoluble in raw material compounds, reaction products, solvents and the like, and therefore can be easily removed after the reaction according to a conventional method. The reaction temperature and reaction time are appropriately selected according to the type and amount of the raw material compound or solid catalyst, but the reaction temperature is usually 0 to 100 ° C, preferably 10 to 70 ° C, more preferably 15 to 50. The reaction time is preferably 10 minutes to 100 hours. If the reaction time exceeds the upper limit, gelation tends to occur.

  In the case of preparing a protective layer-forming coating solution, when a catalyst insoluble in the system is used, it is preferable to use a catalyst that is further dissolved in the system for the purpose of improving the strength, storage stability of the solution, and the like. Such catalysts include, in addition to those described above, aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate), mono (sec-butoxy) aluminum diisopropylate, diisopropoxyaluminum (ethyl acetoacetate). ), Aluminum tris (ethyl acetoacetate), aluminum bis (ethyl acetoacetate) monoacetylacetonate, aluminum tris (acetylacetonate), aluminum diisopropoxy (acetylacetonate), aluminum isopropoxy-bis (acetylacetonate) Organic aluminum compounds such as aluminum tris (trifluoroacetylacetonate) and aluminum tris (hexafluoroacetylacetonate) It is possible to use.

  In addition to organoaluminum compounds, organotin compounds such as dibutyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate; titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis Organic titanium compounds such as (isopropoxy) bis (acetylacetonate); zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate), etc. Zirconium compounds can also be used, but from the viewpoint of safety, low cost, and pot life length, it is preferable to use an organoaluminum compound, particularly an aluminum chelate compound. It is more preferable. Although the usage-amount in particular of these catalysts is not restrict | limited, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group, and 0.3-10 mass parts is especially preferable.

In the present invention, when an organometallic compound is used as a catalyst, it is preferable to add a multidentate ligand from the viewpoint of pot life and curing efficiency. Examples of such multidentate ligands include those shown below and those derived therefrom, but the present invention is not limited to these. Specifically, β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, and dipivaloylmethylacetone; acetoacetates such as methyl acetoacetate and ethyl acetoacetate; bipyridine and derivatives thereof; glycine and its Derivatives; ethylenediamine and derivatives thereof; 8-oxyquinoline and derivatives thereof; salicylaldehyde and derivatives thereof; catechol and derivatives thereof; bidentate ligands such as 2-oxyazo compounds; diethyltriamine and derivatives thereof; nitrilotriacetic acid and derivatives thereof And tridentate ligands such as ethylenediaminetetraacetic acid (EDTA) and derivatives thereof. In addition to the organic ligands as described above, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be exemplified. As the multidentate ligand, a bidentate ligand is particularly preferable, and a bidentate ligand represented by the following general formula (X) is more preferable, and R ¹⁰ and R ^{11 in the following} general formula (X) are more preferable. Are particularly preferred. By making R ¹⁰ and R ^{11 the} same, the coordination power of the ligand near room temperature becomes strong, and the coating solution for forming the protective layer can be further stabilized.

ここで、式（Ｘ）中、Ｒ^１０及びＲ^１１は各々独立に、炭素数１〜１０のアルキル基、フッ化アルキル基、又は炭素数１〜１０のアルコキシ基を示す。

Here, in formula (X), R ¹⁰ and R ¹¹ each independently represent an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, or an alkoxy group having 1 to 10 carbon atoms.

  The compounding amount of the polydentate ligand can be arbitrarily set, but is 0.01 mol or more, preferably 0.1 mol or more, more preferably 1 mol or more, with respect to 1 mol of the organometallic compound used. It is preferable to do this.

  The protective layer 17 can be formed in the absence of a solvent if the coating solution is liquid, but alcohols such as methanol, ethanol, propanol, and butanol; ketones such as acetone and methyl ethyl ketone as necessary. In addition to tetrahydrofuran; ethers such as diethyl ether and dioxane; and the like, various solvents may be used. As such a solvent, those having a boiling point of 100 ° C. or less are preferable, and they can be arbitrarily mixed and used. When the organosilicon compound is contained in the coating solution, the organosilicon compound is likely to be precipitated if the solvent is too small. Therefore, the content is preferably 0.5 to 30 parts by mass with respect to 1 part by mass of the organosilicon compound. More preferably, it is part by mass.

  Furthermore, when crosslinking, a curing catalyst may be used in the protective layer forming coating solution. Curing catalysts include bissulfonyldiazomethanes such as bis (isopropylsulfonyl) diazomethane, bissulfonylmethanes such as methylsulfonyl p-toluenesulfonylmethane, sulfonylcarbonyldiazomethanes such as cyclohexylsulfonylcyclohexylcarbonyldiazomethane, 2-methyl Sulfonylcarbonyl alkanes such as 2- (4-methylphenylsulfonyl) propiophenone, nitrobenzyl sulfonates such as 2-nitrobenzyl p-toluenesulfonate, alkyl and aryl sulfonates such as pyrogallol trismethanesulfonate ( g) Benzoin sulfonates such as benzoin tosylate, N- such as N- (trifluoromethylsulfonyloxy) phthalimide. Sulfonyloxyimides, pyridones such as (4-fluorobenzenesulfonyloxy) -3,4,6-trimethyl-2-pyridone, 2,2,2-trifluoro-1-trifluoromethyl-1- ( Photoacid generators such as sulfonic acid esters such as 3-vinylphenyl) -ethyl-4-chlorobenzenesulfonate, onium salts such as triphenylsulfonium methanesulfonate, diphenyliodonium trifluoromethanesulfonate, protonic acids or Lewis acids. Preferred examples include compounds neutralized with Lewis bases, mixtures of Lewis acids and trialkyl phosphates, sulfonate esters, phosphate esters, onium compounds, and carboxylic anhydride compounds.

Compounds obtained by neutralizing a protonic acid or Lewis acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphoric acid esters, boric acid mono- and diesters, and the like. Various amines such as monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, or trialkylphosphine, triarylphosphine, trialkylphosphite, triaryl Compounds neutralized with phosphite, as well as NureCure 2500X, 4167, X-47-110, 3525, 5225 commercially available as acid-base blocking catalysts (trade name, King Ndasutori Co., Ltd.), and the like. Examples of the compound obtained by neutralizing a Lewis acid with a Lewis base include compounds obtained by neutralizing a Lewis acid such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the above Lewis base.

  Examples of the onium compound include triphenylsulfonium methanesulfonate, diphenyliodonium trifluoromethanesulfonate, and the like.

  Examples of the carboxylic anhydride compound include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, lauric anhydride, oleic anhydride, stearic anhydride, n-caproic anhydride, n-caprylic anhydride, and n-capric anhydride. , Palmitic anhydride, myristic anhydride, trichloroacetic anhydride, dichloroacetic anhydride, monochloroacetic anhydride, trifluoroacetic anhydride, heptafluorobutyric anhydride, and the like.

  Specific examples of Lewis acids include, for example, boron trifluoride, aluminum trichloride, ferrous chloride, ferric chloride, ferrous chloride, ferric chloride, zinc chloride, zinc bromide, stannous chloride. , Metal halides such as stannic chloride, stannous bromide, stannic bromide, organometallic compounds such as trialkylboron, trialkylaluminum, dialkylaluminum halide, monoalkylaluminum halide, tetraalkyltin , Diisopropoxyethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, tris (acetylacetonato) aluminum, diisopropoxy bis (ethyl acetoacetate) titanium, diisopropoxy bis (acetylacetonato) titanium, tetrakis (N-propylacetoacetate Zirconium, tetrakis (acetylacetonato) zirconium, tetrakis (ethylacetoacetate) zirconium, dibutyl bis (acetylacetonato) tin, tris (acetylacetonato) iron, tris (acetylacetonato) rhodium, bis (acetyl) Acetonato) zinc, tris (acetylacetonato) cobalt and other metal chelate compounds, dibutyltin dilaurate, dioctyltin ester malate, magnesium naphthenate, calcium naphthenate, manganese naphthenate, iron naphthenate, cobalt naphthenate, copper naphthenate , Zinc naphthenate, zirconium naphthenate, lead naphthenate, calcium octylate, manganese octylate, iron octylate, cobalt octylate, zinc octylate, zirconium octylate, Tin chill acid, lead octylate, zinc laurate, magnesium stearate, aluminum stearate, calcium stearate, cobalt stearate, zinc stearate, and metal soaps such as stearate lead. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Although the usage-amount of these catalysts is not restrict | limited, 0.1-20 mass parts is preferable with respect to the total 100 mass parts of solid content contained in the coating liquid for protective layer formation, and 0.3-10 mass parts is preferable. Particularly preferred.

  When the coating liquid for forming the protective layer is applied onto the charge transport layer 6, the coating methods are blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating. Ordinary methods such as a method can be used. And after application | coating, the protective layer 7 forms by drying a coating film.

  In addition, in the case of application | coating, when a required film thickness cannot be obtained by one application | coating, a required film thickness can be obtained by apply | coating several times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application.

  The reaction temperature and reaction time for curing the curable component in the coating liquid for forming the protective layer are not particularly limited, but the reaction temperature is preferably 60 ° C. from the viewpoint of mechanical strength and chemical stability of the obtained resin. As mentioned above, More preferably, it is 80-200 degreeC, and reaction time becomes like this. Preferably it is 10 minutes-5 hours. In addition, maintaining the organic layer obtained by curing the coating liquid in a high humidity state is effective in stabilizing the characteristics of the organic layer. Furthermore, the protective layer 7 obtained can be hydrophobized by subjecting it to surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like according to the application.

  The thickness of the protective layer 7 is preferably 0.5 to 15 μm, more preferably 1 to 10 μm, and further preferably 1 to 5 μm.

  Further, since the protective layer 7 formed from the above-mentioned coating solution for forming a protective layer has excellent mechanical strength and sufficient photoelectric properties, it can be used as it is as a charge transport layer of a multilayer photoreceptor. it can.

  Further, as the protective layer 7, a phenol containing a phenol derivative having a methylol group and the above charge transport material having at least one selected from a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group and an amino group When forming a derivative-containing layer, it is preferable to form such a phenol derivative-containing layer by the following method.

The phenol derivative-containing layer is formed by applying a coating solution for forming a protective layer containing a constituent material on the charge transport layer 6 and curing it, as in the method for forming the protective layer 7 described above. Here, it is preferable that the infrared absorption spectrum of the phenol derivative-containing layer satisfies the condition represented by the following formula (C). Thereby, it is possible to further improve the electrical characteristics and the image quality.
(P ₂ / P ₁ ) ≦ 0.2 (C)
Here, in the formula (C), _{P 1} is the absorbance of the maximum absorption peaks at ^{1560cm -1 ~1640cm} -1, _{P 2} represents the absorbance of the maximum absorption peaks at ^{1645cm -1 ~1700cm} -1.

  It is preferable to add a catalyst to the coating liquid for forming the protective layer, or to use the catalyst when preparing the coating liquid for forming the protective layer. Catalysts used include inorganic acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide, water An alkali catalyst such as sodium oxide, calcium hydroxide, ammonia, triethylamine, or a solid catalyst insoluble in the system can also be used.

  In addition, in order to remove the catalyst at the time of synthesis from a phenol derivative having a methylol group, the phenol derivative is dissolved in a suitable solvent such as methanol, ethanol, toluene, ethyl acetate, washed with water, reprecipitation using a poor solvent, etc. It is preferable to perform the above treatment or to perform treatment using an ion exchange resin or an inorganic solid. As the ion exchange resin and the inorganic solid, the same ones as described above can be used.

  For the coating liquid for forming the protective layer, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran; ethers such as diethyl ether and dioxane; Can be used. In order to apply a dip coating method generally used for production of an electrophotographic photosensitive member, an alcohol solvent, a ketone solvent, or a mixed solvent thereof is preferable. In addition, the boiling point of the solvent used is preferably 50 to 150 ° C., and these can be arbitrarily mixed and used.

  In addition, since an alcohol solvent, a ketone solvent, or a mixed solvent thereof is preferable as the solvent, the charge transport material used for forming the protective layer 7 to be used is soluble in these solvents. Is preferred.

  The amount of the solvent can be set arbitrarily, but if the amount is too small, the constituent materials are likely to be precipitated. Parts, more preferably 1 to 20 parts by mass.

  As a coating method when forming the protective layer 7 using the coating liquid for forming the protective layer, the same method as described above can be used.

After applying the coating liquid for forming the protective layer on the charge transport layer 6, a curing process is performed. Usually, during the curing treatment, the curing temperature is higher and the curing time is preferably longer in order to promote the crosslinking reaction of the phenol derivative and increase the mechanical strength of the protective layer 7. However, in such a case, the absorbance ratio (P ₂ / P ₁ ) tends to exceed 0.2, and in this case, the electric characteristics tend to be lowered. Therefore, it is preferable to control the curing temperature, the curing time, the crosslinking atmosphere, or the curing catalyst so that the IR spectrum of the protective layer 7 satisfies the above conditions.

  That is, in order for the IR spectrum of the protective layer 7 to satisfy the condition represented by the above formula (C), the curing temperature during the curing treatment is preferably 100 to 170 ° C, more preferably 100 to 150 ° C, ˜140 ° C. is more preferable. The curing time is preferably 30 minutes to 2 hours, more preferably 30 minutes to 1 hour.

Further, as the atmosphere for performing the curing treatment (crosslinking reaction), the absorbance ratio (P ₂ / P ₁ ) is under a so-called oxidation inert gas atmosphere (inert gas atmosphere) such as nitrogen, helium or argon. It is effective to make it small. When the crosslinking reaction is performed in an inert gas atmosphere, the curing temperature can be set higher than in an air atmosphere (oxygen-containing atmosphere), and the curing temperature is 100 to 160 ° C. (preferably 110 to 150 ° C.). Is possible. The curing time can be 30 minutes to 2 hours (preferably 30 minutes to 1 hour).

  As the charging device 21, for example, a contact charger using a conductive or semiconductive charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube or the like can be used. Further, a non-contact type roller charger using a charging roller in the vicinity of the photoconductor 10, a known charger such as a scorotron charger using a corona discharge, a corotron charger, or the like can also be used.

  Examples of the exposure apparatus 30 include optical system devices that can expose the surface of the photoreceptor 1 with light such as semiconductor laser light, LED light, and liquid crystal shutter light in a desired image-like manner. The wavelength of the light source is in the spectral sensitivity region of the photoreceptor. As the wavelength of the semiconductor laser, near infrared having an oscillation wavelength near 780 nm is the mainstream. However, the present invention is not limited to this wavelength, and an oscillation wavelength laser in the 600 nm range or a laser having an oscillation wavelength in the vicinity of 400 to 450 nm as a blue laser can be used. For color image formation, a surface-emitting laser light source capable of multi-beam output is also effective.

  As the developing device 25, for example, a general developing device that performs development by bringing a magnetic or non-magnetic one-component developer or two-component developer into contact or non-contact with each other can be used. Such a developing device is not particularly limited as long as it has the functions described above, and can be appropriately selected according to the purpose. For example, a known developing device having a function of attaching the one-component developer or the two-component developer to the photosensitive member 1 using a brush, a roller, or the like can be used.

  Hereinafter, the toner used for the developing device 25 will be described.

The toner used in the image forming apparatus of the present embodiment preferably has an average shape factor (ML ² / A) of 100 to 150 from the viewpoint of obtaining high developability and transferability and high image quality, and 105 to 145. More preferably, it is more preferably 110-140. Further, the toner preferably has a volume average particle diameter of 3 to 12 μm, more preferably 3.5 to 10 μm, and still more preferably 4 to 9 μm. By using a toner satisfying such an average shape factor and volume average particle diameter, developability and transferability are improved, and a high-quality image called so-called photographic image quality can be obtained.

  The toner is not particularly limited by the production method as long as it satisfies the above average shape factor and volume average particle diameter. For example, the toner may include a binder resin, a colorant, a release agent, and the like. A kneading and pulverizing method in which a charge control agent is added, kneading, pulverizing, and classifying; a method in which the shape of particles obtained by the kneading and pulverizing method is changed by mechanical impact force or thermal energy; Emulsion polymerization of the body, and the resulting dispersion is mixed with a dispersion of a colorant, a release agent and, if necessary, a charge control agent, and then agglomerated and heat-fused to obtain toner particles. Suspension polymerization method in which a polymerizable monomer for obtaining a binder resin, a colorant, a release agent, and a charge control agent, if necessary, are suspended in an aqueous solvent and polymerized; A water-based solution of a resin, a colorant, a release agent, and a solution such as a charge control agent as necessary. Toner is used which is suspended in and produced by a dissolution suspension method in which granulated.

  In addition, a known method such as a production method in which the toner obtained by the above method is used as a core, and agglomerated particles are further adhered and heat-fused to give a core-shell structure can be used. As a toner production method, a suspension polymerization method, an emulsion polymerization aggregation method, and a dissolution suspension method in which an aqueous solvent is used are preferable from the viewpoint of shape control and particle size distribution control, and an emulsion polymerization aggregation method is particularly preferable.

  The toner base particles are composed of a binder resin, a colorant, and a release agent, and include silica and a charge control agent as necessary.

  Binder resins used for toner base particles include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Α-methylene aliphatics such as vinyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers and copolymers of monocarboxylic acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone Polyester resins by copolymerization of dicarboxylic acids and diols.

  Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. A polymer, polyethylene, polypropylene, a polyester resin, etc. can be mentioned. In addition, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can also be mentioned.

  In addition, as colorants, magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, Lamp Black, Rose Bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.

  Typical examples of the release agent include low molecular weight polyethylene, low molecular weight polypropylene, Fischer tropic wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  As the charge control agent, known ones can be used, and azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups can be used. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  The toner used in the developing device 25 can be manufactured by mixing the toner base particles and the external additive with a Henschel mixer or a V blender. In addition, when the toner base particles are produced by a wet method, external addition can also be performed by a wet method.

  Lubricating particles may be added to the toner used in the developing device 25. Lubricating particles include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids and fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, silicones having a softening point upon heating, oleic amides Aliphatic amides such as erucic acid amide, ricinoleic acid amide, stearic acid amide, etc., plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animals such as beeswax Minerals such as system waxes, montan waxes, ozokerites, ceresins, paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, etc., petroleum waxes, and modified products thereof can be used. These can be used individually by 1 type or in combination of 2 or more types. However, the average particle size is preferably in the range of 0.1 to 10 μm, and the particles having the above chemical structure may be pulverized to make the particle sizes uniform. The amount added to the toner is preferably in the range of 0.05 to 2.0 mass%, more preferably 0.1 to 1.5 mass%.

  To the toner used in the developing device 25, inorganic fine particles, organic fine particles, composite fine particles obtained by attaching inorganic fine particles to the organic fine particles, and the like can be added for the purpose of removing deposits and deteriorated matters on the surface of the electrophotographic photoreceptor. .

  Inorganic fine particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used.

  In addition, the inorganic fine particles are mixed with titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, γ- (2- Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxy Silane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxy The treatment may be performed with a silane coupling agent such as silane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane. In addition, those hydrophobized with higher fatty acid metal salts such as silicone oil, aluminum stearate, zinc stearate and calcium stearate are also preferably used.

  Examples of the organic fine particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles.

  The particle diameter is preferably a number average particle diameter of 5 nm to 1000 nm, more preferably 5 nm to 800 nm, and still more preferably 5 nm to 700 nm. If the average particle size is less than the lower limit, the polishing ability tends to be lacking. On the other hand, if the average particle size exceeds the upper limit, the surface of the electrophotographic photoreceptor tends to be damaged. Moreover, it is preferable that the sum of the addition amount of the particle | grains mentioned above and lubricity particle | grains is 0.6 mass% or more.

  Other inorganic oxides added to the toner are small-diameter inorganic oxides with a primary particle size of 40 nm or less for powder flowability, charge control, etc. It is preferable to add a larger-diameter inorganic oxide. These inorganic oxide fine particles may be known ones, but it is preferable to use silica and titanium oxide in combination for precise charge control. Further, the surface treatment of the small-diameter inorganic fine particles increases the dispersibility and increases the powder flowability. Furthermore, it is also preferable to add carbonates such as calcium carbonate and magnesium carbonate and inorganic minerals such as hydrotalcite in order to remove the discharge purified product.

  In addition, the color toner for electrophotography is used by mixing with a carrier. As the carrier, iron powder, glass beads, ferrite powder, nickel powder, or those having a resin coating on the surface thereof are used. The mixing ratio with the carrier can be set as appropriate.

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

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

  In addition to the above-described devices, the image forming apparatus 100 may include, for example, an optical static elimination device that performs optical static elimination on the photoreceptor 1.

  FIG. 13 is a schematic view showing another embodiment of the image forming apparatus of the present invention. In the image forming apparatus 110 shown in FIG. 13, the electrophotographic photosensitive member 1 is fixed to the image forming apparatus main body, and the charging device 22, the developing device 25, and the cleaning device 27 are respectively formed into cartridges. It is provided independently as a cleaning cartridge. Note that the charging device 22 includes a charging device for charging by a corona discharge method.

  In the image forming apparatus 110, the electrophotographic photosensitive member 1 and other apparatuses are separated, and the charging device 22, the developing device 25, and the cleaning device 27 are fixed to the image forming apparatus main body by screws, caulking, adhesion, or welding. It is possible to detach it by the operation by pulling out and pushing in without being done.

  Since the electrophotographic photosensitive member of the present invention uses a resin having a crosslinked structure as a constituent material of the protective layer, the surface of the photosensitive member is excellent in wear resistance, so that it may not be necessary to make a cartridge. . Therefore, the charging device 22, the developing device 25, or the cleaning device 27 can be detached and attached by an operation by pulling out and pushing in without being fixed to the main body by screws, caulking, adhesion, or welding. The member cost per hit can be reduced. Further, two or more of these devices can be detachable as an integrated cartridge, thereby further reducing the member cost per print.

  The image forming apparatus 110 has the same configuration as that of the image forming apparatus 100 except that the charging device 22, the developing device 25, and the cleaning device 27 are each formed as a cartridge.

  FIG. 14 is a schematic view showing another embodiment of the image forming apparatus of the present invention. The image forming apparatus 120 is a tandem full-color image forming apparatus equipped with four process cartridges 20. In the image forming apparatus 120, four process cartridges 20 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member can be used for one color. The image forming apparatus 120 has the same configuration as that of the image forming apparatus 100 except that it is a tandem system.

  In the tandem-type image forming apparatus 120, the amount of wear of each electrophotographic photosensitive member varies depending on the use ratio of each color, and thus the electrical characteristics of each electrophotographic photosensitive member tend to vary. Along with this, the toner development characteristics gradually change from the initial state, and the hue of the print image changes, so that a stable image cannot be obtained. In particular, in order to reduce the size of the image forming apparatus, a small-diameter electrophotographic photosensitive member tends to be used, and this tendency becomes remarkable when one having a diameter of 30 mmΦ or less is used. Here, when the configuration of the electrophotographic photosensitive member according to the present invention is adopted for the electrophotographic photosensitive member, the wear of the surface is sufficiently suppressed even when the diameter is 30 mmΦ or less. Therefore, the electrophotographic photosensitive member according to the present invention is particularly effective for a tandem image forming apparatus.

  FIG. 15 is a schematic view showing another embodiment of the image forming apparatus of the present invention. The image forming apparatus 130 shown in FIG. 15 is a so-called four-cycle type image forming apparatus that forms toner images of a plurality of colors with one electrophotographic photosensitive member. The image forming apparatus 130 includes a photosensitive drum 1 that is rotated by a driving device (not shown) at a predetermined rotational speed in the direction of arrow A in the figure, and above the photosensitive drum 1 is a photosensitive member. A charging device 22 for charging the outer peripheral surface of the drum 1 is provided.

  Further, an exposure device 30 having a surface emitting laser array as an exposure light source is disposed above the charging device 22. The exposure device 30 modulates a plurality of laser beams emitted from a light source in accordance with an image to be formed and deflects the laser beams in the main scanning direction so that the axis of the photosensitive drum 1 is on the outer peripheral surface of the photosensitive drum 1. Scan in parallel. Thereby, an electrostatic latent image is formed on the outer peripheral surface of the charged photosensitive drum 1.

  A developing device 25 is disposed on the side of the photosensitive drum 1. The developing device 25 includes a roller-shaped container that is rotatably arranged. Four containers are formed inside the container, and developing units 25Y, 25M, 25C, and 25K are provided in each container. The developing devices 25Y, 25M, 25C, and 25K each include a developing roller 26, and store Y, M, C, and K color toners therein.

  The full-color image is formed by the image forming apparatus 130 while the photosensitive drum 1 is rotated four times. That is, during four rotations of the photosensitive drum 1, the charging device 22 charges the outer peripheral surface of the photosensitive drum 1, and the exposure device 20 includes Y, M, C, K image data representing a color image to be formed. Scanning the outer peripheral surface of the photosensitive drum 1 with the laser beam modulated according to any one is repeated while switching the image data used for modulation of the laser beam each time the photosensitive drum 1 rotates. Further, the developing device 25 operates the developing device corresponding to the outer peripheral surface in a state where any of the developing rollers 26 of the developing devices 25Y, 25M, 25C, and 25K corresponds to the outer peripheral surface of the photosensitive drum 1. The photosensitive drum 1 is the one that develops the electrostatic latent image formed on the outer peripheral surface of the photosensitive drum 1 to a specific color and forms a toner image of the specific color on the outer peripheral surface of the photosensitive drum 1. Each time it rotates, the process is repeated while rotating the container so that the developing unit used for developing the electrostatic latent image is switched. Thus, every time the photosensitive drum 1 rotates, Y, M, C, and K toner images are formed on the outer peripheral surface of the photosensitive drum 1.

  An endless intermediate transfer belt 50 is disposed substantially below the photosensitive drum 1. The intermediate transfer belt 50 is wound around rollers 51, 53, and 55, and is disposed so that the outer peripheral surface is in contact with the outer peripheral surface of the photosensitive drum 1. The rollers 51, 53, and 55 are rotated by a driving force of a motor (not shown) and rotate the intermediate transfer belt 50 in the direction of arrow B in FIG.

  A transfer device (transfer device) 40 is disposed on the opposite side of the photosensitive drum 1 across the intermediate transfer belt 50, and the toner image formed on the outer peripheral surface of the photosensitive drum 1 is intermediate transferred by the transfer device 40. The image is transferred onto the image forming surface of the belt 50. The intermediate transfer belt 50 is also rotated in accordance with the rotation of the photosensitive drum 1, and a full-color toner image is formed on the intermediate transfer belt 50 when the photosensitive drum 1 is rotated four times.

  A lubricant supply device 29 and a cleaning device 27 are disposed on the outer peripheral surface of the photosensitive drum 1 on the opposite side of the developing device 25 with the photosensitive drum 1 interposed therebetween. When the toner image formed on the outer peripheral surface of the photosensitive drum 12 is transferred to the intermediate transfer belt 50, the lubricant is supplied to the outer peripheral surface of the photosensitive drum 1 by the lubricant supply device 31, and the The area carrying the transferred toner image is cleaned by the cleaning device 27 and the contact member 29.

  A tray 60 is disposed below the intermediate transfer belt 50, and a large number of sheets P as recording materials are accommodated in the tray 60 in a stacked state. A take-out roller 61 is disposed obliquely above and to the left of the tray 60, and a roller pair 63 and a roller 65 are arranged in this order on the downstream side in the take-out direction of the paper P by the take-out roller 61. The uppermost recording sheet in the stacked state is taken out from the tray 60 by the take-out roller 61 rotating, and is conveyed by the roller pair 63 and the roller 65.

  A transfer device 42 is disposed on the opposite side of the roller 55 with the intermediate transfer belt 50 interposed therebetween. The paper P conveyed by the roller pair 63 and the roller 65 is sent between the intermediate transfer belt 50 and the transfer device 42, and the toner image formed on the image forming surface of the intermediate transfer belt 50 is transferred by the transfer device 42. . A fixing device 44 having a pair of fixing rollers is arranged on the downstream side of the transfer device 42 in the conveyance direction of the paper P. The paper P on which the toner image is transferred is transferred by the fixing device 44. After being fused and fixed, the sheet is discharged out of the image forming apparatus 130 and placed on a discharge tray (not shown).

  As the fixing device 44, for example, a commonly used device such as a heat roll fixing device or an oven fixing device can be used. The toner image transferred onto the transfer medium can be fixed by the fixing device 44.

(Process cartridge)
Next, the process cartridge of the present invention will be described. FIG. 16 is a schematic diagram showing the basic configuration of a preferred embodiment of the process cartridge of the present invention.

  The process cartridge 300 is integrated in the case 311 using the charging device 21, the exposure device 30, the developing device 25, the contact member 29 and the cleaning device 27, and the mounting rail 313 together with the electrophotographic photosensitive member 1. It is. The process cartridge 300 is detachable from the main body of the image forming apparatus including the transfer device 40, the fixing device 44, and other components (not shown), and constitutes the image forming apparatus together with the main body of the image forming apparatus. To do. Further, in the process cartridge 300, the developing device 25 may be separable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the following examples, “part” means part by mass.

<Production of photoconductor>
(Base photoconductor 1)
First, a cylindrical aluminum substrate having an outer diameter of 84 mmφ was prepared. This aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness was set to Rz = 0.6 μm. In order to clean the aluminum substrate subjected to the centerless polishing treatment, a degreasing treatment, an etching treatment with a 2% by mass sodium hydroxide solution for 1 minute, a neutralization treatment and a pure water washing were performed in this order. Next, an anodic oxide film (current density 1.0 A / dm ² ) was formed on the surface of the aluminum base material with a 10% by mass sulfuric acid solution. After washing with water, sealing treatment was performed by dipping in a 1 mass% nickel acetate solution at 80 ° C. for 20 minutes. Further, pure water washing and drying treatment were performed. In this way, an aluminum base material having a 7 μm anodic oxide film formed on the surface was obtained.

  Next, chlorogallium phthalocyanine having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in the X-ray diffraction spectrum is 1 Parts, polyvinyl butyral (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate are mixed and treated with a glass shaker with a paint shaker for 1 hour and dispersed to form a coating for forming a charge generation layer A liquid was obtained. This coating solution was dip coated on the obtained aluminum substrate and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts of a benzidine compound represented by the following formula (CT-1), 3 parts of a polymer compound (viscosity average molecular weight 39,000) having a structural unit represented by the following formula (B-1), and chlorobenzene 20 parts of the mixture was mixed and dissolved to obtain a charge transport layer forming coating solution.

ＣＴ−１

CT-1

  This coating solution was applied onto the charge generation layer by a dip coating method, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm. In this way, the photoreceptor in which the charge generation layer and the charge transport layer were formed on the aluminum base material on which the anodized film was formed was designated as “base photoreceptor 1”.

(Base photoconductor 2)
First, a cylindrical aluminum substrate having an outer diameter of 84 mmφ subjected to a honing treatment was prepared. Next, 100 parts of a zirconium compound (trade name: Olgatrix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts of a silane compound (trade name: A1100, manufactured by Nihon Unicar Co., Ltd.), 400 parts of isopropanol, and 200 parts of butanol are mixed. Thus, a coating solution for forming the undercoat layer was obtained. This coating solution was dip-coated on an aluminum substrate and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.1 μm.

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and Mix 1 part of hydroxygallium phthalocyanine with a strong diffraction peak at 28.3 °, 1 part of polyvinyl butyral (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate, and paint with glass beads. Dispersion was carried out with a shaker for 1 hour to obtain a coating solution for forming a charge generation layer. This coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts of a charge transport material represented by the following formula (CT-2), 3 parts of a polymer compound having a structural unit represented by the above formula (B-1) (viscosity average molecular weight 39,000), and 20 parts of chlorobenzene was mixed to obtain a coating solution for forming a charge transport layer.

  This coating solution was applied onto the charge generation layer by a dip coating method and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm. In this way, the photoconductor in which the undercoat layer, the charge generation layer, and the charge transport layer were formed on the honing-treated aluminum substrate was designated as “base photoconductor 2”.

(Base photoconductor 3)
First, a cylindrical aluminum substrate having an outer diameter of 84 mmφ was prepared. This aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness was set to Rz = 0.6 μm. In order to clean the aluminum substrate subjected to the centerless polishing treatment, a degreasing treatment, an etching treatment with a 2% by mass sodium hydroxide solution for 1 minute, a neutralization treatment and a pure water washing were performed in this order. Next, an anodic oxide film (current density 1.0 A / dm ² ) was formed on the surface of the aluminum base material with a 10% by mass sulfuric acid solution. After washing with water, sealing treatment was performed by dipping in a 1 mass% nickel acetate solution at 80 ° C. for 20 minutes. Further, pure water washing and drying treatment were performed. In this way, an aluminum base material having a 7 μm anodic oxide film formed on the surface was obtained.

  Next, 1 part of titanyl phthalocyanine having a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum of 27.2 °, polyvinyl butyral (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) 1 part and 100 parts of n-butyl acetate were mixed, treated with a glass shaker with a paint shaker for 1 hour, and dispersed to obtain a coating solution for forming a charge generation layer. This coating solution was dip coated on the obtained aluminum substrate and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts of a benzidine compound represented by the above formula (CT-1), 3 parts of a polymer compound having a structural unit represented by the above formula (B-1) (viscosity average molecular weight 39,000) and chlorobenzene 20 parts of the mixture was mixed and dissolved to obtain a charge transport layer forming coating solution. This coating solution was applied onto the charge generation layer by a dip coating method, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm. In this way, the photoreceptor in which the charge generation layer and the charge transport layer were formed on the aluminum base material on which the anodized film was formed was referred to as “base photoreceptor 3”.

(Base photoconductor 4)
First, 100 parts of zinc oxide (SMZ-017N: manufactured by Teika) and 500 parts of toluene were mixed with stirring, and 2 parts of a silane coupling agent (A1100: manufactured by Nihon Unicar) were added and stirred for 5 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the Si element strength was 1.8 × 10 ⁻⁴ of the zinc element strength.

  35 parts of surface-treated zinc oxide, 15 parts of blocked isocyanate (Sumijour 3175, manufactured by Sumitomo Bayern Urethane) as a curing agent, 6 parts of butyral resin (BM-1, manufactured by Sekisui Chemical Co., Ltd.), and 44 parts of methyl ethyl ketone was mixed and dispersed for 2 hours with a sand mill using 1 mmφ glass beads to obtain a dispersion. As a catalyst, 0.005 part of dioctyltin dilaurate and 17 parts of Tospearl 130 (manufactured by GE Toshiba Silicon Corporation) were added to the resulting dispersion to obtain a coating liquid for forming an undercoat layer. This coating solution was applied onto an aluminum substrate (outer diameter 84 mmφ, cylindrical shape) by a dip coating method, followed by drying and curing at 160 ° C. for 100 minutes to form an undercoat layer having a thickness of 20 μm. The surface roughness was measured using a surface roughness profile measuring device Surfcom 570A manufactured by Tokyo Seimitsu Co., Ltd., at a measurement distance of 2.5 mm and a scanning speed of 0.3 mm / sec, and had an Rz value of 0.24.

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and Mix 1 part of hydroxygallium phthalocyanine with a strong diffraction peak at 28.3 °, 1 part of polyvinyl butyral (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate, and paint with glass beads. Dispersion was carried out with a shaker for 1 hour to obtain a coating solution for forming a charge generation layer. This coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts of a benzidine compound represented by the above formula (CT-1), 3 parts of a polymer compound having a structural unit represented by the above formula (B-1) (viscosity average molecular weight 39,000) and chlorobenzene 20 parts of the mixture was mixed and dissolved to obtain a charge transport layer forming coating solution. This coating solution was applied onto the charge generation layer by a dip coating method, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm. In this way, the photoreceptor in which the undercoat layer, the charge generation layer, and the charge transport layer were formed on the aluminum base material was designated as “base photoreceptor 4”.

(Photoreceptor 1)
2 parts of the compound represented by (F-17), 2 parts of methyltrimethoxysilane, 0.5 part of tetramethoxysilane, 0.1 part of colloidal silica and 0.5 part of fluorine graft polymer (ZX007C, manufactured by Fuji Kasei) It was dissolved in a mixed solvent of 5 parts of isopropyl alcohol, 3 parts of tetrahydrofuran and 0.3 part of distilled water. To this solution, 0.5 part of an ion exchange resin (Amberlyst 15E) was added, followed by hydrolysis at room temperature for 24 hours.

  0.1 parts of aluminum trisacetylacetonate (Al (aqaq) 3) and 3,5-di-t-butyl-4-hydroxytoluene are obtained by filtering the ion exchange resin from the reaction mixture after hydrolysis. (BHT) 0.4 part was added and the coating liquid for protective layer formation was obtained. This coating solution is applied onto the charge transport layer of the base photoreceptor 1 by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 170 ° C. for 1 hour to provide a film thickness of about 5 μm. A layer was formed. The obtained photoreceptor is referred to as “Photoreceptor 1”.

(Photoreceptor 2)
A film is formed in the same manner as in the photoreceptor 1 except that the base photoreceptor 3 is used in place of the base photoreceptor 1 and the compound of the above formula (II-1) is used in place of the compound represented by (F-17). A protective layer having a thickness of about 7 μm was formed. The obtained photoreceptor is referred to as “Photoreceptor 2”.

(Photoreceptor 3)
2 parts of the compound represented by (F-17), 2 parts of methyltrimethoxysilane, 0.5 part of tetramethoxysilane, 0.1 part of colloidal silica, 0.5 part of fluorine graft polymer (ZX007C, manufactured by Fuji Kasei) and fluorine 0.2 part of a coupling agent (KBM-7803, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in a mixed solvent of 5 parts of isopropyl alcohol, 3 parts of tetrahydrofuran and 0.3 part of distilled water. To this solution, 0.5 part of an ion exchange resin (Amberlyst 15E) was added, followed by hydrolysis at room temperature for 24 hours.

  0.1 parts of aluminum trisacetylacetonate (Al (aqaq) 3) and 3,5-di-t-butyl-4-hydroxytoluene are obtained by filtering the ion exchange resin from the reaction mixture after hydrolysis. (BHT) 0.4 part was added and the coating liquid for protective layer formation was obtained. This coating solution is applied on the charge transport layer of the base photoreceptor 2 by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 170 ° C. for 1 hour to provide a film thickness of about 5 μm. A layer was formed. The obtained photoreceptor is referred to as “Photoreceptor 3”.

(Photoreceptor 4)
2 parts of the compound represented by (F-17), 2.1 parts of methyltrimethoxysilane, 0.5 part of Me (MeO) ₂ —Si— (CH ₂ ) ₄ —Si—Me (OMe) ₂ , fluorine graft polymer (ZX007C, manufactured by Fuji Kasei) 0.5 part, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) 0.1 part of methyldimethoxysilane, 0.3 part of tetrahydrodecyl) methyldimethoxysilane and butyral resin ( BX-L (product of Sekisui Chemical) was dissolved in a mixed solvent of 5 parts of n-butyl alcohol, 3 parts of tetrahydrofuran and 0.3 part of distilled water. To this solution, 0.5 part of an ion exchange resin (Amberlyst 15E) was added, followed by hydrolysis at room temperature for 24 hours.

  0.1 parts of aluminum trisacetylacetonate (Al (aqaq) 3) and 3,5-di-t-butyl-4-hydroxytoluene are obtained by filtering the ion exchange resin from the reaction mixture after hydrolysis. (BHT) 0.4 part was added and the coating liquid for protective layer formation was obtained. This coating solution is applied on the charge transport layer of the base photoreceptor 4 by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 170 ° C. for 1 hour to protect the film with a thickness of about 5 μm. A layer was formed. The obtained photoreceptor is referred to as “Photoreceptor 4”.

(Photoreceptor 5)
30 parts of a curable acrylic resin represented by the following formula (B-2), 5 parts of a fluorine graft polymer (ZX022H: manufactured by Fuji Kasei) and 5.2 parts of 2-methylthioxanthone as a photopolymerization initiator are dissolved in 50 parts of butanol. Furthermore, 21 parts of a compound represented by the following formula (II-13) as a charge transport material having a hydroxyalkyl group was dissolved to obtain a coating solution for forming a protective layer. This coating solution is dip-coated on the charge transport layer of the base photoreceptor 2 to form a film, followed by photocuring with a high-pressure mercury lamp at a light intensity of 800 mW / cm ² for 60 seconds, and then at 120 ° C. for 2 hours. It dried with hot air and formed the protective layer with a film thickness of 3 micrometers. The obtained photoreceptor is referred to as “Photoreceptor 5”.
_{HOCH 2 -C (CH 2 OCOCH =} CH 2) 3 (B-2)

(Photoreceptor 6)
2 parts of the compound represented by the above formula (II-1), 3 parts of Resist Top PL4852 (manufactured by Gunei Chemical), 0.1 part of a hindered phenol antioxidant (AO-80: manufactured by Asahi Denka), Fluorine graft polymer (ZX007C: manufactured by Fuji Chemical Co., Ltd.) 0.2 part and fluorine coupling agent (KBM-7803: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 part are mixed and dissolved in 10 parts of isopropyl alcohol to form a protective layer. A coating solution was obtained. This coating solution is applied onto the charge transport layer of the base photoreceptor 2 by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 135 ° C. for 1 hour to protect the film with a thickness of about 5 μm. A layer was formed. The obtained photoreceptor is referred to as “photoreceptor 6”.

(Photoreceptor 7)
A protective layer was formed in the same manner as the photoreceptor 6 except that the compound represented by (F-1) was used instead of the compound represented by the formula (II-1). The obtained photoreceptor is referred to as “Photoreceptor 7”.

(Photoreceptor 8)
2.5 parts of the compound represented by the formula (III-3), 3 parts of Shonor BRL-204 (manufactured by Showa Polymer), 0 of hindered phenol antioxidant (AO-80: manufactured by Asahi Denka) .1 part, 0.2 part of fluorine graft polymer (ZX007C: manufactured by Fuji Kasei) and 0.1 part of fluorine coupling agent (KBM-7803: manufactured by Shin-Etsu Chemical) are mixed, 5 parts of isopropyl alcohol, methyl butyl ketone Dissolved in 5 parts, a coating solution for forming a protective layer was obtained. This coating solution is applied onto the charge transport layer of the base photoreceptor 2 by a ring-type dip coating method, air-dried at room temperature for 30 minutes, and then cured by heat treatment at 150 ° C. for 1 hour to provide a film thickness of about 3 μm A layer was formed. The obtained photoreceptor is referred to as “Photoreceptor 8”.

(Photoreceptor 9)
A protective layer was formed in the same manner as in the photoreceptor 8, except that the compound represented by the above formula (III-5) was used instead of the compound represented by the above formula (III-3). The obtained photoreceptor is referred to as “Photoreceptor 9”.

(Photoreceptor 10)
A protective layer was formed in the same manner as in the photoreceptor 8, except that the compound represented by the above formula (IV-9) was used instead of the compound represented by the above formula (III-3). The obtained photoreceptor is referred to as “Photoreceptor 10”.

(Photoreceptor 11)
A protective layer was formed in the same manner as the photoreceptor 8 except that the compound represented by the above formula (V-4) was used instead of the compound represented by the above formula (III-3). The obtained photoreceptor is referred to as “photoreceptor 11”.

(Developer 1)
Developer 1 was produced by first producing a toner and a carrier, and using them. In the following description, the particle size distribution of the toner and composite particles was measured using a multisizer (manufactured by Nikka Kisha Co., Ltd.) with an aperture diameter of 100 μm. Further, the average shape factor ML ² / A of the toner and the composite particles means a value calculated by the following formula. In the case of a true sphere, ML ² / A = 100.
ML ² / A = (maximum length) ² × π × 100 / (area × 4).

  The average shape factor is calculated by taking the toner projection image from an optical microscope into an image analyzer (LUZEX (III), manufactured by Nireco), measuring the equivalent circle diameter, and calculating the maximum length and area of each particle according to the above formula. It can be obtained by fitting.

(Manufacture of toner)
In producing the toner, first, a resin fine particle dispersion, a colorant dispersion, and a release agent dispersion were produced, and toner base particles were produced using them. Next, a toner was manufactured using it.

(Resin fine particle dispersion)
370 parts of styrene, 30 parts of n-butyl acrylate, 8 parts of acrylic acid, 24 parts of dodecanethiol, and 4 parts of carbon tetrabromide were mixed and dissolved. In the solution, 6 parts of nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.), 10 parts of anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and ion exchange The mixture was added to a flask containing 550 parts of water and subjected to emulsion polymerization, and 50 parts of ion-exchanged water having 4 parts of ammonium persulfate dissolved therein was added to the flask while slowly mixing for 10 minutes. After carrying out nitrogen substitution, the inside of the flask was stirred with an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin fine particle dispersion in which resin particles having an average particle size of 150 nm, a Tg of 58 ° C., and a mass average molecular weight (Mw) of 11500 is obtained. The solid content concentration of this dispersion was 40% by mass.

(Colorant dispersion (1))
60 parts of carbon black (Mogal L, manufactured by Cabot), 6 parts of nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 240 parts of ion-exchanged water were mixed and dissolved. The mixture is stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then dispersed with an optimizer to disperse colorant (carbon black) particles having an average particle size of 250 nm. A colorant dispersant (1) was prepared.

(Colorant dispersion (2))
60 parts of a cyan pigment (B15: 3), 5 parts of a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 240 parts of ion-exchanged water were mixed and dissolved. The mixture is stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then dispersed with an optimizer to disperse colorant (cyan pigment) particles having an average particle size of 250 nm. A colorant dispersant (2) was prepared.

(Colorant dispersion (3))
60 parts of magenta pigment (R122), 5 parts of nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 240 parts of ion-exchanged water were mixed and dissolved. The mixture is stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA) and then dispersed with an optimizer to disperse colorant (magenta pigment) particles having an average particle size of 250 nm. A colorant dispersant (3) was prepared.

(Colored dispersion (4))
90 parts of a yellow pigment (Y180), 5 parts of a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 240 parts of ion-exchanged water were mixed and dissolved. The mixture is stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then dispersed with an optimizer to disperse colorant (yellow pigment) particles having an average particle size of 250 nm. A colorant dispersant (4) was prepared.

(Release agent dispersion)
100 parts of paraffin wax (HNP0190, manufactured by Nippon Seiwa Co., Ltd., melting point 85 ° C.), 5 parts of cationic surfactant (Sanisol B50, manufactured by Kao Corporation) and 240 parts of ion-exchanged water are mixed, and round stainless steel Dispersion treatment was carried out for 10 minutes in a steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA). Furthermore, a release agent dispersion liquid was prepared by dispersing the release agent particles having an average particle diameter of 550 nm by dispersing with a pressure discharge type homogenizer.

(Toner mother particle K1)
234 parts of resin fine particle dispersion (obtained at the time of preparation of composite fine particles), 30 parts of colorant dispersion (1), 40 parts of release agent dispersion, polyaluminum hydroxide (Paho2S, manufactured by Asada Chemical Co.) 5 parts and 600 parts of ion-exchanged water were mixed, dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then stirred in the oil bath for heating. Heated to 40 ° C. After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a D50 of 4.5 μm were produced. Furthermore, when the temperature of the oil bath for heating was raised and held at 56 ° C. for 1 hour, D50 was 5.3 μm. Thereafter, 26 parts of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was maintained at 50 ° C. for 30 minutes. After adding 1N sodium hydroxide to the dispersion containing the aggregate particles and adjusting the pH of the system to 7.0, the stainless steel flask is sealed and heated to 80 ° C. while continuing stirring using a magnetic seal. And held for 4 hours. After cooling, the toner base particles were separated by filtration, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K1. The toner base particle K1 had a D50 of 5.9 μm and an average shape factor ML ² / A of 132.

(Toner mother particle C1)
Toner base particles C1 were prepared in the same manner as toner base particles K1, except that the colored particle dispersion liquid (2) was used instead of the colored particle dispersion liquid (1). The toner base particle C1 had a D50 of 5.8 μm and an average shape factor ML ² / A of 131.

(Toner mother particle M1)
Toner base particles M1 were produced in the same manner as toner base particles K1, except that the colored particle dispersion liquid (3) was used instead of the colored particle dispersion liquid (1). The toner base particle M1 had a D50 of 5.5 μm and an average shape factor ML ² / A of 135.

(Toner mother particle Y1)
Toner base particles Y1 were prepared in the same manner as toner base particles K1, except that the colored particle dispersion (4) was used instead of the colored particle dispersion (1). The toner base particle Y1 had a D50 of 5.9 μm and an average shape factor ML ² / A of 130.

  100 parts of each of the toner base particles K1, C1, M1, Y1 is 1 part of rutile type titanium oxide (particle diameter 20 nm, treated with n-decyltrimethoxysilane), silica (particle diameter 40 nm, silicone oil treatment, Gas phase oxidation method) 2 parts, cerium oxide (average particle size 0.7 μm) 1 part, and higher fatty acid alcohol (700 molecular weight higher fatty acid alcohol and zinc stearate are mixed at a weight ratio of 5: 1, jet mill And 0.3 parts) were blended at a peripheral speed of 30 m / s for 15 minutes using a 5 L Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain toner 1.

(Career)
First, 14 parts of toluene, 2 parts of a styrene-methacrylate copolymer (component ratio 90/10) and 0.2 part of carbon black (R330, manufactured by Cabot) were stirred for 10 minutes with a stirrer to disperse the coating solution. Prepared. Next, this coating solution and 100 parts of ferrite particles (average particle size 50 μm) are put in a vacuum degassing type kneader, stirred at 60 ° C. for 30 minutes, and then degassed by depressurization while heating and dried. To get a career. This carrier had a volume resistivity of 10 ¹¹ Ωcm when an applied electric field of 1000 V / cm.

  Next, 100 parts of this carrier was added to 5 parts of the toner obtained above and stirred for 20 minutes at 40 rpm using a V-blender. Thereafter, developer 1 was obtained by sieving with a sieve having an opening of 212 μm.

(Developer 2)
(Toner mother particle K2)
234 parts of resin fine particle dispersion (formed at the time of preparing composite fine particles), 30 parts of colorant dispersion (1), 40 parts of mold release agent dispersion, polyaluminum hydroxide (manufactured by Asada Chemical Co., Paho2S) 0.5 parts and 600 parts of ion-exchanged water were prepared. The above ingredients were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then heated to 40 ° C. while stirring the flask in a heating oil bath. . After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a D50 of 4.5 μm were produced. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and D50 was 5.3 μm. Thereafter, 26 parts of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The dispersion containing the aggregated particles is added with 1N sodium hydroxide to adjust the pH of the system to 5.0, and then the stainless steel flask is sealed and heated to 95 ° C. while stirring with a magnetic seal. And held for 4 hours. After cooling, the toner base particles were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K2. The toner base particle K2 had a D50 of 5.8 μm and an average shape factor ML ² / A of 109.

(Toner mother particle C2)
Toner base particles C2 were obtained in the same manner as K2 except that the colored particle dispersion (2) was used instead of the colored particle dispersion (1). D50 of the toner base particle C2 was 5.7 μm, and the average shape factor ML ² / A was 110.

(Toner mother particle M2)
Toner mother particles M2 were obtained in the same manner as K2 except that the colored particle dispersion (3) was used instead of the colored particle dispersion (1). D50 of the toner mother particles M2 was 5.6 μm, and the average shape factor ML ² / A was 114.

(Toner mother particle Y2)
Toner base particles Y2 were obtained in the same manner as above except that the colored particle dispersion (4) was used instead of the colored particle dispersion (1). D50 of the toner base particle Y2 was 5.8 μm, and the average shape factor ML ² / A was 108.

  Similar to toner 1 except that K2, C2, M2, Y2 are used as toner base particles, and aluminum oxide (average particle size 0.1 μm) is used instead of 1 part of cerium oxide (average particle size 0.7 μm). Toner 2 was produced, and developer 2 was obtained using toner 2 in the same manner as developer 1.

(Developer 3)
100 parts of polyester resin (linear polyester obtained from terephthalic acid-bisphenol A ethylene oxide adduct-cyclohexanedimethanol, Tg: 62 ° C., Mn 12000, Mw: 32000), 4 parts of carbon black, 5 parts of carnauba wax Mixed.

The above mixture was kneaded with an extruder, pulverized with a jet mill, and then classified with an air classifier to obtain toner base particles K3 having an average particle size of 5.9 μm and a shape factor (ML ² / A) of 145.

(Toner mother particle C3)
Toner base particles C3 having an average particle size of 5.6 μm and a shape factor (ML ² / A) of 141 are obtained in the same manner as K3 except that a cyan colorant (CI Pigment Blue 15: 3) is used instead of carbon black. Obtained.

(Toner mother particle M3)
Toner mother particles M3 having an average particle diameter of 5.9 μm and a shape factor (ML ² / A) of 149 were obtained in the same manner as K3 except that magenta colorant (R122) was used instead of carbon black.

(Toner mother particle Y3)
A toner base particle Y3 having an average particle size of 5.8 μm and a shape factor (ML ² / A) of 144 was obtained in the same manner as K3 except that a yellow colorant (Y180) was used instead of carbon black.

  A toner 3 was produced in the same manner as the toner 2 except that K3, C3, M3, and Y3 were used as toner base particles, and a developer 3 was obtained using the toner 3 in the same manner as the developer 2.

(Contact member 1)
A urethane foam (MF-80, manufactured by INOAC) with a thickness of 2 mm, 334 mm x 18 mm can be swelled on a L-shaped aluminum plate with a thickness of 1 mm, 334 mm x 15 mm x 8 mm with double-sided tape at a position of 8 mm in the aluminum plate. Then, a non-woven fabric of ultra-fine fibers (made by Kanebo, Super Multi Cloth using Krauzen fabric, approximately 0.2d) cut into 334 mm x 18 mm is stacked thereon, and fixed with double-sided tape. A contact member 1 having the same configuration as that shown was produced. Further, five 3.3 mm round holes arranged in the direction of the photoreceptor were opened at positions where the nonwoven fabric of the contact member was not provided. When using this contact member, the non-woven fabric of the contact member was attached to the photosensitive member at a linear pressure of 20 g / cm on a metal part of a cleaning blade with five 3 mm screw holes.

(Contact member 2)
A SUS shaft with an outer diameter of 5 mmφ and a length of 333 mm is bonded to a 2 mm thick, 330 mm urethane foam (MF-80, manufactured by INOAC) with double-sided tape, and is further cut into 330 mm x 20 mm nonwoven fabric (Toray Industries, Inc.) The contact member 2 having the same configuration as that shown in FIG. 2 was manufactured by superimposing and pasting a product name “Toraysee” (about 0.2 d). When this contact member was used, the contact member was attached to the image forming apparatus so that the nonwoven fabric contacted the photoconductor with a linear pressure of 15 g / cm and rotated.

(Contact member 3)
Contact member is the same as Contact member 2 except that “Miemie” (trade name, 45% acrylic, 52% polyester, 3% polyurethane, 0.2d) is used instead of “Toraysee”. Produced. This was designated as contact member 3. When this contact member was used, it was attached to the image forming apparatus in the same manner as the contact member 2.

(Contact member 4)
A foamed urethane layer having a thickness of 2 mm was formed on the outer periphery of a SUS rod having a length of 350 mm and a diameter of 5 mmφ, and this was used as a pressing roll. Next, a non-woven fabric of ultrafine fibers (made by Toray, trade name “Toroshi”, about 0.2 d) wound around a supply roll was prepared, and one end of this non-woven fabric was connected to the take-up roll. And the contact member which has the structure similar to what was shown in FIG. 6 by combining these was produced. This was designated as contact member 4. When this contact member was used, it was attached to the image forming apparatus so that the non-woven fabric of ultrafine fibers extending between the supply roll and the take-up roll was pressed against the photoreceptor with a linear pressure of 2 g / cm. The non-woven fabric was wound from the supply roll to the take-up roll at a speed of 1 cm per 1000 rotations of the photoconductor so that the new surface of the non-woven fabric was in contact with the photoconductor.

Example 1

The photoreceptor 1 was installed in a photoreceptor unit of an image forming apparatus (manufactured by Fuji Xerox Co., Ltd., composite printer DocuCenter Color 500CP, equipped with a cleaning blade), and the contact member 1 was further placed in contact with the photoreceptor 1. Then, the developer 1 was used to perform an image formation test on 20,000 sheets in a high temperature and high humidity (28 ° C., 75% RH) environment, and then in a low temperature and low humidity (10 ° C., 20% RH) environment. Ten thousand image formation tests were conducted. Subsequent ghosting of the photoconductor, presence or absence of adhesion to the photoconductor, toner cleaning properties under high temperature and high humidity (28 ° C., 75% RH) environment (charger contamination and image quality deterioration due to poor cleaning), image quality Evaluated. The results obtained are shown in Table 46.
The ghost was determined by printing the chart of the pattern shown in FIG. 17 and determining the appearance of the letter G on the solid black part: ○: good to slight, Δ: slightly conspicuous, ×: clearly visible.
Adhesion was judged visually, ○: no adhesion, Δ: partial adhesion (no problem in terms of image quality), x: adhesion.
The cleaning property was judged by visual observation, and it was assumed that ○: good, Δ: image quality defects such as streaks partially (no problem in image quality), x: extensive image quality defect (image quality problems).
The image quality was judged by visual observation, and “◯” was judged good. Δ: Partially defective (there is a problem in image quality), x: extensively defective (can be easily found visually, there is a problem in image quality).

(Examples 2 to 20 and Comparative Examples 1 to 10)
The photoconductors 1 to 3, the contact members 1 to 4, and the developers 1 to 3 were combined as shown in Table 46, and an image formation test was performed in the same manner as in Example 1 to evaluate the image quality. The results obtained are shown in Table 46. In Comparative Example 10, the base photoconductor 1 was used as the photoconductor.

1 is a schematic diagram showing a preferred embodiment of an image forming apparatus of the present invention. It is explanatory drawing which shows suitable one Embodiment of the contact member which concerns on this invention. It is a schematic sectional drawing of the contact member of the III-III line direction shown by FIG. It is explanatory drawing which shows other suitable embodiment of the contact member which concerns on this invention. It is a schematic sectional drawing of the contact member of the VV line direction shown by FIG. It is explanatory drawing which shows other suitable embodiment of the contact member which concerns on this invention. It is a schematic sectional drawing of the contact member of the VII-VII line direction shown by FIG. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member according to the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member according to the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member according to the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member according to the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member according to the present invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram showing a preferred embodiment of the process cartridge of the present invention. It is the pattern chart used for the judgment standard of the evaluation of the ghost in the evaluation test of an Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photosensitive member, 2 ... Conductive support body, 3 ... Photosensitive layer, 4 ... Undercoat layer, 5 ... Charge generation layer, 6 ... Charge transport layer, 7 ... Protective layer, 8 ... Single layer type photosensitive layer, 21, 22 ... charging device, 24 ... developing device, 27 ... cleaning device, 29,129,229 ... contact member, 30 ... exposure device, 40 ... transfer device, 50,56 ... support, 51 ... continuous surface, 52 elasticity , 54 ... contact part, 55 ... contact member, 58 ... take-up roll, 60 ... supply roll, 62 ... press roll, 100, 110, 120, 130 ... image forming apparatus, 300 ... process cartridge.

Claims (7)

An electrophotographic photosensitive member having a conductive support and a photosensitive layer formed on the conductive support, charging means for charging the electrophotographic photosensitive member, and exposing the charged electrophotographic photosensitive member to electrostatic latent An image forming apparatus comprising: an exposure unit that forms an image; a developing unit that develops the electrostatic latent image with toner to form a toner image; and a transfer unit that transfers the toner image to a transfer medium.
The photosensitive layer has a charge transporting outermost surface layer containing a resin having a crosslinked structure on the side far from the conductive support, and
The image forming apparatus includes a contact member having a continuous surface configured to include a fibrous substance substantially continuously.
The image forming apparatus, wherein the contact member is arranged such that the continuous surface is in contact with the outermost surface layer. The image forming apparatus according to claim 1, wherein a shape of the contact member is a roller shape, a blade shape, or a belt shape. The image forming apparatus further includes a cleaning unit that removes toner remaining on the electrophotographic photosensitive member after the transfer of the toner image,
3. The image forming apparatus according to claim 1, wherein the cleaning unit includes at least one selected from the group consisting of a cleaning blade, a cleaning brush, and a cleaning magnetic brush. The image forming apparatus according to claim 1, wherein the resin having a crosslinked structure is a siloxane-based resin. The image forming apparatus according to claim 1, wherein the outermost surface layer further contains a charge transport material. The outermost surface layer contains a phenol derivative having a methylol group and a charge transport material having at least one selected from a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group and an amino group The image forming apparatus according to claim 1, wherein the image forming apparatus is a layer. The charge transport material includes a compound represented by the following general formula (I), the following general formula (II), the following general formula (III), the following general formula (IV) or the following general formula (V) or a derivative thereof. The image forming apparatus according to claim 5, wherein the image forming apparatus is an image forming apparatus.
F- [D-Si (R ¹ ) _(3-a) Q _a ] _b (I)
[In the formula (I), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group. Alternatively, a substituted or unsubstituted aryl group, Q is a hydrolyzable group, a is an integer of 1 to 3, and b is an integer of 1 to 4. ]
F-[(X ¹ ) _n1 R ² —ZH] _n2 (II)
[In formula (II), F represents an organic group derived from a compound having a hole transporting ability, X ¹ represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z represents an oxygen atom, a sulfur atom, N Or COO, n1 represents 0 or 1, and n2 represents an integer of 1 to 4. In (II), ZH represents a hydroxyl group, a thiol group, an amino group, or a carboxyl group. ]
_{^{F - [(X 2) n3}} - (R 3) n4 - (Z) n5 G] n6 (III)
[In formula (III), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ³ represents an alkylene group, Z represents an oxygen atom, a sulfur atom, NH Or COO, G represents an epoxy group, n3, n4 and n5 each independently represents 0 or 1, and n6 represents an integer of 2 to 4. ]

[In the formula (IV), F represents an n7-valent organic group having a hole transport property, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ are independent of each other. Represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m1 represents 0 or 1, and n7 represents an integer of 1 to 4, respectively. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In the formula (V), F represents an n8-valent organic group having hole transportability, T represents a divalent group, R ⁸ represents a monovalent organic group, m2 represents 0 or 1, and n8 represents 1 Integers of ~ 4 are shown respectively. ]

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