JP5183100B2 - Process cartridge - Google Patents

Description

  The present invention relates to a process cartridge used in an electrophotographic image forming apparatus (hereinafter referred to as “electrophotographic apparatus”) such as a copying machine or a laser beam printer (LBP).

  With recent improvements in the performance of computers and peripheral devices, image forming apparatuses serving as output devices are required to have higher functions year by year. For example, with the trend toward colorization and graphics, output images from electrophotographic devices are required to have higher image quality and faithful reproducibility of input images, and process cartridges have higher image quality and higher durability. It has become increasingly important.

  In response to such a tendency, an electrophotographic photosensitive member (hereinafter simply referred to as “photosensitive member”) has sensitivity, electrical characteristics, mechanical characteristics, and optical characteristics according to the electrophotographic process. Is required. In particular, since electrical and mechanical external forces such as charging, exposure, development, transfer, and cleaning are directly applied to the surface of the photoreceptor to be used repeatedly, durability against them is required. Furthermore, resistance to ozone and nitrogen oxides generated during charging is also required. In particular, in recent years, organic photoreceptors, which have become mainstream from the viewpoint of productivity and durability, often have a relatively low hardness, and as an important factor for improving durability, surface lubricity and The strength of the resin used is mentioned.

  For improving lubricity, a method of adding silicone oil or fluorine-based oil to the surface layer (Patent Document 1), a method using a polycarbonate having a main chain copolymerized with a siloxane chain as a binder resin of the surface layer (Patent Document 2). 3). In addition, a method has been proposed in which a polycarbonate resin in which isopropylidene at the center of bisphenol A is changed to hexafluoroisopropylidene is used as a binder resin (Patent Document 4).

  However, if it is attempted to improve the lubricity of the surface of the photoreceptor by these methods, the mechanical strength of the resin is lowered and the durability may be insufficient, although a difference occurs depending on the amount ratio. there were. In addition, when a silicone oil such as polydimethylsiloxane is added, the residual potential tends to increase remarkably even if a small amount is added, and the coating of the charge transport layer, which is one layer of the photosensitive layer, becomes cloudy. There was also a problem. Due to these problems, there is a drawback that the image quality of the output image is deteriorated, or that a memory image such as a thin density and a ghost is generated due to the sensitivity decrease.

  On the other hand, with respect to the charging member, a DC contact charging method has become widespread as one of methods for charging the surface of the photoreceptor from the viewpoint of downsizing and cost reduction of the charging device. The DC contact charging method is a method in which only a direct current voltage is applied to the charging member to cause a slight discharge in the vicinity of the contact portion between the charging member and the photosensitive member. The charging member is brought into contact with the photosensitive member. By forming a sufficient nip, the surface of the photoreceptor can be uniformly charged.

  The characteristics required for the charging member are that there is almost no bleed-out of low molecular weight components that erode or contaminate the photoreceptor layer of the photoreceptor, and that the contact nip with the photoreceptor is sufficiently and uniformly secured. In addition to having the flexibility described above, there are wear resistance and electrical characteristics. In order to satisfy these required characteristics, conventionally, a charging member having a support, an elastic layer (conductive elastic layer), and a surface layer in this order has been proposed.

  For example, Patent Document 5 discloses a charging member in which an outer layer containing a water-based fluororesin is formed on the surface of an elastic body to prevent uniform charging and toner contamination. Specifically, this technique forms a coating layer made of a polyester resin in which carbon is dispersed on a conductive elastic roller, and further a coating layer made of a water-based fluororesin in which carbon is dispersed thereon. Is the technology to create.

However, if a conductive roller with such a resin layer as the surface layer is repeatedly used for charging, friction and pressure contact with the photoreceptor will occur, resulting in deterioration of the surface layer and uneven charging. And may cause image defects.
JP 2001-255675 A JP-A-6-136108 JP-A-5-72753 JP-A 63-65444 JP-A-9-171285

  The object of the present invention is to solve the above problems, the photoreceptor has electrical characteristics, solvent crack resistance / mechanical strength and high lubricity surface, and the charging member has good slidability with the photoreceptor, It is an object of the present invention to provide a process cartridge that maintains high durability and high image quality for repeated use.

  The present inventors diligently studied to solve the above problems, and finally reached the present invention.

That is, the present invention is a process cartridge that is detachable from an electrophotographic apparatus main body and includes at least a photosensitive member and a charging member that charges the photosensitive member, and the photosensitive member includes a conductive support and a photosensitive layer. and has, and has a repeating structural unit represented by the repeating structural unit represented by the following general formula represented by the following general formula (1) (2), one or both ends represented by the following general formula (3) has a terminal structure, also represented by the general formulas (2) and (3) a polycarbonate polymer relationship average repeating number m and n of the siloxane portion is Ru m = n der in the following chemical formula (4) The charging member has a hydrolyzable silane compound represented by the following formula (5) and a hydrolyzate having an aryl group represented by the following formula (6). Degradable sila The cationically polymerizable group of a condensate having a cationically polymerizable group obtained by hydrolyzing a compound and a hydrolyzable silane compound having a cationically polymerizable group represented by the following formula (7) is cleaved: And having a surface layer having an outermost surface whose contact angle with respect to the polydimethylsiloxane represented by the chemical formula (4) is 10.0 ° or more and 70.0 ° or less. It is a process cartridge characterized by being.

（式（１）中、Ｘは、単結合、−Ｏ−、−Ｓ−又は置換若しくは無置換のアルキリデン基であり、Ｒ¹¹乃至Ｒ¹⁸は、それぞれ独立に、水素原子、ハロゲン原子、アルコキシ基、ニトロ基、置換若しくは無置換のアルキル基又は置換若しくは無置換のアリール基である。また、＊は結合位置を示す。）

(In formula (1), X is a single bond, —O—, —S—, or a substituted or unsubstituted alkylidene group, and R ^{11 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, or an alkoxy group. A nitro group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and * represents a bonding position.)

（式（２）中、Ｒ²¹及びＲ²²は、それぞれ独立に、水素原子、アルキル基又はアリール基であり、Ｒ²³乃至Ｒ²⁶は、それぞれ独立に、水素原子、ハロゲン原子、置換若しくは無置換のアルキル基又はアリール基であり、ａは１乃至３０の整数、ｍは１乃至５００の整数を示す。また、＊は結合位置を示す。）

(In the formula (2), R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group or an aryl group, and R ^{23 to} R ²⁶ are each independently a hydrogen atom, a halogen atom, substituted or unsubstituted. A represents an integer of 1 to 30, m represents an integer of 1 to 500, and * represents a bonding position.)

（式（３）中、Ｒ³¹及びＲ³²は、それぞれ独立に、水素原子、ハロゲン原子、アルコキシ基、ニトロ基、置換若しくは無置換のアルキル基又はアリール基であり、Ｒ³³及びＲ³⁴は、それぞれ独立に、水素原子、アルキル基又はアリール基であり、Ｒ³⁵乃至Ｒ³⁹は、それぞれ独立に、水素原子、ハロゲン原子、置換若しくは無置換のアルキル基又はアリール基であり、ｂは１乃至３０の整数、ｎは１乃至５００の整数を示す。また、＊は結合位置を示す。）

(In formula (3), R ³¹ and R ³² are each independently a hydrogen atom, a halogen atom, an alkoxy group, a nitro group, a substituted or unsubstituted alkyl group or an aryl group, and R ³³ and R ³⁴ are Each independently represents a hydrogen atom, an alkyl group or an aryl group; R ^{35 to} R ³⁹ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or an aryl group; and b represents 1 to 30 And n represents an integer of 1 to 500. * represents a bonding position.)

（式（４）中、ｌは繰り返し単位数の平均値を示す。）

（式（５）中、Ｒ ⁵¹ 及びＲ ⁵² はそれぞれ独立に、置換若しくは無置換のアルキル基であり、Ｚ ⁵¹ は、２価の有機基であり、Ｒｆ ⁵¹ は炭素数１乃至１１のフッ化アルキル基である。ｆは０乃至２の整数、ｇは１乃至３の整数で、かつ、ｆ＋ｇ＝３である。）

（式（６）中、Ｒ ⁶¹ 及びＲ ⁶² はそれぞれ独立に、置換若しくは無置換のアルキル基であり、Ａｒ ⁶¹ は、アリール基である。ｉは０乃至２の整数、ｊは１乃至３の整数で、かつ、ｉ＋ｊ＝３である。）

（式（７）中、Ｒ ⁷¹ 及びＲ ⁷² はそれぞれ独立に、置換若しくは無置換のアルキル基であり、Ｚ ⁷¹ は、２価の有機基であり、Ｒｃ ⁷¹ は、カチオン重合可能な基である。ｄは０乃至２の整数、ｅは１乃至３の整数で、かつ、ｄ＋ｅ＝３である。）

(In formula (4), l represents the average number of repeating units.)

(In the formula (5), R ⁵¹ and R ⁵² are each independently a substituted or unsubstituted alkyl group, Z ⁵¹ is a divalent organic group, and Rf ⁵¹ is a fluorinated C 1-11 carbon atom. An alkyl group, f is an integer of 0 to 2, g is an integer of 1 to 3, and f + g = 3.)

(In Formula (6), R ⁶¹ and R ⁶² are each independently a substituted or unsubstituted alkyl group, Ar ⁶¹ is an aryl group, i is an integer of 0 to 2, j is 1 to 3) (It is an integer and i + j = 3.)

(In formula (7), R ⁷¹ and R ⁷² are each independently a substituted or unsubstituted alkyl group, Z ⁷¹ is a divalent organic group, and Rc ⁷¹ is a cationically polymerizable group. D is an integer from 0 to 2, e is an integer from 1 to 3, and d + e = 3.)

  According to the present invention, there is provided a photosensitive member having a highly lubricious surface without impairing electrical characteristics, solvent crack resistance and mechanical strength, and a charging member having a surface layer having a low affinity for the photosensitive member. When used in combination, the slidability between the photosensitive member and the charging member is improved. As a result, a process cartridge that maintains high durability and high image quality even when used repeatedly can be provided.

  As described above, in the process cartridge of the present invention, the photosensitive member has a photosensitive layer on a conductive support. Further, the outermost surface layer of the photosensitive layer has a repeating structural unit of the general formula (1) and a repeating structural unit of the general formula (2), and at least one of the terminals has a terminal structure of the general formula (3). It contains a polycarbonate polymer and polydimethylsiloxane of the chemical formula (4). The relationship between the average number of repetitions m and n of the siloxane moiety in the general formulas (2) and (3) is m = n. The charging member is characterized in that the contact angle X of the polydimethylsiloxane of the chemical formula (4) used for the photosensitive layer on the surface thereof is 10.0 ° or more and 70.0 ° or less.

（式（１）中、Ｘは、単結合、−Ｏ−、−Ｓ−又は置換若しくは無置換のアルキリデン基であり、Ｒ¹¹乃至Ｒ¹⁸は、それぞれ独立に、水素原子、ハロゲン原子、アルコキシ基、ニトロ基、置換若しくは無置換のアルキル基又は置換若しくは無置換のアリール基である。また、＊は結合位置を示す。）

(In formula (1), X is a single bond, —O—, —S—, or a substituted or unsubstituted alkylidene group, and R ^{11 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, or an alkoxy group. A nitro group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and * represents a bonding position.)

（式（２）中、Ｒ²¹及びＲ²²は、それぞれ独立に、水素原子、アルキル基又はアリール基であり、Ｒ²³乃至Ｒ²⁶は、それぞれ独立に、水素原子、ハロゲン原子、置換若しくは無置換のアルキル基又はアリール基であり、ａは１乃至３０の整数、ｍは１乃至５００の整数を示す。また、＊は結合位置を示す。）

(In the formula (2), R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group or an aryl group, and R ^{23 to} R ²⁶ are each independently a hydrogen atom, a halogen atom, substituted or unsubstituted. A represents an integer of 1 to 30, m represents an integer of 1 to 500, and * represents a bonding position.)

（式（３）中、Ｒ³¹及びＲ³²は、それぞれ独立に、水素原子、ハロゲン原子、アルコキシ基、ニトロ基、置換若しくは無置換のアルキル基又はアリール基であり、Ｒ³³及びＲ³⁴は、それぞれ独立に、水素原子、アルキル基又はアリール基であり、Ｒ³⁵乃至Ｒ³⁹は、それぞれ独立に、水素原子、ハロゲン原子、置換若しくは無置換のアルキル基又はアリール基であり、ｂは１乃至３０の整数、ｎは１乃至５００の整数を示す。また、＊は結合位置を示す。）

(In formula (3), R ³¹ and R ³² are each independently a hydrogen atom, a halogen atom, an alkoxy group, a nitro group, a substituted or unsubstituted alkyl group or an aryl group, and R ³³ and R ³⁴ are Each independently represents a hydrogen atom, an alkyl group or an aryl group; R ^{35 to} R ³⁹ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or an aryl group; and b represents 1 to 30 And n represents an integer of 1 to 500. * represents a bonding position.)

（式（４）中、ｌは繰り返し単位数の平均値を示す。）

(In formula (4), l represents the average number of repeating units.)

  Hereinafter, embodiments of the present invention will be described in detail.

[1] Process Cartridge First, an electrophotographic apparatus provided with the process cartridge of the present invention will be described. FIG. 1 is a schematic configuration diagram of an example of the electrophotographic apparatus.

  Reference numeral 1 denotes a rotating drum type photoreceptor as an image carrier. The photoreceptor 1 is driven to rotate at a predetermined peripheral speed (process speed) in the direction of the arrow about the shaft 2. Process speed is variable. In this figure, a photoreceptor 1 is a photoreceptor having a roll-shaped conductive support and a photosensitive layer comprising a charge generation layer and a charge transport layer on the support. The photoreceptor 1 may further include a charge injection layer for charging the surface of the photoreceptor to a predetermined polarity and potential. Note that the photoreceptor, which is an important component in the present invention, will be described later.

  Reference numeral 3 denotes a charging member. The charging member 3 generally has a roller shape (hereinafter, this roller-shaped charging member is particularly referred to as a “charging roller”). A charging unit is configured by the charging roller 3 and a charging bias application power source (not shown) that applies a charging bias to the charging roller 3. A voltage is applied to the charging member from the charging bias application power source only with a DC voltage or with an AC voltage superimposed on the DC voltage. It is preferable to use the process cartridge of the present invention in an electrophotographic apparatus having a voltage applying means for applying only a DC voltage as the charging member. The charging roller 3 is brought into contact with the photosensitive member 1 with a predetermined pressing force, and is driven to rotate in the forward direction with respect to the rotation of the photosensitive member 1 in this example. By applying a DC voltage (for example, −1000 V) from the charging bias application power source to the charging roller 3, the surface of the photoreceptor 1 is uniformly charged to a polar potential (for example, a dark portion potential of −500 V). . The charging member will also be described later.

  Reference numeral 4 denotes exposure light (image exposure light). Slit exposure and laser beam scanning exposure output from an exposure means (not shown) correspond to the exposure light 4. When exposure light 4 is irradiated onto the charging surface of the photosensitive member 1, the potential of the exposed bright portion of the photosensitive member charging surface is selectively lowered (attenuated) according to the target image (for example, the bright portion potential is -150V). An electrostatic latent image is formed on the surface of the photoreceptor 1.

  Reference numeral 5 denotes developing means. As the developing means 5, a known means can be used. For example, the developing means 5 in this figure regulates the developer container that contains toner, the toner carrier that is disposed in the opening of the toner container and carries the toner, and the amount of toner carried on the toner carrier surface (toner layer thickness). And a toner regulating member (not shown). The developing means 5 selectively attaches toner (negative toner) charged to the same polarity as the charged polarity of the photosensitive member 1 to the exposed bright portion of the electrostatic latent image on the surface of the photosensitive member 1 to form an electrostatic latent image. Visualize (develop) toner image. In the drawing, a voltage is applied to the toner carrier so that the developing bias potential is −350V. Examples of the development of the electrostatic latent image on the surface of the photoreceptor 1 include a jumping development method, a contact development method, and a magnetic brush method. The contact development method is preferable from the viewpoint of improving toner scattering properties. As the toner carrier, it is desirable to use an elastic material such as rubber from the viewpoint of ensuring contact stability. For example, a developing roller provided with an elastic layer imparted with conductivity on a conductive support such as metal can be exemplified. In the developing roller, a foam obtained by foaming an elastic material may be used as the elastic layer. Further, a surface layer may be provided thereon or surface treatment may be performed. Examples of the surface treatment include a surface treatment using UV and an electron beam, and a surface modification treatment for attaching and impregnating a compound or the like on the surface.

  Reference numeral 6 denotes transfer means, which shows a transfer roller in this drawing. As the transfer roller 6, a known means can be used. For example, a transfer roller formed by coating an elastic resin layer adjusted to a medium resistance on a conductive support such as metal can be exemplified. The transfer roller 6 is in contact with the photosensitive member 1 with a predetermined pressing force so that a transfer nip portion is formed, and the circumferential speed is approximately the same as the rotational peripheral speed of the photosensitive member 1 in the forward direction with the rotation of the photosensitive member 1. Rotate with. In addition, a transfer voltage having a polarity opposite to the charging characteristics of the toner is applied to the transfer roller from a transfer bias application power source (not shown). A transfer material (paper or the like) P is fed from a transfer material supply means (not shown) between the photoconductor 1 and the transfer roller 6 (transfer nip portion) in synchronization with the rotation of the photoconductor 1. The back surface of the transfer material P is charged by a transfer roller 6 to which a transfer voltage is applied, so that the toner image carried on the surface of the photoreceptor 1 at the transfer nip portion is transferred to the transfer material. Electrostatic transfer to the surface of P.

  The transfer material P that has received the transfer of the toner image is separated from the photoreceptor 1 and introduced into the toner fixing means 8 where the image is fixed and discharged out of the apparatus as an image formed product (print, copy). In the case of the double-sided image forming mode or the multiple image forming mode, this image formed product is introduced into a recirculation conveyance mechanism (not shown) and reintroduced into the transfer nip portion.

  After the toner image is transferred, the photosensitive member 1 is cleaned by a cleaning means (cleaning blade or the like) 7 to remove the transfer residual developer (toner). The photoreceptor 1 is repeatedly used for image formation after being subjected to charge removal processing by pre-exposure from a pre-exposure unit (not shown) as required. When the charging unit is a contact charging unit as shown in the figure, pre-exposure is not always necessary.

  In this figure, the photosensitive member 1, the charging member (charging roller) 3, the developing means 5 and the cleaning means 7 are integrated into a process cartridge 9, which can be attached to and detached from the electrophotographic apparatus main body by a guide rail 10. It has become. However, in the process cartridge of the present invention, as long as the photosensitive member 1 and the charging member 3 are configured as described in detail below, it is not necessary to be integrated with the constituent means other than the photosensitive member 1 and the charging member 3.

[2] Photoreceptor The photoreceptor used in the present invention is a photoreceptor having a photosensitive layer on a conductive support. The outermost surface layer of the photosensitive layer contains the above-described polycarbonate polymer having a siloxane portion and polydimethylsiloxane represented by the chemical formula (4). In the polycarbonate polymer, the relationship between the average repeating number m and n of the siloxane part in the repeating structural unit of the general formula (2) and the terminal structure of the general formula (3) is m = n.

  The reason why the photoreceptor containing the polycarbonate polymer in the outermost surface layer of the photosensitive layer exhibits extremely high lubricity, and also has solvent crack resistance and good electrophotographic characteristics will be described.

  This polycarbonate polymer has a terminal structure having a polysiloxane portion at at least one end of the polycarbonate main chain, and the main chain also has a siloxane portion. Therefore, by having the polysiloxane part at the terminal, the degree of freedom of the siloxane part is increased, and the siloxane part is more locally disposed near the surface. For this reason, it seems to show very high initial lubricity. At this time, when the chain length of the siloxane part is larger, it is effective for improving the lubricity of the surface, and when the number of repeating units n of the siloxane part in the general formula (2) and the general formula (3) is 10 or more, Particularly high lubricity. In this case, the contact angle of the surface with pure water is as extremely high as 100 ° or more. This works effectively to avoid troubles such as blade reversal and blade squeezing that are most likely to occur in the initial stage of use, and is particularly effective even in the most severe high humidity environments.

  Further, since the siloxane chain is also present in the main chain, there is an effect of relieving internal stress, which is strain when the polycarbonate polymer itself becomes a cast film. And even if chemicals penetrate into the photosensitive layer to some extent, solvent cracks are unlikely to occur.

  The siloxane part in the polycarbonate polymer is derived from polyalkylsiloxane, polyarylsiloxane, polyalkylarylsiloxane or the like. Specific examples include a dimethylsiloxane chain, a diethylsiloxane chain, a diphenylsiloxane chain, and a methylphenylsiloxane chain. Two or more of these may be mixed. The length of the siloxane part is represented by m and n, which are the average number of repetitions in general formula (2) and general formula (3), and m and n are 1 to 500, preferably 10 to 100. . In order to obtain sufficient lubricity, it is preferable that it is large to some extent. However, when m and n exceed 500, the properties of polysiloxane are stronger than polycarbonate polymer, which is not practical.

  It is desirable that the average repeating numbers m and n are the same, and in the present invention, the transparency of the coating of the charge transport layer is greatly increased, which is preferable from the viewpoint of the optical properties of the coating. When the siloxane portion has such an average number of repetitions, the effect of suppressing the generation of memory images such as high sensitivity and ghost at a low residual potential is also seen.

  Furthermore, when the polycarbonate polymer and the polydimethylsiloxane represented by the chemical formula (4) are mixed and used, even higher initial slip properties are exhibited without deterioration of characteristics.

  The mixing ratio of the polydimethylsiloxane represented by the chemical formula (4) is preferably 5% by mass or more and 20% by mass or less with respect to the polycarbonate polymer, and the total content of these two types is the maximum. 0.1 mass% or more and 5.0 mass% or less are preferable with respect to the total solid of a surface layer. When the mixing ratio is 5% by mass or more and 20% by mass or less, a very high slip property is exhibited particularly in the initial stage when the photosensitive member is used due to a synergistic effect with the polycarbonate polymer. When the total content of these two types is 0.1% by mass or more and 5.0% by mass or less with respect to the total solid content of the outermost surface layer, even if polydimethylsiloxane is contained, the coating becomes clouded. This prevents the deterioration of electrophotographic characteristics such as increase in residual power and decrease in sensitivity. In addition, the average repeating number l of the siloxane moiety in the chemical formula (4) is preferably 10 to 100. When the amount exceeds 100, even when added in a small amount, the coating layer tends to become cloudy when formed into a photosensitive layer, which may be undesirable from the optical characteristics of the coating layer. If the average repeating numbers m, n, and l of these components are the same, it is useful for preventing deterioration of electrophotographic characteristics such as prevention of clouding of the coating, increase in residual power, and decrease in sensitivity.

  Even if polydimethylsiloxane is added alone, the high slipperiness as in the photoconductor according to the present invention is not exhibited, and even if a small amount is added, the residual potential is remarkably increased and the coating becomes cloudy. Therefore, from the viewpoint of the optical characteristics of the film, the image quality is deteriorated, and a memory phenomenon such as low density and ghost due to a decrease in sensitivity occurs. However, when used in the above-mentioned mixing ratio with the above polycarbonate polymer and added to the outermost surface layer in the above proportion, such a problem does not occur, and a memory image such as a ghost due to high sensitivity and durability at a low residual potential. The occurrence of was also not seen. Here, it is preferable that the average number of repetitions of m, n, and l is the same in the state of a mixture with polydimethylsiloxane as well as the polycarbonate polymer for the reason described above.

  The average number of repetitions of the polycarbonate polymer and polydimethylsiloxane can be measured by, for example, a time-of-flight mass spectrometer “MALDI-TOF-MS” manufactured by BRUKER. In this specification, “the average number of repetitions is the same” means that it is within a range of ± 3 in consideration of measurement error. Therefore, “m = n” represents “m = n ± 3”.

  Below, the said polycarbonate polymer is obtained as follows. That is, a resin constituent material forming a repeating structural unit represented by the general formula (1), a siloxane compound forming a repeating structural unit represented by the general formula (2), and a terminal structure represented by the general formula (3) are formed. It is produced by mixing a siloxane compound and forming a carbonic ester.

  Specific examples of the resin constituent material (hereinafter also referred to as “bisphenol compound”) forming the repeating structural unit represented by the general formula (1) are shown in Tables 1 and 2. In addition, these are illustrations and are not limited to these.

  Next, Table 3 shows specific examples of the siloxane compound forming the structural unit represented by the general formula (2) (hereinafter also referred to as “siloxane compound 1”). In the table, m is the average number of repeating siloxane chains and is 1 to 500. Moreover, these are illustrations and are not limited to these.

The compound (2-1), the compound (2-2), the compound (2-5), and the compound in which the average number of repetitions a in the general formula (2) is 3 or less and all of R ^{23 to} R ²⁶ are methyl groups (2-6) and compound (2-8) are preferable, and compound (2-1) is particularly preferable.

  Next, Table 4 shows specific examples of the siloxane compound (hereinafter also referred to as “siloxane compound 2”) that forms the terminal structure represented by the general formula (3). In the table, n is the average number of repeating siloxane chains and is 1 to 500. Moreover, these are illustrations and are not limited to these.

The compound (3-1), the compound (3-2) and the compound (3-3) in which the average number of repetitions b in the general formula (3) is 3 or less and all of R ^{33 to} R ³⁹ are methyl groups are preferable. In particular, the compound (3-1) is preferable.

  In addition, it is preferable that the total amount of the siloxane part in the said polycarbonate polymer is 10 mass% or more and 60 mass% or less. In addition, the siloxane part in this invention refers to the repeating part of a Si-O bond, and also includes the substituent directly couple | bonded with Si. If the total amount of siloxane parts is less than 10% by mass, it is difficult to exhibit high lubricity unless the ratio of addition to the charge transport layer is increased, and it may be difficult to achieve both durability. On the other hand, when the amount is more than 60% by mass, the production is difficult, and the transparency and electrophotographic characteristics of the film may be hindered. Here, the total amount of the siloxane part means that the total mass (total) of the siloxane part in the repeating structural unit of the general formula (2) and the siloxane part in the terminal structure of the general formula (3) is the whole polymer. The percentage of the mass is expressed in mass%.

  In addition, the polycarbonate polymer preferably has a viscosity average molecular weight (Mv) of 5,000 or more and 200,000 or less, particularly preferably 10,000 or more and 100,000 or less. In the synthesis, in order to adjust the molecular weight, in addition to the monofunctional siloxane compound, another monofunctional compound may be used as a terminal terminator. Examples of such a terminator include compounds usually used in producing a polycarbonate such as phenol, p-cumylphenol, pt-butylphenol, benzoic acid, and benzyl chloride.

  The polycarbonate polymer has excellent lubricity and excellent strength, but is preferably mixed with a resin having higher strength. The mixing ratio is preferably 1 part by mass or more and 99 parts by mass or less for the other resin with respect to 0.5 part by mass of the polycarbonate polymer according to the present invention. Since the polycarbonate polymer according to the present invention tends to concentrate near the surface of the photosensitive layer, it exhibits high lubricity even with a small blend ratio.

  In addition, when a polycarbonate polymer is produced using only a monofunctional siloxane compound without adding a bifunctional siloxane compound at the time of synthesis, the main chain does not have a siloxane chain, and either one or both ends have a siloxane chain. An end-capped polycarbonate polymer is obtained. This polycarbonate polymer may be used in combination with a polycarbonate polymer having a siloxane chain at both the main chain and the terminal according to the present invention.

  Next, the structure of the photoreceptor used in the present invention will be described.

  The surface layer of the photoreceptor, that is, the outermost surface layer of the photosensitive layer is the photosensitive layer itself when the photosensitive layer is a single layer type containing the charge transport material and the charge generation material in the same layer, and contains the charge transport material. The charge transport layer is a two-layer laminate type of a charge transport layer and a charge generation layer containing a charge generation material. Furthermore, when a protective layer is provided on the charge transport layer, the surface layer of the photoreceptor is a protective layer. The protective layer may contain conductive particles such as a conductive metal oxide. In the present invention, a laminate type is preferable from the viewpoint of electrophotographic characteristics.

  Hereinafter, the structure of the laminated type photoreceptor will be described.

  The conductive support of the photosensitive member has at least a surface of conductivity and has rigidity to withstand contact charging. That is, a cylindrical shape made of a metal or alloy such as aluminum, nickel, copper, gold, or iron is suitable. In addition, the surface of an insulating material such as polyester, polycarbonate, polyimide, glass, etc., where a conductive thin film is formed of a metal such as aluminum, silver, or gold, indium oxide, tin oxide, etc., carbon or conductive filler is contained in the resin. A material made of a dispersed conductive resin can also be used. A metal such as aluminum is preferable in view of mechanical strength, ease of manufacture, and the like.

  The surface of the conductive support is subjected to electrochemical treatment such as anodic oxidation to improve electrical characteristics or adhesion, or an acidic solution mainly composed of an alkaline phosphate aqueous solution, phosphoric acid or tannic acid. Chemical treatment may be performed in a solution in which a metal salt of a fluorine compound is dissolved in an aqueous solution.

  In addition, when the present photoreceptor is used in a printer using a single wavelength laser beam, it is preferable that the surface of the conductive support is appropriately roughened in order to suppress interference fringes. Specifically, the support surface is a support subjected to a treatment such as honing, blasting, cutting, and electric field polishing. In addition, a support made of aluminum or an aluminum alloy and having a conductive film made of a conductive metal oxide and a binder resin on its surface can also be used.

  As the honing treatment, there are a dry method and a wet method. The wet method honing treatment is a method in which a powdery abrasive is suspended in a liquid such as water and sprayed onto the surface of the support substrate at a high speed to roughen the surface. The surface roughness is the spray pressure, speed, and amount of abrasive. It can be controlled by the type, shape, size, hardness, specific gravity, suspension temperature and the like. Similarly, the dry method honing treatment is a method in which an abrasive is blown onto the surface of the conductive support at high speed with air, and the surface roughness can be controlled in the same manner as the wet honing treatment. . As an abrasive | polishing agent used for these honing processes, particles, such as a silicon carbide, an alumina, iron, a glass bead, are mentioned.

  A conductive layer may be provided between the support and the charge generation layer or an intermediate layer to be described later for the purpose of preventing interference fringes due to scattering of laser light or the like and covering the scratches on the support.

  The conductive layer can be formed by dispersing conductive particles such as carbon black, metal particles, and metal oxide particles in a binder resin. Suitable metal oxide particles include zinc oxide and titanium oxide particles. Moreover, the electroconductive particle may be coat | covered.

  The volume resistivity of the conductive particles is preferably 0.1 Ω · cm to 1000.0 Ω · cm, and more preferably 1 Ω · cm to 1000 Ω · cm. The average particle size of the conductive particles is preferably 0.05 μm or more and 1.00 μm or less, and more preferably 0.07 μm or more and 0.70 μm or less. The ratio of the conductive particles in the conductive layer is preferably 1.0% by mass or more and 90% by mass or less, and more preferably 5.0% by mass or more and 80.0% by mass or less with respect to the total mass of the conductive layer. The volume resistivity of the powder is a value measured using a resistance measuring device “Loresta AP” (trade name, manufactured by Mitsubishi Chemical Corporation) using a measurement sample that is hardened at a pressure of 49 MPa to form a coin. It is. The average particle diameter is a value measured by a centrifugal sedimentation method.

  Examples of the binder resin used for the conductive layer include phenol resin, polyurethane resin, polyamide resin, polyimide resin, polyamideimide resin, polyamide resin, polyvinyl acetal resin, epoxy resin, acrylic resin, melamine resin, and polyester resin. . These are independent and can be used by 2 or more types as a mixture or a copolymer. These binder resins have good adhesion to the support, improve the dispersibility of the conductive particles, and have good solvent resistance after film formation. Among these, a phenol resin, a polyurethane resin, and a polyamide resin are preferable. The thickness of the conductive layer is preferably 0.1 μm or more and 30.0 μm or less, and more preferably 0.5 μm or more and 20.0 μm or less.

The volume resistivity of the conductive layer is preferably 10 ¹³ Ω · cm or less, and more preferably 10 ⁵ Ω · cm or more and 10 ¹² Ω · cm or less. The volume resistivity of the conductive layer is determined by forming a film on the aluminum plate with the same material used for forming the conductive layer to be measured, forming a gold thin film on the film, This is a value obtained by measuring a current value flowing between both electrodes of the thin film with a pA meter.

  Further, the conductive layer may contain fluorine or antimony as necessary, and a leveling agent may be added to improve the surface properties of the conductive layer.

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

  The intermediate layer is acrylic resin, allyl resin, alkyd resin, ethyl cellulose resin, ethylene-acrylic acid copolymer, epoxy resin, casein resin, silicone resin, gelatin resin, phenol resin, butyral resin, polyacrylate resin, polyacetal resin, polyamideimide resin , Polyamide resin, polyallyl ether resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyvinyl alcohol resin, polybutadiene resin, polypropylene resin, urea resin, aluminum oxide, etc. It can be formed using the material.

  The film thickness of the intermediate layer is preferably 0.05 μm or more and 5.00 μm or less, and more preferably 0.30 μm or more and 3.00 μm or less.

  In the case of a laminated type photoreceptor, a charge generation layer is formed on a support, a conductive layer or an intermediate layer. The charge generation layer can be formed by applying and drying a dispersion in which a charge generation material is well dispersed in a solvent together with a binder resin of 0.3 to 4 times by mass. For dispersion, a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor, roll mill, liquid collision type high-speed disperser, or the like can be used.

  As the charge generation material, selenium-tellurium, pyrylium, thiapyrylium dyes, phthalocyanine, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine pigments can be used. Among various charge generation materials, phthalocyanine pigments have been widely used in recent years because of their high sensitivity.

  Representative phthalocyanine pigments include oxytitanium phthalocyanine, chlorogallium phthalocyanine, dichlorotin phthalocyanine, hydroxygallium phthalocyanine, and the like.

  Examples of the binder resin used for the charge generation layer include acrylic resin, allyl resin, alkyd resin, epoxy resin, diallyl phthalate resin, silicone resin, styrene-butadiene copolymer, cellulose resin, phenol resin, butyral resin, benzal resin, Melamine resin, polyacrylate resin, polyacetal resin, polyamideimide resin, polyamide resin, polyallyl ether resin, polyarylate resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyvinyl acetal resin , Polyvinyl methacrylate resin, polyvinyl acrylate resin, polybutadiene resin, polypropylene resin, methacrylic resin, urea resin, vinyl chloride - vinyl acetate copolymer, vinyl acetate resins, vinyl chloride resins. In particular, a butyral resin is preferred. These are independent and can use 2 or more types as a mixture or a copolymer.

  The solvent used in the coating solution for the charge generation layer is selected from the solubility and dispersion stability of the binder resin and charge generation material used. Preferred organic solvents include alcohols, sulfoxides, ketones, ethers, esters, aliphatic halogenated hydrocarbons, aromatic compounds and the like.

  The thickness of the charge generation layer is preferably 5 μm or less, more preferably 0.01 μm or more and 2.00 μm or less, and even more preferably 0.05 μm or more and 0.30 μm or less.

  In addition, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers, electron transport agents, and the like can be added to the charge generation layer as necessary.

  A charge transport layer is formed on the charge generation layer. The charge transport layer contains a charge transport material. As the charge transport material, for example, triarylamine compounds, hydrazone compounds, styryl compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, triarylmethane compounds, and the like can be used. These charge transport materials may be only one type or two or more types. In the present invention, when the charge transport layer is the outermost surface layer, it is essential to contain at least the polycarbonate polymer having the siloxane portion and the polydimethylsiloxane represented by the chemical formula (4). Furthermore, the charge generation layer can be formed by blending another binder resin as necessary, applying a solution dissolved using an appropriate solvent, and drying. The drying temperature is more preferably 100 ° C. or higher because the polycarbonate polymer or polydimethylsiloxane is easily transferred to the surface and exhibits higher lubricity.

  Examples of the binder resin to be blended include acrylic resin, acrylonitrile resin, allyl resin, alkyd resin, epoxy resin, silicone resin, phenol resin, phenoxy resin, butyral resin, polyacrylamide resin, polyacetal resin, polyamideimide resin, polyamide resin, Polyallyl ether resin, polyarylate resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, polystyrene resin, polysulfone resin, polyvinyl butyral resin, polyphenylene oxide resin, polybutadiene resin, polypropylene resin, methacrylic resin, Urea resin, vinyl chloride resin, and vinyl acetate resin can be used. In particular, a polyarylate resin and a polycarbonate resin are preferable from the viewpoint of compatibility with the polycarbonate polymer according to the present invention, electrophotographic characteristics, and durability improvement. These are independent and can use 2 or more types as a mixture or a copolymer.

  The charge transport material and the binder resin are preferably used in a mass ratio of 2: 1 to 1: 2. The thickness of the charge transport layer is preferably 5 μm or more and 50 μm or less, and more preferably 7 μm or more and 30 μm or less.

  The charge transport layer may contain an antioxidant, an ultraviolet absorber, a plasticizer, a surfactant such as fluorine oil, a filler such as fluororesin powder, and an additive such as a fluorine atom-containing compound.

  In the case where the photosensitive layer is a single layer type, a solution in which the charge generation material or charge transport material as described above is dispersed in a binder resin together with the polycarbonate polymer having the siloxane portion and the polysiloxane represented by the chemical formula (4). The photosensitive layer can be formed by coating and drying. In that case, the film thickness of the photosensitive layer is preferably 5 μm or more and 40 μm or less, and more preferably 15 μm or more and 30 μm or less.

  When applying the coating liquid for each of the above layers, for example, a coating method such as a dip coating method (dip coating method), a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method, a blade coating method, or the like should be used. The liquid viscosity at the time of coating that can be applied is preferably 1 mPa · s or more and 500 mPa · s or less in view of coating properties.

[3] Charging member What characteristics should be imparted to the charging member used in contact with the photosensitive member having good lubricity as described above is effective in further improving the slidability? The present inventors examined. As a result, the lower the affinity of the outermost surface of the charging member with respect to the photoreceptor that is presumed to contain much polydimethylsiloxane represented by the chemical formula (4) on the outermost surface as in this example, the adhesion force And the frictional force is suppressed, and it has been found that it is effective for further improving the slidability.

  That is, when the contact angle X of the polydimethylsiloxane represented by the chemical formula (4) on the outermost surface of the charging member is 10.0 ° or more and 70.0 ° or less, very good slidability is exhibited and repeated. It was found that high durability and high image quality can be maintained without wear even when used. When the outermost surface of the charging member realizes the contact angle X as described above, the number ratio Y of fluorine atoms contained per unit area of the outermost surface of the charging member is 5.00% or more and 40.00%. I also found that:

  In addition, when X is less than 10.0 °, the affinity at the contact portion between the charging member and the photosensitive member is increased, and the adhesion force and the frictional force are increased, thereby achieving the desired high durability and high image quality. The required slidability between the photosensitive member and the charging member becomes insufficient. When X is greater than 70.0 °, the number ratio Y of fluorine atoms to the total number of atoms contained per unit area of the outermost surface of the charging member is greater than 40.00%. As a result, the dynamic friction coefficient on the surface of the charging member becomes too large, and it is difficult to obtain good slidability with the photoreceptor. More preferable X is 20.0 ° or more and 50.0 ° or less.

  The contact angle X was measured as follows using a contact angle measuring device “contact angle meter CA-X ROLL type” (trade name, manufactured by Kyowa Interface Co., Ltd.).

  First, polydimethylsiloxane “DMS-T21-100GM” (trade name, manufactured by GELEST) whose structure is represented by the chemical formula (4) was placed in a syringe and attached to a contact angle meter. The charging member was set on the sample stage while being careful not to touch the tip of the syringe. In addition, when the charging member was a charging roll, it was performed while visually confirming that the tip of the syringe was at the top of the roll. Thereafter, a polydimethylsiloxane droplet was extruded from the syringe and deposited on the charging member. Then, as shown in FIG. 3, the droplet 103b landed on the charging member surface 103a, and the angle θ between the droplet 103b and the charging member surface 103a was measured. This measurement was performed at any nine locations on the surface of the charging member, and the average value was taken as the contact angle X of the charging member. In the charging roller, the measurement was performed at a total of nine points: arbitrary three points in the circumferential direction and arbitrary three points in the longitudinal direction.

[Detailed contact angle measurement conditions]
Measurement: Droplet method (perfect circle fitting)
Liquid volume: 1 μl
Droplet recognition: Automatic Image processing: Algorithm-Non-reflective Image mode: Frame Threshold level: Automatic

  The number ratio Y of fluorine atoms was measured as follows using an X-ray photoelectron spectrometer (ESCA) “Quantum 2000” (trade name, manufactured by ULVAC-PHI). First, an arbitrary 10 locations on the surface of the charging member were selected, and a sample was collected by razor in a square shape of 2 mm in the depth direction and 5 mm square on the surface from the surface of the charging member. The sample was placed on the platen so that the surface layer side of the sample was irradiated with X-rays, and secured by restraining a part of the sample with an aluminum cover to ensure conduction. The average value of atom% of 10 fluorine atoms (F) quantitatively analyzed under the following conditions was defined as Y.

[Detailed measurement conditions for F atom atom%]
X-ray: Monochrome Al Kα ray 25W / 15kV
Measurement area: Point φ100μm
Pass energy: 58.70eV
Step width: 0.125 eV
Analysis designated elements (Sweep times): F1s (5 times), Zn2p3 (5 times), S2p (10 times), N1s (10 times), Si2p (5 times), O1s (5 times), C1s (5 times), Ca2p (5 times) (measured in this order)
Setting time: 3 minutes

  As a material constituting the surface layer of the charging member, a material that can achieve the contact angle X with the polydimethylsiloxane can be appropriately selected from resins and elastomers. As the resin, silicone resin, polyurethane resin, polyamide resin, acrylic resin, butyral resin, styrene-ethylene / butylene-olefin copolymer (CEBC) and the like can be used. As the elastomer, synthetic rubber and thermoplastic elastomer can be used. Examples of the synthetic rubber include natural rubber (vulcanization treatment, etc.), EPDM, SBR, silicone rubber, urethane rubber, IR, BR, NBR, CR, and the like. Thermoplastic elastomers include polyolefin thermoplastic elastomers, polyamide polyolefin thermoplastic elastomers, polybutadiene polyolefin thermoplastic elastomers, ethylene vinyl acetate polyolefin thermoplastic elastomers, polyvinyl chloride polyolefin thermoplastic elastomers and chlorinated polyethylene polyolefin thermals. A plastic elastomer is mentioned. These materials may be used alone or in combination of two or more, or may be a copolymer. In particular, it is preferable to contain a polysiloxane having an oxyalkylene group in consideration of a reduction in the thickness of the surface layer associated with cost reduction and improvement in electrical characteristics, bleed-out resistance, and adhesion contamination resistance.

The polysiloxane having an oxyalkylene group constituting the charging member can be obtained, for example, through the following step A and step B.
Step A: a condensation step in which a hydrolyzable silane compound and a hydrolyzable silane compound having a cationically polymerizable group are condensed by hydrolysis.
Step B: a cross-linking step of cross-linking the hydrolytic condensation obtained in step A by cleaving a cationically polymerizable group.

  As the hydrolyzable silane compound, a hydrolyzable silane compound having an optionally substituted aryl group is preferably used. Among these, a hydrolyzable silane compound having an aryl group having a structure represented by the following general formula (6) is preferable.

〔式（６）中、Ｒ⁶¹及びＲ⁶²は、それぞれ独立に、置換若しくは無置換のアルキルであり、Ａｒ⁶¹は、アリール基である。ｉは０乃至２の整数、ｊは１乃至３の整数で、かつ、ｉ＋ｊ＝３である。〕

[In Formula (6), R ⁶¹ and R ⁶² are each independently substituted or unsubstituted alkyl, and Ar ⁶¹ is an aryl group. i is an integer of 0 to 2, j is an integer of 1 to 3, and i + j = 3. ]

In the general formula (6), the alkyl group of R ⁶¹ or R ⁶² is preferably a methyl group, an ethyl group or a propyl group, and the aryl group of Ar ⁶¹ is preferably a phenyl group.

Specific examples of the hydrolyzable silane compound having an aryl group represented by the general formula (6) are shown below.
(6-1) Phenyltrimethoxysilane (6-2) Phenyltriethoxysilane (6-3) Phenyltripropoxysilane

  As the hydrolyzable silane compound having a group capable of cationic polymerization, a hydrolyzable silane compound having a structure represented by the following general formula (7) is suitable.

〔式（７）中、Ｒ⁷¹及びＲ⁷²は、それぞれ独立に、置換若しくは無置換のアルキル基であり、Ｚ⁶¹は２価の有機基であり、Ｒｃ⁶¹はカチオン重合可能な基である。ｄは０乃至２の整数、ｅは１乃至３以下の整数で、かつ、ｄ＋ｅ＝３である。〕

[In formula (7), R ⁷¹ and R ⁷² are each independently a substituted or unsubstituted alkyl group, Z ⁶¹ is a divalent organic group, and Rc ⁶¹ is a group capable of cationic polymerization. d is an integer from 0 to 2, e is an integer from 1 to 3, and d + e = 3. ]

Cationically polymerizable group Rc ⁷¹ in the general formula (7) generates an oxyalkylene group by cleavage means a cationically polymerizable organic groups, for example, cyclic ether groups such as an epoxy group and an oxetane group, And vinyl ether groups. Among these, an epoxy group is preferable from the viewpoints of availability and reaction control.

  The oxyalkylene group is a divalent group having a structure represented by —O—R— (—R—: alkylene group) (sometimes referred to as “alkylene ether group”).

The alkyl group of R ⁷¹ or R ⁷² in the general formula (7), preferably a linear or branched alkyl group having 1 to 3 carbon atoms, in particular, a methyl group, an ethyl group are more preferable.

Examples of the divalent organic group represented by Z ^{71 in} the general formula (7) include an alkylene group and an arylene group. Among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an ethylene group is particularly preferable.

Further, e in the general formula (7) is preferably 3. When d in the general formula (7) is 2, two R ⁷¹ may be different from each other. When e is 2 or 3, two or three R ^{72 s} may be different from each other.

Below, the specific example of the hydrolysable silane compound which has a structure shown by the said General formula (7) is shown.
(7-1): Glycidoxypropyltrimethoxysilane (7-2): Glycidoxypropyltriethoxysilane (7-3): Epoxycyclohexylethyltrimethoxysilane (7-4): Epoxycyclohexylethyltriethoxysilane

  Further, from the viewpoint of improving the releasability of the surface of the manufactured charging member, not only these hydrolyzable silane compounds but also the third raw material is represented by the following general formula (5) in the above step A. It is more preferable to use a hydrolyzable silane compound having a structure in combination. By using the hydrolyzable silane compound having the structure represented by the general formula (5), the resulting polysiloxane becomes a polysiloxane having a fluorinated alkyl group (perfluoroalkyl group).

〔式（５）中、Ｒ⁵¹及びＲ⁵²は、それぞれ独立に、置換若しくは無置換のアルキル基であり、Ｚ⁵¹は２価の有機基であり、Ｒｆ⁵¹は炭素数１乃至１１のフッ化アルキル基である。ｆは０乃至２の整数、ｇは１乃至３の整数で、かつ、ｆ＋ｇ＝３である。）

[In the formula (5), R ⁵¹ and R ⁵² are each independently a substituted or unsubstituted alkyl group, Z ⁵¹ is a divalent organic group, and Rf ⁵¹ is a fluoride having 1 to 11 carbon atoms. It is an alkyl group. f is an integer of 0 to 2, g is an integer of 1 to 3, and f + g = 3. )

The alkyl group of R ⁵¹ and R ^{52 in} the general formula (5) is preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.

The divalent organic group Z ⁵¹ in the general formula (5), for example, alkylene groups and arylene groups. Among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an ethylene group is particularly preferable. As the fluorinated alkyl group having 1 to 31 carbon atoms of Rf ⁵¹ in the above general formula (5), from the viewpoint of processability, particularly preferably a linear fluorinated alkyl group having 6 to 11 carbon atoms.

G in the general formula (5) is preferably 3. Moreover, when f in the said General formula (5) is 2, two ^R51 may mutually differ. When g in the general formula (5) is 2 or 3, two or three R ⁵² may be different from each other.

Below, the specific example of the hydrolysable silane compound which has a structure shown by the said General formula (5) is shown. In the formula, R is a methyl group or an ethyl group.
(5-1): CF ₃ (CH ₂ ) ₂ Si (OR) ₃
(5-2): F (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OR) ₃
(5-3): F (CF ₂ ) ₄ (CH ₂ ) ₂ Si (OR) ₃
(5-4): F (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OR) ₃
(5-5): F (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OR) ₃
(5-6): F (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (OR) ₃

  Among these, the compound (3-4) to the compound (3-6) are preferable.

  Each of these hydrolyzable silane compounds may be used alone or in combination of two or more.

  In the present invention, in the step A, a hydrolyzable silane other than the above hydrolyzable silane compound may be further used in combination. Examples of hydrolyzable silanes other than the above-mentioned hydrolyzable silane compounds include hydrolyzable silane compounds having a structure represented by the following general formula (8).

〔式（８）中、Ｒ⁸¹は、フェニル基置換のアルキル基若しくは無置換のアルキル基、又は、アルキル基置換のアリール基若しくは無置換のアリール基であり、Ｒ⁸²は飽和若しくは不飽和の１価の炭化水素基である。ｈは０乃至３の整数、ｋは１乃至４の整数で、かつ、ｈ＋ｋ＝４である。）

[In the formula (8), R ⁸¹ is a phenyl group-substituted alkyl group or an unsubstituted alkyl group, or an alkyl group-substituted aryl group or an unsubstituted aryl group, and R ⁸² is a saturated or unsaturated 1 Valent hydrocarbon group. h is an integer of 0 to 3, k is an integer of 1 to 4, and h + k = 4. )

As the alkyl group of the phenyl group-substituted alkyl group or unsubstituted alkyl group represented by R ^{81 in} the general formula (8), a linear alkyl group having 1 to 21 carbon atoms is preferable. As the aryl group of the alkyl group-substituted aryl group or unsubstituted aryl group of R ^{81 in} the general formula (8), a phenyl group is preferable.

  H in the general formula (8) is preferably an integer of 1 to 3, and more preferably 1. Further, k in the general formula (8) is preferably an integer of 1 to 3, and more preferably 3.

Examples of the saturated or unsaturated monovalent hydrocarbon group for R ^{82 in} the general formula (8) include an alkyl group, an alkenyl group, and an aryl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group, an ethyl group, and an n-propyl group are particularly preferable.

When h in the general formula (8) is 2 or 3, two or three R ⁸¹ may be different from each other. Further, when k in the above formula (8) is 2, 3 or 4, two, three or four R ⁸² may be different from each other.

Specific examples of the hydrolyzable silane compound having the structure represented by the general formula (8) are shown below.
(8-1): Tetramethoxysilane (8-2): Tetraethoxysilane (8-3): Tetrapropoxysilane (8-4): Methyltrimethoxysilane (8-5): Methyltriethoxysilane (8- 6): methyltripropoxysilane (8-7): ethyltrimethoxysilane (8-8): ethyltriethoxysilane (8-9): ethyltripropoxysilane (8-10): propyltrimethoxysilane (8- 11): Propyltriethoxysilane (8-12): Propyltripropoxysilane (8-13): Hexyltrimethoxysilane (8-14): Hexyltriethoxysilane (8-15): Phenyltripropoxysilane (8- 16): Decyltrimethoxysilane (8-17): Decyltriethoxysilane (8-18): Dec Le tripropoxysilane

  Here, the polysiloxane having an oxyalkylene group has a fluorinated alkyl group, and the aryl group is 2% by mass to 40% by mass and the alkyl group is 2% by mass or more with respect to the total mass of the polysiloxane. From the surface characteristics, it is preferably 30% by mass or less, 5% by mass or more and 90% by mass or less of the oxyalkylene group, and 2% by mass or more and 50% by mass or less of the fluorinated alkyl group.

  In the present specification, among the hydrolyzable silane compounds, the hydrolyzable silane compound represented by the general formula (6) is referred to as a “hydrolyzable silane compound having a group capable of cationic polymerization”, and other hydrolyzable silane compounds. The decomposable silane compound is referred to as “another hydrolyzable silane compound”.

  Next, the structure of the charging member according to the present invention will be described including a specific method for forming the surface layer containing the polysiloxane.

  FIG. 2 is a schematic cross-sectional view of a charging roller, which is an example of the charging member of the present invention, on a plane perpendicular to the axial direction. In FIG. 2, 101 is a charging member support, 102 is a conductive elastic layer, and 103 is a surface layer. From the viewpoint of ensuring a sufficient contact nip between the photosensitive member and the charging member, the charging member includes, for example, a conductive elastic layer 102 between the charging member support 101 and the surface layer 103 as shown in FIG. The provided structure is preferable. In other words, the charging member has a charging member support 101, a conductive elastic layer 102 formed on the support 101, and a surface layer 103 formed on the conductive elastic layer 102. It is preferable. One or more other layers may be provided between the charging member support 101 and the conductive elastic layer 102 or between the conductive elastic layer 102 and the surface layer 103.

  Hereinafter, a charging member having a charging member support, a conductive elastic layer formed on the charging member support, and a surface layer formed on the conductive elastic layer will be described as an example.

  The charging member support only needs to have conductivity (conductive support). For example, a support made of metal (made of alloy) such as iron, copper, stainless steel, aluminum, aluminum alloy, nickel, or the like is used. be able to. In addition, for the purpose of imparting scratch resistance to these surfaces, surface treatment such as plating treatment may be performed within a range not impairing conductivity.

  As a material constituting the conductive elastic layer, one or more elastic bodies such as rubber and thermoplastic elastomer used for the conventional elastic layer (conductive elastic layer) of the charging member can be used.

  Examples of the rubber include urethane rubber, silicone rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, polynorbornene rubber, styrene-butadiene-styrene rubber, acrylonitrile rubber, epichlorohydrin rubber, and alkyl ether. For example, rubber.

  Examples of the thermoplastic elastomer include styrene elastomers and olefin elastomers. Examples of commercially available styrene elastomers include “Lavalon” (trade name, manufactured by Mitsubishi Chemical Corporation) and “Septon Compound” (trade name, manufactured by Kuraray Co., Ltd.). Examples of commercially available olefin elastomers include “Thermolan (trade name, manufactured by Mitsubishi Chemical Corporation)”, “Milastomer” (trade name, manufactured by Mitsui Chemicals Co., Ltd.), “Sumitomo TPE” (trade name, Sumitomo Chemical). Co., Ltd.), “Sant Plain” (trade name, manufactured by Advanced Elastomer Systems), etc.

Moreover, the electroconductivity can be set to a predetermined value by appropriately using a conductive agent in the conductive elastic layer. The electrical resistance of the conductive elastic layer can be adjusted by appropriately selecting the type and amount of the conductive agent, and the preferred range of the electrical resistance is 10 ² Ω or more and 10 ⁸ Ω or less, more suitable. The range is from 10 ³ Ω to 10 ⁶ Ω.

  Examples of the conductive agent used in the conductive elastic layer include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, an antistatic agent, and an electrolyte.

  As the cationic surfactant, for example, lauryltrimethylammonium, stearyltrimethylammonium, octadodecyltrimethylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium and quaternary ammonium salts such as modified fatty acid and dimethylethylammonium may be used. it can. Specific examples of the quaternary ammonium salt include perchlorate, chlorate, borofluoride, ethosulphate salt, and halogenated benzyl salt (such as benzyl bromide salt and benzyl chloride salt). .

  Examples of the anionic surfactant include aliphatic sulfonate, higher alcohol sulfate ester salt, higher alcohol ethylene oxide addition sulfate ester salt, higher alcohol phosphate ester salt and higher alcohol ethylene oxide addition phosphate ester salt. it can.

  Examples of the antistatic agent include nonionic antistatic agents such as higher alcohol ethylene oxide, polyethylene glycol fatty acid ester and polyhydric alcohol fatty acid ester.

Examples of the electrolyte include salts (such as quaternary ammonium salts) of metals (Li, Na, K, etc.) belonging to Group 1 of the periodic table. Specific examples of the metal salt of Group 1 of the periodic table include LiCF ₃ SO ₃ , NaClO ₄ , LiAsF ₆ , LiBF ₄ , NaSCN, KSCN, and NaCl.

In addition, as a conductive agent, a salt (Ca (ClO ₄ ) ₂ or the like) of a metal of Group 2 of the periodic table (Ca or Ba or the like) or an antistatic agent derived therefrom is an isocyanate (a primary amino group or a secondary amino group). A group having one or more groups (such as a hydroxyl group or a carboxyl group) having an active hydrogen capable of reacting with a group can also be used. Also, complexes of these with polyhydric alcohols (1,4-butanediol, ethylene glycol, polyethylene glycol, propylene glycol, polyethylene glycol, etc.) or derivatives thereof, and monools (ethylene glycol monomethyl ether, ethylene glycol monoethyl) An ion conductive conductive agent such as a complex with ether or the like) can also be used.

  Further, as the conductive agent, conductive carbon such as ketjen black EC (trade name), acetylene black, carbon for rubber, carbon for color (ink) subjected to oxidation treatment, and pyrolytic carbon can also be used. . Specific examples of carbon for rubber include SAF (super wear resistance), ISAF (quasi-super wear resistance), HAF (high wear resistance), FEF (good extrudability), GPF (general versatility), SRF ( Medium reinforcing carbon), carbon for rubbers such as FT (fine grain pyrolysis), MT (medium grain pyrolysis), and the like. Moreover, graphite, such as natural graphite and artificial graphite, can also be used. Further, as a conductive agent for the conductive elastic layer, metal oxides such as tin oxide, titanium oxide, and zinc oxide, and metals such as nickel, copper, silver, and germanium can be used. In addition, conductive polymers such as polyaniline, polypyrrole, and polyacetylene can also be used.

  Moreover, you may add an inorganic or organic filler and a crosslinking agent to a conductive elastic layer.

  Examples of the filler include silica (white carbon), calcium carbonate, magnesium carbonate, clay, talc, zeolite, alumina, barium sulfate, and aluminum sulfate. Examples of the crosslinking agent include sulfur, peroxide, crosslinking aid, crosslinking accelerator, crosslinking acceleration aid, crosslinking retarder and the like.

  The hardness of the conductive elastic layer is preferably 70 degrees or more in Asker C hardness from the viewpoint of suppressing deformation of the charging member when the charging member and the electrophotographic photosensitive member that is the object to be charged are brought into contact with each other. More preferably, it is 73 degrees or more. In the present invention, the Asker C hardness is measured by contacting a push needle of a rubber hardness meter “Asker rubber hardness meter C type” (trade name, manufactured by Kobunshi Keiki Co., Ltd.) on the surface to be measured, under a condition of 1000 g load. went.

  Examples of a method for mixing these rubber materials include a mixing method using a closed mixer such as a Banbury mixer and a pressure kneader, a mixing method using an open mixer such as an open roll, and the like.

  The mixed unvulcanized rubber material is formed into a tube shape by a vent type extruder. FIG. 4 schematically shows an outline of the vent type extruder. In the extruder 50, an extrusion screw 52 is rotatably inserted in a cylinder 51. A cross head 53 is attached to the end of the cylinder 51 on the tip side of the screw 52. The cylinder 51 is provided with a vent port 55. The vent port 55 is connected to a vacuum pump (not shown), and the inside of the cylinder 51 is evacuated by the vacuum pump. Unvulcanized rubber introduced from the material introduction port 54 is conveyed to the crosshead 53 side by the rotation of the extrusion screw 52. When the unvulcanized rubber material passes through the cylinder, the volatile component of the unvulcanized rubber is removed by a vacuum pump connected to the vent port. The unvulcanized rubber conveyed to the cross head 53 is laminated on the outer periphery of the core metal 31 supplied from a core metal supply device (not shown), passes through the die 56 at the tip of the cross head, and is coextruded with the core metal 31. The

  The cylinder 51, the screw 52, and the cross head 53 of the extruder 50 are each maintained at a temperature specified by a temperature controller (not shown). The higher the temperature during extrusion, the better the venting effect, and the volatile components of the unvulcanized molded product can be reduced. This is because the higher the gas permeability of rubber, the higher the temperature. However, if the temperature is raised too high, a problem of so-called burn (also called scorch) occurs, in which the vulcanization reaction starts during extrusion. Therefore, the preferable set temperature of the extruder 50 is 60 ° C. or higher and 100 ° C. or lower.

  FIG. 5 schematically shows an outline of a continuous vulcanizing apparatus for rollers extruded from an extruder. The unvulcanized rubber roller in which the unvulcanized rubber is laminated on the outer periphery of the cored bar 31 is continuously conveyed to the vulcanizing furnace 60 by an extruder (not shown) by the extruder 50. The vulcanization furnace 60 is previously maintained at the vulcanization temperature, and the vulcanization time is adjusted according to the speed of conveyance and the length of the vulcanization furnace 60. The vulcanization temperature and time depend on the type of raw rubber used, but are generally 140 ° C. to 200 ° C., 15 minutes to 120 minutes.

  Furthermore, in order to obtain a precise conductive elastic layer shape, the vulcanized roller-shaped conductive elastic body is preferably formed by polishing. In order to precisely finish the delicate crown shape, it is more preferable to polish using a rotating grindstone that is wider than the entire length in the axial direction of the conductive elastic layer.

  An example of polishing is shown in FIG. As shown in FIG. 6, the elastic roller 71 is held and rotated in parallel with the rotating grindstone 72. By changing the distance while keeping the rotation axis of the elastic roller and the rotation axis of the grindstone parallel, the surface is polished, the surface shape of the conductive elastic layer becomes a crown shape, and the surface roughness is also constant. The shape of the grindstone is adjusted to a precise shape using a diamond blade 73 so that the conductive elastic layer has a good crown shape. The material of the grindstone is a known material such as green carborundum, and the count of the grindstone is determined according to the polishing conditions.

  Hereinafter, an example of a specific method for forming the surface layer will be described.

  First, by hydrolyzing a hydrolyzable silane compound having an aryl group, a hydrolyzable silane compound having a cationically polymerizable group, and, if necessary, other hydrolyzable silane compounds in the presence of water. A hydrolysis condensate is obtained (step A). During the hydrolysis reaction, the degree of condensation of the hydrolysis condensate can be adjusted by controlling temperature, pH, and the like.

  In the hydrolysis reaction, the degree of condensation may be controlled by using a metal alkoxide or the like as a catalyst for the hydrolysis reaction. Examples of the metal alkoxide include aluminum alkoxide, titanium alkoxide, zirconia alkoxide and the like, and complexes thereof (acetylacetone complex and the like).

In addition, the blending ratio of the hydrolyzable silane compound having an aryl group and the hydrolyzable silane compound having a group capable of cationic polymerization in the step A is such that the content of the group and the siloxane part in the obtained polysiloxane is as follows. It is preferable to be in the range.
Aryl group content: 2% to 40% by mass
Alkyl group content: 2% by mass to 30% by mass
Oxyalkylene group content: 5% by mass to 90% by mass

  The above contents all indicate a percentage with respect to the total mass of the polysiloxane, and the total content of the aryl group, the oxyalkylene group and the siloxane part is usually preferably 5% by mass or more and 90% by mass or less, It is more preferable to set it to 50 mass% or more. Moreover, it is more preferable to mix the hydrolyzable silane compound having an aryl group so as to be 20 mol% or more and 70 mol% or less with respect to the total hydrolyzable silane compound.

In Step A, when the hydrolyzable silane compound having the structure represented by the above formula (6) is used in combination, the content of groups and moieties in the resulting polysiloxane is preferably in the following range. .
Aryl group content: 2% to 40% by mass
Alkyl group content: 2% by mass to 30% by mass
Oxyalkylene group content: 5% by mass to 90% by mass
Fluorinated alkyl group content: 2% by mass to 50% by mass

  The above contents all indicate a percentage with respect to the total mass of the polysiloxane compound, and the combined content of the aryl group, oxyalkylene group, fluorinated alkyl group and siloxane part is usually 10% by mass or more and 90% by mass or less. It is preferable to set it to 15 mass% or more and 50 mass% or less. More preferably, the molar ratio of the hydrolyzable silane compound having a group capable of cationic polymerization to the hydrolyzable silane compound containing a fluorinated alkyl group is 10: 1 to 1:10.

  Next, a coating solution for the surface layer containing a hydrolysis condensate is prepared, and the prepared surface layer is formed on a layer (for example, a conductive elastic layer, which may be a charging member support) immediately below the surface layer. Apply the coating solution.

  In preparing the surface layer coating solution, an appropriate solvent may be used in addition to the hydrolysis-condensation product in order to improve coating properties. Suitable solvents include, for example, alcohols such as ethanol and 2-butanol, ethyl acetate, methyl isobutyl ketone, methyl ethyl ketone, or a mixture thereof. Moreover, when apply | coating the coating liquid for surface layers on a conductive elastic member (conductive elastic layer), methods, such as roll coater application | coating, dip coating, and ring coating, are employable.

  As the hydrolyzable silane compound, a hydrolyzable silane compound having at least one group selected from substituted and unsubstituted aryl groups is preferably used. Among these, a hydrolyzable silane compound having an aryl group having a structure represented by the general formula (5) is preferable.

  Next, an active energy ray is irradiated to the surface layer coating liquid layer coated on the conductive elastic member (conductive elastic layer). Then, the cationically polymerizable group contained in the hydrolyzable condensate contained in the surface layer coating solution layer is cleaved. Thereby, the hydrolysis-condensation product in the surface coating liquid layer can be crosslinked. The hydrolysis-condensation product is cured by crosslinking, and when this is dried, a surface layer is formed (step B).

  When the conductive elastic layer of the conductive elastic member expands due to the heat generated during irradiation with active energy and then contracts due to cooling, the surface layer has many wrinkles and cracks if the surface layer does not sufficiently follow this expansion / contraction. It may become. When ultraviolet rays are used for the cross-linking reaction, the hydrolyzable condensate can be cross-linked in a short time (within 15 minutes), and the generation of heat is small, and the surface layer is not easily wrinkled or cracked. Also, when the charging member is placed in an environment where the temperature and humidity change is abrupt, the surface layer will not wrinkle or wrinkle unless the surface layer sufficiently follows the expansion and contraction of the conductive elastic layer due to the change in temperature and humidity. Cracks may occur. If the cross-linking reaction is performed by ultraviolet rays that generate less heat, the adhesion between the conductive elastic layer and the surface layer is improved, and the surface layer can sufficiently follow the expansion and contraction of the conductive elastic layer. Wrinkles and cracks in the surface layer due to changes in temperature and humidity can also be suppressed. In addition, if the crosslinking reaction is performed using ultraviolet rays, it is possible to suppress deterioration of the conductive elastic layer due to thermal history, and thus it is possible to suppress a decrease in electrical characteristics of the conductive elastic layer. For these reasons, it is preferable to use ultraviolet rays as active energy rays.

  For irradiation with ultraviolet rays, a high pressure mercury lamp, a metal halide lamp, a low pressure mercury lamp, an excimer UV lamp, or the like can be used. Among these, an ultraviolet ray source rich in light having an ultraviolet wavelength of 150 nm to 480 nm is preferably used. .

The integrated light quantity of ultraviolet rays is defined as follows.
UV integrated light quantity [mJ / cm ² ] = UV intensity [mW / cm ² ] × irradiation time [s]

  The adjustment of the integrated amount of ultraviolet light can be performed by the irradiation time, lamp output, distance between the lamp and the irradiated object, and the like. Moreover, you may give a gradient to integrated light quantity within irradiation time. In the case of using a low-pressure mercury lamp, the integrated light amount of ultraviolet rays can be measured using an ultraviolet integrated light amount meter UIT-150-A (trade name) or UVD-S254 (trade name) manufactured by USHIO INC. When an excimer UV lamp is used, the integrated light amount of ultraviolet rays can be measured using an ultraviolet integrated light amount meter UIT-150-A (trade name) or VUV-S172 (trade name) manufactured by USHIO INC.

  In the crosslinking reaction, it is preferable that a cationic polymerization catalyst (polymerization initiator) is allowed to coexist from the viewpoint of improving the crosslinking efficiency. For example, since an epoxy group exhibits high reactivity with respect to an onium salt of a Lewis acid activated by an active energy ray, the above cationic polymerizable group is an epoxy group. It is preferable to use an onium salt of an acid.

  Examples of other cationic polymerization catalysts include borate salts, compounds having an imide structure, compounds having a triazine structure, azo compounds, and peroxides. Among various cationic polymerization catalysts, aromatic sulfonium salts and aromatic iodonium salts are preferable from the viewpoint of sensitivity, stability, and reactivity. In particular, bis (4-tert-butylphenyl) iodonium salt, the compound “Adekaoptomer SP150” (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) of the following chemical formula (9), and the compound “Irgacure” "261" (trade name, manufactured by Ciba Specialty Chemicals) is preferable.

  It is preferable that the usage-amount of a cationic polymerization catalyst is 0.1 to 3.0 mass% with respect to a hydrolysis-condensation product.

  Further, in order to suppress the adhesion of the toner and the external additive to the surface of the charging member, the surface roughness of the charging member (= surface of the surface layer) (Rzjis; measured according to JIS B 0601: 2001) is It is preferably 10 μm or less, and more preferably 7 μm or less.

  Further, from the viewpoint of ensuring a sufficient contact nip with the electrophotographic photosensitive member, the elastic modulus of the surface layer of the charging member is preferably 30 GPa or less. On the other hand, in general, the crosslinking density tends to decrease as the elastic modulus of the surface layer decreases. For this reason, when the conductive elastic layer is provided on the charging member, the low molecular weight component in the conductive elastic layer is prevented from bleeding out on the surface of the charging member and contaminating the surface of the electrophotographic photosensitive member. From the viewpoint, the elastic modulus of the surface layer is preferably 100 MPa or more.

  Further, since the effect of suppressing the bleed out of the low molecular weight component tends to increase as the surface layer thickness increases, when the conductive elastic layer is provided on the charging member, the surface layer thickness is 0.010 μm. It is preferable that it is above, and it is more preferable that it is 0.050 μm or more. On the other hand, since the charging performance of the charging member tends to be improved as the surface layer is thinner, the surface layer is preferably 1.000 μm or less, more preferably 0.300 μm or less.

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

(Synthesis Example 1 Polycarbonate Polymer I)
In 500 ml of 10% aqueous sodium hydroxide solution, 120 g of bisphenol compound (1-13) was dissolved. To this solution, 300 ml of dichloromethane was added and stirred, and 100 g of phosgene was blown in over 1 hour while maintaining the solution temperature at 10 ° C. to 15 ° C. When about 70% of phosgene was blown in, 25 g of siloxane compound (2-1) (average number of repetitions m = 40) and 55 g of siloxane compound (3-1) (average number of repetitions n = 40) were added to the solution. After the introduction of phosgene, the reaction mixture was emulsified by vigorous stirring, 0.2 ml of triethylamine was added, and the mixture was further stirred for 1 hour. Thereafter, the dichloromethane phase was separated, neutralized with phosphoric acid, and then washed with water until the pH reached about 7. Subsequently, this liquid phase was dropped into isopropanol, and the precipitate was filtered and dried to obtain a white powdery polycarbonate polymer I.

  Composition analysis and physical property measurement of the obtained polycarbonate polymer I were performed as follows.

Measurement by FT-IR (manufactured by Shimadzu Corporation): absorption by carbonyl group, absorption by ether bond, 1240 cm ⁻¹ and carbonate bond were confirmed. Further, there was almost no absorption at 3650 cm ^{−1 to} 3200 cm ⁻¹ , and no hydroxyl group was observed. Furthermore, a peak attributed to siloxane having 1100 cm ^{−1 to} 1000 cm ⁻¹ was also confirmed. ^{Also in 1} H-NMR, it was confirmed that a siloxane site and a polycarbonate site were present. When measured by MALDI-TOF-MS, the siloxane part formed from the compound (2-1) and the siloxane part formed from the compound (3-1) were about 1: 2, and the average number of repetitions was It was confirmed that the ratio m: n was approximately 40:40. The viscosity average molecular weight (Mv) is 20600, and the mass composition ratio of the siloxane part is about 40%. Therefore, this polycarbonate polymer has a structure having a polysiloxane part at both ends and a structure having a siloxane part in the main chain.

The viscosity average molecular weight (Mv) was determined by calculating the intrinsic viscosity from the specific viscosity measured using a Ubelode viscometer, and this was calculated by the Mark-Houwink viscosity equation. Specifically, 0.5 g of the sample was dissolved in 100 ml of dichloromethane, the specific viscosity at 25 ° C. was measured with an Ubbelohde viscometer, and the intrinsic viscosity was determined from this specific viscosity. The viscosity average molecular weight was calculated with K and a in the Mark-Houwink viscosity formula being 1.23 × 10 ⁻⁴ and 0.83, respectively.

(Synthesis Example 2 Polycarbonate Polymer II)
Except for the siloxane compound (2-1) having an average number of repetitions m = 20 and the siloxane compound (3-1) having an average number of repetitions n = 20, the polycarbonate weight Compound II was obtained. This product was confirmed to have an ether bond and a carbonate bond by FT-IR. Moreover, in the measurement of MALDI-TOF-MS, the siloxane part formed from the compound (2-1) and the siloxane part formed from the compound (3-1) are about 1: 2, and the average number of repetitions The ratio m: n was confirmed to be approximately 20:20. The viscosity average molecular weight (Mv) is 26000, and the mass composition ratio of the siloxane part is about 40%. Therefore, this polycarbonate polymer II has a structure having a polysiloxane part at both ends, and also has a structure having a siloxane part in the main chain.

(Synthesis Example 3 Polycarbonate Polymer III)
A polycarbonate polymer III was obtained in the same manner as in Synthesis Example 1 except that the siloxane compound (2-1) had an average repeating number m = 10. This product was confirmed to have an ether bond and a carbonate bond by FT-IR. Moreover, in the measurement of MALDI-TOF-MS, the siloxane part formed from the compound (2-1) and the siloxane part formed from the compound (3-1) are about 1: 2, and the average number of repetitions The ratio m: n was confirmed to be approximately 10:40. The viscosity average molecular weight (Mv) is 19000, and the mass composition ratio of the siloxane part is about 20%. Therefore, this polycarbonate polymer III has a structure having a polysiloxane portion at both ends, and also has a siloxane portion in the main chain.

<Production Example 1 Photoconductor 1>
An aluminum cylinder having a diameter of 30 mm and a length of 260 mm was used as a support.

  50 parts of titanium oxide particles coated with tin oxide containing 10% by weight antimony oxide, 25 parts of resol type phenol resin, 30 parts of methoxypropanol, 30 parts of methanol and silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, weight average) 0.002 part of molecular weight: 3000) was dispersed for 2 hours in a sand mill using glass beads having a diameter of 1 mm to prepare a coating solution for a conductive layer. This conductive layer coating solution was dip-coated on a support and cured at 140 ° C. for 20 minutes to form a conductive layer having a thickness of 20 μm.

  Next, 5 parts of N-methoxymethylated 6 nylon was dissolved in 95 parts of methanol to prepare an intermediate layer coating solution. This intermediate layer coating solution was dip-coated on a support and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.5 μm.

  Bragg angles (2θ ± 0.2 °) of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 in CuKα characteristic X-ray diffraction 10 parts of a crystalline hydroxygallium phthalocyanine crystal (charge generating substance) having a strong peak at 0 °, 0.1 part of a compound of the following chemical formula (11), and polyvinyl butyral resin “ESREC BX-1 (trade name, Sekisui Chemical Co., Ltd.) (Company) 5 parts was dissolved, and then 250 parts of ethyl acetate was added to prepare a coating solution for charge generation layer, which was dip-coated on the intermediate layer at 100 ° C. The film was dried for 10 minutes to form a charge generation layer having a thickness of 0.16 μm.

  Next, 35 parts of a compound represented by the following chemical formula (12) and 5 parts of a compound represented by the following chemical formula (13) are used as a charge transport material.

50 parts of a polycarbonate resin having a repeating structural unit represented by the following structural formula (14) (weight average molecular weight: 55000), 1.8 parts of the polycarbonate polymer I obtained in Synthesis Example 1, and a polycrystal represented by the chemical formula (4) It melt | dissolved in 400 parts of monochlorobenzene with 0.2 part of dimethylsiloxane, and obtained the solution (viscosity 220 mPa * s) for charge transport layers.

〔式（１４）中、＊は結合位置を示す。〕

[In formula (14), * indicates a bonding position. ]

  This solution was dip-coated on the charge generation layer prepared above and dried by heating at 120 ° C. for 1 hour to form a charge transport layer having a film thickness of 15 μm.

<Production Example 2 Photoconductor 2>
A photoconductor 2 was produced in the same manner as in Production Example 1, except that the polycarbonate polymer I was 4.0 parts and the polydimethylsiloxane represented by the chemical formula (4) was 0.4 parts.

<Production Example 3 Photoconductor 3>
Photoreceptor 3 was produced in the same manner as in Production Example 1, except that 0.1 part of polycarbonate polymer I and 0.01 part of polydimethylsiloxane represented by chemical formula (4) were used.

<Production Example 4 Photoconductor 4>
Photosensitive member 4 was produced in the same manner as in Production Example 1, except that 0.05 part of polycarbonate polymer I and 0.01 part of polydimethylsiloxane represented by chemical formula (4) were used.

<Production Example 5 Photoconductor 5>
A photoconductor 5 was produced in the same manner as in Production Example 1 except that 0.5 part of polydimethylsiloxane represented by the chemical formula (4) was changed.

<Production Example 6 Photoconductor 6>
Photoreceptor 6 was produced in the same manner as in Production Example 1, except that 4.0 parts of polycarbonate polymer I and 1.0 part of polydimethylsiloxane represented by chemical formula (4) were used.

<Production Example 7 Photoconductor 7>
A photoconductor 7 was produced in the same manner as in Production Example 1 except that the polydimethylsiloxane represented by the chemical formula (4) was changed to 0.1 part.

<Production Example 8 Photoconductor 8>
A photoconductor 8 was produced in the same manner as in Production Example 1 except that 0.07 part of polydimethylsiloxane represented by the chemical formula (4) was used.

<Production Example 9 Photoconductor 9>
A photoconductor 9 was produced in the same manner as in Production Example 1 except that the polydimethylsiloxane represented by the chemical formula (4) was changed to 0.4 part.

<Production Example 10 Photoconductor 10>
A photoconductor 10 was produced in the same manner as in Production Example 1 except that the polycarbonate polymer I was replaced with the polycarbonate polymer II obtained in Synthesis Example 2.

<Production Example 11 Photoconductor 11>
A photoconductor 11 was produced in the same manner as in Example 1 except that the polycarbonate polymer I and the polydimethylsiloxane represented by the chemical formula (4) were not added.

<Production Example 12 Photoconductor 12>
Photoconductor 12 was prepared in the same manner as in Production Example 1 except that polycarbonate polymer I was not used and 4.0 parts of siloxane compound (3-1) was used instead.

<Production Example 13 Photoconductor 13>
A photoconductor 13 was produced in the same manner as in Production Example 1 except that the polycarbonate polymer I was not used and the polydimethylsiloxane represented by the chemical formula (4) was increased to 4.0 parts instead.

<Production Example 14 Photoconductor 14>
A photoconductor 14 was produced in the same manner as in Production Example 1 except that the polycarbonate polymer I was changed to the polycarbonate polymer III obtained in Synthesis Example 3 and polydimethylsiloxane represented by the chemical formula (4) was not added. did.

  Table 5 shows the blending amounts of raw materials for forming the surface layers of the photoreceptors of Production Examples 1 to 14 and the physical properties of the obtained photoreceptors.

<Production Example 15 Charging Member 1>
(Production of charging roller)
-Preparation of unvulcanized rubber composition for elastic layer 100 parts of NBR "JSR N230SV" (trade name, manufactured by JSR Corporation) as raw rubber, 1 part of zinc stearate as processing aid, oxidation as vulcanization acceleration aid 5 parts of zinc, 20 parts of calcium carbonate “Nanox # 30” (trade name, manufactured by Maruo Calcium Co., Ltd.) as a filler, and 48 parts of carbon black “Toka Black # 7360SB” (trade name, manufactured by Tokai Carbon Co., Ltd.) as a conductive agent Was mixed with a 6-liter pressure kneader “TD6-15MDX” (trade name, manufactured by Toshin Co., Ltd.) at a filling rate of 70 vol% and a blade rotation speed of 30 rpm for 16 minutes to obtain an A-kneaded rubber composition. For 174 parts by mass of this unvulcanized rubber composition, 1.2 parts of sulfur as a crosslinking agent and 4.5 parts of tetrabenzylthiuram disulfide “PERKACIT-TBzTD” (trade name, manufactured by FLEXSYS) as a vulcanization accelerator. Using an open roll with a roll diameter of 12 inches, the front roll rotation speed was 8 rpm, the rear roll rotation speed was 10 rpm, and the roll gap was 2 mm. And an unvulcanized rubber composition for the elastic layer was obtained.

-Formation of elastic layer The obtained unvulcanized rubber composition was simultaneously extruded into a cylindrical shape coaxially around a core metal (diameter 6 mm, length 252 mm) by extrusion using a crosshead Was cut to produce an unvulcanized rubber roller in which an unvulcanized elastic layer was laminated on the outer periphery of the cored bar. The extruder used was an extruder with a cylinder diameter of 45 mm (Φ45) and L / D = 20. The temperature during extrusion was 90 ° C., 90 ° C. cylinder, and 90 ° C. screw.

  200 unvulcanized rubber rollers were continuously extruded and immediately vulcanized at 160 ° C. for 60 minutes in a continuous vulcanizing furnace. After vulcanization, both ends are cut and the axial width of the elastic layer portion is set to 228 mm, and then the surface of the conductive elastic layer portion is polished with a rotating grindstone to form a conductive elastic roller (conductive elastic roller after surface polishing). ) This conductive elastic roller has a crown-shaped conductive elastic layer having an end diameter of 8.2 mm and a central diameter of 8.5 mm, and the ten-point average roughness (Rzjis) of the surface of the conductive elastic layer. Was 5.23 μm and the deflection was 28 μm. The Asker C hardness of the conductive elastic layer was 78 degrees.

  Ten-point average roughness (Rzjis) was measured according to JIS B 0601: 2001.

  The shake was measured using a high-precision laser measuring machine “LSM-430v” (trade name, manufactured by Mitutoyo Corporation). Specifically, the outer diameter is measured using the measuring device, and the difference between the maximum outer diameter value and the minimum outer diameter value is defined as the outer diameter difference run. This measurement is performed at five points, and the average of the five outer diameter difference shakes is measured. The value was the runout of the object to be measured.

  The Asker C hardness is measured as described above by contacting the surface of the object to be measured with a pusher of a rubber hardness meter “Asker rubber hardness meter C type” (trade name), and 1000 g in a 23 ° C./50% RH environment. It was performed under the condition of weighting.

With respect to the 200th extruded elastic roller, the electrical resistance and its circumferential unevenness were measured using the electrical resistance measuring device of the elastic roller schematically shown in FIG. The elastic roller 40 is pressed against the cylindrical aluminum drum 42 by pressing means (not shown) at both ends of the core metal 31 and is driven to rotate as the aluminum drum 42 is driven to rotate. In this state, a DC voltage was applied to the cored bar portion 31 of the elastic roller 40 using the power source 43, and the electric resistance of the rubber roller was calculated from the voltage applied to the resistor 43 connected in series to the 42 aluminum drum. The measurement was performed by applying a voltage of DC 200 V between the metal core and the aluminum drum for 3 seconds in an environment of a temperature of 23 ° C. and a humidity of 50% RH (also described as N / N). The electrical resistance was the average value for the last 2 seconds, the maximum value and the minimum value for 2 seconds were measured at the same time, and the maximum value / minimum value was defined as circumferential unevenness. As a result, the electric resistance of this elastic roller was 1.2 × 10 ⁴ Ω, and the circumferential unevenness was 1.2 times.

-Preparation of coating solution for surface layer Next, after mixing the following raw materials, the mixture was stirred at room temperature and then heated to reflux (120 ° C) for 24 hours to obtain a hydrolyzable silane compound condensate.
-44.43 g (0.185 mol) of phenyltriethoxysilane (PhTES) (corresponding to 57.75 mol% with respect to the total amount of hydrolyzable silane compound))
・ Glycidoxypropyltriethoxysilane (GPTES) 17.15 g (0.062 mol)
-Hexyltrimethoxysilane (HETMS) 13.18 g (0.064 mol)
Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (FTS, carbon number 6 of perfluoroalkyl group) 4.90 g (0.010 mol)
・ Water 25.93g
-Ethanol 58.63g

  By adding this condensate to a mixed solvent of 2-butanol / ethanol, a condensate-containing alcohol solution having a solid content of 7% by mass was prepared. To 100 g of this, 2 g of a photocationic polymerization initiator solution obtained by diluting a photocationic polymerization initiator “Adekaoptomer SP-150” (trade name) to 10% by mass with methyl isobutyl ketone (MIBK) was added. Furthermore, it diluted with ethanol and the coating liquid for surface layers whose solid content is 1 mass% was prepared.

-Formation of surface layer Next, the surface layer coating liquid is ring-applied on the conductive elastic layer of the conductive elastic roller after surface polishing produced above (discharge amount: 0.020 ml / s, speed of the ring portion: 85 mm / s, total discharge amount: 0.065 ml). Then, the surface layer coating liquid was irradiated with ultraviolet light having a wavelength of 254 nm so that the integrated light amount was 11000 mJ / cm ² to cure the surface layer coating liquid (curing by a crosslinking reaction). This cured product was allowed to stand for several seconds (2 to 3 seconds) and dried to form a surface layer. A low-pressure mercury lamp manufactured by Harrison Toshiba Lighting Co., Ltd. was used for ultraviolet irradiation. It is considered that the glycidoxy group from glycidoxypropyltriethoxysilane is cleaved by irradiation with ultraviolet rays, and the crosslinking reaction of the condensate occurs.

  As described above, a charging roller (charging member 1) having a support, a conductive elastic layer formed on the support, and a surface layer formed on the conductive elastic layer was produced.

(Measurement of physical properties of charging roller)
The physical properties of the obtained charging roller were measured by the following methods.
Contact angle of the surface layer: measured by the method described above.
Number of fluorine atoms in surface layer: Measured by the method described above.

-Elastic modulus of the surface layer The elastic modulus of the surface layer of the charging roller was measured using a surface film physical property tester “Fischer Scope H100V” (trade name, manufactured by Fisher Instruments) in an environment of 23 ° C./50% RH. did. The value obtained when the indenter was allowed to enter from the surface of the measurement object at a speed of 1 μm / s was defined as the elastic modulus. For the sample for elastic modulus measurement, the above surface layer coating solution is applied on an aluminum sheet so that the film thickness after curing is 10 μm or more, and UV curing or heat treatment is performed under the same conditions as those for preparing the charging roller. A cured product was used.

-Layer thickness of surface layer Film thickness was measured by ESCA depth direction analysis. ESCA was measured under the following conditions using “QUANTUM2000” (trade name, manufactured by ULVAC-PHI, Inc.) as an apparatus.
X-ray generation conditions: Monochrome Al, kα ray, 25W, 15kV
Measurement method: Si2p peak in a region of Φ100 μm at a tilt of 45 °, the Si2p peak intensity is constant by repeated sputtering with a pass energy of 23.5 eV, a step width of 0.1 eV and a scan count of 5 times, and a sputtering time of 6 seconds. Measured until

  For sputtering, Ar ions were used, the sputtering conditions were an acceleration voltage of 4 kV, and the sputtering area was 2 × 2 mm. Here, the total sputtering time required until the Si2p peak intensity became constant was converted into a film thickness at a sputtering rate determined in advance. The sputtering rate at this time was 30 nm / min. The sputtering rate was determined by performing a depth direction analysis by ESCA on a sample equivalent to the film thickness measured by SEM, TEM, or the like.

  The ESCA measurement sample was cut from the surface of the roller so that the surface layer had a size of 5 × 5 mm. The average film thickness was obtained by averaging five points measured on the roller.

-Ten-point average roughness of the surface layer The ten-point average roughness (Rzjis) of the surface layer of the charging roller was measured in accordance with JIS B0601: 2001.

-Dynamic friction coefficient of surface layer FIG. 8 shows a schematic diagram of a measuring machine used for measuring the dynamic friction coefficient in the present invention. In FIG. 8, 201 is a charging roll (charging member) to be measured, and 202 is a belt (thickness 100 μm, width 30 mm, length 180 mm, polyethylene terephthalate (PET)) which is in contact with the charging roll at a predetermined angle θ. (Trade name: Lumirror S10 # 100, manufactured by Toray Industries, Inc.). Reference numeral 203 denotes a weight connected to one end of the belt 202, 204 denotes a load meter connected to the other end of the belt 202, and 205 denotes a recorder connected to the load meter 204. In the state shown in FIG. 8, when the charging roll 201 is rotated at a predetermined direction and at a predetermined speed, the force measured by the load meter 204 is F [g weight], and the sum of the weight of the weight and the weight of the belt is calculated. Assuming W [g weight], the friction coefficient is obtained by the following equation. This measuring method is based on Euler's belt type.
Friction coefficient = (1 / θ) ln (F / W)

  An example of a chart obtained by this measurement method is shown in FIG. In the figure, the value immediately after the charging member is rotated is the force necessary to start the rotation, and the subsequent force is the force necessary to continue the rotation. Therefore, the rotation start point (that is, t = 0). The friction coefficient at [second] is the static friction coefficient. The friction coefficient at an arbitrary time when t> 0 [seconds] is a dynamic friction coefficient at an arbitrary time. In the present invention, the friction coefficient obtained after 10 seconds from the rotation start point is used as the dynamic friction coefficient (μ). In the present invention, W = 100 g weight, the charging member rotation speed was 115 rpm, and the measurement environment was 23 ° C./50% RH.

・ Content of functional group in polysiloxane A sample of about 1 mg from the surface layer of the charging roller using a three-dimensional coarse / fine motion micromanipulator (manufactured by Narishige Co., Ltd.) installed in an optical microscope under a 10 to 1000 times optical microscope. Were collected. The collected sample was traced as a function of temperature simultaneously with the weight change by the TG-MS method (the MS device was directly connected to the TG device) at the same time as the weight change. Table 6 shows the measurement conditions.

  According to a TG-DTG (Derivative thrombometry) curve obtained by measurement under the above conditions, two-stage significant weight loss was observed at around 400 ° C. to 500 ° C. and around 500 ° C. to 650 ° C.

  Here, peaks such as mass numbers (m / z) 16, 31, 41, 43, 58, 59, 78, 91 were observed for gases generated at 400 ° C. to 500 ° C. About these peaks, mass numbers (m / z) 31, 43, 58, 59 are derived from oxyalkylene groups, mass numbers (m / z) 78 (benzene), 91 (toluene) are derived from aryl groups, and masses. Numbers (m / z) 16, 41, etc. were identified as originating from alkyl groups. The oxyalkylene group is derived from a glycidoxy group from glycidoxypropyltriethoxysilane. From these peaks, the amount of gas components derived from the above groups generated from polysiloxane decomposed at 400 to 500 ° C. was determined. Moreover, the weight reduction rate by the gas component originating in each said group generate | occur | produced at each temperature was calculated | required from the quantity of the gas component originating in each of these groups, and the measured weight reduction rate. This was integrated over the said 400 to 500 degreeC, and content of the oxyalkylene group, the aryl group, and the alkyl group in polysiloxane was calculated | required.

  Further, for gases generated at 500 ° C. to 650 ° C., fluorinated alkyl groups (tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane) having mass numbers (m / z) 51, 69, 119, and 131 are used. From the fluorinated alkyl group). From these peaks, the amount of the gas component derived from the fluorinated alkyl group generated from the polysiloxane decomposed at each temperature of 500 ° C. to 650 ° C. was determined. Moreover, the weight reduction rate by the gas component derived from the fluorinated alkyl group generated at each temperature was determined from the amount of the gas component derived from the fluorinated alkyl group and the measured weight reduction rate. This was integrated over the above temperature range of 500 ° C. to 600 ° C. to determine the content of fluorinated alkyl groups in the polysiloxane.

  In addition, it is thought that a residue is a siloxane part in polysiloxane.

<Production Example 16 Charging member 2>
A charging member 2 was produced in the same manner as in Production Example 15 except that the formulation of the hydrolyzable silane compound in the preparation of the surface layer coating solution was changed as follows.
・ PhTES 42.12 g (0.175 mol)
(Equivalent to 54.75 mol% with respect to the total amount of hydrolyzable silane compound)
・ GPTES 16.26 g (0.058 mol)
・ HETMS 13.18 g (0.064 mol)
FTS (carbon number of perfluoroalkyl group 6) 11.42 g (0.022 mol)
・ Water 25.93g
・ Ethanol 67.21g

<Production Example 17 Charging member 3>
The charging member 3 was produced in the same manner as in Production Example 15 except that the formulation of the hydrolyzable silane compound in the preparation of the surface layer coating solution was changed as follows.
・ PhTES 43.08 g (0.179 mol)
(Equivalent to 56.00 mol% with respect to the total amount of hydrolyzable silane compounds)
・ GPTES 12.47 g (0.045 mol)
・ HETMS 13.18 g (0.064 mol)
FTS (carbon number of perfluoroalkyl group 6) 16.32 g (0.032 mol)
・ Water 25.93g
・ Ethanol 72.54g

<Production Example 18 charging member 4>
The charging member 4 was produced in the same manner as in Production Example 15 except that the formulation of the hydrolyzable silane compound in the preparation of the surface layer coating solution was changed as follows.
・ PhTES 53.54 g (0.223 mol)
(Equivalent to 69.60 mol% with respect to the total amount of hydrolyzable silane compound))
・ GPTES 15.50 g (0.056 mol)
・ HETMS 6.59g (0.032mol)
-FTS (carbon number of perfluoroalkyl group 6) 4.90 g (0.010 mol)
・ Water 25.93g
・ Ethanol 57.40g

<Production Example 19 Charging Member 5>
A charging member 5 was produced in the same manner as in Production Example 15 except that the formulation of the hydrolyzable silane compound in the preparation of the coating solution for the surface layer was changed as follows.
・ PhTES 40.62 g (0.169 mol)
(Equivalent to 52.80 mol% with respect to the total amount of hydrolyzable silane compound)
・ GPTES 11.76 g (0.042 mol)
・ HETMS 13.18 g (0.064 mol)
FTS (carbon number of perfluoroalkyl group 6) 22.85 g (0.045 mol)
・ Water 25.93g
・ 81.18g of ethanol

<Production Example 20 charging member 6>
A charging member 6 was produced in the same manner as in Production Example 15 except that the formulation of the hydrolyzable silane compound in the preparation of the surface layer coating solution was changed as follows.
-PhTES 48.62g (0.202mol)
(Equivalent to 63.20 mol% with respect to the total amount of hydrolyzable silane compound)
・ GPTES 14.08 g (0.051 mol)
・ HETMS 13.18 g (0.064 mol)
FTS (carbon number of perfluoroalkyl group 6) 1.63 g (0.003 mol)
・ Water 25.93g
・ Ethanol 53.11g

<Production Example 21 Charging member 7>
A charging member 7 was produced in the same manner as in Production Example 15 except that the formulation of the hydrolyzable silane compound in the preparation of the surface layer coating solution was changed as follows.
・ PhTES 42.46g (0.177 mol)
(Equivalent to 55.20 mol% with respect to the total amount of hydrolyzable silane compounds)
・ GPTES 12.29g (0.044mol)
・ HETMS 6.59g (0.032mol)
-FTS (carbon number of perfluoroalkyl group 6) 34.27 g (0.067 mol)
・ Water 25.93g
・ 96.26g of ethanol

<Production Example 22 Charging member 8>
A coating solution for the surface layer was prepared in the same manner as in Production Example 15 except that the formulation of the hydrolyzable silane compound was changed as follows.
・ PhTES 44.47g (0.185mol)
(Equivalent to 59.49 mol% with respect to the total amount of hydrolyzable silane compounds)
・ HETMS 25.96 g (0.126 mol)
・ Water 24.77g
・ Ethanol 45.07g

  Next, a surface layer coating solution is ring-applied onto the conductive elastic layer of the conductive elastic roller after surface polishing produced in the same manner as in Production Example 15 (discharge amount: 0.020 ml / s, ring portion speed: 85 mm / s, total discharge amount: 0.065 ml). Then, it was left to stand in a hot air circulating furnace adjusted to 160 ° C. for 2 hours to cure the surface layer coating solution. The cured product is allowed to cool at room temperature for 1 hour to form a surface layer, and a support, a conductive elastic layer formed on the support, and a surface formed on the conductive elastic layer A charging roller (charging member 8) having a layer was produced.

<Manufacturing Example 23 Charging Member 9>
For the surface layer of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) prepared as follows on the conductive elastic layer of the conductive elastic roller after surface polishing produced in the same manner as in Production Example 15. The coating solution was spray applied. Then, it was left for 5 minutes in the hot air circulating furnace temperature-controlled at 250 degreeC, and the coating liquid for surface layers was hardened. The cured product is quenched with cold water, and is left to cool at room temperature for 1 hour to form a surface layer. The support, the conductive elastic layer formed on the support, and the conductive layer Charging roller (charging member 9) having a surface layer formed on an elastic layer

  Aqueous dispersion of PFA (trade name: AD2-CR aqueous dispersion, solid content concentration = 45 mass% to 50 mass%, specific gravity = 1.4, viscosity (25 ° C. · mPa · s) = 250 to 500, Daikin Industries Co., Ltd.) diluted 10 times with water was used as the surface layer coating solution.

  Compounding amount of raw materials for forming the surface layer of the charging member of Production Examples 15 to 23, physical properties of the charging member, and oxyalkylene group, aryl group, alkyl group, fluorinated alkyl group and siloxane contained in the surface layer of the charging member The contents of the parts are shown in Table 7.

Examples 1-16 and Comparative Examples 1-4
Using the photoreceptors shown in Production Examples 1 to 12 and the charging members shown in Production Examples 13 to 21, combinations shown in Table 8 were incorporated into the process cartridge as photoreceptors and charging members. The process cartridge is for a laser beam printer “Color Laser Printer 3500” (trade name, manufactured by Hewlett-Packard Japan). With this process cartridge, the slidability when repeatedly passing paper was evaluated.

  The above process cartridge was incorporated into a laser beam printer “Color Laser Printer 3500”, and output was performed in an intermittent output mode in which 10000 sheets at a process speed of 94 mm / s and idle rotation for 4 seconds were performed every two sheets. Image output in the intermittent output mode is more rigorous for evaluating wear resistance because the number of friction between the charging member and the photoconductor is greater even with the same number of sheets than in continuous sheet feeding. is there. Image output was performed in an environment of 30 ° C./80% RH, and an E character pattern with a printing rate of 1% was formed on A4 paper. The toner used for the evaluation includes particles obtained by suspension polymerization of a polymerizable monomer system containing a wax, a charge control agent, a dye, styrene, butyl acrylate, and an ester monomer in an aqueous medium. Polymerized toner. This toner is obtained by externally adding silica fine particles and titanium oxide fine particles to the above particles. The polymer toner has a glass transition temperature of 63 ° C. and a volume average particle size of 6 μm.

  The process cartridge used for image output was stabilized for 24 hours in a 30 ° C./80% RH environment with a photoreceptor and charging member incorporated.

(Image evaluation)
In the image evaluation, regarding the slidability, vertical stripes and horizontal stripes were observed as being caused by deterioration of the slidability between the charging member and the photosensitive member. The vertical stripe is a stripe-like image defect that appears as a toner density difference in a direction parallel to the long side of A4 paper. On the other hand, the horizontal streak is a streak-like image defect that appears in the vertical direction with respect to the vertical streak, and may be the period of the charging member and the photosensitive member period. Longitudinal streaks are considered to be mainly due to wear of the charging member or the photosensitive member accompanying deterioration of slidability. On the other hand, the horizontal streak is considered to be due to a charging failure accompanying deterioration of slidability. As an image used for the observation, an image (halftone image) in which a horizontal line having a width of 1 dot and an interval of 2 dots was formed on A4 paper in the direction perpendicular to the rotation direction of the electrophotographic photoreceptor. The output images obtained when the first image was output (initial stage), when the 5000th image was output, and when the 10,000th image was output were visually evaluated according to the following criteria.
A: No streak is observed at all.
○: Only a few streaks were observed.
Δ: A few streaks were observed.
X: Streaks were considerably observed.

  The obtained results are shown in Table 9.

  As described above, the process cartridge of the present invention exhibits excellent slidability even after repeated use, and can maintain high durability and high image quality.

It is a figure which shows an example of schematic structure of the process cartridge of this invention. It is a cross-sectional schematic diagram of a charging roller which is an example of a charging member of the present invention. It is a schematic diagram for demonstrating the contact angle measuring method in this invention. It is a schematic diagram for demonstrating the example of the vent type extruder in this invention. It is a schematic diagram for demonstrating the example of the continuous vulcanizer in this invention. It is a schematic diagram for demonstrating grinding | polishing of the elastic layer of the elastic roller in this invention. It is a schematic diagram for demonstrating the resistance measuring method of the elastic roller in this invention. It is a schematic diagram for demonstrating the method to measure the dynamic friction coefficient in this invention. It is a chart of an example of the measurement result of the dynamic friction coefficient in this invention.

Explanation of symbols

1 Photoconductor 2 Axis 3 Charging member (charging roller)
4 Exposure light 5 Developing means 6 Transfer means (transfer roller)
7 Cleaning means (cleaning blade)
8 Fixing means 9 Process cartridge 10 Guide means (guide rail)
P Transfer material 31 Core 40 Elastic roller 41 Aluminum drum 42 External power source 43 Reference resistance 50 Extruder 51 Cylinder 52 Screw 53 Cross head 54 Material inlet 55 Vent port 56 Die 57 Screw dam part 60 Vulcanization furnace 71 Elastic roller 72 Rotation Grinding wheel 73 Diamond blade 101 Support 102 Conductive elastic layer 103 Surface layer 103a Charging member surface 103b Droplet 201 Charging member 202 Belt 203 Weight 204 Load meter 205 Recorder

Claims (6)

A process cartridge that includes at least a photosensitive member and a charging member that charges the photosensitive member, and is detachable from an electrophotographic apparatus main body,
The photoreceptor is
A conductive support and a photosensitive layer; and
It has a repeating structural unit represented by the following general formula (1) and a repeating structural unit represented by the following general formula (2), one or both of the terminals have a terminal structure represented by the following general formula (3) , also includes a general formula (2) and the general formula (3) is m = n der relationship average repeating number m and n of the siloxane unit Ru in polycarbonate polymer, a polydimethylsiloxane represented by the following chemical formula (4) It has a surface layer,
The charging member includes a hydrolyzable silane compound represented by the following formula (5), a hydrolyzable silane compound having an aryl group represented by the following formula (6), and a cationic polymerizable compound represented by the following formula (7). A polysiloxane obtained by cleaving the cationically polymerizable group of a condensate having a cationically polymerizable group obtained by hydrolyzing a hydrolyzable silane compound having a different group, and having the chemical formula (4) A process cartridge having a surface layer having an outermost surface having a contact angle with respect to polydimethylsiloxane represented by the formula of 10.0 ° to 70.0 ° .

(In formula (1), X is a single bond, —O—, —S—, or a substituted or unsubstituted alkylidene group, and R ^{11 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, or an alkoxy group. A nitro group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and * represents a bonding position.)

(In the formula (2), R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group or an aryl group, and R ^{23 to} R ²⁶ are each independently a hydrogen atom, a halogen atom, substituted or unsubstituted. A represents an integer of 1 to 30, m represents an integer of 1 to 500, and * represents a bonding position.)

(In Formula (3), R ³¹ and R ³² are each independently a hydrogen atom, a halogen atom, an alkoxy group, a nitro group, a substituted or unsubstituted alkyl group or an aryl group, and R ³³ and R ³⁴ are each Independently a hydrogen atom, an alkyl group or an aryl group, R ^{35 to} R ³⁹ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or an aryl group, and b is 1 to 30 (An integer, n represents an integer of 1 to 500. * represents a bonding position.)

(In formula (4), l represents the average number of repeating units.)

(In the formula (5), R ⁵¹ and R ⁵² are each independently a substituted or unsubstituted alkyl group, Z ⁵¹ is a divalent organic group, and Rf ⁵¹ is a fluorinated C 1-11 carbon atom. An alkyl group, f is an integer of 0 to 2, g is an integer of 1 to 3, and f + g = 3.)

(In Formula (6), R ⁶¹ and R ⁶² are each independently a substituted or unsubstituted alkyl group, Ar ⁶¹ is an aryl group, i is an integer of 0 to 2, j is 1 to 3) (It is an integer and i + j = 3.)

(In formula (7), R ⁷¹ and R ⁷² are each independently a substituted or unsubstituted alkyl group, Z ⁷¹ is a divalent organic group, and Rc ⁷¹ is a cationically polymerizable group. D is an integer from 0 to 2, e is an integer from 1 to 3, and d + e = 3.) The surface layer of the photoreceptor is
The polydimethylsiloxane represented by the chemical formula (4) is contained in a proportion of 5% by mass or more and 20% by mass or less based on the polycarbonate polymer , and
The polydimethylsiloxane represented by the chemical formula (4) and the polycarbonate polymer are contained at a ratio of 0.1% by mass or more and 5.0% by mass or less with respect to the total solid content of the surface layer. Process cartridge. M in the general formula (2), n in the general formula (3), and l in the chemical formula (4) are 10 to 100 , and m = n = 1, The process cartridge according to claim 1 or 2, wherein the proportion of the siloxane part in the coalescence is 10 mass% or more and 60 mass% or less. Wherein a in the general formula (2) is 3 or less, neither R ²³ or R ²⁶ is a methyl group, and wherein it b is 3 or less in the general formula (3), both R ³³ to R ³⁹ is the process cartridge according to any one of claims 1 to 3 methyl groups. A process cartridge according to any one of claims 1 to 4 number ratio Y of fluorine atoms contained per unit area of the outermost surface is less than 40.00% or more 5.00% of the surface layer of the charging member . The process cartridge according to claim 1 , wherein the cationically polymerizable group is an epoxy group.

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