JP2016142916A - Image forming apparatus and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming apparatus that suppresses the occurrence of unevenness in image density and wear and chipping of a cleaning blade even after a single image is repeatedly formed.SOLUTION: An image forming apparatus comprises: a photoreceptor that includes an outermost surface layer formed of a cured film of a composition including a reactive charge transport material; means that is arranged in contact or in proximity with the surface of the photoreceptor and charges the surface of the photoreceptor; means that forms an electrostatic latent image on the charged surface of the photoreceptor; means that stores a developer containing toner including toner particles and inorganic particles having a volume average particle diameter of 1 μm or less, and develops the electrostatic latent image formed on the surface of the photoreceptor with the developer to form a toner image; transfer means that transfers the toner image onto the surface of a recording medium; and means that includes a cleaning blade that is formed of a rubber-modified part injected with plasma ions at least at a contact part with the photoreceptor.SELECTED DRAWING: Figure 4

Description

  The present invention relates to an image forming apparatus and a process cartridge.

  An electrophotographic image forming apparatus generally has the following configuration and process. That is, the surface of the electrophotographic photosensitive member is charged to polarity and potential, and the surface of the charged electrophotographic photosensitive member is selectively neutralized by image exposure to form an electrostatic latent image, and then the electrostatic latent image is formed. By applying toner to the image, the latent image is developed as a toner image, and the toner image is transferred to a recording medium to be discharged as an image formed product.

  In recent years, an electrophotographic photosensitive member has an advantage that high-speed and high printing quality can be obtained, so that it is increasingly used in fields such as a copying machine and a laser beam printer.

  As electrophotographic photoreceptors used in these image forming apparatuses, conventional electrophotographic photoreceptors (inorganic photoreceptors) using inorganic photoconductive materials such as selenium, selenium-tellurium alloys, selenium-arsenic alloys, and cadmium sulfide are known. In recent years, organic photoreceptors (organic photoreceptors) using organic photoconductive materials, which are inexpensive and have excellent advantages in terms of manufacturability and disposal, have come to dominate.

  In order to increase the life and reliability of the electrophotographic photosensitive member, it has been proposed to improve the strength by providing a protective layer on the surface of the electrophotographic photosensitive member.

The following materials have been proposed as a material system for forming the protective layer.
That is, for example, Patent Document 1 includes a conductive powder dispersed in a phenol resin, Patent Document 2 includes an organic-inorganic hybrid material, and Patent Document 3 includes an alcohol-soluble charge transport material and a phenol resin. Are disclosed respectively.
Patent Document 4 discloses a cured film of an alkyl etherified benzoguanamine / formaldehyde resin and an electron-accepting carboxylic acid or an electron-accepting polycarboxylic acid anhydride, and Patent Document 5 discloses a benzoguanamine resin containing iodine, A cured film doped with an organic sulfonic acid compound or ferric chloride is disclosed in Patent Document 6 as a cured film of a specific additive and a phenol resin, a melamine resin, a benzoguanamine resin, a siloxane resin, or a urethane resin. Is disclosed as a protective layer.

In recent years, a protective layer made of an acrylic material has attracted attention. For example, Patent Document 7 discloses a film obtained by curing a liquid containing a photocurable acrylic monomer, and Patent Document 8 discloses a monomer having a carbon-carbon double bond and a charge transfer having a carbon-carbon double bond. A film formed by reacting a carbon-carbon double bond of the monomer and a carbon-carbon double bond of the charge transfer material with a mixture of a material and a binder resin by heat or light energy is disclosed in Patent Literature Nos. 9 and 10 disclose a film made of a compound obtained by polymerizing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule as a protective layer. Patent Document 11 discloses an electrophotographic photoreceptor using a film made of a compound obtained by polymerizing a styryl group-modified hole transporting compound.
Since these hole-transporting compounds having a chain polymerizable functional group are strongly affected by curing conditions, curing atmosphere, etc., for example, Patent Document 12 discloses heating in a vacuum or inert gas after irradiation with radiation. Patent Document 13 discloses a film formed by heating and curing in an inert gas.
Furthermore, for example, Patent Documents 8 and 14 disclose that the charge transport material itself is acrylic-modified so that it can be crosslinked and a reactive monomer having no charge transport property is added to improve the film strength. ing.

Furthermore, the following things are proposed as a protective layer by a reaction material and a cured film.
For example, Patent Document 15 discloses a protective layer containing a compound obtained by modifying the charge transport material itself into a polyfunctional compound having three or more functions and polymerizing the same. Patent Document 16 discloses a technique in which a polymer of a charge transport material having a chain polymerizable functional group is used for a protective layer, and also contains fluorine atoms as a lubricant in order to improve friction characteristics. A technique for containing a compound in a protective layer is disclosed. In addition, Patent Document 17 discloses that both the mechanical characteristics and the electrical characteristics can be achieved by increasing the concentration of the charge transport material having a chain polymerizable functional group from the outermost surface toward the inside.

  Patent Document 18 discloses a first charge transporting compound having one or more chain polymerizable functional groups and a chain polymerizable property of 5.0 to 45.0 wt% with respect to the first charge transporting compound. The inclusion of a second charge transporting compound having no functional group is disclosed. Patent Document 19 discloses that a first charge transporting compound having at least an acryloyloxy group or a methacryloyloxy group and a second charge transporting compound having a hydroxyl group are contained. Patent Document 20 discloses that the same low molecular charge transport material as that of the charge transport layer is further contained in the cross-linked charge transport layer.

On the other hand, the following has been proposed as a cleaning blade for cleaning the surface of the electrophotographic photosensitive member.
For example, Patent Document 21 discloses that a cured layer having a predetermined shape is formed by reacting an isocyanate compound and a polyurethane resin at a toner holding member contact portion, and a tan δ of a cured layer and a tan δ of a free length portion. A cleaning blade for controlling the relationship is disclosed.
Further, Patent Document 22 discloses an electrophotographic cleaner blade whose surface is covered with a plasma polymerization film made of an amorphous carbon film in which an organic compound is deposited by glow discharge plasma in vacuum.
Further, in Patent Document 23, in a cleaning device that cleans image-forming particles remaining on an image carrier, the shape of the contact portion with the image carrier and the contact with the image carrier is irrespective of the stoppage of the movement of the image carrier. The cleaning member has a non-deformed state, and the cleaning member includes a plate-like base substrate and a coating layer that covers at least a portion of the base substrate corresponding to the contact portion with the image carrier. And the coating layer includes: a. Vickers hardness is 1500 Hv or more, b. The coefficient of friction is smaller than the coefficient of friction of the base substrate before coating, c. A cleaning member that satisfies that the surface roughness is equal to or less than the surface roughness of the base substrate before coating is disclosed.

Patent Document 24 discloses a cleaning blade in which a urethane lubricant cleaning blade is cured with an isocyanate compound at a contact portion with a member to be cleaned, and a CVD lubricating film is formed by plasma ion implantation / film formation. Has been.

Patent Document 25 discloses a blade for an image forming apparatus which is made of a sheet-like polyurethane rubber molded body and rubs the surface of a moving member to which toner is adhered, and carbon is plasma-polymerized on the surface of the polyurethane rubber molded body. An image forming apparatus blade in which the low friction layer 1a is combined is disclosed.

Japanese Patent No. 3287678 Japanese Patent Laid-Open No. 12-019749 JP 2002-82469 A Japanese Patent Laid-Open No. 62-251757 Japanese Patent Laid-Open No. 7-146564 JP 2006-84711 A JP-A-5-40360 JP-A-5-216249 JP 2000-206715 A JP 2001-166509 A Japanese Patent No. 2852464 Japanese Patent Laid-Open No. 2004-12986 Japanese Patent Laid-Open No. 7-72640 JP 2004-302450 A JP 2000-206717 A JP 2001-175016 A JP 2007-86522 A Japanese Patent Laid-Open No. 2005-62301 Japanese Patent Laid-Open No. 2005-62302 Japanese Patent Laid-Open No. 2006-13895 JP 2001-343874 A JP-A 64-90484 JP-A-2005-274592 JP2013-80077A JP-A-9-160457

  An object of the present invention is a cured film of a composition containing a reactive charge transport material, an electrophotographic photosensitive member having an outermost surface layer formed thereon, and disposed in contact with or close to the surface of the electrophotographic photosensitive member. Charging means for charging the surface of the photoreceptor, electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged electrophotographic photoreceptor, toner particles, and inorganic particles having a volume average particle diameter of 1 μm or less. A developer containing toner is accommodated, and the developer is used to develop the electrostatic latent image formed on the surface of the electrophotographic photosensitive member to form a toner image, and the toner image is transferred to the surface of the recording medium. A cleaning blade that contacts the surface of the electrophotographic photosensitive member with the transfer means and cleans the surface of the electrophotographic photosensitive member, and at least the contact portion with the electrophotographic photosensitive member is composed of an unmodified rubber portion. Cleaning blur Compared with an image forming apparatus comprising: a cleaning unit having a de, and even when repeatedly formed with the same image, the occurrence of image density unevenness is to provide an inhibiting image forming apparatus wear and chipping of the cleaning blade.

  The above problem is solved by the following means.

The invention according to claim 1
An electrophotographic photosensitive member having a conductive substrate and a photosensitive layer provided on the conductive substrate, and a cured film of a composition containing a reactive charge transport material, the outermost surface layer of which is formed;
A charging means disposed in contact with or in proximity to the surface of the electrophotographic photosensitive member to charge the surface of the electrophotographic photosensitive member;
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged electrophotographic photosensitive member;
A developer containing toner having toner particles and inorganic particles having a volume average particle size of 1 μm or less is accommodated, and the electrostatic latent image formed on the surface of the electrophotographic photosensitive member is developed with the developer to form a toner image. Developing means for forming;
Transfer means for transferring the toner image to the surface of the recording medium;
A cleaning blade that contacts the surface of the electrophotographic photosensitive member and cleans the surface of the electrophotographic photosensitive member, wherein at least the contact portion with the electrophotographic photosensitive member is a rubber-modified portion into which plasma ions are implanted Cleaning means having a cleaning blade,
An image forming apparatus comprising:

The invention according to claim 2
The image forming apparatus according to claim 1, wherein the contact portion of the cleaning blade is formed of a rubber reforming portion containing carbon having sp3 bonds.

The invention according to claim 3
The contact portion of the cleaning blade is a rubber modified portion containing carbon having sp3 bonds, and a carbon layer containing carbon having sp3 bonds provided on the surface of the rubber modified portion on the electrophotographic photoreceptor side, The image forming apparatus according to claim 1, comprising:

The invention according to claim 4
The contact portion of the cleaning blade includes a rubber modified portion containing carbon having sp3 bonds, and a diamond-like carbon layer provided on the surface of the rubber modified portion on the electrophotographic photoreceptor side. The image forming apparatus according to claim 1.

The invention according to claim 5
The image according to any one of claims 1 to 4, wherein the reactive charge transport material is at least one selected from chain polymerizable compounds represented by the following general formulas (I) and (II). Forming equipment.

  [In general formula (I), F represents a charge transporting skeleton. L represents a divalent linking group containing two or more selected from the group consisting of an alkylene group, an alkenylene group, -C (= O)-, -N (R)-, -S-, and -O-. Show. R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. m represents an integer of 1 or more and 8 or less. ]

  [In General Formula (II), F represents a charge transporting skeleton. L ′ represents a trivalent or tetravalent group derived from an alkane or alkene, and an alkylene group, alkenylene group, —C (═O) —, —N (R) —, —S—, and —O—. (N + 1) -valent linking groups containing two or more selected from the group consisting of: R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. m ′ represents an integer of 1 to 6. n represents an integer of 2 or more and 3 or less. ]

The invention according to claim 6
An electrophotographic photosensitive member having a conductive substrate and a photosensitive layer provided on the conductive substrate, and a cured film of a composition containing a reactive charge transport material, the outermost surface layer of which is formed;
A charging means disposed in contact with or in proximity to the surface of the electrophotographic photosensitive member to charge the surface of the electrophotographic photosensitive member;
A developer containing toner having toner particles and inorganic particles having a volume average particle size of 1 μm or less is accommodated, and the electrostatic latent image formed on the surface of the electrophotographic photosensitive member is developed with the developer to form a toner image. Developing means for forming;
A cleaning blade that contacts the surface of the electrophotographic photosensitive member and cleans the surface of the electrophotographic photosensitive member, wherein at least the contact portion with the electrophotographic photosensitive member is a rubber-modified portion into which plasma ions are implanted Cleaning means having a cleaning blade,
With
A process cartridge that can be attached to and detached from an image forming apparatus.

  According to the invention according to claim 1, 2, 3, or 4, an electrophotographic photosensitive member having an outermost surface layer formed of a cured film of a composition containing a reactive charge transport material, and a surface of the electrophotographic photosensitive member A charging means for charging the surface of the electrophotographic photosensitive member, which is disposed in contact with or in proximity to the photosensitive member, an electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged electrophotographic photosensitive member, toner particles and volume A developing unit that contains a developer containing toner having inorganic particles having an average particle diameter of 1 μm or less, and develops the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with the developer to form a toner image; A transfer means for transferring the toner image to the surface of the recording medium; and a cleaning blade for contacting the surface of the electrophotographic photosensitive member and cleaning the surface of the electrophotographic photosensitive member, wherein at least a contact portion with the electrophotographic photosensitive member is provided The rubber part is not modified. Compared with an image forming apparatus having a cleaning means having a cleaning blade, an image forming apparatus is provided that suppresses wear and chipping of the cleaning blade as well as occurrence of uneven image density even when the same image is repeatedly formed. The

  According to the fifth aspect of the present invention, the rubber modified in which plasma ion implantation is performed on at least the contact portion between the electrophotographic photosensitive member having the outermost surface layer containing only the non-reactive charge transporting material as the charge transporting material. An image forming method is provided that suppresses excessive wear of the electrophotographic photosensitive member when the same image is repeatedly formed as compared with a case where a cleaning unit having a cleaning blade composed of a material portion is provided.

According to the invention of claim 6, the cured film of the composition containing the reactive charge transport material, the electrophotographic photosensitive member having the outermost surface layer, and the surface of the electrophotographic photosensitive member are arranged in contact with or close to each other. Charging means for charging the surface of the electrophotographic photosensitive member, electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged electrophotographic photosensitive member, and inorganic particles having a volume average particle size of 1 μm or less. A developing unit that contains a developer containing toner having particles and develops the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with the developer to form a toner image; and the surface of the electrophotographic photosensitive member A cleaning blade that cleans the surface of the electrophotographic photosensitive member in contact with the cleaning member, wherein at least a contact portion with the electrophotographic photosensitive member includes a cleaning blade that is formed of an unmodified rubber portion; The Compared to example was the process cartridge, even when forming repeatedly the same image, the occurrence of uneven image density, inhibit the process cartridge is provided with wear and chipping of the cleaning blade.
.

1 is a schematic partial cross-sectional view illustrating an example of a layer configuration of an electrophotographic photoreceptor according to an exemplary embodiment. FIG. 6 is a schematic partial cross-sectional view illustrating another example of the layer configuration of the electrophotographic photosensitive member according to the exemplary embodiment. FIG. 6 is a schematic partial cross-sectional view illustrating another example of the layer configuration of the electrophotographic photosensitive member according to the exemplary embodiment. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows another example of the image forming apparatus which concerns on this embodiment. It is a schematic diagram showing an example of a cleaning blade provided in the image forming apparatus according to the present embodiment. It is a schematic diagram which shows the image pattern output by an initial image test. It is a schematic diagram which shows the image pattern output by the output test of evaluation of image density nonuniformity. It is a schematic diagram which shows the image pattern output by evaluation of image density nonuniformity. It is a schematic diagram for demonstrating image density nonuniformity.

  Hereinafter, the present embodiment which is an example of the present invention will be described.

  An image forming apparatus according to the present embodiment includes an electrophotographic photosensitive member (hereinafter also referred to as “photosensitive member”), a charging unit that is in contact with or close to the surface of the photosensitive member, and charges the surface of the photosensitive member. An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the photoreceptor and a developer containing toner are accommodated, and the electrostatic latent image formed on the surface of the photoreceptor is developed with the developer. A developing unit that forms a toner image; a transfer unit that transfers the toner image to the surface of the recording medium; and a cleaning unit that has a cleaning blade that contacts the surface of the photoconductor and cleans the surface of the photoconductor.

  The image forming apparatus according to the present embodiment includes a charging step for charging the surface of the photoconductor by a charging unit disposed in contact with or close to the surface of the photoconductor, and an electrostatic latent image on the surface of the charged photoconductor. An electrostatic latent image forming step for forming, a developing step for developing the electrostatic latent image formed on the surface of the photoreceptor with a developer containing toner to form a toner image, and the toner image on the surface of the recording medium. An image forming method including a transfer step of transferring and a cleaning step of cleaning the surface of the photoconductor by a cleaning blade in contact with the surface of the photoconductor is performed.

The photoreceptor has a conductive substrate and a photosensitive layer provided on the conductive substrate, and is a cured film of a composition containing a reactive charge transporting material, and a photoreceptor (hereinafter referred to as “cured”). Also referred to as “type photoreceptor”.
In the cleaning blade, at least a contact portion (hereinafter also referred to as “photoreceptor contact portion”) with the curable photoreceptor is a rubber reforming portion (hereinafter also simply referred to as “rubber reforming portion”) in which plasma ions are implanted. It is configured.
The developer includes toner having toner particles and inorganic particles having a volume average particle diameter of 1 μm or less.

  In the image forming apparatus according to the present embodiment, with the above configuration, even when the same image is repeatedly formed, the occurrence of image density unevenness and the wear and chipping of the cleaning blade are suppressed. The reason for this is not clear, but is presumed to be as follows.

  First, a technique is known in which inorganic particles having a volume average particle diameter of 1 μm are externally added to toner particles in order to improve the fluidity of the toner. When the toner having inorganic particles is used and the same image is repeatedly formed, the residual toner locally reaches the cleaning blade, so that the inorganic particles contained in the toner may slip through. This is because the mechanical strength of the outermost surface layer of the curable photoconductor is high, so that a load is easily applied to the cleaning blade side, and the blade tip portion (contact portion with the photoconductor) is partially crushed and the curable photoconductor This is presumably because a phenomenon (hereinafter also referred to as “tuck under”) that creates a space with the outermost surface layer occurs. When this inorganic particle slips through, when a contact type or proximity type charging method is employed, the inorganic particle may partially adhere to the charging means, resulting in partial charging failure and uneven image density. .

In addition, the curable photoconductor having the outermost surface layer composed of a cured film of a composition containing a reactive charge transporting material has a characteristic that the outermost surface layer is difficult to wear because the outermost surface layer has high mechanical strength. Have. If the outermost surface layer is not properly worn, the discharge product or the like remains adhered to the surface of the outermost surface layer, charging failure or the like may occur, and image defects such as image flow may occur.
However, if the outermost surface layer of the curable photoconductor having high mechanical strength is appropriately worn, the cleaning blade is likely to be worn and chipped.

  On the other hand, if the photosensitive member contact portion of the cleaning blade is composed of a rubber modified portion modified by plasma ion implantation, both the mechanical strength and sliding property and toughness (flexibility) of the photosensitive member contact portion can be achieved. . When plasma ions are injected into a rubber part composed of rubber, it is considered that plasma ions break bonds between carbons in rubber, or bonds between carbon and hydrogen in rubber, and are replaced with carbon or hydrogen in rubber. It is done. As a result, the rubber part is modified by the plasma ions injected, and the rubber modified part has toughness (flexibility) derived from the rubber part, and the slidability is enhanced along with the mechanical strength. Because it is.

  For this reason, when a cleaning blade having at least a photoreceptor contact portion composed of a rubber reforming portion is used as a cleaning blade, a toner having inorganic particles having a volume average particle diameter of 1 μm is used, and when the same image is repeatedly formed, Even if the toner locally reaches the cleaning blade, the occurrence of tack under of the cleaning blade can be suppressed. Thereby, slipping of the inorganic particles contained in the toner is suppressed, and occurrence of image density unevenness that occurs when the contact type or proximity type charging method is adopted is suppressed. Even if the outermost surface layer of the curable photoconductor having high mechanical strength is appropriately worn, the cleaning blade is hardly worn or chipped.

  From the above, it is presumed that the image forming apparatus according to the present embodiment suppresses wear and chipping of the cleaning blade as well as occurrence of image density unevenness even when the same image is repeatedly formed.

In particular, in an environment of high temperature and high humidity (for example, 28 ° C. and 85% RH), the hardness of the cleaning blade is lowered, and tack-under is likely to occur. However, in the image forming apparatus according to the present embodiment, even if the same image is repeatedly formed in an environment of high temperature and high humidity (for example, 28 ° C. and 85% RH), the tacking under of the cleaning blade is suppressed, and the image density unevenness is reduced. Occurrence is suppressed.
Further, slipping through the inorganic particles tends to occur remarkably when the content (external addition amount) of the inorganic particles is high (for example, when the content of the inorganic particles is 0.5% by mass or more based on the toner particles). . However, in the image forming apparatus according to the present embodiment, even when the content (external addition amount) of the inorganic particles is high, the slipping of the inorganic particles is suppressed, and the occurrence of uneven image density is suppressed.
Further, in the image forming apparatus according to the present embodiment, since the mechanical contact and the sliding property of the photosensitive member contact portion of the cleaning blade are high, the outermost surface layer of the curable photosensitive member having high mechanical strength is formed over a long period of time. It is moderately worn. As a result, the state in which the discharge product or the like is fixed to the surface of the outermost surface layer of the curable photoconductor is easily resolved, and the image flow is easily suppressed over a long period of time.

  In addition, in a color image forming method (apparatus) that is a combination of an image forming process (image forming unit) of a cyan image, a magenta image, a yellow image, and a black image that are commonly used, about an image output in the market. 20% to 30% are color images. That is, in the market, image formation using an image forming process (image forming unit) of a cyan image, a magenta image, a yellow image, and a black image is only about 20% to 30% of the total output. On the other hand, in the market, an image forming unit (image forming process) for black images is used for almost all outputs, and therefore, the image is not uniform in image density, and the cleaning blade is likely to be worn and chipped. This is the same because a monochrome image forming method (apparatus) using only a black image forming unit (image forming process) is also used most in the market.

For this reason, the image forming apparatus according to the present embodiment is preferably applied with an image forming unit (image forming process) of a black image that is most utilized in use.
Specifically, the image forming apparatus according to the present embodiment stores a developer containing black toner, and develops an electrostatic latent image formed on the surface of the photoreceptor with the developer to develop a black ( It is preferable to provide developing means for forming a black) toner image. Then, the image forming method performed by the image forming apparatus according to the present embodiment develops the electrostatic latent image formed on the surface of the photosensitive member with a developer containing black (black) toner, thereby black (black). It is preferable to have a developing step for forming a toner image.

In the image forming apparatus according to the present invention, the reactive charge transport material has at least a charge transporting skeleton and a chain polymerizable functional group in the same molecule from the viewpoint of high mechanical strength and suppressing excessive wear of the photoreceptor. It is preferable that it is a chain polymerizable compound.
In particular, in addition to the same viewpoint, from the viewpoint of electrical characteristics, the chain polymerizable compound is a chain polymerizable compound represented by the general formulas (I) and (II) (hereinafter also referred to as “specific chain polymerizable charge transport material”). It is good that it is at least one selected from. The reason for this is not clear, but is thought to be as follows.

A cured film of a composition containing at least one selected from a specific chain polymerizable charge transport material (a film containing a polymer or a cross-linked product (particularly a cross-linked product) of a specific chain polymerizable charge transport material) As a result, the outermost surface layer has excellent electrical properties and mechanical strength. Moreover, thickening of the outermost surface layer (for example, 10 μm or more) is also realized. This is because the specific chain polymerizable charge transport material itself has excellent charge transport performance, and there are few polar groups that hinder carrier transport such as -OH and -NH-, and styryl groups having π electrons effective for carrier transport. This is considered to be because the material is linked by polymerization with (vinylphenyl group), so that residual strain is suppressed and formation of a structural trap for trapping charges is suppressed.
In addition, since a specific chain polymerizable charge transport material has a property of being more hydrophobic and less susceptible to moisture than an acrylic material, it is considered that electric characteristics are easily maintained over a long period of time.
Therefore, a cured film of a composition containing at least one selected from a specific chain polymerizable charge transport material (a film containing a polymer or a crosslinked product of a specific chain polymerizable charge transport material) is used as the outermost layer. As a result, the electrical characteristics and mechanical strength of the outermost surface layer are easily increased.

On the other hand, a specific chain-polymerizable charge transport material has a styryl group, and this styryl group has high affinity with a general non-reactive charge transport material having no reactive group. That is, it is easy to increase the amount of the non-reactive charge transport material included in the outermost surface layer. For this reason, adjustment of the mechanical strength of the outermost surface layer (for example, intentional reduction of the mechanical strength) is easily realized by the amount of the non-reactive charge transport material to be included.
In particular, among specific chain polymerizable charge transport materials, a material having an ether bond (—O—) as a linking group between a charge transport skeleton and a chain polymerizable functional group (for example, L in the general formula (I)) A material in which the group shown has an ether bond (—O—), a material in which the group represented by L ′ in the general formula (II) has an ether bond (—O—), the general formula (IIA-a3) or (IIA— The material having a4), etc. has a low polarity, so has a high charge transporting property and a high affinity with a non-reactive charge transporting material, and adjustment of the mechanical strength of the outermost surface layer (for example, mechanical strength) (Intentional reduction) is easy to achieve.
Therefore, applying a specific chain polymerizable charge transport material as the reactive charge transport material is effective in controlling the wear rate of the photoreceptor.

Here, the image forming apparatus according to the present embodiment includes a fixing unit that fixes the toner image transferred to the surface of the recording medium; the toner image formed on the surface of the electrophotographic photosensitive member is directly transferred to the recording medium. Direct transfer system device; primary transfer of the toner image formed on the surface of the electrophotographic photosensitive member to the surface of the intermediate transfer member, and secondary transfer of the toner image transferred to the surface of the intermediate transfer member to the surface of the recording medium An intermediate transfer system device; a device equipped with a charge eliminating means for irradiating the surface of an image holding member with a charge eliminating light after charging a toner image and before charging; increasing the temperature of the electrophotographic photosensitive member to reduce the relative temperature For example, a known image forming apparatus such as an apparatus provided with an electrophotographic photosensitive member heating member is used.
In the case of an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body on which a toner image is transferred to the surface and a primary transfer that primarily transfers the toner image formed on the surface of the image holding body to the surface of the intermediate transfer body. And a secondary transfer unit that secondarily transfers the toner image transferred onto the surface of the intermediate transfer member onto the surface of the recording medium.

The image forming method performed by the image forming apparatus according to the present embodiment includes a fixing step of fixing the toner image transferred onto the surface of the recording medium; and a toner image formed on the surface of the electrophotographic photosensitive member. A direct transfer method in which the toner image formed on the surface of the electrophotographic photosensitive member is primarily transferred to the surface of the intermediate transfer member, and the toner image transferred to the surface of the intermediate transfer member is transferred to the recording medium; Method of intermediate transfer method for secondary transfer to the surface; Method of having a charge eliminating step of irradiating the surface of the image carrier with charge removing light before charging after transferring the toner image; Increasing the temperature of the electrophotographic photosensitive member A known image forming method such as a method having a step of reducing the relative temperature is applied.
In the case of the intermediate transfer method, the transfer method includes, for example, a primary transfer method in which a toner image formed on the surface of the image carrier is primarily transferred onto the surface of the intermediate transfer member, and a toner transferred on the surface of the intermediate transfer member. And a secondary transfer method for secondary transfer of the image onto the surface of the recording medium.

  The image forming apparatus according to the present embodiment may be either a dry developing type image forming apparatus or a wet developing type (developing type using a liquid developer).

  Note that in the image forming apparatus according to the present embodiment, for example, the portion including the electrophotographic photosensitive member may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, a process cartridge including an electrophotographic photosensitive member, a developing unit, and a cleaning unit is preferably used. In addition to the electrophotographic photosensitive member, the process cartridge may include at least one selected from the group consisting of a charging unit, an electrostatic latent image forming unit, and a transfer unit.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

FIG. 4 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present embodiment.
As shown in FIG. 4, the image forming apparatus 100 according to this embodiment includes a process cartridge 300 including an electrophotographic photosensitive member 7, an exposure device 9 (an example of an electrostatic latent image forming unit), and a transfer device 40 (primary. Transfer device) and an intermediate transfer member 50. In the image forming apparatus 100, the exposure device 9 is disposed at a position where the electrophotographic photosensitive member 7 can be exposed from the opening of the process cartridge 300, and the transfer device 40 is interposed between the electrophotographic photosensitive member via the intermediate transfer member 50. 7, and a part of the intermediate transfer member 50 is disposed in contact with the electrophotographic photosensitive member 7. Although not shown, it also has a secondary transfer device that transfers the toner image transferred to the intermediate transfer member 50 to a recording medium (for example, paper). The intermediate transfer member 50, the transfer device 40 (primary transfer device), and the secondary transfer device (not shown) correspond to an example of a transfer unit.

  In the process cartridge 300 in FIG. 4, an electrophotographic photosensitive member 7, a charging device 8 (an example of a charging unit), a developing device 11 (an example of a developing unit), and a cleaning device 13 (an example of a cleaning unit) are integrated in a housing. I support it. The cleaning device 13 includes a cleaning blade (an example of a cleaning member) 131, and the cleaning blade 131 is disposed so as to contact the surface of the electrophotographic photosensitive member 7.

  In FIG. 4, as an image forming apparatus, a fibrous member 132 (roll shape) for supplying the lubricant 14 to the surface of the electrophotographic photosensitive member 7 and a fibrous member 133 (flat brush shape) for assisting cleaning are shown. Examples are provided, but these are arranged as necessary.

  Hereinafter, each configuration of the image forming apparatus according to the present embodiment will be described.

(Electrophotographic photoreceptor)
The electrophotographic photoreceptor 7 has a conductive substrate and a photosensitive layer provided on the conductive substrate. The outermost surface layer of the photoreceptor is composed of a cured film of a composition containing a reactive charge transport material.

In the electrophotographic photoreceptor 7, the outermost surface layer only needs to form the uppermost surface of the electrophotographic photoreceptor 7 itself, and is provided as a layer that functions as a protective layer or a layer that functions as a charge transport layer. . When the outermost surface layer is a layer functioning as a protective layer, a photosensitive layer composed of a charge transport layer and a charge generation layer or a single-layer type photosensitive layer is provided under the protective layer.
Specifically, in the case where the outermost surface layer functions as a protective layer, a photosensitive layer (a charge generation layer and a charge transport layer or a single-layer type photosensitive layer) is formed on the conductive substrate, and a protective layer is formed as the outermost surface layer. Are formed sequentially. On the other hand, in the case where the outermost surface layer functions as a charge transport layer, an embodiment in which a charge generation layer and a charge transport layer as the outermost surface layer are sequentially formed on a conductive substrate can be mentioned.

  Hereinafter, the electrophotographic photoreceptor 7 in the case where the outermost surface layer is a layer functioning as a protective layer will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 1 is a schematic cross-sectional view showing an example of the electrophotographic photosensitive member according to the present embodiment. 2 to 3 are schematic sectional views showing other examples of the electrophotographic photosensitive member according to this embodiment.

  An electrophotographic photoreceptor 7A shown in FIG. 1 is a so-called function-separated photoreceptor (or laminated photoreceptor), and an undercoat layer 1 is provided on a conductive substrate 4, on which a charge generation layer 2 and a charge are formed. The transport layer 3 and the protective layer 5 have a structure formed sequentially. In the electrophotographic photoreceptor 7A, the charge generation layer 2 and the charge transport layer 3 constitute a photosensitive layer.

An electrophotographic photoreceptor 7B shown in FIG. 2 is a function-separated type photoreceptor in which the functions are separated into the charge generation layer 2 and the charge transport layer 3 like the electrophotographic photoreceptor 7A shown in FIG.
In the electrophotographic photoreceptor 7B shown in FIG. 2, a structure in which an undercoat layer 1 is provided on a conductive substrate 4, and a charge transport layer 3, a charge generation layer 2, and a protective layer 5 are sequentially formed thereon. It is what has. In the electrophotographic photoreceptor 7B, the charge transport layer 3 and the charge generation layer 2 constitute a photosensitive layer.

  The electrophotographic photoreceptor 7C shown in FIG. 3 contains a charge generation material and a charge transport material in the same layer (single layer type photosensitive layer 6). The electrophotographic photoreceptor 7C shown in FIG. 3 has a structure in which an undercoat layer 1 is provided on a conductive substrate 4, and a single-layer type photosensitive layer 6 and a protective layer 5 are sequentially formed thereon. .

In the electrophotographic photoreceptors 7A, 7B and 7C shown in FIGS. 1, 2 and 3, the protective layer 5 is the outermost surface layer disposed on the side farthest from the conductive substrate 4, and The surface layer has the above-described configuration.
In the electrophotographic photosensitive member shown in FIGS. 1, 2, and 3, the undercoat layer 1 may or may not be provided.

  Hereinafter, each element will be described based on the electrophotographic photosensitive member 7A shown in FIG. 1 as a representative example. Note that the reference numerals are omitted.

(Conductive substrate)
Examples of the conductive substrate include metal plates (eg, aluminum, copper, zinc, chromium, nickel, molybdenum, vanadium, indium, gold, platinum, etc.) or alloys (stainless steel, etc.), metal drums, metal belts, etc. Is mentioned. In addition, as the conductive substrate, for example, paper, resin film, belt, etc. coated, vapor-deposited or laminated with a conductive compound (for example, conductive polymer, indium oxide, etc.), metal (for example, aluminum, palladium, gold, etc.) or an alloy. Also mentioned. Here, “conductive” means that the volume resistivity is less than 10 ¹³ Ωcm.

  When the electrophotographic photosensitive member is used in a laser printer, the surface of the conductive substrate has a center line average roughness Ra of 0.04 μm or more and 0.5 μm for the purpose of suppressing interference fringes generated when laser light is irradiated. The surface is preferably roughened below. When non-interfering light is used as a light source, roughening for preventing interference fringes is not particularly required, but it is suitable for extending the life because it suppresses generation of defects due to irregularities on the surface of the conductive substrate.

  Examples of roughening methods include wet honing by suspending an abrasive in water and spraying the conductive substrate, centerless grinding in which the conductive substrate is pressed against a rotating grindstone, and grinding is performed continuously. And anodizing treatment.

  As a roughening method, without roughening the surface of the conductive substrate, conductive or semiconductive powder is dispersed in the resin to form a layer on the surface of the conductive substrate. The method of roughening by the particle | grains disperse | distributed in a layer is also mentioned.

  In the roughening treatment by anodic oxidation, a metal (for example, aluminum) conductive substrate is used as an anode, and an oxide film is formed on the surface of the conductive substrate by anodizing in an electrolyte solution. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the porous anodic oxide film formed by anodic oxidation is chemically active as it is, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores of the oxide film are blocked by the volume expansion due to the hydration reaction in pressurized water vapor or boiling water (a metal salt such as nickel may be added) against the porous anodic oxide film, and more stable hydration oxidation It is preferable to perform a sealing treatment for changing to a product.

  The thickness of the anodized film is preferably, for example, 0.3 μm or more and 15 μm or less. When this film thickness is within the above range, the barrier property against implantation tends to be exhibited, and the increase in residual potential due to repeated use tends to be suppressed.

The conductive substrate may be treated with an acidic treatment liquid or boehmite treatment.
The treatment with the acidic treatment liquid is performed as follows, for example. First, an acidic treatment liquid containing phosphoric acid, chromic acid and hydrofluoric acid is prepared. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is, for example, in the range of 10% by mass to 11% by mass of phosphoric acid, in the range of 3% by mass to 5% by mass of chromic acid, The concentration of these acids is preferably in the range of 13.5% by mass or more and 18% by mass or less. The treatment temperature is preferably 42 ° C. or higher and 48 ° C. or lower, for example. The film thickness is preferably from 0.3 μm to 15 μm.

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

(Undercoat layer)
The undercoat layer is, for example, a layer containing inorganic particles and a binder resin.

Examples of the inorganic particles include inorganic particles having a powder resistance (volume resistivity) of 10 ² Ωcm or more and 10 ¹¹ Ωcm or less.
Among these, as the inorganic particles having the resistance value, for example, metal oxide particles such as tin oxide particles, titanium oxide particles, zinc oxide particles, and zirconium oxide particles are preferable, and zinc oxide particles are particularly preferable.

The specific surface area of the inorganic particles by the BET method is preferably 10 m ² / g or more, for example.
The volume average particle diameter of the inorganic particles is, for example, preferably from 50 nm to 2000 nm (preferably from 60 nm to 1000 nm).

  For example, the content of the inorganic particles is preferably 10% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 80% by mass or less with respect to the binder resin.

  The inorganic particles may be subjected to a surface treatment. Two or more inorganic particles having different surface treatments or particles having different particle diameters may be mixed and used.

  Examples of the surface treatment agent include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and a surfactant. In particular, a silane coupling agent is preferable, and an amino group-containing silane coupling agent is more preferable.

  Examples of the silane coupling agent having an amino group include 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl) -3-amino. Examples include, but are not limited to, propylmethyldimethoxysilane, N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, and the like.

  Two or more silane coupling agents may be used in combination. For example, a silane coupling agent having an amino group and another silane coupling agent may be used in combination. Other silane coupling agents include, for example, vinyltrimethoxysilane, 3-methacryloxypropyl-tris (2-methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycol. Sidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropylmethyldimethoxysilane, N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, and the like, but are not limited thereto. It is not a thing.

  The surface treatment method using the surface treatment agent may be any method as long as it is a known method, and may be either a dry method or a wet method.

  The treatment amount of the surface treatment agent is preferably 0.5% by mass or more and 10% by mass or less with respect to the inorganic particles, for example.

  Here, the undercoat layer may contain an electron-accepting compound (acceptor compound) together with the inorganic particles from the viewpoint of enhancing the long-term stability of the electric characteristics and the carrier blocking property.

Examples of the electron accepting compound include quinone compounds such as chloranil and bromoanil; tetracyanoquinodimethane compounds; 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9-fluorenone, and the like. 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,5-bis (4-naphthyl) -1,3,4- Oxadiazole compounds such as oxadiazole and 2,5-bis (4-diethylaminophenyl) -1,3,4 oxadiazole; xanthone compounds; thiophene compounds; 3,3 ′, 5,5 ′ tetra- electron transporting substances such as diphenoquinone compounds such as t-butyldiphenoquinone;
In particular, the electron-accepting compound is preferably a compound having an anthraquinone structure. As the compound having an anthraquinone structure, for example, a hydroxyanthraquinone compound, an aminoanthraquinone compound, an aminohydroxyanthraquinone compound, and the like are preferable, and specifically, for example, anthraquinone, alizarin, quinizarin, anthralfin, and purpurin are preferable.

  The electron-accepting compound may be dispersed and included in the undercoat layer together with the inorganic particles, or may be included in a state of being attached to the surface of the inorganic particles.

  Examples of the method for attaching the electron accepting compound to the surface of the inorganic particles include a dry method or a wet method.

  In the dry method, for example, while stirring inorganic particles with a mixer having a large shearing force or the like, an electron-accepting compound dissolved directly or in an organic solvent is dropped and sprayed with dry air or nitrogen gas. It is a method of adhering to the surface of inorganic particles. When the electron-accepting compound is dropped or sprayed, it is preferably performed at a temperature not higher than the boiling point of the solvent. After dropping or spraying the electron-accepting compound, baking may be performed at 100 ° C. or higher. The baking is not particularly limited as long as it is a temperature and time for obtaining electrophotographic characteristics.

  In the wet method, for example, an electron-accepting compound is added while dispersing inorganic particles in a solvent by stirring, ultrasonic waves, a sand mill, an attritor, a ball mill, etc., and after stirring or dispersing, the solvent is removed to remove electrons. This is a method of attaching a receptive compound to the surface of inorganic particles. The solvent removal method is distilled off by filtration or distillation, for example. After removing the solvent, baking may be performed at 100 ° C. or higher. The baking is not particularly limited as long as it is a temperature and time for obtaining electrophotographic characteristics. In the wet method, the water content of the inorganic particles may be removed before adding the electron-accepting compound. Examples thereof include a method of removing while stirring and heating in a solvent, and a method of removing by azeotropic distillation with a solvent. Can be mentioned.

  The attachment of the electron-accepting compound may be performed before or after the surface treatment with the surface treatment agent is performed on the inorganic particles, or may be performed simultaneously with the attachment of the electron-accepting compound and the surface treatment with the surface treatment agent.

  The content of the electron-accepting compound is, for example, from 0.01% by mass to 20% by mass with respect to the inorganic particles, and preferably from 0.01% by mass to 10% by mass.

Examples of the binder resin used for the undercoat layer include acetal resins (eg, polyvinyl butyral), polyvinyl alcohol resins, polyvinyl acetal resins, casein resins, polyamide resins, cellulose resins, gelatin, polyurethane resins, polyester resins, and unsaturated polyesters. Resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, urea resin, phenol resin, phenol-formaldehyde resin, melamine resin, Known polymer compounds such as urethane resin, alkyd resin, epoxy resin; zirconium chelate compound; titanium chelate compound; aluminum chelate compound; titanium alkoxide compound ; Organic titanium compounds; known materials silane coupling agent, and the like.
Examples of the binder resin used for the undercoat layer include a charge transport resin having a charge transport group, a conductive resin (for example, polyaniline) and the like.

Among these, as the binder resin used for the undercoat layer, a resin insoluble in the upper coating solvent is preferable, and in particular, a urea resin, a phenol resin, a phenol-formaldehyde resin, a melamine resin, a urethane resin, and an unsaturated polyester. Thermosetting resins such as resins, alkyd resins, and epoxy resins; at least one resin selected from the group consisting of polyamide resins, polyester resins, polyether resins, methacrylic resins, acrylic resins, polyvinyl alcohol resins, and polyvinyl acetal resins; Resins obtained by reaction with curing agents are preferred.
When these binder resins are used in combination of two or more, the mixing ratio is set as necessary.

The undercoat layer may contain various additives for improving electrical characteristics, improving environmental stability, and improving image quality.
Additives include known materials such as electron transport pigments such as polycyclic condensation systems and azo systems, zirconium chelate compounds, titanium chelate compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, and silane coupling agents. It is done. The silane coupling agent is used for the surface treatment of the inorganic particles as described above, but may be further added to the undercoat layer as an additive.

  Examples of the silane coupling agent as the additive include vinyltrimethoxysilane, 3-methacryloxypropyl-tris (2-methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (Aminoethyl) -3-aminopropylmethylmethoxysilane, N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane and the like can be mentioned.

  Examples of the zirconium chelate compound include zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, Zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.

  Examples of the titanium chelate compound include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, and titanium lactate ammonium salt. , Titanium lactate, titanium lactate ethyl ester, titanium triethanolamate, polyhydroxy titanium stearate and the like.

  Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) and the like.

  These additives may be used alone or as a mixture or polycondensate of a plurality of compounds.

The undercoat layer preferably has a Vickers hardness of 35 or more.
The surface roughness (ten-point average roughness) of the undercoat layer is adjusted from 1 / 4n (n is the refractive index of the upper layer) to 1 / 2λ of the exposure laser wavelength λ used to suppress moire images. It should be done.
Resin particles or the like may be added to the undercoat layer for adjusting the surface roughness. Examples of the resin particles include silicone resin particles and cross-linked polymethyl methacrylate resin particles. Further, the surface of the undercoat layer may be polished for adjusting the surface roughness. Examples of the polishing method include buffing, sandblasting, wet honing, and grinding.

  There is no particular limitation on the formation of the undercoat layer, and a well-known formation method is used. For example, a coating film for forming an undercoat layer in which the above components are added to a solvent is formed, and the coating film is dried. And heating as necessary.

Solvents for preparing the coating solution for forming the undercoat layer include known organic solvents such as alcohol solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ketone solvents, ketone alcohol solvents, ether solvents. Examples include solvents and ester solvents.
Specific examples of these solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, Examples include ordinary organic solvents such as n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene.

  Examples of the dispersion method of the inorganic particles when preparing the coating liquid for forming the undercoat layer include known methods such as a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker.

  Examples of the method for applying the coating liquid for forming the undercoat layer onto the conductive substrate include, for example, a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method. The usual methods, such as these, are mentioned.

  The thickness of the undercoat layer is, for example, preferably set in the range of 15 μm or more, more preferably 20 μm or more and 50 μm or less.

(Middle layer)
Although illustration is omitted, an intermediate layer may be further provided between the undercoat layer and the photosensitive layer.
An intermediate | middle layer is a layer containing resin, for example. Examples of the resin used for the intermediate layer include an acetal resin (for example, polyvinyl butyral), polyvinyl alcohol resin, polyvinyl acetal resin, casein resin, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, Polymer compounds such as polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, melamine resin, and the like can be given.
The intermediate layer may be a layer containing an organometallic compound. Examples of the organometallic compound used for the intermediate layer include organometallic compounds containing metal atoms such as zirconium, titanium, aluminum, manganese, and silicon.
The compounds used for these intermediate layers may be used alone or as a mixture or polycondensate of a plurality of compounds.

  Among these, the intermediate layer is preferably a layer containing an organometallic compound containing a zirconium atom or a silicon atom.

The formation of the intermediate layer is not particularly limited, and a well-known formation method is used. For example, a coating film of an intermediate layer forming coating solution in which the above components are added to a solvent is formed, and the coating film is dried and necessary. It is performed by heating according to.
As the coating method for forming the intermediate layer, usual methods such as a dip coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, a knife coating method, and a curtain coating method are used.

  For example, the thickness of the intermediate layer is preferably set in a range of 0.1 μm to 3 μm. An intermediate layer may be used as the undercoat layer.

(Charge generation layer)
The charge generation layer is, for example, a layer containing a charge generation material and a binder resin. The charge generation layer may be a vapor deposition layer of a charge generation material. The vapor-deposited layer of the charge generation material is suitable when an incoherent light source such as an LED (Light Emitting Diode) or an organic EL (Electro-Luminescence) image array is used.

  Examples of the charge generation material include azo pigments such as bisazo and trisazo; fused aromatic pigments such as dibromoanthanthrone; perylene pigments; pyrrolopyrrole pigments; phthalocyanine pigments; zinc oxide;

  Among these, in order to cope with near-infrared laser exposure, it is preferable to use a metal phthalocyanine pigment or a metal-free phthalocyanine pigment as the charge generation material. Specifically, for example, hydroxygallium phthalocyanine disclosed in JP-A-5-263007, JP-A-5-279591, etc .; chlorogallium phthalocyanine disclosed in JP-A-5-98181; More preferred are dichlorotin phthalocyanines disclosed in JP-A No. 140472, JP-A No. 5-140473 and the like; and titanyl phthalocyanine disclosed in JP-A No. 4-189873.

  On the other hand, in order to cope with laser exposure in the near-ultraviolet region, as the charge generation material, condensed aromatic pigments such as dibromoanthanthrone; thioindigo pigments; porphyrazine compounds; zinc oxide; trigonal selenium; Bisazo pigments and the like disclosed in 2004-78147 and JP-A-2005-181992 are preferred.

  In the case of using an incoherent light source such as an LED having a central wavelength of light emission of 450 nm or more and 780 nm or less, an organic EL image array, etc., the charge generation material may be used. When the thin film is used, the electric field strength in the photosensitive layer is increased, and a charge reduction due to charge injection from the base material, so-called image defects called black spots are likely to occur. This becomes conspicuous when a charge generating material that easily generates a dark current is used in a p-type semiconductor such as trigonal selenium or a phthalocyanine pigment.

On the other hand, when an n-type semiconductor such as a condensed ring aromatic pigment, perylene pigment, azo pigment or the like is used as the charge generation material, dark current hardly occurs and even a thin film can suppress image defects called black spots. . Examples of the n-type charge generation material include compounds (CG-1) to (CG-27) described in paragraphs [0288] to [0291] of JP2012-155282A. It is not limited.
The n-type determination is performed by using a time-of-flight method that is usually used, and is determined by the polarity of the flowing photocurrent, and an n-type is more likely to flow electrons as carriers than holes.

The binder resin used for the charge generation layer is selected from a wide range of insulating resins, and the binder resin is selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinyl anthracene, polyvinyl pyrene, and polysilane. You may choose.
As the binder resin, for example, polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol and aromatic divalent carboxylic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, Examples thereof include polyamide resin, acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, and the like. Here, “insulating” means that the volume resistivity is 10 ¹³ Ωcm or more.
These binder resins are used singly or in combination of two or more.

  The mixing ratio of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10 by mass ratio.

  In addition, the charge generation layer may contain a known additive.

  The formation of the charge generation layer is not particularly limited, and a known formation method is used. For example, a coating film of a charge generation layer forming coating solution in which the above components are added to a solvent is formed, and the coating film is dried. And heating as necessary. The charge generation layer may be formed by vapor deposition of a charge generation material. Formation of the charge generation layer by vapor deposition is particularly suitable when a condensed ring aromatic pigment or perylene pigment is used as the charge generation material.

  Solvents for preparing the charge generation layer forming coating solution include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-acetate. -Butyl, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene and the like. These solvents are used alone or in combination of two or more.

Examples of a method for dispersing particles (for example, a charge generation material) in a coating solution for forming a charge generation layer include, for example, a media disperser such as a ball mill, a vibrating ball mill, an attritor, a sand mill, a horizontal sand mill, a stirring, an ultrasonic disperser, etc. Medialess dispersers such as roll mills and high-pressure homogenizers are used. Examples of the high-pressure homogenizer include a collision method in which a dispersion liquid is dispersed by liquid-liquid collision or liquid-wall collision in a high pressure state, and a penetration method in which a fine flow path is dispersed in a high pressure state.
In this dispersion, it is effective that the average particle size of the charge generation material in the coating solution for forming the charge generation layer is 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. .

  Examples of methods for applying the charge generation layer forming coating solution on the undercoat layer (or on the intermediate layer) include blade coating, wire bar coating, spray coating, dip coating, bead coating, and air knife coating. And usual methods such as a curtain coating method.

  The film thickness of the charge generation layer is, for example, preferably set in the range of 0.1 μm to 5.0 μm, more preferably 0.2 μm to 2.0 μm.

(Charge transport layer)
The charge transport layer is, for example, a layer containing a charge transport material and a binder resin. The charge transport layer may be a layer containing a polymer charge transport material.

  Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl and anthraquinone; tetracyanoquinodimethane compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone; xanthone compounds; benzophenone compounds A cyanovinyl compound; an electron transporting compound such as an ethylene compound; Examples of the charge transporting material include hole transporting compounds such as triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, and hydrazone compounds. These charge transport materials may be used alone or in combination of two or more, but are not limited thereto.

  As the charge transport material, from the viewpoint of charge mobility, a triarylamine derivative represented by the following structural formula (a-1) and a benzidine derivative represented by the following structural formula (a-2) are preferable.

In Structural Formula (a-1), Ar ^T1 , Ar ^T2 , and Ar ^T3 are each independently a substituted or unsubstituted aryl group, —C ₆ H ₄ —C (R ^T4 ) ═C (R ^T5 ) (R ^T6), or _{-C 6 H 4 -CH = CH-} CH = C (R T7) shows the ^{(R T8).} R ^T4 , R ^T5 , R ^T6 , R ^T7 , and R ^T8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
Examples of the substituent for each group include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Examples of the substituent of each group also include a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms.

In Structural Formula (a-2), R ^T91 and R ^T92 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ^T101 , R ^T102 , R ^T111 and R ^T112 are each independently ^substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. A substituted amino group, a substituted or unsubstituted aryl group, —C (R ^T12 ) ═C (R ^T13 ) (R ^T14 ), or —CH═CH— ^CH═C (R ^T15 ) (R ^T16 ), R ^T12 , R ^T13 , R ^T14 , R ^T15 and R ^T16 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Tm1, Tm2, Tn1, and Tn2 each independently represent an integer of 0 or more and 2 or less.
Examples of the substituent for each group include a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Examples of the substituent of each group also include a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms.

Here, among the triarylamine derivative represented by the structural formula (a-1) and the benzidine derivative represented by the structural formula (a-2), in particular, “—C ₆ H ₄ —CH═CH—CH═ Triarylamine derivatives having “C (R ^T7 ) (R ^T8 )” and benzidine derivatives having “—CH═CH— ^CH═C (R ^T15 ) (R ^T16 )” are preferable from the viewpoint of charge mobility.

  As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole and polysilane are used. In particular, polyester-based polymer charge transport materials disclosed in JP-A-8-176293, JP-A-8-208820 and the like are particularly preferable. The polymer charge transport material may be used alone or in combination with a binder resin.

The binder resin used for the charge transport layer is polycarbonate resin, polyester resin, polyarylate resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, Vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N -Vinylcarbazole, polysilane, etc. are mentioned. Among these, as the binder resin, a polycarbonate resin or a polyarylate resin is preferable. These binder resins are used alone or in combination of two or more.
The mixing ratio of the charge transport material and the binder resin is preferably 10: 1 to 1: 5 by mass ratio.

  In addition, the charge transport layer may contain a known additive.

  The formation of the charge transport layer is not particularly limited, and a known formation method is used. For example, a coating film of a charge transport layer forming coating solution in which the above components are added to a solvent is formed, and the coating film is dried. This is done by heating as necessary.

  Solvents for preparing the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; ketones such as acetone and 2-butanone; methylene chloride, chloroform and ethylene chloride. Halogenated aliphatic hydrocarbons: Usual organic solvents such as cyclic or linear ethers such as tetrahydrofuran and ethyl ether. These solvents are used alone or in combination of two or more.

  Coating methods for applying the charge transport layer forming coating solution on the charge generation layer include blade coating method, wire bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain A usual method such as a coating method may be mentioned.

The thickness of the charge transport layer is, for example, preferably set in the range of 5 μm to 50 μm, more preferably 10 μm to 30 μm.
.

(Protective layer)
The protective layer (outermost surface layer) is the outermost surface layer in the electrophotographic photosensitive member, and is composed of a cured film of a composition containing a reactive charge transport material. That is, the protective layer contains a polymer or a crosslinked body (preferably a crosslinked body) of the reactive charge transport material.
The protective layer may be composed of a composition further including other additives such as a non-reactive charge transport material and a compound having an unsaturated bond (unsaturated double bond). That is, the protective layer may further contain other additives such as a polymer of a reactive charge transporting material and a compound having an unsaturated bond, a crosslinked product (preferably a crosslinked product), or a non-reactive charge transporting material. Good.

  As a method for curing the cured film, addition reaction by heat or condensation reaction, or radical polymerization by heat, light, radiation, or the like is performed. In particular, in the case of radical polymerization, adjusting the reaction not to proceed too quickly improves the mechanical strength and electrical properties of the protective layer (outermost surface layer), and also suppresses the occurrence of film unevenness and wrinkles, Polymerization is preferably performed under conditions where radical generation occurs relatively slowly. From this point, thermal polymerization that allows easy adjustment of the polymerization rate is preferred. That is, the composition for forming the cured film constituting the protective layer (outermost surface layer) preferably contains a thermal radical generator or a derivative thereof.

  Hereinafter, the detail of each element of the protective layer (outermost surface layer) comprised with the cured film is demonstrated.

-Reactive charge transport material-
The reactive charge transport material is selected from known materials as long as the compound has a charge transport skeleton and a reactive group in the same molecule. Here, examples of the reactive group include a chain polymerizable group, which may be a functional group capable of radical polymerization, for example, a functional group having a group containing at least a carbon double bond. Specifically, the chain polymerizable group is not particularly limited as long as it is a functional group capable of radical polymerization, for example, a functional group having at least a group containing a carbon double bond. Specific examples include a group containing at least one selected from a vinyl group, a vinyl ether group, a vinyl thioether group, a styryl group, an acryloyl group, a methacryloyl group, and derivatives thereof. Among them, the chain polymerizable functional group is a group containing at least one selected from a vinyl group, a styryl group, an acryloyl group, a methacryloyl group, and derivatives thereof because of its excellent reactivity. Is preferred. Other reactive groups include epoxy groups, —OH, —OR [where R represents an alkyl group], —NH ₂ , —SH, —COOH, —SiR ^Q1 _3-Qn (OR ^Q2 ) _Qn [provided that , R ^Q1 represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, and R ^Q2 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. Well-known reactive groups, such as _Qn represents an integer of 1 to 3, are also included.
The charge transporting skeleton is not particularly limited as long as it is a known structure in an electrophotographic photosensitive member. For example, nitrogen-containing hole transport such as triarylamine compounds, benzidine compounds, and hydrazone compounds is possible. And a structure that is conjugated to a nitrogen atom. Among these, a triarylamine skeleton is preferable.

  As the reactive charge transporting material, a chain polymerizable compound having at least a charge transporting skeleton and a chain polymerizable functional group in the same molecule is preferable from the viewpoint of high mechanical strength and suppressing excessive wear of the photoreceptor. In particular, among the chain polymerizable compounds, at least selected from a specific chain polymerizable charge transport material (chain polymerizable compounds represented by the general formulas (I) and (II)) from the viewpoint of electrical characteristics together with the same viewpoint. One is preferred.

-Specific reactive charge transport material-
The specific reactive charge transport material is at least one selected from the group consisting of reactive compounds represented by the general formulas (I) and (II).

In general formula (I), F represents a charge transporting skeleton.
L represents a divalent linking group containing two or more selected from the group consisting of an alkylene group, an alkenylene group, -C (= O)-, -N (R)-, -S-, and -O-. Show. R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
m represents an integer of 1 or more and 8 or less.

In general formula (II), F represents a charge transporting skeleton.
L ′ represents a trivalent or tetravalent group derived from an alkane or alkene, and an alkylene group, alkenylene group, —C (═O) —, —N (R) —, —S—, and —O—. And an (n + 1) -valent linking group containing two or more selected from the group consisting of: R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. The trivalent or tetravalent group derived from alkane or alkene means a group obtained by removing three or four hydrogen atoms from alkane or alkene. The same applies hereinafter.
m ′ represents an integer of 1 to 6. n represents an integer of 2 or more and 3 or less.

  In general formulas (I) and (II), F represents a charge transporting skeleton, that is, a structure having charge transporting properties. Specifically, phthalocyanine compounds, porphyrin compounds, azobenzene compounds, triarylamine compounds Examples thereof include structures having charge transporting properties such as compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, quinone compounds, and fluorenone compounds.

In general formula (I), examples of the linking group represented by L include:
A divalent linking group in which —C (═O) —O— is interposed in the alkylene group,
A divalent linking group in which —C (═O) —N (R) — is interposed in an alkylene group,
A divalent linking group in which —C (═O) —S— is interposed in the alkylene group,
A divalent linking group in which -O- is interposed in the alkylene group,
A divalent linking group in which -N (R)-is interposed in the alkylene group,
A divalent linking group in which -S- is interposed in the alkylene group,
Is mentioned.
The linking group represented by L is an alkylene group, -C (= O) -O-, -C (= O) -N (R)-, -C (= O) -S-, -O. Two groups of-or -S- may be present.

Specific examples of the linking group represented by L in the general formula (I) include:
* — (CH ₂ ) _p —C (═O) —O— (CH ₂ ) _q —,
_{* - (CH 2) p -O} -C (= O) - (CH 2) r -C (= O) -O- (CH 2) q -,
* — (CH ₂ ) _p —C (═O) —N (R) — (CH ₂ ) _q —,
_{* - (CH 2) p -C} (= O) -S- (CH 2) q -,
_{* - (CH 2) p -O-} (CH 2) q -,
_{* - (CH 2) p -N} (R) - (CH 2) q -,
_{* - (CH 2) p -S-} (CH 2) q -,
_{* - (CH 2) p -O-} (CH 2) r -O- (CH 2) q -
Etc.
Here, in the linking group represented by L, p represents 0 or an integer of 1 to 6 (preferably 1 to 5). q represents an integer of 1 to 6 (preferably 1 to 5). r represents an integer of 1 to 6 (preferably 1 to 5).
In the linking group represented by L, “*” represents a site linked to F.

On the other hand, in the general formula (II), as the linking group represented by L ′, for example,
A (n + 1) -valent linking group in which —C (═O) —O— is interposed in a branchedly linked alkylene group,
A (n + 1) -valent linking group in which —C (═O) —N (R) — is interposed in a branchedly linked alkylene group,
A (n + 1) -valent linking group in which —C (═O) —S— is interposed in a branchedly linked alkylene group,
(N + 1) -valent linking group in which —O— is interposed in a branched alkylene group,
A (n + 1) -valent linking group in which —N (R) — is interposed in a branchedly linked alkylene group,
A (n + 1) -valent linking group in which -S- is interposed in a branched alkylene group;
Is mentioned.
In addition, the linkage represented by L ′ is in a branched alkylene group, —C (═O) —O—, —C (═O) —N (R) —, —C (═O). Two groups of -S-, -O-, or -S- may be present.

In the general formula (II), as the linking group represented by L ′, for example,
* — (CH ₂ ) _p —CH [C (═O) —O— (CH ₂ ) _q —] ₂ ,
* — (CH ₂ ) _p —CH═C [C (═O) —O— (CH ₂ ) _q —] ₂ ,
_{* - (CH 2) p -CH} [C (= O) -N (R) - (CH 2) q -] 2,
_{* - (CH 2) p -CH} [C (= O) -S- (CH 2) q -] 2,
* — (CH ₂ ) _p —CH [(CH ₂ ) _r —O— (CH ₂ ) _q —] ₂ ,
_{* - (CH 2) p -CH} = C [(CH 2) r -O- (CH 2) q -] 2,
_{* - (CH 2) p -CH} [(CH 2) r -N (R) - (CH 2) q -] 2,
_{* - (CH 2) p -CH} [(CH 2) r -S- (CH 2) q -] 2,


* — (CH ₂ ) _p —O—C [(CH ₂ ) _r —O— (CH ₂ ) _q —] ₃
* — (CH ₂ ) _p —C (═O) —O—C [(CH ₂ ) _r —O— (CH ₂ ) _q —] ₃
Etc.
Here, in the linking group represented by L ′, p represents 0 or an integer of 1 to 6 (preferably 1 to 5). q represents an integer of 1 to 6 (preferably 1 to 5). r represents an integer of 1 to 6 (preferably 1 to 5). s represents an integer of 1 to 6 (preferably 1 to 5).
In the linking group represented by L ′, “*” represents a site linked to F.

Among these, in the general formula (II), as the linking group represented by L ′,
* — (CH ₂ ) _p —CH [C (═O) —O— (CH ₂ ) _q —] ₂ ,
* — (CH ₂ ) _p —CH═C [C (═O) —O— (CH ₂ ) _q —] ₂ ,
* — (CH ₂ ) _p —CH [(CH ₂ ) _r —O— (CH ₂ ) _q —] ₂ ,
_{* - (CH 2) p -CH} = C [(CH 2) r -O- (CH 2) q -] 2,
Is good.
Specifically, the group connected to the charge transporting skeleton represented by F of the reactive compound represented by the general formula (II) (corresponding to the group represented by the general formula (IIA-a)) is represented by the following general formula ( It may be a group represented by IIA-a1), the following general formula (IIA-a2), the following general formula (IIA-a3), or the following general formula (IIA-a4).

In general formula (IIA-a1) or (IIA-a2), ^Xk1 represents a divalent linking group. kq1 represents an integer of 0 or 1. X ^k2 represents a divalent linking group. kq2 represents an integer of 0 or 1.
Here, the divalent linking group represented by X ^k1 and X ^k2 is, for example, — (CH ₂ ) _p — (wherein p represents an integer of 1 to 6 (preferably 1 to 5))). Can be mentioned. Examples of the divalent linking group also include an alkyleneoxy group.

In general formula (IIA-a3) or (IIA-a4), ^Xk3 represents a divalent linking group. kq3 represents an integer of 0 or 1. X ^k4 represents a trivalent linking group. kq4 represents an integer of 0 or 1.
Here, the divalent linking group represented by X ^k3 and X ^k4 is, for example, — (CH ₂ ) _p — (wherein p represents an integer of 1 to 6 (preferably 1 to 5))). Can be mentioned. Examples of the divalent linking group also include an alkyleneoxy group.

In general formulas (I) and (II), in the linking group represented by L or L ′, the alkyl group represented by R of “—N (R) —” has 1 to 5 carbon atoms (preferably 1 4 or less) linear and branched alkyl groups, and specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the aryl group represented by R in “—N (R) —” include aryl groups having 6 to 15 carbon atoms (preferably 6 to 12 carbon atoms). Specific examples include phenyl groups and toluyl groups. Group, xylidyl group, naphthyl group and the like.
Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms (preferably 7 to 14 carbon atoms). Specific examples include a benzyl group, a phenethyl group, and a biphenylmethylene group.

In general formulas (I) and (II), m preferably represents an integer of 1 to 6.
m ′ preferably represents an integer of 1 to 6.
n preferably represents an integer of 2 or more and 3 or less.

Next, preferred compounds of the reactive compounds represented by the general formulas (I) and (II) will be described.
As the reactive compound represented by the general formulas (I) and (II), a reactive compound having a charge transporting skeleton (structure having charge transporting property) derived from a triarylamine compound as F is preferable.
Specifically, the reactive compound represented by the general formula (I) includes the general formula (Ia), the general formula (Ib), the general formula (Ic), and the general formula (Id). At least one compound selected from the group consisting of reactive compounds represented by
On the other hand, as the reactive compound represented by the general formula (II), the reactive compound represented by the general formula (II-a) is preferable.

-Reactive compound shown by general formula (Ia) The reactive compound shown by general formula (Ia) is demonstrated.
When the reactive compound represented by the general formula (Ia) is applied as the specific reactive charge transport material, it is easy to suppress deterioration of electrical characteristics due to environmental changes. The reason is not clear, but is thought to be as follows.
First, since the reactive compound having a (meth) acrylic group that has been used conventionally has a strong hydrophilicity of the (meth) acrylic group with respect to a skeleton part that expresses charge transport performance during polymerization, It is considered that a certain kind of layer separation state is formed, which hinders hopping conduction. For this reason, a charge transporting film containing a polymer of a reactive compound having a (meth) acrylic group or a crosslinked product has a reduced efficiency of charge transport, and further has a reduced environmental stability due to partial moisture adsorption or the like. It is considered a thing.
On the other hand, the reactive compound represented by the general formula (Ia) has a vinyl-based chain polymerizable group that is not strongly hydrophilic, and further has a skeleton that exhibits charge transport performance within one molecule. The skeletons are linked by a flexible linking group that does not have a conjugated bond such as an aromatic ring or a conjugated double bond. Since it has such a structure, it is considered that efficient charge transport performance and high strength can be achieved, and formation of a layer separation state during polymerization is suppressed. As a result, the protective layer (outermost surface layer) containing the polymer or cross-linked product of the reactive compound represented by the general formula (Ia) is excellent in both charge transport performance and mechanical strength. It is thought that the environment dependence (temperature and humidity dependence) of transport performance can be reduced.
From the above, it is considered that when the reactive compound represented by the general formula (Ia) is applied, deterioration of electrical characteristics due to environmental changes is easily suppressed.

In the general formula (Ia), Ar ^{a1 to} Ar ^a4 each independently represent a substituted or unsubstituted aryl group. Ar ^a5 and Ar ^a6 each independently represent a substituted or unsubstituted arylene group. Xa represents a divalent linking group formed by combining groups selected from an alkylene group, -O-, -S-, and an ester. Da represents a group represented by the following general formula (IA-a). ac1 to ac4 each independently represents an integer of 0 or more and 2 or less. However, the total number of Da is 1 or 2.

In the general formula ^{(IA-a), L} a _{is, * - (CH 2) an} -O-CH 2 - is represented by the divalent linking group linked to the group represented by ^Ar a1 ^{to Ar a4} at * Indicates. an represents an integer of 1 or 2.

Details of the general formula (Ia) will be described below.
In general formula (Ia), the substituted or unsubstituted aryl groups represented by Ar ^{a1 to} Ar ^a4 may be the same or different.
Here, as a substituent in the substituted aryl group, other than “Da”, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. Examples thereof include a substituted phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom.

In general formula (Ia), Ar ^{a1 to} Ar ^a4 are preferably any one of the following structural formulas (1) to (7).
In addition, the following structural formulas (1) to (7) collectively indicate “— (Da) _ac1 ” to “— (Da) _ac1 ” that can be connected to each of Ar ^{a1 to} Ar ^a4. ) _C ”.

In the structural formulas (1) to (7), R ¹¹ is substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. And a phenyl group, an unsubstituted phenyl group, and an aralkyl group having 7 to 10 carbon atoms. R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms. 1 group selected from the group consisting of an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom. R ¹⁴ each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, 1 type chosen from the group which consists of a C7-C10 aralkyl group and a halogen atom is shown. Ar represents a substituted or unsubstituted arylene group. s represents 0 or 1. t represents an integer of 0 or more and 3 or less. Z ′ represents a divalent organic linking group.

  Here, in the formula (7), Ar is preferably one represented by the following structural formula (8) or (9).

In structural formulas (8) and (9), R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Represents one selected from the group consisting of a phenyl group substituted with a group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom, and t1 and t2 each represent an integer of 0 to 3 Show.

  In the formula (7), Z ′ is preferably one represented by any of the following structural formulas (10) to (17).

In Structural Formulas (10) to (17), R ¹⁷ and R ¹⁸ are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. 1 type selected from the group consisting of a phenyl group substituted with a group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, and a halogen atom. W represents a divalent group. q1 and r1 each independently represents an integer of 1 or more and 10 or less. t3 and t4 each represent an integer of 0 or more and 3 or less.

  In the structural formulas (16) to (17), W is preferably any one of divalent groups represented by the following structural formulas (18) to (26). However, in Formula (25), u shows the integer of 0-3.

In the general formula (Ia), in the substituted or unsubstituted arylene group represented by Ar ^a5 and Ar ^a6 , the arylene group is a target position from the aryl group exemplified in the description of Ar ^{a1 to} Ar ^a4. And an arylene group in which one hydrogen atom is removed.
Moreover, as a substituent in a substituted arylene group, it is the same as that of what is mentioned as substituents other than "Da" in a substituted aryl group by description of Ar < ^a1 > -Ar < ^a4 >.

In general formula (Ia), the divalent linking group represented by Xa is an alkylene group or a divalent group formed by combining alkylene groups, —O—, —S—, and groups selected from esters. Thus, the linking group does not contain a conjugated bond such as an aromatic ring or a conjugated double bond.
Specifically, examples of the divalent linking group represented by Xa include an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 10 carbon atoms and —O—, —S—, and —O. A divalent group formed by combining a group selected from —C (═O) — and —C (═O) —O— is also included.
When the divalent linking group represented by Xa is an alkylene group, the alkylene group may have a substituent such as alkyl, alkoxy, halogen, etc., and two of these substituents are bonded to each other, A structure such as a divalent linking group represented by Structural Formula (26) described as a specific example of W in Structural Formulas (16) to (17) may be used.

-Reactive compound shown by general formula (Ib) The reactive compound shown by general formula (Ib) is demonstrated.
When the reactive compound represented by the general formula (Ib) is applied as the specific reactive charge transporting material, wear of the protective layer (outermost surface layer) is suppressed and generation of uneven density in the image is easily suppressed. Become. The reason is not clear, but is thought to be as follows.
First, the bulky charge transport skeleton and the polymerization site (styryl group) are structurally close, and if it is rigid, the polymerization sites will not move easily, residual strain due to the curing reaction tends to remain, and the charge transport skeleton is distorted. As a result, a change in the level of HOMO (the highest occupied orbit) that leads to carrier transport occurs, and as a result, the energy distribution is likely to be widened (energy disorder: σ is large).
On the other hand, through a methylene group and an ether group, flexibility is obtained in the molecular structure, and a small σ is easily obtained. Further, the methylene group and the ether group are compared with an ester group, an amide group, etc. The dipole moment (dipole moment) is small, and this effect also contributes to the reduction of σ and is considered to improve the electrical characteristics. In addition, it is considered that the flexibility of the molecular structure increases the degree of freedom of movement of the reaction site (reaction site), and the reaction rate also improves, resulting in a strong film. A structure in which a flexible connecting chain is interposed between the polymerization sites is preferable.
For this reason, it is considered that the reactive compound represented by the general formula (Ib) increases the molecular weight of the molecule itself due to the curing reaction, makes the center of gravity difficult to move, and has a high degree of freedom of the styryl group. As a result, the protective layer (outermost surface layer) containing the polymer or crosslinked product of the reactive compound represented by the general formula (Ib) is considered to have excellent electrical properties and high strength.
From the above, it is considered that when the reactive compound represented by the general formula (Ib) is applied, wear of the protective layer (outermost surface layer) is suppressed and occurrence of uneven density in the image is easily suppressed.

In the general formula (Ib), Ar ^{b1 to} Ar ^b4 each independently represent a substituted or unsubstituted aryl group. Ar ^b5 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group. Db represents a group represented by the following general formula (IA-b). bc1 to bc5 each independently represent an integer of 0 or more and 2 or less. bk represents 0 or 1. However, the total number of Db is 1 or 2.

In General Formula (IA-b), L ^b includes a group represented by * — (CH ₂ ) _bn —O—, and is a divalent linking group linked to a group represented by Ar ^{b1 to} Ar ^b5 at *. Indicates. bn represents an integer of 3 to 6.

Hereinafter, the details of the general formula (Ib) will be described.
In general formula (Ib), the substituted or unsubstituted aryl group represented by Ar ^{b1 to} Ar ^b4 is the substituted or unsubstituted aryl group represented by Ar ^{a1 to} Ar ^a4 in general formula (Ia). It is the same.
Ar ^b5 represents a substituted or unsubstituted aryl group when bk is 0, and examples of the substituted or unsubstituted aryl group include substituted or unsubstituted Ar ^{a1 to} Ar ^a4 in the general formula (Ia) Same as unsubstituted aryl group.
Ar ^b5 represents a substituted or unsubstituted arylene group when bk is 1, and the substituted or unsubstituted arylene group includes a substituent represented by Ar ^a5 and Ar ^a6 in the general formula (Ia) or The same as the unsubstituted arylene group.

Next, the details of the general formula (IA-b) will be described.
In the general formula (IA-b), examples of the divalent linking group represented by ^{L b,} for example,
* — (CH ₂ ) _bp —O—,
* — (CH ₂ ) _bp —O— (CH ₂ ) _bq —O—
Etc.
Here, in the linking group represented by L ^b, bp represents an integer of 3 to 6 (preferably 3 to 5). bq represents an integer of 1 to 6 (preferably 1 to 5).
Incidentally, in the linking group represented by ^{L b, "*"} represents a site connecting to a group represented by Ar b1 ^{to Ar b5.}

-Reactive compound shown by general formula (Ic) The reactive compound shown by general formula (Ic) is demonstrated.
When the reactive compound represented by the general formula (Ic) is applied as the specific reactive charge transporting material, scratches are hardly generated on the surface even when used repeatedly, and image quality deterioration is easily suppressed. The reason is not clear, but is thought to be as follows.
First, when forming the outermost surface layer containing a polymer or cross-linked product of a specific reactive charge transport material, film shrinkage accompanying the polymerization reaction or cross-linking reaction, and structure around the charge transport structure and chain polymerizable group It is thought that aggregation occurs. Therefore, when the surface of the electrophotographic photosensitive member is subjected to a mechanical load by repeated use, the film itself is worn or the chemical structure in the molecule is cut, so that the film contraction and aggregation state change, and the electrophotographic photosensitive member changes. It is considered that the electrical characteristics of the image change and cause image quality degradation.
On the other hand, since the reactive compound represented by the general formula (Ic) has a styrene skeleton as a chain polymerizable group, it has good compatibility with the aryl group which is the main skeleton of the charge transport material, and the film shrinks. It is considered that the aggregation of the charge transport structure and the structure around the chain polymerizable group due to polymerization reaction or crosslinking reaction is suppressed. As a result, the electrophotographic photosensitive member having a protective layer (outermost surface layer) containing a polymer or crosslinked product of the reactive compound represented by the general formula (Ic) is considered to suppress image quality deterioration due to repeated use. It is done.
In addition, the reactive compound represented by the general formula (Ic) includes a charge transporting skeleton and a styrene skeleton, a specific group such as —C (═O) —, —N (R) —, and —S—. It is thought that the interaction between the specific group and the nitrogen atom in the charge transporting skeleton, the interaction between the specific groups, and the like are caused by linking via the linking group including, as a result, the general formula (I- It is thought that the strength of the protective layer (outermost surface layer) containing the polymer or crosslinked product of the reactive compound represented by c) is further improved.
From the above, it is considered that when the reactive compound represented by the general formula (Ic) is applied, scratches are hardly generated on the surface even when used repeatedly, and image quality deterioration is easily suppressed.
Note that specific groups such as -C (= O)-, -N (R)-, and -S- are attributed to the polarity and hydrophilicity, causing the charge transportability and image quality deterioration under high humidity conditions. However, since the reactive compound represented by the general formula (Ic) has a styrene skeleton having higher hydrophobicity than (meth) acryl or the like as a chain polymerizable group, the charge transportability is deteriorated or the previous cycle is deteriorated. It is considered that image quality deterioration such as an afterimage phenomenon (ghost) due to the history hardly occurs.

In the general formula (Ic), Ar ^{c1 to} Ar ^c4 each independently represent a substituted or unsubstituted aryl group. Ar ^c5 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group. Dc represents a group represented by the following general formula (IA-c). cc1 to cc5 each independently represents an integer of 0 or more and 2 or less. ck represents 0 or 1. However, the total number of Dc is 1 or more and 8 or less.

In the general formula (IA-c), ^{L C} is, -C (= O) -, - N (R) -, - S-, and, -C (= O) - and -O -, - N (R )-Or -S- represents a divalent linking group containing one or more groups selected from the group consisting of groups. R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.

Details of the general formula (Ic) will be described below.
In general formula (Ic), the substituted or unsubstituted aryl group represented by Ar ^{c1 to} Ar ^c4 is a substituted or unsubstituted aryl group represented by Ar ^{a1 to} Ar ^a4 in general formula (Ia). It is the same.
Ar ^c5 represents a substituted or unsubstituted aryl group when ck is 0, and examples of the substituted or unsubstituted aryl group include a substituted group represented by Ar ^{a1 to} Ar ^a4 in formula (Ia) or Same as unsubstituted aryl group.
Ar ^c5 represents a substituted or unsubstituted arylene group when ck is 1, and the substituted or unsubstituted arylene group includes a substituent represented by Ar ^a5 and Ar ^a6 in formula (Ia) or The same as the unsubstituted arylene group.
The total number of Dc is preferably 2 or more, more preferably 4 or more, from the viewpoint of obtaining a protective layer (outermost surface layer) with higher strength. In general, if the number of chain polymerizable groups in one molecule is too large, as the polymerization (crosslinking) reaction proceeds, the molecules become difficult to move and the chain polymerization reactivity decreases, and the proportion of unreacted chain polymerizable groups increases. Therefore, the total number of Dc is preferably 7 or less, more preferably 6 or less.

Next, the details of the general formula (IA-c) will be described.
In the general formula (IA-c), ^examples of the divalent linking group represented by L ^c include —C (═O) —, —N (R) —, —S—, and —C (═O) —. And a divalent linking group containing a group in which —O—, —N (R) —, or —S— is combined (hereinafter referred to as “specific linking group”).
Here, the specific linking group includes, for example, —C (═O) —, —N (R) —, and —S— from the viewpoint of the balance between the strength and polarity (hydrophobicity) of the protective layer (outermost surface layer). , -C (= O) -O-, -C (= O) -N (R)-, -C (= O) -S-, -O-C (= O) -O-, -O-C (═O) —N (R) — is preferred, preferably —N (R) —, —S—, —C (═O) —O—, —C (═O) —N (H) —, — C (= O) -O-, more preferably -C (= O) -O-.
Examples of the divalent linking group represented by L ^c include a specific linking group, a saturated hydrocarbon (including linear, branched, and cyclic) or aromatic hydrocarbon residue, oxygen, and the like. And a divalent linking group formed by combining atoms with each other. Among these, a specific linking group, a linear saturated hydrocarbon residue, and an oxygen atom are used in combination. A valent linking group is preferred.
The total number of carbon atoms contained in the divalent linking group represented by L ^c is, for example, from 1 to 20 in terms of the density of the styrene skeleton in the molecule and chain polymerization reactivity, and preferably from 2 to 10 It is as follows.

Specific examples of the divalent linking group represented by L ^c in the general formula (IA-c) include, for example,
_{* - (CH 2) cp -C} (= O) -O- (CH 2) cq -,
* — (CH ₂ ) _cp —O—C (═O) — (CH ₂ ) _cr —C (═O) —O— (CH ₂ ) _cq —,
* — (CH ₂ ) _cp —C (═O) —N (R) — (CH ₂ ) _cq —,
_{* - (CH 2) cp -C} (= O) -S- (CH 2) cq -,
_{* - (CH 2) cp -N} (R) - (CH 2) cq -,
_{* - (CH 2) cp -S-} (CH 2) cq -,
Etc.
Here, in the linking group represented by ^{L c,} cp is 0, or 1 to 6 (preferably 1 to 5) represents an integer of. cq represents an integer of 1 to 6 (preferably 1 to 5). cr represents an integer of 1 to 6 (preferably 1 to 5).
In the linking group represented by L ^c , “*” represents a site linked to the group represented by Ar ^{c1 to} Ar ^c5 .

Among these, in the general formula (IA-c), the divalent linking group represented by ^{_{L c, * - (CH 2}} ) cp -C (= O) -O-CH 2 - is preferred. That is, the group represented by the general formula (IA-c) is preferably a group represented by the following general formula (IA-c1). However, in general formula (IA-c1), cp1 shows the integer of 0-4.

-Reactive compound shown by general formula (Id) The reactive compound shown by general formula (Id) is demonstrated.
When the reactive compound represented by the general formula (Id) is applied as the specific reactive charge transporting material, wear of the protective layer (outermost surface layer) is suppressed and generation of density unevenness in the image is easily suppressed. Become. Although the reason is not certain, it is thought to be due to the same reason as the reactive compound represented by the general formula (Ib).
In particular, the reactive compound represented by the general formula (Id) has a higher total number of Dd of 3 or more and 8 or less than the general formula (Ib). It is considered that a crosslinked network is easily formed, and wear of the protective layer (outermost surface layer) is more easily suppressed.

In the general formula (Id), Ar ^{d1 to} Ar ^d4 each independently represent a substituted or unsubstituted aryl group. Ar ^d5 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted arylene group. Dd represents a group represented by the following general formula (IA-d). dc1 to dc5 each independently represents an integer of 0 or more and 2 or less. dk represents 0 or 1. However, the total number of Dd is 3 or more and 8 or less.

In General Formula (IA-d), L ^d includes a group represented by * — (CH ₂ ) _dn —O—, and represents a divalent linking group that is coupled to Ar ^{d1 to} Ar ^d5 by *. Show. dn represents an integer of 1 to 6.

Details of the general formula (Id) will be described below.
In general formula (Id), the substituted or unsubstituted aryl group represented by Ar ^{d1 to} Ar ^d4 is the substituted or unsubstituted aryl group represented by Ar ^{a1 to} Ar ^a4 in general formula (Ia). It is the same.
Ar ^d5 represents a substituted or unsubstituted aryl group when dk is 0, and examples of the substituted or unsubstituted aryl group include substituted or unsubstituted Ar ^{a1 to} Ar ^a4 in the general formula (Ia) Same as unsubstituted aryl group.
Ar ^d5 represents a substituted or unsubstituted arylene group when dk is 1, and the substituted or unsubstituted arylene group includes a substituent represented by Ar ^a5 and Ar ^a6 in the general formula (Ia) or The same as the unsubstituted arylene group.
The total number of Dd is preferably 4 or more from the viewpoint of obtaining a protective layer (outermost surface layer) with higher strength.

Next, the details of the general formula (IA-d) will be described.
In the general formula (IA-d), examples of the divalent linking group represented by L ^d include:
* — (CH ₂ ) _dp —O—,
_{* - (CH 2) dp -O-} (CH 2) dq -O-
Etc.
Here, in the linking group represented by L ^d , dp represents an integer of 1 to 6 (preferably 1 to 5). dq represents an integer of 1 to 6 (preferably 1 to 5).
In the linking group represented by L ^d , “*” represents a site linked to the group represented by Ar ^{d1 to} Ar ^d5 .

-Reactive compound shown by general formula (II-a) The reactive compound shown by general formula (II-a) is demonstrated.
When a reactive compound represented by the general formula (II) (particularly the general formula (II-a)) is applied as a specific reactive charge transport material, it is easy to suppress deterioration of electrical characteristics even when used repeatedly over a long period of time. Become. The reason is not clear, but is thought to be as follows.
First, the reactive compound represented by the general formula (II) (particularly the general formula (II-a)) has two or three chain polymerizable reactive groups from a charge transporting skeleton through one linking group. It is a compound having (styrene group).
Therefore, the reactive compound represented by the general formula (II) (particularly the general formula (II-a)) was polymerized or cross-linked by the presence of this linking group while maintaining a high degree of curing and the number of cross-linking sites. At this time, it is difficult to cause distortion in the charge transporting skeleton, and it is considered that it is easy to realize both high curing degree and excellent charge transport performance.
In addition, conventionally used charge transporting compounds having a (meth) acryl group are likely to be distorted as described above, and the reactive sites are highly hydrophilic and the charge transporting sites are highly hydrophobic. Therefore, the reactive compound represented by the general formula (II) (particularly the general formula (II-a)) has a styrene group as a reactive group, whereas microscopic phase separation (microphase separation) is likely to occur. Furthermore, the structure has a linking group that is difficult to cause distortion in the charge transporting skeleton when cured (crosslinked), and both the reactive site and the charge transporting site are hydrophobic. Since separation is difficult to occur, it is considered that efficient charge transport performance and high strength can be achieved. As a result, the protective layer (outermost surface layer) containing a polymer or a crosslinked product of the reactive compound represented by the general formula (II) (particularly the general formula (II-a)) has excellent mechanical strength and charge. It is considered that the transport performance (electrical characteristics) is superior.
From the above, it is considered that when the reactive compound represented by the general formula (II) (particularly, the general formula (II-a)) is applied, deterioration of electric characteristics is easily suppressed even when used repeatedly over a long period of time.

In the general formula (II-a), Ar ^{k1 to} Ar ^k4 each independently represents a substituted or unsubstituted aryl group. Ar ^k5 represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted arylene group. Dk represents a group represented by the following general formula (IIA-a). kc1 to kc5 each independently represents an integer of 0 or more and 2 or less. kk represents 0 or 1. However, the total number of Dk is 1 or more and 8 or less.

In the general formula (IIA-a), L ^k represents a trivalent or tetravalent group derived from an alkane or alkene, an alkylene group, an alkenylene group, -C (= O)-, -N (R)- A (kn + 1) -valent linking group containing two or more selected from the group consisting of, -S-, and -O-. R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. kn represents an integer of 2 or more and 3 or less.

Hereinafter, the details of the general formula (II-a) will be described.
In general formula (II-a), the substituted or unsubstituted aryl group represented by Ar ^{k1 to} Ar ^k4 is the substituted or unsubstituted aryl group represented by Ar ^{a1 to} Ar ^a4 in general formula (Ia). It is the same.
Ar ^k5 represents a substituted or unsubstituted aryl group when kk is 0. ^Examples of the substituted or unsubstituted aryl group include substituted or unsubstituted Ar ^{a1 to} Ar ^a4 in the general formula (Ia) Same as unsubstituted aryl group.
Ar ^k5 represents a substituted or unsubstituted arylene group when kk is 1, and the substituted or unsubstituted arylene group includes a substituent represented by Ar ^a5 and Ar ^a6 in the general formula (Ia) or The same as the unsubstituted arylene group.
The total number of Dk is preferably 2 or more, more preferably 4 or more, from the viewpoint of obtaining a protective layer (outermost surface layer) with higher strength. In general, if the number of chain polymerizable groups in one molecule is too large, as the polymerization (crosslinking) reaction proceeds, the molecules become difficult to move and the chain polymerization reactivity decreases, and the proportion of unreacted chain polymerizable groups increases. Therefore, the total number of Dk is preferably 7 or less, more preferably 6 or less.

Next, the detail of general formula (IIA-a) is demonstrated.
In the general formula (IIA-a), the (kn + 1) -valent linking group ^represented by L ^k is, for example, the same as the (n + 1) -valent linking group represented by L ′ in the general formula (II).

Specific examples of the specific reactive charge transport material are shown below.
Specifically, the charge transporting skeleton F of the general formulas (I) and (II) (for example, a portion corresponding to the skeleton excluding Da in the general formula (Ia) and Dk of the general formula (II-a)). Together with specific examples of functional groups linked to the charge transporting skeleton F (for example, a site corresponding to Da in the general formula (Ia) or Dk in the general formula (II-a)). Specific examples of the reactive compound represented by (II) and (II) are shown below, but are not limited thereto.
In the specific examples of the charge transporting skeleton F in the general formulas (I) and (II), the “*” part means that the “*” part of the functional group linked to the charge transporting skeleton F is linked. To do.
That is, for example, the exemplary compound (Ib) -1 is shown as a specific example of the charge transporting skeleton F: (M1) -1, and a specific example of the functional group: (R2) -1. The typical structure shows the following structure.

  First, specific examples of the charge transporting skeleton F are shown below.

  Next, specific examples of the functional group linked to the charge transporting skeleton F are shown.

  Next, specific examples of the compound represented by the general formula (I), specifically, the general formula (Ia) are shown.

  Next, specific examples of the compound represented by the general formula (I), specifically, the general formula (Ib) are shown.

  Next, specific examples of the compound represented by the general formula (I), specifically, the general formula (Ic) are shown.

  Next, specific examples of the compound represented by the general formula (I), specifically, the general formula (Id) will be shown.

  Next, specific examples of the compound represented by the general formula (II), specifically, the general formula (II-a) are shown.

A specific chain polymerizable charge transport material (particularly, a chain polymerizable compound represented by the general formula (I)) is synthesized, for example, as follows.
That is, a specific chain polymerizable charge transport material is synthesized by etherification with a carboxylic acid or alcohol as a precursor and a corresponding chloromethylstyrene or the like.

  An example of the synthesis route of the exemplary compound (Id) -22 of a specific chain polymerizable charge transport material is shown below.

The arylamine compound carboxylic acid is an ester group of an arylamine compound, for example, as described in Experimental Chemistry Course, 4th edition, volume 20, p. As described in No. 51 and the like, it can be obtained by hydrolysis using a basic catalyst (NaOH, K ₂ CO ₃ etc.) and an acidic catalyst (eg phosphoric acid, sulfuric acid etc.).
In this case, various solvents can be used, and it is preferable to use alcohols such as methanol, ethanol, ethylene glycol, or a mixture of water.
Furthermore, when the solubility of the arylamine compound is low, methylene chloride, chloroform, toluene, dimethyl sulfoxide, ether, tetrahydrofuran or the like may be added.
Although there is no restriction | limiting in particular in the quantity of a solvent, For example, it is 1 mass part or more and 100 mass parts or less with respect to 1 mass part of arylamine compounds containing an ester group, Preferably it is used by 2 mass parts or more and 50 mass parts or less. Good.
The reaction temperature is set, for example, in the range from room temperature (for example, 25 ° C.) to the boiling point of the solvent, and is preferably 50 ° C. or higher in view of the reaction rate.
Although there is no restriction | limiting in particular about the quantity of a catalyst, For example, 0.001 mass part or more and 1 mass part or less with respect to 1 mass part of arylamine compounds containing an ester group, Preferably it is 0.01 mass part or more and 0.5 It is good to use below mass parts.
When hydrolysis is performed with a basic catalyst after the hydrolysis reaction, the generated salt is neutralized with an acid (for example, hydrochloric acid or the like) and released. Furthermore, after washing thoroughly with water, use after drying, or if necessary, recrystallize and purify with an appropriate solvent such as methanol, ethanol, toluene, ethyl acetate, acetone, etc. Also good.

  The alcohol form of the arylamine compound may be prepared by reacting the ester group of the arylamine compound with, for example, Experimental Chemistry Course, 4th Edition, Volume 20, As described in No. 10 and the like, it is synthesized by reducing to the corresponding alcohol using lithium aluminum hydride, sodium borohydride or the like.

  For example, when a reactive group is introduced by an ester bond, normal esterification in which an arylamine compound carboxylic acid and hydroxymethylstyrene are dehydrated and condensed with an acid catalyst, an arylamine compound carboxylic acid, and a halogenated methylstyrene are combined. , Pyridine, piperidine, triethylamine, dimethylaminopyridine, trimethylamine, DBU, sodium hydride, sodium hydroxide, potassium hydroxide and other methods of condensation can be used. This is preferred because the product is suppressed.

The halogenated methylstyrene is preferably added in an amount of 1 equivalent or more, preferably 1.2 equivalents or more, more preferably 1.5 equivalents or more with respect to the acid of the arylamine compound carboxylic acid. It is preferably used in an amount of from 8 equivalents to 2.0 equivalents, preferably from 1.0 equivalents to 1.5 equivalents.
Solvents include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether and tetrahydrofuran, toluene, chlorobenzene, 1 An aromatic solvent such as chloronaphthalene is effective, and is in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 1 part by weight of the arylamine compound carboxylic acid. It should be used.
The reaction temperature is not particularly limited. After completion of the reaction, the reaction solution is poured into water, extracted with a solvent such as toluene, hexane, or ethyl acetate, washed with water, and further purified using an adsorbent such as activated carbon, silica gel, porous alumina, or activated clay if necessary. May be.

In addition, when introduced by an ether bond, arylamine compound alcohol and halogenated methylstyrene are converted into bases such as pyridine, piperidine, triethylamine, dimethylaminopyridine, trimethylamine, DBU, sodium hydride, sodium hydroxide, potassium hydroxide, etc. It is preferable to use a method of condensing with.
The halogenated methylstyrene is preferably added in an amount of 1 equivalent or more, preferably 1.2 equivalents or more, more preferably 1.5 equivalents or more with respect to the alcohol of the arylamine compound alcohol. It is 8 to 2.0 equivalents, preferably 1.0 to 1.5 equivalents.
Solvents include aprotic polar solvents such as N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether and tetrahydrofuran, toluene, chlorobenzene, 1 -Aromatic solvents such as chloronaphthalene are effective, and they are used in the range of 1 to 100 parts by mass, preferably 2 to 50 parts by mass with respect to 1 part by mass of the arylamine compound alcohol. It is good.
The reaction temperature is not particularly limited. After completion of the reaction, the reaction solution is poured into water, extracted with a solvent such as toluene, hexane, or ethyl acetate, washed with water, and further purified using an adsorbent such as activated carbon, silica gel, porous alumina, or activated clay if necessary. May be.

Specific chain-polymerizable charge transport materials (especially chain-polymerizable compounds represented by the general formula (II)) include, for example, the following general charge transport material synthesis methods (formylation, esterification, etherification, hydrogenation) ) And synthesized.
-Formylation: Aromatic compounds with electron donating groups-Heterocyclic compounds-Reactions suitable for introducing formyl groups into alkenes. In general, DMF and phosphorus oxytrichloride are used, and the reaction temperature is often from room temperature (for example, 25 ° C.) to about 100 ° C.
Esterification: A condensation reaction between an organic acid and a compound containing a hydroxyl group such as alcohol or phenol. It is preferable to use a method of biasing the equilibrium toward the ester side by coexisting a dehydrating agent or removing water out of the system.
Etherification: A Williamson synthesis method in which an alkoxide and an organic halogen compound are condensed is common.
-Hydrogenation: A method in which hydrogen is reacted with an unsaturated bond using various catalysts.

  In addition to the specific chain-polymerizable charge transport material, the reactive charge transport material may be a compound described in [0110] to [0153] of JP2012-163693A, [0055] of Japanese Patent No. 4365960. ] To [0082], the compounds described in Japanese Patent No. 4429340, [0040] to [0043], the compounds described in JP 2013-195762 [0161] to [0166], and the like. Can be mentioned.

  The content of the reactive charge transporting material is, for example, preferably 40% by mass or more and 95% by mass or less, and preferably 50% by mass or more and 95% by mass or less with respect to the total solid content in the composition for layer formation. is there.

-Resin particles-
The film constituting the protective layer (outermost surface layer) may contain resin particles.
Examples of the resin particles include polycarbonate resin particles such as bisphenol A type or bisphenol Z type, acrylic resin, methacrylic resin, polyarylate resin, polyester resin, polyvinyl chloride resin, polystyrene resin, acrylonitrile-styrene copolymer resin, Acrylonitrile-butadiene copolymer resin, polyvinyl acetate resin, polyvinyl formal resin, polysulfone resin, styrene-acrylic copolymer, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-vinyl acetate- Insulating resin particles such as maleic anhydride resin, silicone resin, phenol-formaldehyde resin, polyacrylamide resin, polyamide resin, chlorine rubber, and polyvinylcarbazole, poly Examples thereof include particles of an organic photoconductive polymer such as vinyl anthracene and polyvinyl pyrene.
These resin particles may be hollow particles.
The resin particles may be used alone or in combination of two or more.

The film constituting the protective layer (outermost surface layer) may contain fluorine-containing resin particles as resin particles.
Examples of the fluorine-containing resin particles include homopolymers of fluoroolefins and copolymers of two or more types, which are copolymers of one or more types of fluoroolefins and non-fluorinated monomers. .

  Examples of the fluoroolefin include perhaloolefin such as tetrafluoroethylene (TFE), perfluorovinyl ether, hexafluoropropylene (HFP), and chlorotrifluoroethylene (CTFE), vinylidene fluoride (VdF), trifluoroethylene, and fluoride. Non-perfluoroolefins such as vinyl can be mentioned, and VdF, TFE, CTFE, HFP and the like are preferable.

  On the other hand, examples of non-fluorine monomers include hydrocarbon olefins such as ethylene, propylene and butene, alkyl vinyl ethers such as cyclohexyl vinyl ether (CHVE), ethyl vinyl ether (EVE), butyl vinyl ether and methyl vinyl ether, and polyoxyethylene allyl ether. (POEAE), alkenyl vinyl ethers such as ethyl allyl ether, organosilicon compounds having reactive α, β-unsaturated groups such as vinyltrimethoxysilane (VSi), vinyltriethoxysilane, vinyltris (methoxyethoxy) silane, and acrylic acid Acrylic esters such as methyl and ethyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, vinyl acetate, vinyl benzoate, (Trade name, vinyl ester manufactured by Shell) and the like, and alkyl vinyl ethers, allyl vinyl ethers, vinyl esters, and organosilicon compounds having a reactive α, β-unsaturated group are preferred.

  Among these, those having a high fluorination rate are preferable, such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA). ), Ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and the like are preferable. Among these, PTFE, FEP, and PFA are particularly preferable.

As the fluorine-containing resin particles, for example, particles (fluorine resin aqueous dispersion) produced by a method such as emulsion polymerization of a fluorine-based monomer may be used as they are, or may be used after thoroughly washing with water and drying. Good.
The average particle size of the fluorine-containing resin particles is preferably 0.01 μm or more and 100 μm or less, and particularly preferably 0.03 μm or more and 5 μm or less.
In addition, the average particle diameter of the said fluorine-containing resin particle means the value measured using the laser diffraction type particle size distribution measuring device LA-700 (made by Horiba Ltd.).

  As the fluorine-containing resin particles, commercially available ones may be used. For example, as PTFE particles, Fullon L173JE (Asahi Glass Co., Ltd.), Taniion THV-221AZ, Taniion 9205 (Sumitomo 3M), Lubron L2, Lubron And L5 (manufactured by Daikin).

  The fluorine-containing resin particles may be irradiated with laser light having an oscillation wavelength in the ultraviolet region. The laser beam irradiated to the fluorine-containing resin particles is not particularly limited, and examples thereof include an excimer laser. As the excimer laser light, an ultraviolet laser light having a wavelength of 400 nm or less, particularly 193 nm or more and 308 nm or less is suitable. In particular, KrF excimer laser light (wavelength: 248 nm) and ArF excimer laser light (wavelength: 193 nm) are preferred. Excimer laser light irradiation is usually performed in the air at room temperature (25 ° C.), but may be performed in an oxygen atmosphere.

The irradiation conditions of excimer laser light depend on the type of fluororesin and the required degree of surface modification, but general irradiation conditions are as follows.
Fluence: 50 mJ / cm ² / pulse or more Incident energy: 0.1 J / cm ² or more Shot number: 100 or less

Particularly suitable irradiation conditions for particularly suitable KrF excimer laser light and ArF excimer laser light are as follows.
KrF
Fluence: 100 mJ / cm ² / pulse or more 500 mJ / cm ² / pulse or less incident energy: 0.2 J / cm ² or more 2.0 J / cm ² or less number of shots: 1 to 20

ArF
Fluence: 50 mJ / cm ² / pulse or more 150 mJ / cm ² / pulse or less incident energy: 0.1 J / cm ² or more 1.0 J / cm ² or less number of shots: 1 to 20

  The content of the fluorine-containing resin particles is preferably 1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 12% by mass or less with respect to the total solid content of the protective layer (outermost surface layer).

-Fluorine-containing dispersant-
The film constituting the protective layer (outermost surface layer) may contain a fluorine-containing dispersant together with the fluorine-containing resin particles.
Since the fluorine-containing dispersant is used to disperse the fluorine-containing resin particles in the protective layer (outermost surface layer), it preferably has a surface active action, that is, has a hydrophilic group in the molecule. A substance having a hydrophobic group is preferable.

Examples of the fluorine-containing dispersant include resins obtained by polymerizing the following reactive monomers (hereinafter referred to as “specific resins”). Specifically, a random or block copolymer of an acrylate having a perfluoroalkyl group and a monomer having no fluorine, a methacrylate homopolymer, and an acrylate having the perfluoroalkyl group, and not having the fluorine Examples thereof include random or block copolymers of monomers and random or block copolymers of methacrylate and monomers not containing fluorine. Examples of the acrylate having a perfluoroalkyl group include 2,2,2-trifluoroethyl methacrylate and 2,2,3,3,3-pentafluoropropyl methacrylate.
Moreover, as a monomer which does not have fluorine, for example, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate Phenoxypolyethyleneglycol Le acrylate, phenoxy polyethylene glycol methacrylate, hydroxyethyl o- phenylphenol acrylate, o- phenylphenol glycidyl ether acrylate. Also, block or branch polymers disclosed in US Pat. No. 5,637,142 and Patent No. 4,251,662 can be used. In addition, a fluorine-type surfactant is mentioned. Specific examples of the fluorosurfactant include Surflon S-611, Surflon S-385 (manufactured by AGC Seimi Chemical Co., Ltd.), Aftergent 730FL, Aftergent 750FL (manufactured by Neos), PF-636, and PF-6520 (Kitamura). Chemical Co., Ltd.), Megafac EXP, TF-1507, Megafac EXP, TF-1535 (manufactured by DIC), FC-4430, FC-4432 (manufactured by 3M), and the like.
The weight average molecular weight of the specific resin is preferably 100 or more and 50000 or less.

  The content of the fluorine-containing dispersant is preferably 0.1% by mass or more and 1% by mass or less, and more preferably 0.2% by mass or more and 0.5% by mass or less with respect to the total solid content of the protective layer (outermost surface layer). preferable.

  As a method of attaching the fluorine-containing dispersant to the surface of the fluorine-containing resin particles, the fluorine-containing dispersant may be attached directly to the surface of the fluorine-containing resin particles, or first, the above monomer is added to the fluorine-containing resin particles. The specific resin may be formed on the surface of the fluorine-containing resin particles by polymerizing after adsorbing on the surface.

  The fluorine-containing dispersant may be used in combination with other surfactants. However, the amount is preferably as small as possible, and the content of the other surfactant is preferably 0 part by mass or more and 0.1 part by mass or less, preferably 0 part by mass with respect to 1 part by mass of the fluorine-containing resin particles. It is 0.05 parts by mass or less, more preferably 0 parts by mass or more and 0.03 parts by mass or less.

Other surfactants are preferably nonionic surfactants, such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyls. Examples thereof include esters, glycerin esters, fluorosurfactants and derivatives thereof.
Specific examples of polyoxyethylenes include, for example, Emulgen 707 (manufactured by Kao Corporation), NAROACTY CL-70, NAROACTY CL-85 (manufactured by Sanyo Chemical Industries), Leocor TD-120 (manufactured by Lion Corporation), and the like. It is done.

-Compound having an unsaturated bond-
The film constituting the protective layer (outermost surface layer) may be used in combination with a compound having an unsaturated bond.
As a compound which has an unsaturated bond, any of a monomer, an oligomer, and a polymer may be sufficient. Examples of the compound having an unsaturated bond include those having no charge transporting skeleton.

Examples of the compound having an unsaturated bond include those having no charge transporting skeleton as follows.
Monofunctional monomers include, for example, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl Acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate, phenoxy polyethylene glycol acrylate The Roh carboxymethyl polyethylene glycol methacrylate, hydroxyethyl o- phenylphenol acrylate, o- phenylphenol glycidyl ether acrylate, styrene, and the like.

Examples of the bifunctional monomer include diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth). Examples thereof include acrylate, divinylbenzene, diallyl phthalate and the like.
Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, aliphatic tri (meth) acrylate, trivinylcyclohexane, and the like.
Examples of the tetrafunctional monomer include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and aliphatic tetra (meth) acrylate.
Examples of the pentafunctional or higher monomer include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, as well as (meth) acrylate having a polyester skeleton, a urethane skeleton, and a phosphazene skeleton.

  Among the compounds having an unsaturated bond, examples of the polymer include, for example, JP-A-5-216249, JP-A-5-323630, JP-A-11-52603, JP-A 2000-264961, Examples disclosed in Japanese Unexamined Patent Application Publication No. 2005-2291.

When using the compound which has an unsaturated bond which does not have a charge transport component, it is used individually or in mixture of 2 or more types.
The content of the compound having an unsaturated bond having no charge transport component is, for example, preferably 60% by mass or less, based on the total solid content of the composition used when forming the protective layer (outermost surface layer). Preferably, it is 55 mass% or less, More preferably, it is 50 mass% or less.

-Non-reactive charge transport material-
The film constituting the protective layer (outermost surface layer) may be used in combination with a non-reactive charge transport material. Since the non-reactive charge transport material does not have a reactive group, the concentration of the charge transport component increases when the non-reactive charge transport material is used for the protective layer (outermost surface layer), and the electrical characteristics are improved. It is effective for further improvement. Further, a non-reactive charge transport material may be added to reduce the crosslink density and adjust the strength.

As the non-reactive charge transport material, a known charge transport material may be used. Specifically, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds. Anthracene compounds, hydrazone compounds and the like are used.
Among these, those having a triphenylamine skeleton are preferable from the viewpoint of charge mobility and compatibility.

  The non-reactive charge transport material is preferably used in an amount of 0% by mass to 30% by mass, more preferably 1% by mass to 25% by mass with respect to the total solid content in the coating liquid for layer formation. More preferably, it is 5 mass% or more and 25 mass% or less.

-Other additives-
The film constituting the protective layer (outermost surface layer) is further mixed with other coupling agents, especially fluorine-containing coupling agents, for the purpose of adjusting the film formability, flexibility, lubricity, and adhesion. May be used. As such a compound, various silane coupling agents and commercially available silicone hard coat agents are used. Moreover, you may use the silicon compound and fluorine-containing compound which have a radically polymerizable group.

As silane coupling agents, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) -3-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane , Dimethyldimethoxysilane, and the like.
As commercially available hard coat agents, KP-85, X-40-9740, X-8239 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), AY42-440, AY42-441, AY49-208 (above, made by Toray Dow Corning) ) And the like.

  In order to impart water repellency and the like, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (hepta) Fluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyl Fluorine-containing compounds such as triethoxysilane may be added.

Although the silane coupling agent is used in an arbitrary amount, the amount of the fluorine-containing compound may be 0.25 times or less by mass with respect to the compound containing no fluorine from the viewpoint of the film formability of the crosslinked film. preferable. Furthermore, you may mix the reactive fluorine compound etc. which are disclosed by Unexamined-Japanese-Patent No. 2001-166510 etc.
Examples of the silicon compound and the fluorine-containing compound having a radical polymerizable group include compounds described in JP-A No. 2007-11005.

It is preferable to add a deterioration inhibitor to the film constituting the protective layer (outermost surface layer). As the deterioration inhibitor, hindered phenols or hindered amines are preferable, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants. You may use well-known antioxidants, such as an agent.
The addition amount of the deterioration inhibitor is preferably 20% by mass or less, and more preferably 10% by mass or less.

Examples of the hindered phenol antioxidant include Irganox 1076, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076 (manufactured by Ciba Japan), 3, 5 -Di-t-butyl-4-hydroxybiphenyl and the like.
Examples of the hindered amine antioxidant include Sanol LS2626, Sanol LS765, Sanol LS770, Sanol LS744 (Sanyo Lifetech Co., Ltd.), Tinuvin 144, Tinuvin 622LD (above, manufactured by Ciba Japan), Mark LA57, Mark LA67, Mark LA62, Mark LA68, Mark LA63 (manufactured by Adeka Co., Ltd.), and thioethers include Sumilizer TPS and Sumitizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.). Mark PEP-8, Mark PEP-24G, Mark PEP-36, Mark 329K, Mark HP-10 (manufactured by Adeka) and the like.

Conductive particles, organic or inorganic particles may be added to the film constituting the protective layer (outermost surface layer).
An example of such particles is silicon-containing particles. The silicon-containing particles are particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone particles. The colloidal silica used as the silicon-containing particles is preferably silica having an average particle diameter of 1 nm to 100 nm, more preferably 10 nm to 30 nm, in an acidic or alkaline aqueous dispersion, or an organic solvent such as alcohol, ketone, or ester. It is selected from those dispersed in. As the particles, commercially available particles may be used.

  The solid content of colloidal silica in the protective layer is not particularly limited, but is 0.1% by mass or more and 50% by mass or less, preferably 0.1% by mass based on the total solid content of the protective layer. % Or more and 30% by mass or less.

The silicone particles used as the silicon-containing particles may be selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and commercially available particles may be used.
These silicone particles are spherical, and the average particle diameter is preferably 1 nm to 500 nm, more preferably 10 nm to 100 nm.
The content of the silicone particles in the surface layer is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, based on the total solid content of the protective layer. .

Other particles include ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO ₂ —TiO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO. Examples thereof include semiconductive metal oxides such as —TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. Furthermore, various known dispersing materials may be used to disperse the particles.

Oil such as silicone oil may be added to the film constituting the protective layer (outermost surface layer).
Silicone oils include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane; amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, mercapto-modified poly Reactive silicone oils such as siloxane and phenol-modified polysiloxane; cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; 1,3,5- Trimethyl-1.3.5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclo Cyclic methylphenylcyclosiloxanes such as trasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane; cyclic phenylcyclosiloxanes such as hexaphenylcyclotrisiloxane Fluorine-containing cyclosiloxanes such as 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane; Hydrosilyl group-containing cyclosiloxanes such as methylhydrosiloxane mixture, pentamethylcyclopentasiloxane, and phenylhydrocyclosiloxane And vinyl group-containing cyclosiloxanes such as pentavinylpentamethylcyclopentasiloxane.

  In order to improve the wettability of the coating film, a silicone-containing oligomer, a fluorine-containing acrylic polymer, a silicone-containing polymer, or the like may be added to the film constituting the protective layer (outermost surface layer).

Metal, metal oxide, carbon black, or the like may be added to the film constituting the protective layer (outermost surface layer). Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, or those obtained by depositing these metals on the surface of resin particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. .
These are used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed or mixed by solid solution or fusion. The average particle size of the conductive particles is preferably 0.3 μm or less, particularly preferably 0.1 μm or less.

-Composition-
The composition used to form the protective layer is preferably prepared as a protective layer-forming coating solution obtained by dissolving or dispersing each component in a solvent.
Specifically, as a solvent for the coating solution for forming the protective layer, for example, methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, ethyl n butyl ketone, di n propyl ketone, methyl n amyl ketone, methyl n butyl ketone, diethyl ketone, Ketones such as methyl n-propyl ketone; isopropyl acetate, isobutyl acetate, ethyl acetate, npropyl acetate, nbutyl acetate, ethyl isovalerate, isoamyl acetate, isopropyl butyrate, isoamyl propionate, butyl butyrate, amyl acetate, butyl propionate And single solvents or mixed solvents such as esters such as ethyl propionate, methyl acetate, methyl propionate, and allyl acetate. Also, 0% by mass or more and 50% by mass or less of an ether solvent (for example, diethyl ether, dioxane, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, etc.), an alkylene glycol solvent (for example, 1-methoxy-2-propanol, 1-ethoxy- 2-propanol, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether acetate, etc.) may be mixed and used.

  As a dispersion method for dispersing the fluorine-containing resin particles in the coating liquid for forming the protective layer, a media dispersion machine such as a ball mill, a vibration ball mill, an attritor, a sand mill, a horizontal sand mill, a stirring, an ultrasonic dispersion machine, a roll mill, Examples thereof include a dispersion method using a medialess disperser such as a high-pressure homogenizer. Furthermore, as the dispersion method, as a high-pressure homogenizer, a collision method in which the dispersion liquid is dispersed by liquid-liquid collision or liquid wall collision in a high-pressure state, a penetration method in which a fine flow path is dispersed in a high-pressure state, etc. A dispersion method is also mentioned.

  The method for preparing the coating liquid for forming the protective layer is not particularly limited, and the charge transport material, the fluorine-containing resin particles, the fluorine-containing dispersant and, if necessary, other components such as a solvent are mixed, You may prepare using the above-mentioned disperser, or two liquids of the liquid mixture A containing a fluorine-containing resin particle, a fluorine-containing dispersing agent, and a solvent, and the liquid mixture B containing at least a charge transport material and a solvent are separately prepared. You may prepare by mixing these liquid mixture A and liquid mixture B after preparing. By mixing the fluorine-containing resin particles and the fluorine-containing dispersant in a solvent, the fluorine-containing dispersant is easily attached to the surface of the fluorine-containing resin particles.

  In addition, when a coating liquid for forming a protective layer is obtained by reacting the above-mentioned components, each component may be simply mixed and dissolved, but is preferably room temperature (20 ° C.) or higher and 100 ° C. or lower, more preferably 30 ° C. Heating is performed at 80 ° C. or lower, preferably 10 minutes or longer and 100 hours or shorter, more preferably 1 hour or longer and 50 hours or shorter. In this case, it is also preferable to irradiate ultrasonic waves.

-Formation of protective layer-
The coating solution for forming the protective layer is formed on the surface to be coated (charge transport layer) by a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, The coating is performed by a normal method such as an inkjet coating method.
Thereafter, light, electron beam or heat is applied to the obtained coating film to cause radical polymerization, thereby curing the coating film.

  As the curing method, heat, light, radiation or the like is used. When curing with heat and light, a polymerization initiator is not necessarily required, but a photocuring catalyst or a thermal polymerization initiator may be used. Known photocuring catalysts and thermal polymerization initiators are used as the photocuring catalyst and the thermal polymerization initiator. The radiation is preferably an electron beam.

-Electron beam curing When an electron beam is used, the acceleration voltage is preferably 300 KV or less, and optimally 150 KV or less. The dose is preferably in the range of 1 Mrad to 100 Mrad, more preferably in the range of 3 Mrad to 50 Mrad. When the acceleration voltage is 300 KV or less, damage caused by electron beam irradiation on the characteristics of the photoreceptor is suppressed. Further, when the dose is 1 Mrad or more, crosslinking is sufficiently performed, and when the dose is 100 Mrad or less, deterioration of the photoreceptor is suppressed.

  Irradiation is performed in an inert gas atmosphere such as nitrogen or argon at an oxygen concentration of 1000 ppm, preferably 500 ppm or less, and may be further heated to 50 ° C. or higher and 150 ° C. or lower during or after irradiation.

-Photocuring As a light source, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, etc. are used, A suitable wavelength may be selected using filters, such as a band pass filter. Irradiation time, the light intensity is selected freely, for example, the illuminance (365 nm) is 300 mW / cm ² or more, preferably 1000 mW / cm ² or less, for example, the case of irradiation with UV light of 600 mW / cm ^2, 5 seconds or more 360 What is necessary is just to irradiate for less than a second.

  Irradiation is performed under an inert gas atmosphere such as nitrogen or argon, preferably at an oxygen concentration of 1000 ppm or less, more preferably 500 ppm or less, and may be further heated to 50 ° C. or more and 150 ° C. or less during or after the irradiation.

Examples of the photocuring catalyst include intramolecular cleavage types such as benzyl ketal, alkylphenone, aminoalkylphenone, phosphine oxide, titanocene, and oxime.
More specifically, examples of the benzyl ketal system include 2,2-dimethoxy-1,2-diphenylethane-1-one.

Examples of the alkylphenone series include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl]. 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl- Examples include propan-1-one, acetophenone, and 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone.
Examples of aminoalkylphenones include p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1 -Butanone and the like.
Examples of the phosphinoxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
Examples of the titanocene include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Examples of oxime compounds include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

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

  These photopolymerization initiators are used alone or in combination of two or more.

-Thermosetting Thermal polymerization initiators include thermal radical generators or derivatives thereof. Specifically, for example, V-30, V-40, V-59, V601, V65, V-70, VF- Azo initiators such as 096, VE-073, Vam-110, Vam-111 (manufactured by Wako Pure Chemical Industries, Ltd.), OTazo-15, OTazo-30, AIBN, AMBN, ADVN, ACVA (Otsuka Chemical); Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Perbutyl H, Parkmill H, Parkmill P, Permenta H, Perocta H, Perbutyl C, Perbutyl D, Perhexyl D, Parroyl IB, Parroyl 355, Parroyl L, Parroyl SA , Nyper BW, Nyper BMT-K40 / M, Parroyl IPP, Parro Il NPP, Parroyl TCP, Parroyl OPP, Parroyl SBP, Park Mill ND, Perocta ND, Perhexyl ND, Perbutyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl PV, Perhexa 250, Perocta O, Perhexyl O, Perbutyl O, Perbutyl L, Perbutyl 355 Perhexyl I, perbutyl I, perbutyl E, perhexa 25Z, perbutyl A, perhexyl Z, perbutyl ZT, perbutyl Z (manufactured by NOF Chemical), Kayaketal AM-C55, Trigonox 36-C75, Laurox, Perkadox L-W75, Parkadox CH-50L, Trigonox TMBH, Kayacumen H, Kayabutyl H-70, Percadox BC-FF, Kaya Hexa AD, Parkadox 14, Kayabuchi C, Kayabutyl D, Kayahexa YD-E85, Parkadox 12-XL25, Parkadox 12-EB20, Trigonox 22-N70, Trigonox 22-70E, Trigonox D-T50, Trigonox 423-C70, Kayaester CND-C70, Kayaester CND-W50, Trigonox 23-C70, Trigonox 23-W50N, Trigonox 257-C70, Kaya ester P-70, Kaya ester TMPO-70, Trigonox 121, Kaya ester O, Kaya ester HTP-65W, Kaya ester AN, Trigonox 42 , Trigonox F-C50, Kaya Butyl B, Kaya Carbon EH-C70, Kaya Carbon EH-W60, Kaya Carbon I-20, Kaya Carbon BIC-75, Trigonok 117, Kayalen 6-70 (manufactured by Kayaku Akzo), Lupelox 610, Lupelox 188, Lupelox 844, Lupelox 259, Lupelox 10, Lupelox 701, Lupelox 11, Lupelox 26, Lupelox 80, Lupelox 7, Lupelox P, Lupelox P, Lupelox 546, Lupelox 554, Lupelox 575, Lupelox TANPO, Lupelox 555, Lupelox 570, Lupelox TAP, Lupelox TBIC, Lupelox TBEC, Lupelox JW, Lupelox TAIC, Lupelox DC, Lupelox DC, Lupelox DC , Lupelox 220, Lupelox 230, Lupelox 23 3, Lupelox 531 (manufactured by Arkema Yoshitomi) and the like.

  Among these, when an azo polymerization initiator having a molecular weight of 250 or more is used, the reaction proceeds without unevenness at a low temperature, so that a high-strength film with suppressed unevenness can be formed. More preferably, the molecular weight of the azo polymerization initiator is 250 or more, and more preferably 300 or more.

  The heating is performed under an inert gas atmosphere such as nitrogen or argon, and the oxygen concentration is preferably 1000 ppm or less, more preferably 500 ppm or less, preferably 50 ° C. or more and 170 ° C. or less, more preferably 70 ° C. or more and 150 ° C. or less. Preferably it is 10 minutes or more and 120 minutes or less, More preferably, 15 minutes or more and 100 minutes or less are heated.

  The total content of the photocuring catalyst or the thermal polymerization initiator is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more, based on the total solid content in the solution for forming the layer. 8 mass% or less is more preferable, and the range of 0.1 mass% or more and 5 mass% or less is especially preferable.

In this embodiment, if the reaction proceeds too quickly, the structure of the coating film is difficult to be relaxed by crosslinking, and the generation of radicals is relatively slow because it tends to cause film unevenness and wrinkles. The curing method is adopted.
In particular, by combining a specific chain polymerizable charge transport material and curing by heat, the structure relaxation of the coating film is promoted, and a high protective layer (outermost surface layer) excellent in surface properties is easily obtained.

  The thickness of the protective layer is, for example, preferably set in the range of 3 μm to 40 μm, more preferably 5 μm to 35 μm, and still more preferably 7 μm to 30 μm.

  The structure of each layer in the function-separated type photosensitive layer has been described with reference to the electrophotographic photoreceptor shown in FIG. 1, but this structure is also applied to each layer in the function-separated type electrophotographic photoreceptor shown in FIG. Can be adopted. Further, in the case of the single-layer type photosensitive layer of the electrophotographic photosensitive member shown in FIG.

That is, the single-layer type photosensitive layer (charge generation / charge transport layer) includes a charge generation material, a charge transport material, and, if necessary, a binder resin and other known additives. Is good. These materials are the same as those described in the charge generation material and the charge transport layer.
In the single-layer type photosensitive layer, the content of the charge generating material is preferably 10% by mass or more and 85% by mass or less, and preferably 20% by mass or more and 50% by mass or less with respect to the total solid content. In the single-layer type photosensitive layer, the content of the charge transport material is preferably 5% by mass or more and 50% by mass or less based on the total solid content.
The method for forming the single-layer type photosensitive layer is the same as the method for forming the charge generation layer and the charge transport layer.
The film thickness of the single-layer type photosensitive layer is, for example, from 5 μm to 50 μm, and preferably from 10 μm to 40 μm.

In the electrophotographic photosensitive member according to the present embodiment, the mode in which the outermost surface layer is the protective layer has been described, but a layer configuration without the protective layer may be employed.
In the case of a layer structure without a protective layer, in the electrophotographic photoreceptor shown in FIG. 1, the charge transport layer located on the outermost surface in the layer structure becomes the outermost surface layer. And the electric charge transport layer used as the said outermost surface layer is comprised with the cured film of the said specific composition.
In the case of a layer structure without a protective layer, in the electrophotographic photoreceptor shown in FIG. 3, the single-layer type photosensitive layer located on the outermost surface in the layer structure is the outermost surface layer. And the single layer type photosensitive layer used as the said outermost surface layer is comprised with the cured film of the said specific composition. However, a charge generating material is blended in the composition.

-Charging device-
As the charging device 8, a charging device that is disposed in contact with or close to the surface of the electrophotographic photosensitive member 7 and charges the surface of the electrophotographic photosensitive member is employed. Here, the arrangement of the charging device 8 in the vicinity means, for example, that the charging device 8 (the conductive member (charging member)) is arranged away from the surface of the electrophotographic photosensitive member 7 in a range of 1 μm to 200 μm. It shows that.
Specifically, as the charging device 8, a contact type charger in which a conductive or semiconductive member such as a charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube or the like is brought into contact with the surface of the electrophotographic photosensitive member 7. A proximity charger in which the conductive or semiconductive member is provided separately from the surface of the electrophotographic photosensitive member 7 can be used.

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

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

  Here, the developer accommodated in the developing device includes toner particles and inorganic particles having a volume average particle diameter of 1 μm or less. Inorganic particles are included in the developer as an external additive.

Next, the configuration of the toner particles will be described.
The toner particles include, for example, a binder resin. The toner particles may contain a colorant, a release agent, and other additives as necessary.

-Binder resin Examples of the binder resin include styrenes (eg, styrene, parachlorostyrene, α-methylstyrene, etc.), (meth) acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid n-). Propyl, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (Eg acrylonitrile, methacrylonitrile, etc.), vinyl ethers (eg vinyl methyl ether, vinyl isobutyl ether etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone etc.), olefins (eg ethyl , Propylene, a homopolymer of a monomer such as butadiene) and the like, or a vinyl-based resin composed of these monomers with two or more combinations copolymer.
As the binder resin, for example, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, non-vinyl resin such as modified rosin, a mixture of these with the vinyl resin, or these Examples also include a graft polymer obtained by polymerizing a vinyl monomer in the coexistence.
These binder resins may be used alone or in combination of two or more.

  The content of the binder resin is, for example, preferably 40% by weight to 95% by weight, more preferably 50% by weight to 90% by weight, and more preferably 60% by weight to 85% by weight with respect to the entire toner particles. Further preferred.

Colorants Examples of the colorant include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, and brilliant carmine. 3B, Brilliant Carmine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Pigment Red, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Pigment Blue, Various pigments such as phthalocyanine green and malachite green oxalate, or acridine series, xanthate , Azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazole And various dyes.
A colorant may be used individually by 1 type and may use 2 or more types together.

  As the colorant, a surface-treated colorant may be used as necessary, or it may be used in combination with a dispersant. A plurality of colorants may be used in combination.

  The content of the colorant is, for example, preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 15% by mass or less with respect to the entire toner particles.

-Release agent Examples of release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; fatty acid esters, montanate esters, etc. And ester waxes. The release agent is not limited to this.

The melting temperature of the release agent is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.
The melting temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC) according to the “melting peak temperature” described in JIS K-1987 “Method for measuring the transition temperature of plastics”.

  The content of the release agent is, for example, preferably 1% by mass to 20% by mass and more preferably 5% by mass to 15% by mass with respect to the entire toner particles.

Other additives Examples of the other additives include well-known additives such as magnetic materials, charge control agents, and inorganic powders. These additives are contained in the toner particles as internal additives.

Toner particle characteristics, etc. The toner particles may be toner particles having a single layer structure, or a so-called core-shell comprising a core (core particle) and a coating layer (shell layer) covering the core. It may be toner particles having a structure.
Here, the core / shell structure toner particles include, for example, a core portion including a binder resin and, if necessary, other additives such as a colorant and a release agent, and a binder resin. It is good to be comprised with the comprised coating layer.

  The volume average particle diameter (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

The various average particle diameters and various particle size distribution indexes of the toner particles are measured using Coulter Multisizer II (manufactured by Beckman-Coulter), and the electrolyte is measured using ISOTON-II (manufactured by Beckman-Coulter). The
In the measurement, 0.5 mg to 50 mg of a measurement sample is added as a dispersant to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate). This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolyte in which the sample is suspended is dispersed for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm to 60 μm is measured using a 100 μm aperture with a Coulter Multisizer II. taking measurement. The number of particles to be sampled is 50,000.
For the particle size range (channel) divided based on the measured particle size distribution, the cumulative distribution is drawn from the smaller diameter side to the volume and number, respectively, and the particle size to be 16% is the volume particle size D16v, the number particle size D16p, a particle size that is 50% cumulative is defined as a volume average particle size D50v, a cumulative number average particle size D50p, and a particle size that is 84% cumulative is defined as a volume particle size D84v and a number particle size D84p.
Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D84p / D16p) ^1/2 .

  The shape factor SF1 of the toner particles is preferably 110 or more and 150 or less, and more preferably 120 or more and 140 or less.

The shape factor SF1 is obtained by the following formula.
Formula: SF1 = (ML ² / A) × (π / 4) × 100
In the above formula, ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.
Specifically, the shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows. That is, by capturing an optical microscope image of particles dispersed on the surface of a slide glass into a Luzex image analyzer using a video camera, obtaining the maximum length and projected area of 100 particles, calculating by the above formula, and obtaining the average value can get.

External Additive The external additive includes inorganic particles having a volume average particle diameter of 1 μm or less (hereinafter also referred to as “small-diameter inorganic particles”). The external additive may include known external additives such as fatty acid metal salt particles in addition to the small-diameter inorganic particles.

The volume average particle diameter of the small-diameter inorganic particles is preferably 5 nm to 500 nm, more preferably 10 nm to 400 nm, and still more preferably 20 nm to 250 nm.
The volume average particle diameter of the small-diameter inorganic particles is 50% of the cumulative frequency of equivalent-circle diameters obtained by observing 100 primary particles of inorganic particles with a scanning electron microscope (SEM) apparatus and analyzing the primary particles. It is a diameter (D50v) and is measured by this method.

Examples of the small-diameter inorganic particles include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, CaO, K ₂ O, Na ₂ O, and ZrO _{2. , CaO · SiO 2, K 2} O · (TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4 , etc. particles.
As the small-diameter inorganic particles, SiO ₂ (silica) particles and TiO ₂ (titanium oxide) particles are preferable.

The surface of the small-diameter inorganic particles is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing small-diameter inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually, for example, 1 part by mass or more and 10 parts by mass with respect to 100 parts by mass of the small-diameter inorganic particles.

  The external addition amount (content) of the small-diameter inorganic particles is, for example, preferably 0.5% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 3.0% by mass or less with respect to the toner particles. 0.5 mass% or more and 2.0 mass% or less are more preferable.

Examples of the fatty acid metal salt particles include fatty acids (for example, fatty acids such as stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, lauric acid, and other organic acids) and metals (for example, calcium, zinc, magnesium, aluminum, Other examples include metal salt particles with metals (Na, Li, etc.).
Specific examples of fatty acid metal salt particles include zinc stearate, calcium stearate, iron stearate, copper stearate, magnesium palmitate, calcium palmitate, manganese oleate, lead oleate, zinc laurate, zinc palmitate And the like.
Among these, the fatty acid metal salt particles are preferably zinc stearate particles from the viewpoint of lubricity, hydrophobicity, and wettability to the electrophotographic photoreceptor 7.

  The fatty acid metal salt particles may be mixed particles of a plurality of types of fatty acid metal salts. The fatty acid metal salt particles may be particles containing a fatty acid metal salt and other components. Examples of other components include higher fatty acid alcohols. However, the fatty acid metal salt particles contain 10% by mass or more of the fatty acid metal salt.

The median diameter based on volume of the fatty acid metal salt particles is preferably 0.1 μm or more and 10.0 μm or less, more preferably 0.2 μm or more and 10.0 μm or less, and further preferably 0.2 μm or more and 8.0 μm or less.
The median diameter based on volume of the fatty acid metal salt particles is a value measured by the following method. As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. For setting the measurement conditions and analyzing the measurement data, the dedicated software “HORIBA LA-920 for Windows (registered trademark) WET (LA-920) Ver. 2.02 (Horiba, Ltd.)” attached to LA-920 is used. . As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.

  The external addition amount (content) of the fatty acid metal salt particles is preferably 0.01% by mass or more and 5% by mass or less, and more preferably 0.05% by mass or more and 0.5% by mass or less with respect to the toner particles.

  Other known external additives include inorganic lubricant particles, inorganic abrasive particles, resin lubricant particles, resin particles (resin particles such as polystyrene, PMMA, and melamine resin), cleaning activators (for example, fluorine-based additives) High molecular weight particles) and the like.

Toner Manufacturing Method Next, a toner manufacturing method according to the present embodiment will be described.
The toner according to the exemplary embodiment can be obtained by externally adding an external additive to the toner particles after the toner particles are manufactured.

  The toner particles may be produced by any of a dry production method (for example, a kneading and pulverizing method) and a wet production method (for example, an aggregation coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). The production method of the toner particles is not particularly limited, and a known production method is adopted.

  The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained dry toner particles and mixing them. Mixing may be performed, for example, with a V blender, a Henschel mixer, a Ladyge mixer, or the like. Furthermore, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

-Carrier There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. As a carrier, for example, a coated carrier in which the surface of a core made of magnetic powder is coated with a coating resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin; a porous magnetic powder is impregnated with a resin Resin impregnated type carriers; and the like.
Note that the magnetic powder-dispersed carrier and the resin-impregnated carrier may be a carrier in which the constituent particles of the carrier are used as a core material and coated with a coating resin.

  The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner: carrier = 1: 100 to 30: 100, and more preferably 3: 100 to 20: 100.

-Cleaning device-
As the cleaning device 13, a cleaning blade type device including a cleaning blade 131 is used.

As the cleaning blade 131, a cleaning blade in which at least the photosensitive member contact portion is constituted by a rubber modified portion modified by plasma ion implantation is applied.
Here, the rubber modifying portion is a portion containing rubber and an element or compound derived from plasma ions. The photosensitive member contact portion is a portion where the cleaning blade 131 is in contact with the photosensitive member when the rotation of the electrophotographic photosensitive member 7 is stopped, and cleaning when the electrophotographic photosensitive member 7 is rotating. This is an area including both portions where the blade 131 is in contact with the photosensitive member.

  Examples of the plasma ions injected into the rubber reforming part include plasma ions of carbon, gallium, boron, silicon and the like.

  Among these, from the viewpoint of mechanical strength and slidability, the plasma ions are preferably carbon plasma ions. That is, the rubber reforming part is preferably a rubber reforming part containing carbon having sp3 bonds.

Details of the cleaning blade 131 will be described below. The configuration in which the rubber modifying portion is a rubber modifying portion containing carbon having sp3 bonds will be described in detail.
Specifically, the cleaning blade 131 includes, for example, at least a rubber base material (hereinafter simply referred to as “base material”). The entire substrate is made of rubber. The base material has a contact portion (photoconductor contact portion) that comes into contact with the electrophotographic photoreceptor 7 and satisfies any of the following requirements (A) or (B).
(A) The photoreceptor contact portion is composed of a rubber modifying portion containing carbon having sp3 bonds. In this case, the rubber modified portion is in direct contact with the electrophotographic photoreceptor 7.
(B) The photoreceptor contact portion includes a rubber modified portion containing carbon having sp3 bonds, and a carbon layer containing carbon having sp3 bonds provided on the surface of the rubber modified portion on the electrophotographic photoreceptor 7 side (particularly , Diamond-like carbon layer). In this case, the carbon layer is in direct contact with the electrophotographic photoreceptor 7. The carbon layer does not include rubber.

  In the base material, the rubber in the rubber modifying portion and the rubber in the region other than the rubber modifying portion are made of the same material. That is, the base material has a structure in which a rubber modifying portion is provided by carbon plasma ion implantation in a region to be a photoreceptor contact portion.

In the cleaning blade 131 having a base material that satisfies the requirement (A), the rubber modifying portion that constitutes the photosensitive member contact portion includes rubber and carbon having sp3 bonds, so that the carbon component having sp3 bonds has. Mechanical strength and rubbing properties are compatible with toughness (flexibility) of the rubber component. Accordingly, it is considered that the cleaning blade 131 can easily maintain a stable contact state with the electrophotographic photosensitive member 7 in the long term while suppressing the occurrence of tack-under in addition to the wear resistance and chipping resistance.
In addition, in the photosensitive member contact portion of the cleaning blade 131 having a base material that satisfies the requirement (A), the physical property change (elastic modulus, Young's modulus, etc.) of the rubber is small even when the environment changes, and the toughness (flexibility) is improved. Therefore, chipping with respect to local stress concentration caused by collision with foreign matter such as iron powder is also suppressed.

  On the other hand, in the cleaning blade 131 having the base material satisfying the requirement (B), the photosensitive member contact portion is composed of a carbon layer containing carbon having sp3 bonds in addition to the rubber modified portion. The rubbing property can be further improved in the initial stage. However, the carbon layer has the property of becoming more easily peeled off as the rubbing becomes more intense and the frictional force increases, and tends to disappear as the use continues. However, even after the carbon layer has disappeared, there is a rubber modified portion containing carbon having sp3 bonds, so that wear resistance and chipping resistance are maintained.

  Next, details of the cleaning blade 131 will be described with reference to the drawings.

As shown in FIG. 6, the cleaning blade 131 has at least a base material 135. The base material 135 has a rubber modified portion 135B (carbon-containing region) containing carbon having sp3 bonds on the contact side with the electrophotographic photoreceptor 7. In the base material 135, a region 135A other than the rubber modified portion 135B (carbon-containing region) is a region made of a rubber portion that does not contain carbon (plasma ions).
Further, the cleaning blade 131 includes a carbon layer 136 that does not contain rubber and contains carbon having sp3 bonds on the surface of the rubber modified portion 135B (carbon-containing region) on the contact side with the electrophotographic photoreceptor 7. Also good. In this case, the rubber modifying portion 135B (carbon-containing region) and the carbon layer 136 constitute a contact portion with the electrophotographic photosensitive member 7. On the other hand, when the carbon layer 136 is not provided, the rubber modified portion 135 </ b> B (carbon-containing region) constitutes a contact portion with the electrophotographic photoreceptor 7.

  The cleaning blade 131 may be a photoreceptor contact portion configured by the rubber modifying portion 135B or a single layer structure of the base material 135 configured by the rubber modifying portion 135B and the carbon layer 136. A multilayer structure composed of the base material 135 and a back surface layer provided on the opposite side of the base material 135 to the opposite side of the electrophotographic photoreceptor 7 may be used. This back layer may also be a single layer or multiple layers.

  Next, constituent materials of the cleaning blade will be described in detail. Note that the reference numerals are omitted.

(Base material)
-Resin-
The base material contains rubber in its entirety.
Examples of the rubber include polyurethane rubber, silicon rubber, fluorine rubber, chloroprene rubber, and butadiene rubber. In particular, polyurethane rubber is desirable, and highly crystallized polyurethane rubber is more desirable.

Polyurethane rubber is usually synthesized by polymerizing polyisocyanate and polyol. Moreover, you may use resin which has a functional group which can react with an isocyanate group other than a polyol. The polyurethane rubber preferably has a hard segment and a soft segment.
Here, the “hard segment” and the “soft segment” are materials in which the former constituting the polyurethane rubber is relatively harder than the material constituting the latter. This means a segment made of a material that is relatively softer than the material constituting the former.
The “polyisocyanate” may not form a crosslinked structure in the synthesized rubber.

  The combination of the material constituting the hard segment (hard segment material) and the material constituting the soft segment (soft segment material) is not particularly limited. One is relatively hard with respect to the other and the other is against the other However, in the present embodiment, the following combinations are suitable.

-Soft segment material First, as the soft segment material, as the polyol, polyester polyol obtained by dehydration condensation of diol and dibasic acid, polycarbonate polyol obtained by reaction of diol and alkyl carbonate, polycaprolactone polyol, polyether polyol, etc. Is mentioned. In addition, as a commercial item of the said polyol used as a soft segment material, the Daicel Chemical Co., Ltd. Plaxel 205, Plaxel 240, etc. are mentioned, for example.

Hard segment material As the hard segment material, it is desirable to use a resin having a functional group capable of reacting with an isocyanate group. In addition, a flexible resin is desirable, and an aliphatic resin having a linear structure is more desirable from the viewpoint of flexibility. As a specific example, it is desirable to use an acrylic resin containing two or more hydroxyl groups, a polybutadiene resin containing two or more hydroxyl groups, an epoxy resin having two or more epoxy groups, and the like.

As a commercial item of the acrylic resin containing two or more hydroxyl groups, Act Flow (grade: UMB-2005B, UMB-2005P, UMB-2005, UME-2005, etc.) manufactured by Soken Chemical Co., Ltd. may be mentioned.
As a commercial item of the polybutadiene resin containing two or more hydroxyl groups, Idemitsu Kosan Co., Ltd. make, R-45HT etc. are mentioned, for example.

The epoxy resin having two or more epoxy groups does not have a hard and brittle property like a conventional general epoxy resin, and preferably has a softer toughness than a conventional epoxy resin. As the epoxy resin, for example, in terms of molecular structure, those having a structure (flexible skeleton) that can increase the mobility of the main chain in the main chain structure are suitable. Examples include an alkylene skeleton, a cycloalkane skeleton, a polyoxyalkylene skeleton, and the like, and a polyoxyalkylene skeleton is particularly preferable.
In terms of physical properties, an epoxy resin having a lower viscosity than the molecular weight of the conventional epoxy resin is preferable. Specifically, the weight average molecular weight is preferably in the range of 900 ± 100, the viscosity at 25 ° C. is preferably in the range of 15000 ± 5000 mPa · s, and more preferably in the range of 15000 ± 3000 mPa · s. desirable. As a commercial item of the epoxy resin which has this characteristic, the product made from DIC, EPLICON EXA-4850-150, etc. are mentioned, for example.

When a hard segment material and a soft segment material are used, the mass ratio of the material constituting the hard segment to the total amount of the hard segment material and the soft segment material (hereinafter referred to as “hard segment material ratio”) is 10% by mass or more and 30% by mass or less. It is desirable to be within the range of 13 mass% to 23 mass%, and it is even more desirable to be within the range of 15 mass% to 20 mass%.
Abrasion resistance is obtained when the hard segment material ratio is 10% by mass or more. On the other hand, when the hard segment material ratio is 30% by mass or less, the material does not become too hard, and flexibility and extensibility are obtained, and the occurrence of chipping is suppressed.

-Polyisocyanate Examples of the polyisocyanate used for the synthesis of the polyurethane rubber include 4,4'-diphenylmethane diisocyanate (MDI), 2,6-toluene diisocyanate (TDI), 1,6-hexane diisocyanate (HDI), 1, Examples include 5-naphthalene diisocyanate (NDI) and 3,3-dimethylphenyl-4,4-diisocyanate (TODI).
The polyisocyanate is 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), from the viewpoint of easy formation of hard segment aggregates of the required size (particle diameter). More preferred is hexamethylene diisocyanate (HDI).

The blending amount with respect to 100 parts by mass of the resin having a functional group capable of reacting with the isocyanate group of the polyisocyanate is preferably 20 parts by mass or more and 40 parts by mass or less, more preferably 20 parts by mass or more and 35 parts by mass or less, More preferably, it is more than 30 parts by mass.
When the amount is 20 parts by mass or more, a large amount of urethane bond is ensured, hard segment growth occurs, and the required hardness is obtained. On the other hand, when it is 40 parts by mass or less, the hard segment does not become too large, extensibility is obtained, and occurrence of chipping of the rubbing member is suppressed.

-Crosslinking agent As a crosslinking agent, diol (bifunctional), triol (trifunctional), tetraol (tetrafunctional), etc. are mentioned, You may use these together. An amine compound may be used as a crosslinking agent. In addition, it is desirable that it should be crosslinked using a trifunctional or higher functional crosslinking agent. Examples of the trifunctional crosslinking agent include trimethylolpropane, glycerin, triisopropanolamine and the like.

  As for the compounding quantity with respect to 100 mass parts of resin which has a functional group which can react with respect to the isocyanate group of a crosslinking agent, 2 mass parts or less are desirable. By being 2 parts by mass or less, molecular motion is not restricted by chemical crosslinking, and a hard segment derived from a urethane bond by aging grows greatly, and the required hardness is easily obtained.

-Molding method of base material (base material before forming rubber-modified portion (carbon-containing region)) Base material containing polyurethane rubber which is an example of rubber (however, forming rubber-modified portion (carbon-containing region)) For the production of the previous base material, a general production method of polyurethane such as a prepolymer method or a one-shot method is used. The prepolymer method is suitable because a polyurethane having excellent strength and abrasion resistance can be obtained, but is not limited by the production method.

  The polyurethane rubber is molded by blending the above-described polyol with a polyisocyanate compound and a crosslinking agent. In addition, the shaping | molding of the base material before forming a rubber modification part (carbon-containing area | region) uses the composition for base material formation prepared by the said method, for example using centrifugal molding, extrusion molding, etc., It is produced by forming it into a sheet and cutting it.

  Here, an example is given and the detail of the manufacturing method of the base material before forming a rubber modification part (carbon containing area | region) is demonstrated.

First, a soft segment material (for example, polycaprolactone polyol) and a hard segment material (for example, an acrylic resin containing two or more hydroxyl groups) are mixed (for example, a mass ratio of 8: 2).
Next, an isocyanate compound (for example, 4,4′-diphenylmethane diisocyanate) is added to the mixture of the soft segment material and the hard segment material, and the reaction is performed in, for example, a nitrogen atmosphere. The temperature at this time is preferably 60 ° C. or higher and 150 ° C. or lower, and more preferably 80 ° C. or higher and 130 ° C. or lower. The reaction time is preferably 0.1 hour or more and 3 hours or less, more preferably 1 hour or more and 2 hours or less.

Subsequently, an isocyanate compound is further added and reacted in, for example, a nitrogen atmosphere to obtain a prepolymer. The temperature at this time is preferably 40 ° C. or higher and 100 ° C. or lower, and more preferably 60 ° C. or higher and 90 ° C. or lower. The reaction time is preferably 30 minutes or more and 6 hours or less, and more preferably 1 hour or more and 4 hours or less.
Next, the prepolymer is heated and degassed under reduced pressure. The temperature at this time is preferably 60 ° C. or higher and 120 ° C. or lower, and more preferably 80 ° C. or higher and 100 ° C. or lower. The reaction time is preferably 10 minutes or more and 2 hours or less, more preferably 30 minutes or more and 1 hour or less.
Thereafter, a crosslinking agent (for example, 1,4-butanediol or trimethylolpropane) is added to the prepolymer, and the thixotropic composition is further mixed to prepare a composition for forming a substrate.

Subsequently, the composition for forming a base material is poured into a mold of a centrifugal molding machine and allowed to undergo a curing reaction. In this case, the mold temperature is preferably 80 ° C. or higher and 160 ° C. or lower, and more preferably 100 ° C. or higher and 140 ° C. or lower. The reaction time is preferably 20 minutes or more and 3 hours or less, more preferably 30 minutes or more and 2 hours or less.
Furthermore, it is made to crosslink, and after cooling, it cut | disconnects and the base material before forming a rubber modification part (carbon containing area | region) is formed. The temperature of aging heating during the crosslinking reaction is preferably 70 ° C. or higher and 130 ° C. or lower, more preferably 80 ° C. or higher and 130 ° C. or lower, and further preferably 100 ° C. or higher and 120 ° C. or lower. The reaction time is preferably 1 hour or more and 48 hours or less, and more preferably 10 hours or more and 24 hours or less.

-Physical properties The rubber contained in the substrate is preferably a rubber having a JIS-A hardness of 85 degrees or less, more preferably 70 degrees or more and 85 degrees or less, and more preferably 73 degrees or more and 82 degrees or less. .
The hardness of the above JIS-A is measured by the following method.
It is measured by a test method using a durometer to obtain the hardness from the indentation depth when a push needle having a predetermined shape on the rubber sample surface is pressed through a spring.

  When the rubber contained in the base material is a polyurethane rubber, the weight average molecular weight of the polyurethane rubber is preferably in the range of 1000 or more and 4000 or less, and more preferably in the range of 1500 or more and 3500 or less.

(Method for forming a rubber modified portion (carbon-containing region) and a carbon layer on a base material)
For example, a method for forming a rubber modified portion (carbon-containing region) containing carbon having sp3 bonds on the base material is not particularly limited. For example, plasma ions are directly implanted into the base material containing rubber. By doing so, a method of infiltrating carbon atoms having sp3 bonds into the substrate can be mentioned.
On the other hand, a method of forming a carbon layer containing no carbon and containing sp3 bonds on the surface of the rubber modified portion (surface on the electrophotographic photoreceptor side) of the substrate is not particularly limited. When forming the rubber reforming portion (carbon-containing region) by the above-described direct plasma ion implantation method, the sp3 bond is formed outside the rubber modifying portion (carbon-containing region) by adjusting the ion implantation time. The method of laminating the carbon which has is mentioned.

-Formation of rubber modified part (carbon-containing region) by pulse plasma ion implantation and film formation of carbon layer Here, a pulse for forming a rubber modified part (carbon-containing region) and a carbon layer on a substrate The plasma ion implantation method will be described.
In the pulse plasma ion implantation method, at least one or more ion implantation gas is used and a rubber is formed on the contact side of the substrate with the cleaning blade by a combined process using a pulse plasma and an ion implantation process and a film forming process. A modified portion (carbon-containing region) is formed, and a carbon layer is formed on the surface of the rubber modified portion (carbon-containing region) in contact with the electrophotographic photosensitive member. Moreover, you may provide the surface adjustment process by a pulse plasma before said composite process.

  In the rubber reforming portion (carbon-containing region) formed in this way, by selecting the type of rubber in the base material, the rubber and carbon having sp3 bonds are bonded, and the diamond-like carbon (DLC) layer is formed. It is formed. In addition, the carbon layer formed by the above method is also formed by laminating carbon having sp3 bonds to form a DLC layer.

Here, a more specific formation method will be described.
A high-frequency power source for plasma generation and a power source for high-voltage pulse generation are connected to the base material in the chamber through a common feedthrough, and a high-frequency pulse (pulse RF voltage) is applied from the high-frequency power source for plasma generation to the base material. Is applied to generate plasma around the outer shape of the substrate. Then, a negative high voltage pulse (DC pulse voltage) is applied to the base material from the high voltage pulse generating power source at least once in the plasma or the afterglow plasma, and the application of the high frequency pulse and the negative high voltage pulse are applied. Is repeatedly applied. The number of repetitions of the application of the high frequency pulse and the application of the high voltage pulse is preferably in the range of 100 times / second to 5000 times / second.

  The high-frequency pulse width is preferably a short pulse of 2 μs to 200 μs, and the high voltage pulse width is preferably 0.2 μs to 50 μs. A high voltage pulse is applied after 10 μs or more and 300 μs or less have elapsed since the application of the high frequency pulse.

  As a gas used for the surface conditioning process, a mixed gas containing argon and methane or further hydrogen is used.

  When forming a carbon layer, methane gas is preferably used as the pulse plasma ion implantation gas. As the film forming gas, one or more gases selected from the group consisting of acetylene, propane, butane, hexane, benzene, chlorobenzene, and toluene are used.

  In addition, by injecting plasma ions including at least Si ions and C ions released in the vicinity of the surface of the base material by the high pulse application electrode into the base material in a state excited to a kinetic energy of, for example, 5 keV or more and 30 keV or less, A carbon-containing region can be formed inside the base material while suppressing the processing temperature within a range of 50 ° C. or higher and 100 ° C. or lower. Further, a DLC layer, that is, a carbon layer can be deposited on the surface of the carbon-containing region in a range of 0.2 μm to 1.0 μm.

Further, the rubber modified portion (carbon-containing region) and the carbon layer may further contain N atoms and F atoms as components in addition to the C atoms and Si components having sp3 bonds.
By including N atoms, the fixing of the powder due to frictional charging in the cleaning blade is suppressed. Further, by containing F atoms, the releasability of the rubbing portion in the cleaning blade is improved, and the powder is prevented from sticking.

Examples of the injection gas used when the N atom is contained include a gas in which argon, hydrogen, oxygen, and ammonia gas are mixed.
Further, as an injection gas used when F atoms are contained, for example, hexamethyldisiloxane (HMDSO), acetylene (C ₂ H ₂ ), and fluorocarbon (C ₃ F ₈ ) are used at a flow ratio of 1: 1: 0. And gas mixed at a ratio of 0.1.

  Ion implantation is preferably performed from the side of the substrate (cleaning blade) that contacts the electrophotographic photoreceptor.

-Thickness The thickness of the rubber modified portion (carbon-containing region) (thickness from the contact surface side with the electrophotographic photosensitive member) is preferably 0.1 μm or more and 50 μm or less.
When the thickness of the rubber modified portion (carbon-containing region) is 0.1 μm or more, it is preferable from the viewpoint of obtaining the required low slidability, while the thickness of the rubber modified portion (carbon-containing region) is 5. When it is 0 μm or less, it is preferable from the viewpoint of suppressing the occurrence of chipping or tack-under due to maintaining the toughness (viscoelasticity) of the rubber-modified part (carbon-containing region) as rubber.
Note that the thickness of the rubber modifying portion (carbon-containing region) is controlled by adjusting the applied voltage, current current, number of repetitive pulses, pulse width, delay time, etc., for example, in the above-described ion implantation.

The thickness of the carbon layer is preferably 0 nm to 500 nm, more preferably 10 nm to 200 nm, still more preferably 10 nm to 100 nm.
When the thickness of the carbon layer is 500 nm or less, the peeled pieces generated are small even when the carbon layer is peeled off, so that damage to the contacting electrophotographic photosensitive member due to the peeled pieces is easily suppressed. Is preferable.
The thickness of the carbon layer is controlled, for example, by adjusting the ion implantation time.

  The pressing pressure of the cleaning blade 131 is preferably set to 1.7 gf / mm or more and 6.5 gf / mm or less, more preferably 2.0 gf / mm or more to 6.0 gf / mm or less. When the pressing pressure is equal to or higher than the lower limit, toner cleaning failure is easily suppressed even when a high-hardness blade is used. When the pressing pressure is less than the above upper limit, friction with the photoconductor does not become excessively high, and torque rise, photoconductor wear, generation of streaks due to chipping of the blade edge, and generation of ghost due to friction with the photoconductor are suppressed. It becomes easy to be done.

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

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

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

  The image forming apparatus (process cartridge) according to the present embodiment described above is not limited to the above configuration, and a known configuration may be applied.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

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

60 parts by mass of this alizarin-provided zinc oxide and a curing agent (blocked isocyanate Sumijoule 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.): 13.5 parts by mass and 15 parts by mass of butyral resin (ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.) 38 parts by mass of methyl ethyl ketone dissolved in 85 parts by mass of methyl ethyl ketone and 25 parts by mass of methyl ethyl ketone were mixed and dispersed in a sand mill for 2 hours using 1 mmφ glass beads to obtain a dispersion.
Dioctyltin dilaurate: 0.005 parts by mass and silicone resin particles (Tospearl 145, manufactured by GE Toshiba Silicone): 40 parts by mass were added as catalysts to the resulting dispersion to obtain a coating liquid for forming an undercoat layer.

  A cylindrical aluminum substrate having a diameter of 30 mm, a length of 340 mm, and a thickness of 1 mm was prepared as a conductive substrate, and the resulting coating solution for forming the undercoat layer was applied onto the cylindrical aluminum substrate by a dip coating method. Drying and curing at 40 ° C. for 40 minutes were performed to obtain an undercoat layer having a thickness of 18.7 μm.

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

-Preparation of charge transport layer-
First, a polycarbonate copolymer (1) was obtained as follows.
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 106.9 g (0.398 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as “Z”) under a nitrogen atmosphere, 4'-dihydroxybiphenyl (hereinafter referred to as “BP”) 24.7 g (0.133 mol), hydrosulfite 0.41 g, 9.1% aqueous sodium hydroxide solution 825 ml (sodium hydroxide 2.018 mol), chloride 500 ml of methylene was charged and dissolved, and the mixture was kept in a range of 18 ° C. or higher and 21 ° C. or lower with stirring, and 76.2 g (0.770 mol) of phosgene was required for 75 minutes to perform a blowing phosgenation reaction. After completion of the phosgenation reaction, 1.11 g (0.0075 mol) of p-tert-butylphenol and 54 ml of 25% aqueous sodium hydroxide solution (0.266 mol of sodium hydroxide) were added and stirred, and 0.18 mL (0.0013) of triethylamine was added along the way. Mol) was added and reacted at a temperature of 30 ° C. to 35 ° C. for 2.5 hours. The separated methylene chloride phase was acid washed and washed with water until inorganic salts and amines disappeared, and then methylene chloride was removed to obtain a polycarbonate copolymer (1). This polycarbonate had a molar ratio of the constituent units of Z and BP of 75:25.

Next, 25 parts by mass of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine (TPD), structural formula (A) 20 parts by mass of the compound shown and 55 parts by mass of a polycarbonate copolymer (1) (viscosity average molecular weight: 50,000) as a binder resin were added to 560 parts by mass of tetrahydrofuran and 240 parts by mass of toluene, and dissolved, for a charge transport layer A coating solution was obtained. This coating solution was applied onto the charge generation layer and dried at 135 ° C. for 45 minutes to form a charge transport layer having a thickness of 20 μm.

-Production of protective layer-
100 parts by mass of the exemplary compound “(Id) -28” as a reactive charge transporting material (chain polymerizable charge transporting material) and 2 parts by mass of a polymerization initiator VE-073 (manufactured by Wako Pure Chemical Industries, Ltd.) And 20 parts by mass of a compound represented by the structural formula (C) as a non-reactive charge transport material (also expressed as compound (C)), tetrafluoroethylene polymer particles: Lubron L-2 (manufactured by Daikin Industries) 20 masses Part, 0.1 parts by mass of a fluorinated dispersant (GF-400: manufactured by Toa Gosei Co., Ltd.) and 300 parts by mass of isobutyl acetate are mixed by stirring and stirring at room temperature for 12 hours to prepare a coating solution for forming a protective layer. did.

  Next, the obtained coating liquid for forming a protective layer was applied on the charge transport layer previously formed on the cylindrical aluminum substrate by a ring coating method at a push-up speed of 180 mm / min. Thereafter, a curing reaction was performed in a nitrogen dryer having an oxygen concentration meter at a temperature of 160 ± 5 ° C. for 60 minutes with an oxygen concentration of 200 ppm or less to form a protective layer. The film thickness of the protective layer was 10 μm.

  A photoreceptor (1) was produced as described above. The produced photoreceptor (1) was mounted on an image forming apparatus “Fuji Xerox Co. (Docentre-IV C2260)”. Then, an image pattern shown in FIG. 7 was output by the image forming apparatus, and an initial image quality test for confirming that an image having a target image density was obtained was performed.

  Note that the image pattern shown in FIG. 7 is a repetitive fine line image of 4 dot lines and 4 dot spaces arranged along the paper lateral feed direction (short direction), and a thin line with a width of 2 mm drawn along the paper longitudinal direction. Three images 100A (the image density of only this part is 50%), six solid images 100B each having an image density of 100% of 18 mm × 9 mm square, and 18 mm × 9 mm square, arranged in the longitudinal direction of the paper 4 This is an image pattern composed of six repetitive thin line images of dot lines and 4-dot spaces (image density of only this part is 50%) 100C.

  Here, the image pattern shown in FIG. 7 includes three solid images 100B and three thin line images 100C between three thin line images 100A each having a width of 2 mm drawn along the longitudinal direction of the sheet. These are image patterns arranged alternately at equal intervals. That is, the image pattern shown in FIG. 7 includes a first image pattern 101A having an image density of 1.4% having only the fine line image 100A, and a second image pattern having an image density of 10% having the fine line image 100A and the solid image 100B. This is an image pattern composed of 101B and a third image pattern 101C having an image density of 5.7% having a fine line image 100A and a fine line image 100C.

  The image density of each image pattern is an average value of the image density in the paper feed direction (in this embodiment, the lateral feed direction (short direction)), and is a repetitive thin line image of 4 dot lines and 4 dot spaces. The portion of the first image pattern 101A having only the thin line image 100A of 2 mm is 2 mm × 3 portions (2 × 3 × 50%) / 210 = 1.4% where the image density is 50% with respect to the paper width of 210 mm. Similarly, the portion of the second image pattern 101B having the fine line image 100A and the solid image 100B is {(2 × 3 × 50%) + (9 × 2 × 100%)} / 210 = 10%, The portion of the third image pattern 101C having the fine line image 100A and the fine line image 100C and having an image density of 5.7% is {(2 × 3 × 50%) + (9 × 2 × 50%)} / 210 = 5.7. Is a concentration defined as% .

[Photosensitive members (2) to (5)]
In the same manner as described in the photoreceptor (1), an undercoat layer, a charge generation layer, and a charge transport layer were sequentially formed on a cylindrical aluminum substrate. Then, according to Table 1, the composition of the coating liquid for forming the protective layer [reactive charge transport material (indicated in table, “RCTM”) type and amount, non-reactive charge transport material (indicated in table, “CTM”) The type and amount, and the type and amount of additive] and the thickness of the protective layer were changed, and the protective layer was formed in the same manner as the photoconductor (1), and the photoconductors (2) to (5) were formed. Produced. Then, an initial image quality test was performed in the same manner as the photoconductor (1).

[Photosensitive member (6)]
In the same manner as described in the photoreceptor (1), an undercoat layer, a charge generation layer, and a charge transport layer were sequentially formed on a cylindrical aluminum substrate.
Subsequently, 5 parts by mass of the guanamine compound “Nicalac MW-30 (manufactured by Nippon Carbide)”, 92 parts by mass of the compound represented by the structural formula (D) as a reactive charge transporting material, and 3,5-dioxydioxide as an antioxidant -T-butyl-4-hydroxytoluene (BHT) 4.4 parts by mass, dodecylbenzenesulfonic acid 0.5 parts by mass, leveling agent BYK-302 (manufactured by Big Chemie Japan Co., Ltd.): 0.1 parts by mass, cyclo Pentanol: 160 parts by mass was added to prepare a coating solution for a protective layer. This coating solution was applied onto the charge transport layer by a dip coating method, air dried at room temperature for 30 minutes, and then cured by heat treatment at 150 ° C. for 1 hour to form a protective layer having a thickness of 4 μm.
A photoreceptor (6) was produced as described above. Then, an initial image quality test was performed in the same manner as the photoconductor (1).

[Reference Photoconductors (R1) to (R2)]
A reference photoconductor (R1) was produced in the same manner as the photoconductor (5) except that the thickness of the protective layer of the photoconductor (5) was changed to 10 μm.
A reference photoconductor (R2) was produced in the same manner as the photoconductor (6) except that the thickness of the protective layer of the photoconductor (6) was changed to 10 μm.
Then, an initial image quality test was performed in the same manner as the photoconductor (1). As a result of the initial image quality test, the reference photoconductors (R1) to (R2) significantly decreased in density, and the protective layer having a thickness of 10 μm could not function as a photoconductor.
The photoconductors (5) to (6) on which a protective layer having a thickness of 4 μm is formed have a smaller wear rate than the reference photoconductors (R1) to (R2), and can have a long life. The photoconductors (1) to (4) capable of increasing the thickness of the protective layer can further extend the life.

[Comparative Photoconductor (C1)]
In the same manner as the method described in the photoreceptor (1), an undercoat layer and a charge generation layer were sequentially formed on a cylindrical aluminum substrate.
Next, 25 parts by mass of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine (TPD), represented by structural formula (A) 20 parts by mass of a compound to be obtained, and 55 parts by mass of a polycarbonate copolymer (1) (viscosity average molecular weight: 50,000) as a binder resin, 7.3 parts by mass of tetrafluoroethylene polymer particles (Lublon L-2, manufactured by Daikin) Part, 0.35 parts by mass of a fluorinated dispersant (GF-400, manufactured by Toa Gosei Co., Ltd.) was added to 560 parts by mass of tetrahydrofuran and 240 parts by mass of toluene to dissolve, and a high-pressure wet medialess atomizer (Nanomizer NMS-200ED, Dispersion treatment was performed with a nanomizer) to obtain a charge transport layer coating solution. This coating solution was applied onto the charge generation layer and dried at 135 ° C. for 45 minutes to form a charge transport layer having a thickness of 40 μm.
A comparative photoreceptor (C1) was produced as described above. Then, an initial image quality test was performed in the same manner as the photoconductor (1).

<Preparation of toner particles>
[Preparation of cyan (M color) toner particles (1)]
-Synthesis of polyester resin (1)-
In a heat-dried three-necked flask, 124 parts by mass of ethylene glycol, 22.2 parts by mass of sodium dimethyl 5-sulfoisophthalate, 213 parts by mass of dimethyl sebacate, and 0.3 parts by mass of dibutyltin oxide as a catalyst were added. The air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and stirring was performed at 180 ° C. for 5 hours by mechanical stirring. Thereafter, the temperature was gradually raised to 220 ° C. under reduced pressure, and the mixture was stirred for 4 hours. When it became a viscous state, it was air-cooled, the reaction was stopped, and 220 parts by mass of polyester resin (1) was synthesized.
The weight average molecular weight (M _w ) of the obtained polyester resin (1) was 19000 and the number average molecular weight (M _n ) was 5800 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography.
Further, when the melting point (Tm) of the polyester resin (1) was measured by a differential scanning calorimeter (DSC) by the above-described measuring method, it had a clear peak and the peak top temperature was 70 ° C. It was.

-Preparation of each dispersion-
150 parts by mass of the polyester resin (1) is put in 850 parts by mass of distilled water, mixed and stirred with a homogenizer (manufactured by IKA Japan: Ultra Tarax) while heating to 80 ° C., and the resin particle dispersion (1) is obtained. Obtained.
Next, 250 parts by mass of phthalocyanine pigment (manufactured by Dainichi Seika Co., Ltd .: PV FAST BLUE), 20 parts by mass of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK), 700 parts by mass of ion-exchanged water After mixing and dissolving, a colorant dispersion (1) was prepared by dispersing using a homogenizer (manufactured by IKA: Ultratarax) to disperse the colorant (phthalocyanine pigment).
Next, 100 parts by mass of paraffin wax (HNP0190, Nippon Seiwa Co., Ltd., melting point 85 ° C.), 5 parts by mass of a cationic surfactant (Sanisol B50, manufactured by Kao Corporation), 240 parts by mass of ion-exchanged water, round stainless steel Release agent particles in which release agent particles having an average particle diameter of 550 nm are dispersed by dispersing in a pressure discharge type homogenizer after being dispersed for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA) in a flask. Dispersion liquid (1) was prepared.

-Preparation of aggregated particles-
Resin particle dispersion (1) 2400 parts by weight, colorant dispersion (1) 100 parts by weight, release agent particle dispersion 63 parts by weight, aluminum sulfate 6 parts by weight (manufactured by Wako Pure Chemical Industries, Ltd.), ion-exchanged water 100 Part by mass is contained in a round stainless steel flask and adjusted to pH 2.0, and then dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then heated to 60 ° C. in an oil bath for heating. Heated with stirring. After maintaining at 60 ° C. for 2 hours, observation with an optical microscope confirmed that aggregated particles having an average particle size of about 4.3 μm were formed. Furthermore, after maintaining heating and stirring at 60 ° C. for 1 hour, it was confirmed by observation with an optical microscope that aggregated particles having a volume average particle diameter of 4.4 μm were formed.
The pH of this aggregated particle liquid was 2.4. Therefore, an aqueous solution obtained by diluting sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% by mass was gently added to adjust the pH to 5.0, and then heated to 75 ° C. while stirring was continued for 3 hours. Retained.
Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and then dried using a vacuum dryer to obtain cyan toner particles (1). The resulting cyan toner particle toner had a melting point of 65 ° C.
The resulting cyan toner particles (1) had a volume average particle size = 4.5 μm and a shape factor SF1 = 133.

[Yellow (Y) toner particles (1)]
Yellow (Y) toner particles (1) were obtained in the same manner as in the production of cyan toner particles (1) except that a yellow-azo pigment was used instead of the phthalocyanine pigment.

[Magenta (M) toner particles (1)]
Magenta (M color) toner particles (1) were obtained in the same manner as in the production of cyan toner particles (1) except that quinacridone pigment was used instead of phthalocyanine pigment.

[Black (K color) toner particles (1)]
Black toner particles (1) were obtained with the same formulation except that carbon black was used in place of the phthalocyanine pigment in the production of cyan toner particles (1).

<Production of developer>
[Developer (1)]
To 100 parts by mass of each of the four toner particles (1) obtained, 0.5 parts by mass of hexamethyldisilazane-treated silica particles having a volume average particle diameter of 40 nm and hexamethyldisilazane treatment were used as external additives. 0.5 parts by mass of silica particles having a volume average particle diameter of 200 nm, 0.7 parts by mass of titanium oxide particles having a volume average particle diameter of 30 nm obtained by baking after treatment with 50% isobutyltrimethoxysilane to metatitanic acid, and zinc stearate Particles (Nissan Electol MZ-2: median diameter 1.5 μm based on volume, manufactured by NOF Corporation) 0.18 parts by mass are added, and a total of 5000 parts by mass is mixed with a 75 L Henschel mixer for 10 minutes. Each toner (1) of four colors was produced by sieving with a separator high voltor 300 (manufactured by Shin Tokyo Machine Co., Ltd.).

  Next, a mixture of 0.15 parts by mass of vinylidene fluoride and 1.35 parts by mass of a copolymer of methyl methacrylate and trifluoroethylene (polymerization ratio 80:20) with respect to 100 parts by mass of the ferrite core. Using a kneader apparatus, a ferrite core having an average particle diameter of 50 μm was coated with a resin to produce a carrier.

  Then, 8 parts by mass of each of the obtained four color toners (1) and 100 parts by mass of the obtained carrier were mixed in a 2 liter V blender to prepare four color developers. The resulting set of four color developers was designated as developer (1).

[Developers (2) to (3)]
According to Table 2, each of the four color toners (2) to (3) was prepared in the same manner as each of the four color toners (1) except that the external additive amount was changed. The developer (2) is the same as the developer (1) except that the obtained four color toners (2) to (3) are used in place of the four color toners (1). Each of (3) was produced. In Table 2, the volume average particle diameter is expressed as “D50”.

[Reference developer (R1)]
According to Table 2, each of the four color reference toners (R1) to (R1) was prepared in the same manner as each of the four color toners (1) except that the external additive amount was changed. Then, a reference developer (R1) was produced in the same manner as the developer (1) except that each of the four color toners (1) was used instead of the four color toners (1). did.
The reference developer (R1) was not evaluated because it had low fluidity and part of blocking (thermal aggregation) occurred in the developing device.

<Production of cleaning blade>
[Comparison blade (C1)]
First, polycaprolactone polyol (manufactured by Daicel Chemical Industries, Plaxel 205, average molecular weight 529, hydroxyl value 212 KOHmg / g) and polycaprolactone polyol (manufactured by Daicel Chemical Industries, Plaxel 240, average molecular weight 4155, hydroxyl value 27 KOHmg) / G) was used as the soft segment material of the polyol component. Also, an acrylic resin containing two or more hydroxyl groups (Akaflow UMB-2005B, manufactured by Soken Chemical Co., Ltd.) is used as a hard segment material, and the soft segment material and the hard segment material are in a ratio of 8: 2 (mass ratio). Mixed.

Next, 6.26 parts by mass of 4,4′-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT) is added as an isocyanate compound to 100 parts by mass of the mixture of the soft segment material and the hard segment material. And reacted at 70 ° C. for 3 hours under a nitrogen atmosphere. The amount of the isocyanate compound used in this reaction is selected so that the ratio of isocyanate group to hydroxyl group (isocyanate group / hydroxyl group) contained in the reaction system is 0.5.
Subsequently, 34.3 parts by mass of the above isocyanate compound was further added and reacted at 70 ° C. for 3 hours in a nitrogen atmosphere to obtain a prepolymer. The total amount of isocyanate compound used in the use of the prepolymer was 40.56 parts by mass.
Next, this prepolymer was heated to 100 ° C. and degassed for 1 hour under reduced pressure. Then, to 100 parts by mass of the prepolymer, 7.14 parts by mass of a mixture of 1,4-butanediol and trimethylolpropane (mass ratio = 60/40) was added and mixed so as not to entrain bubbles for 3 minutes. A substrate forming composition A was prepared.

  Next, 7.0 masses of a mixture of 1, 4-butanediol and trimethylolpropane (mass ratio = 30/70) with respect to 100 mass parts of the prepolymer prepared in the same manner as the substrate forming composition A. A part B was added and mixed for 3 minutes so as not to entrain the foam, thereby preparing a substrate-forming composition B.

  Next, the base material forming composition A is poured into a centrifugal molding machine whose mold is adjusted to 140 ° C. to a thickness of 1.8 mm, and further, the base material forming composition B is poured into a thickness of 0.2 mm. The curing reaction was performed for 1 hour. Next, it was aged and heated at 110 ° C. for 24 hours, cooled and then cut to obtain a comparative blade (C1) having a length of 320 mm, a width of 12 mm, and a thickness of 2 mm.

[Blade (2)]
A rubber-modified portion (carbon-containing region) is formed by ion implantation of carbon having sp3 bonds in a region to be a contact portion with the photoreceptor in the comparative blade (C1) by a pulse plasma ion implantation method. A specific pulse plasma ion implantation method will be described below.

  First, a high voltage pulse (+5 kV) was applied to the comparative blade (C1) in methane gas plasma, so that carbon ions were mainly implanted into the comparative blade (C1). As a result, the carbon ions break the bond between carbons in the rubber of the comparative blade (C1) or the bond between carbon and hydrogen in the rubber and are replaced with carbon or hydrogen in the rubber. The injection time here was 15 minutes, and the gas pressure was 0.5 Pa in order to increase the penetration of the rubber reforming part (carbon-containing region). As a result, a rubber modified portion into which carbon was injected was formed from the surface of the comparative blade (C1) (the surface in contact with the photoreceptor) to a depth of at least 0.7 μm. The blade obtained through this plasma ion implantation method was designated as blade (2).

[Blade (3) to (6)]
In the production of the blade (2), after forming the rubber reforming portion (carbon-containing region), at least a low voltage pulse (+2 kV) is applied to the blade (2) in a plasma of a mixed gas of methane, acetylene and toluene. Apply once. As a result, a diamond-like carbon layer (DLC layer: carbon carbon layer having sp3 bond) was deposited without ion implantation on the surface of the rubber modified portion (carbon-containing region) (surface on the side in contact with the photoreceptor). .
Then, blades (3) to (6) having different DLC layer thicknesses were produced by repeating the number of low voltage pulses. The thicknesses of the DLC layers of the blades (3) to (6) are as follows.

-Film thickness of DLC layer of blades (3)-(6)-
Blade (3): DLC layer thickness = 0.03 μm
Blade (4): DLC layer thickness = 0.2 μm
Blade (5): DLC layer thickness = 0.5 μm
Blade (6): DLC layer thickness = 1.0 μm

<Examples 1 to 21 and Comparative Examples 1 to 8>
In combination according to Tables 3 to 4, the photoreceptor, the developer, and the cleaning blade were mounted on an image forming apparatus (“Doccentre-IV C2260” manufactured by Fuji Xerox Co., Ltd.) equipped with a contact charging type charging device. This image forming apparatus was used as an image forming apparatus of Examples 1 to 21 and Comparative Examples 1 to 8.

<Evaluation>
The following evaluation was performed using the image forming apparatus of each example. The following evaluation was performed by outputting a magenta color image.

(Evaluation of uneven image density)
An image pattern shown in FIG. 7 was output by the image forming apparatus of each example, and an initial image quality test was performed to confirm that an image having a target image density was obtained.
Then, 10,000 images of the image pattern shown in FIG. 8 were output in an environment of high temperature and high humidity (28 ° C., 85% RH), and an output test was performed. Here, the image pattern shown in FIG. 8 includes a linear image 100D (length 150 mm × width 10 mm) having an image density of 30% along the paper conveyance direction and an image density of 30% along the direction orthogonal to the paper conveyance direction. This is an image pattern having a linear image 100E. It should be noted that the high temperature and high humidity (28 ° C., 85% RH) environment is a condition in which the hardness of the cleaning blade is lowered, the blade tip part is tucked under, and the blade is easily worn.

  Next, one image pattern (solid image with an image density of 30%) shown in FIG. 9 was output under a low temperature and low humidity (8 ° C., 20% RH) environment, and the image quality was evaluated. In a low-temperature and low-humidity (8 ° C., 20% RH) environment, the photosensitive member is likely to be poorly charged due to inorganic particles that pass through the cleaning blade and adhere to the contact charging type charging device (the charging roll). It is.

As image quality evaluation, image density unevenness caused by the degree of charging failure was evaluated. For example, as shown in FIG. 10, the image density unevenness has an area where the density increases linearly (see an area indicated by 100F in FIG. 10) in the image pattern (solid image with an image density of 30%). This is a phenomenon, and the density difference between a region where the concentration is linearly increased and other regions is visually evaluated. The evaluation criteria are as follows.
-Evaluation criteria for uneven image density-
A +: No density unevenness occurred A: No density unevenness causing image quality problems B: Some density unevenness occurred C: Density unevenness caused image quality problems

  Note that Fuji Xerox P paper (A4 size, short direction feed) was used for evaluation of image density unevenness.

(Photoconductor wear)
In the evaluation of the image density unevenness, after performing an output test, the abrasion amount (μm) of the photoconductor was evaluated as follows.
The wear amount (μm) of the photoconductor is measured from the cross section of the photoconductor (the surface cut along the direction perpendicular to the axial direction) in the longitudinal direction of the photoconductor using an optical film thickness measuring device (line interference film thickness meter). As a result, measurement was performed at four locations of 0 °, 90 °, 180 °, and 270 °, and the average value of these four locations was taken to measure and average the wear profile.

(Electrical characteristics of photoconductor: residual potential)
In the evaluation of image density unevenness, after performing an output test, the electrical characteristics (residual potential) of the photoconductor were evaluated as follows.
The electrical characteristics of the photoconductor are determined by providing a surface potential probe in the region to be measured using a surface potentiometer (Trek 334, manufactured by Trek Co., Ltd.) in a place where no charging failure of the photoconductor occurs. Measure the residual potential (Rp) after static elimination, and determine the difference (ΔRp) between the initial residual potential and the residual potential after outputting 10,000 sheets in a high-temperature, high-humidity environment. Calculated. Then, the residual potential difference (ΔRp) was evaluated according to the following evaluation criteria.
-Evaluation criteria for difference in residual potential (ΔRp)-
A +: Less than 20V A: 20V or more and less than 50V B: 50V or more and less than 80V C: 80V or more

(Wear sectional area of the cleaning blade)
In the evaluation of the image density unevenness, after performing an output test, the wear cross-sectional area of the cleaning blade was evaluated as follows.
The portion of the cleaning blade in contact with the photosensitive member was observed with a laser microscope, and the wear cross-sectional area of the cleaning blade was measured. This wear cross-sectional area was determined as the area obtained by subtracting the wear cross-sectional area after the output test from the cross-sectional area of the portion where the initial blade was in contact with the photoreceptor. Then, the wear cross-sectional area of the cleaning blade was evaluated according to the following evaluation criteria.
-Evaluation criteria for cleaning blade wear cross-section-
A +: Less than 5 μm ² A: 5 μm ² or more and less than 10 μm ² B: 10 μm ² or more and less than 20 μm ² C: 20 μm ² or more In addition, those in which cracking and peeling were observed in the DLC layer are shown in Tables 3 to 4 .

(Cleaning blade missing)
In the evaluation of the image density unevenness, after performing an output test, a solid image with an image density of 30% was further output on A4 paper, and the occurrence of streaks on the image was observed. The chipping of the cleaning blade was evaluated according to the following evaluation criteria.
A: No streaking A: 3 or less minor streaks B: 3 or more and less than 10 streaks C: 10 or more clear streaks

(Image flow)
In the evaluation of unevenness in image density, after performing an output test, a single solid image with an image density of 30% is output to A4 paper, the obtained image is observed, and the image flow is evaluated according to the following evaluation criteria. did.
-Image flow evaluation criteria-
A: No image flow at all A: No image flow causing a problem in image quality B: Some image flow generated C: Image flow causing a problem in image quality

(Comprehensive evaluation)
The above evaluations were combined and a comprehensive evaluation of the photoreceptor and the image forming system was performed, including the expected life of the electrophotographic photoreceptor. The evaluation criteria are as follows.
A +: Particularly excellent A: Excellent B: There are some problems, but there are no major practical problems C: There are practical problems

  Hereinafter, details and evaluation results of each example are listed in Tables 1 to 4.

From the above results, it can be seen that, in this example, both the image density unevenness and the evaluation of the wear cross-sectional area of the blade and the chip are better than the comparative example.
In this example, it can be seen that the evaluation of the electrical characteristics (residual potential) and image flow of the photoconductor is also good.

The details of each abbreviation shown in the table will be described below.
[RCTM: Reactive charge transport material]
(Id) -22: Exemplified compound (Id) -22
(Id) -28: Exemplified compound (Id) -28 (see the synthesis method below)
(II) -185: Exemplified compound (II) -185
Compound (B): Compound represented by the following structural formula (B)

Compound (D): Compound represented by the following structural formula (D)

-Synthesis of Exemplified Compound (Id) -28-
To a 500 ml flask was added 22 g of the following compound (2), 33 g of potassium t-butoxy, 300 ml of tetrahydrofuran and 0.2 g of nitrobenzene, and a solution obtained by dissolving 25 g of 4-chloromethylstyrene in 150 ml of tetrahydrofuran while stirring under a nitrogen stream. It was dripped slowly. After completion of dropping, the mixture was heated to reflux for 4 hours, cooled, poured into water, and extracted with toluene. The toluene layer was washed thoroughly with water and then concentrated, and the resulting oil was purified by silica gel column chromatography to obtain 29 g of oily exemplified compound (Id) -28.

  Other exemplary compounds were also synthesized according to the above synthesis.

[CTM: Non-reactive charge transport material]
Compound (C): Compound represented by the following structural formula (C)

[Additive]
L-2: Tetrafluoroethylene polymer particles “Lublon L-2 (manufactured by Daikin Industries)”
GF400: Fluorine-based dispersant “GF-400 (manufactured by Toa Gosei Co., Ltd.)”
・ BHT: Antioxidant (3,5-di-t-butyl-4-hydroxytoluene)

DESCRIPTION OF SYMBOLS 1 ... Undercoat layer, 2 ... Charge generation layer, 3 ... Charge transport layer, 4 ... Conductive substrate, 5 ... Protective layer, 6 ... Single layer type photosensitive layer, 7A, 7B, 7C, 7 ... Electrophotographic photoreceptor, DESCRIPTION OF SYMBOLS 8 ... Charging device, 9 ... Exposure device, 11 ... Developing device, 13 ... Cleaning device, 14 ... Lubricant, 30 ... Photoconductor, 40 ... Transfer device, 50 ... Intermediate transfer member, 100 ... Image forming device, 120 ... Image Forming apparatus, 300 ... process cartridge

Claims (6)

An electrophotographic photosensitive member having a conductive substrate and a photosensitive layer provided on the conductive substrate, and a cured film of a composition containing a reactive charge transport material, the outermost surface layer of which is formed;
A charging means disposed in contact with or in proximity to the surface of the electrophotographic photosensitive member to charge the surface of the electrophotographic photosensitive member;
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the charged electrophotographic photosensitive member;
A developer containing toner having toner particles and inorganic particles having a volume average particle size of 1 μm or less is accommodated, and the electrostatic latent image formed on the surface of the electrophotographic photosensitive member is developed with the developer to form a toner image. Developing means for forming;
Transfer means for transferring the toner image to the surface of the recording medium;
A cleaning blade that contacts the surface of the electrophotographic photosensitive member and cleans the surface of the electrophotographic photosensitive member, wherein at least the contact portion with the electrophotographic photosensitive member is a rubber-modified portion into which plasma ions are implanted Cleaning means having a cleaning blade,
An image forming apparatus comprising:   The image forming apparatus according to claim 1, wherein the contact portion of the cleaning blade is formed of a rubber reforming portion containing carbon having sp3 bonds.   The contact portion of the cleaning blade is a rubber modified portion containing carbon having sp3 bonds, and a carbon layer containing carbon having sp3 bonds provided on the surface of the rubber modified portion on the electrophotographic photoreceptor side, The image forming apparatus according to claim 1, comprising:   The contact portion of the cleaning blade includes a rubber modified portion containing carbon having sp3 bonds, and a diamond-like carbon layer provided on the surface of the rubber modified portion on the electrophotographic photoreceptor side. The image forming apparatus according to claim 1. The image according to any one of claims 1 to 4, wherein the reactive charge transport material is at least one selected from chain polymerizable compounds represented by the following general formulas (I) and (II). Forming equipment.

[In general formula (I), F represents a charge transporting skeleton. L represents a divalent linking group containing two or more selected from the group consisting of an alkylene group, an alkenylene group, -C (= O)-, -N (R)-, -S-, and -O-. Show. R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. m represents an integer of 1 or more and 8 or less. ]

[In General Formula (II), F represents a charge transporting skeleton. L ′ represents a trivalent or tetravalent group derived from an alkane or alkene, and an alkylene group, alkenylene group, —C (═O) —, —N (R) —, —S—, and —O—. (N + 1) -valent linking groups containing two or more selected from the group consisting of: R represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. m ′ represents an integer of 1 to 6. n represents an integer of 2 or more and 3 or less. ] An electrophotographic photosensitive member having a conductive substrate and a photosensitive layer provided on the conductive substrate, and a cured film of a composition containing a reactive charge transport material, the outermost surface layer of which is formed;
A charging means disposed in contact with or in proximity to the surface of the electrophotographic photosensitive member to charge the surface of the electrophotographic photosensitive member;
A developer containing toner having toner particles and inorganic particles having a volume average particle size of 1 μm or less is accommodated, and the electrostatic latent image formed on the surface of the electrophotographic photosensitive member is developed with the developer to form a toner image. Developing means for forming;
A cleaning blade that contacts the surface of the electrophotographic photosensitive member and cleans the surface of the electrophotographic photosensitive member, wherein at least the contact portion with the electrophotographic photosensitive member is a rubber-modified portion into which plasma ions are implanted Cleaning means having a cleaning blade,
With
A process cartridge that can be attached to and detached from an image forming apparatus.