JP6024555B2 - Electrophotographic photosensitive member, process cartridge, and image forming apparatus - Google Patents

Description

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

  An electrophotographic image forming apparatus generally has the following configuration and process. That is, the surface of the electrophotographic photosensitive member was charged to the polarity and potential determined by the charging device, and the electrostatic latent image was formed by selectively removing the surface of the charged electrophotographic photosensitive member by image exposure. Thereafter, the latent image is developed as a toner image by being attached to the electrostatic latent image by a developing unit, and the toner image is transferred to a transfer medium by a transfer unit, and discharged as an image formed product.

For example, it has been proposed to improve the strength by providing a protective layer on the surface of the electrophotographic photosensitive member.
Examples of the material system for forming the protective layer include a material in which conductive powder is dispersed in a phenol resin (see, for example, Patent Document 1), a material using an organic-inorganic hybrid material (see, for example, Patent Document 2), an alcohol-soluble charge transport material, and the like. The thing by a phenol resin (for example, refer patent document 3) etc. are disclosed. Further, a cured film of an alkyl etherified benzoguanamine / formaldehyde resin and an electron-accepting carboxylic acid or an electron-accepting polycarboxylic acid anhydride (see, for example, Patent Document 4), iodine, an organic sulfonic acid compound, or a chlorinated benzoguanamine resin. A cured film doped with ferric iron (see, for example, Patent Document 5), a cured film of a specific additive and a phenol resin, a melamine resin, a benzoguanamine resin, a siloxane resin, or a urethane resin (for example, see Patent Document 6). It is disclosed.

In recent years, a protective layer made of an acrylic material has attracted attention.
For example, a film obtained by applying and curing a liquid containing a photocurable acrylic monomer (see, for example, Patent Document 7), a monomer having a carbon-carbon double bond, a charge transfer material having a carbon-carbon double bond, and a binder 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 heat or light energy in a resin mixture (see, for example, Patent Document 8); 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 (see, for example, Patent Document 9) is disclosed.

  These acrylic materials are strongly affected by curing conditions, curing atmospheres, etc., and are, for example, films formed by heating after irradiation with radiation in a vacuum or an inert gas (see, for example, Patent Document 10), A film (see, for example, Patent Document 11) that is heat-cured in an active gas is disclosed.

  Further, it is disclosed that the charge transporting material itself can be acrylic-modified and crosslinked, and a reactive monomer having no charge transporting property is added (see, for example, Patent Documents 8 and 12).

In addition, a method for reducing the surface energy of the surface layer of the photoreceptor by incorporating fluorine-containing resin particles in the surface layer has been proposed, and a technique for containing a fluorine atom-containing compound as a lubricant in the protective layer is proposed. It is disclosed (see, for example, Patent Document 13).
In addition, a method of improving the wear resistance strength and electrical characteristics by providing an adhesive layer between the photosensitive layer and the surface layer has been proposed. The trifunctional or higher functional radical polymerizable compound having no charge transport layer structure and the charge are proposed. A photoreceptor having a surface layer containing a radically polymerizable compound having a transport structure and having an adhesive layer between the surface layer and the photosensitive layer (see, for example, Patent Document 14), a surface layer containing a (meth) acryloyl group Photoconductor having a first layer on the outermost surface and a second layer adjacent to the first layer, and the difference in oxidation potential between the first layer and the second layer is 0.1 V or less (for example, Patent Document 15) Reference).

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 Japanese Patent Laid-Open No. 2004-12986 Japanese Patent Laid-Open No. 7-72640 JP 2004-302450 A JP 2001-175016 A JP 2007-17633 A JP 2010-156836 A

  An object of the present invention is to provide an electrophotographic photosensitive member having an outermost surface layer excellent in electrical characteristics and scratch resistance.

  The above problem is solved by the following means. That is,

The invention according to claim 1
A conductive substrate, and a photosensitive layer provided on the conductive substrate,
The first layer which is the outermost surface layer is composed of a cured film of a composition containing at least one selected from reactive compounds represented by the following general formulas (I) and (II),
An electrophotographic photosensitive member, wherein a second layer which is a lower layer adjacent to the outermost surface layer is formed of a charge transporting cured film.

[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 2
The reactive compound represented by the general formula (I) is represented by the following general formula (Ia), the following general formula (Ib), the following general formula (Ic), or the following general formula (Id). The electrophotographic photoreceptor according to claim 1, which is at least one reactive compound selected from the reactive compounds represented by:

[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 linking divalent linked to a group represented by ^Ar a1 ^{to Ar a4} at * Indicates a group. an represents an integer of 1 or 2. ]

[In the general formula (Ib), Ar ^{b1 to} Ar ^b4 each independently represents 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 linkage linked to a group represented by Ar ^{b1 to} Ar ^b5 at *. Indicates a group. bn represents an integer of 3 to 6. ]

[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. ]

[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 is a divalent linkage linked to a group represented by Ar ^{d1 to} Ar ^d5 at *. Indicates a group. dn represents an integer of 1 to 6. ]

The invention according to claim 3
The electrophotographic photosensitive member according to claim 2, wherein the group represented by the general formula (IA-c) is a group represented by the following general formula (IA-c1).

[In the general formula (IA-c1), cp1 represents an integer of 0 or more and 4 or less. ]

The invention according to claim 4
The electrophotographic photoreceptor according to claim 1, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (II-a).

[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- is shown. 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. ]

The invention according to claim 5
The group connected to the charge transporting skeleton represented by F of the compound represented by the general formula (II) is a group represented by the following general formula (IIA-a3) or (IIA-a4). The electrophotographic photosensitive member according to any one of the above.

[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 divalent linking group. kq4 represents an integer of 0 or 1. ]

The invention according to claim 6
The group linked to the charge transporting skeleton represented by F of the compound represented by the general formula (II) is a group represented by the following general formula (IIA-a1) or (IIA-a2). The electrophotographic photosensitive member according to any one of the above.

[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. ]

The invention according to claim 7 provides:
The electrophotographic photosensitive member according to claim 1, wherein the first layer as the outermost surface layer contains fluororesin particles.

The invention according to claim 10 is:
The electrophotographic photosensitive member according to any one of claims 1 to 9 ,
A process cartridge that can be attached to and detached from an image forming apparatus.

The invention according to claim 11 is:
The electrophotographic photosensitive member according to any one of claims 1 to 9 ,
Charging means for charging 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;
Developing means for developing the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with a developer containing toner to form a toner image;
Transfer means for transferring the toner image to a transfer medium;
An image forming apparatus comprising:

According to the invention according to claim 1, 2, 3, 4, 5, or 6, the first layer which is the outermost surface layer is composed of a cured film of the composition containing the reactive compound, and is adjacent to the outermost surface layer. An electrophotographic photosensitive member having an outermost surface layer excellent in electrical characteristics and scratch resistance is provided as compared with the case where the second layer, which is the lower layer, is an uncured film.
According to the invention concerning Claim 7, the 1st layer which is the outermost surface layer is comprised with the cured film of the composition containing the said reactive compound, and the 2nd layer which is the lower layer adjacent to an outermost surface layer is a non-hardened film. Compared to the case, an electrophotographic photosensitive member having an outermost surface layer in which uneven distribution of fluorine-containing resin particles is suppressed is provided.

According to the invention concerning Claim 10 or 11 , the 1st layer which is an outermost surface layer is comprised with the cured film of the composition containing the said reactive compound, and the 2nd layer which is a lower layer adjacent to an outermost surface layer is A process cartridge or an image forming apparatus having a long life is provided as compared with a case where an electrophotographic photosensitive member which is a non-cured film is provided.

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 block diagram which shows another example of the image forming apparatus which concerns on this embodiment. FIG. 7 is a schematic configuration diagram illustrating a developing device in the image forming apparatus illustrated in FIG. 6. It is a schematic block diagram which shows another example of the image forming apparatus which concerns on this embodiment. FIG. 9 is a schematic diagram illustrating a meniscus of a liquid developer formed around a recording electrode of a developing device and a state of liquid transfer to an image portion in the image forming apparatus illustrated in FIG. 8. FIG. 9 is a schematic configuration diagram illustrating another example of the developing device in the image forming apparatus illustrated in FIGS. 6 and 8.

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

[Electrophotographic photoreceptor]
The electrophotographic photoreceptor according to the exemplary embodiment includes a conductive substrate and a photosensitive layer provided on the conductive substrate.
The first layer which is the outermost surface layer is selected from reactive compounds represented by the following general formulas (I) and (II) (hereinafter sometimes referred to as “specific reactive group-containing charge transport material”) It is comprised with the cured film of the composition containing at least 1 sort (s). On the other hand, the second layer, which is the lower layer adjacent to the outermost surface layer, is composed of a charge transporting cured film.

Here, the first layer is a layer constituting the outermost surface layer of the electrophotographic photosensitive member. The outermost surface layer is a layer provided at a position farthest from the conductive substrate among the layers provided on the conductive substrate in the electrophotographic photosensitive member. Specifically, the first layer is provided, for example, as a layer that functions as a protective layer, a layer that functions as a charge transport layer, or a layer that has both of these functions.
On the other hand, the second layer is a lower layer adjacent to the first layer, and is provided, for example, as a layer that functions as a charge transport layer.

The electrophotographic photosensitive member according to the present embodiment is an electrophotographic photosensitive member having an outermost surface layer excellent in electrical characteristics and scratch resistance due to the above configuration.
The reason for this is not clear, but is thought to be due to the following reasons.

First, when a cured film of a composition containing at least one selected from specific reactive group-containing charge transport materials (reactive compounds represented by general formulas (I) and (II)) is used as the outermost surface layer, It is considered that the outermost surface layer realizes excellent electrical characteristics and mechanical strength.
This is because the specific reactive group-containing charge transport material itself has excellent charge transport performance, and there are few polar groups that hinder charge transport such as —OH and —NH—, and styryl having π electrons effective for charge transport. This is because, since the material is linked by polymerization, residual strain is suppressed, and it is considered that formation of a structural trap for trapping charges is suppressed.
In addition, the specific reactive group-containing charge transporting material is considered to maintain its electrical characteristics over a long period of time because it has a property of being more hydrophobic and less likely to get moisture than an acrylic material.

However, in order to form a cured film of a composition containing a specific reactive group-containing charge transport material on the lower photosensitive layer (for example, a charge transport layer) as the outermost surface layer of the electrophotographic photoreceptor, the material is used. A coating solution containing the coating solution is formed on the lower photosensitive layer (for example, a charge transport layer). For this reason, depending on the type of solvent used for preparing the coating solution, when the outermost surface layer is applied and formed, the charge transporting material contained in the lower photosensitive layer (for example, the charge transporting layer) moves to the outermost surface layer. May occur.
If a large amount of the charge transporting material that migrates to the outermost surface layer migrates, it is considered that it becomes a barrier against charge injection, and the electrical characteristics deteriorate.

On the other hand, when the outermost surface layer is applied and formed, depending on the type of solvent used for preparing the coating solution, the binder resin contained in the lower photosensitive layer (for example, the charge transport layer) dissolves or swells, and the outermost surface layer It may cause a phenomenon to shift to.
When the binder resin migrates to the outermost surface layer, it is considered to enter between molecules of the specific reactive group-containing charge transporting material and inhibit the polymerization reaction, so that the film strength of the cured film is lowered and the scratch resistance is lowered. Moreover, it is thought that the density | concentration of a specific reactive group containing charge transport material falls, the film | membrane intensity | strength of a cured film falls, and scratch resistance falls.

  On the other hand, the second layer adjacent to the outermost surface layer (first layer) is used as a charge transporting cured film, and the outermost surface layer is provided on the second layer, thereby providing the outermost surface layer. Migration of the charge transport material and the binder resin with respect to is suppressed. For this reason, in the outermost surface layer, the deterioration of the electrical characteristics due to the transfer of the charge transport material is suppressed, and the decrease in the film strength due to the transfer of the binder resin is suppressed.

From the above, it is considered that the electrophotographic photosensitive member according to this embodiment is an electrophotographic photosensitive member having an outermost surface layer excellent in electrical characteristics and scratch resistance.
In addition, the life of the image forming apparatus (or process cartridge) including the electrophotographic photosensitive member according to this embodiment is realized.

  In the electrophotographic photosensitive member according to this embodiment, since the transfer of the charge transport material and the binder resin to the outermost surface layer is suppressed, the film thickness fluctuation of the outermost surface layer due to this transfer is also suppressed. That is, it becomes easy to control the film thickness of the target outermost layer.

In the electrophotographic photoreceptor according to the exemplary embodiment, when the outermost surface layer includes fluorine-containing resin particles, uneven distribution of the fluorine-containing resin particles in the outermost surface layer is suppressed.
Here, when the outermost surface layer is applied and formed, when the phenomenon that the binder resin contained in the lower photosensitive layer (for example, the charge transport layer) dissolves or swells and moves to the outermost layer occurs, In some cases, the outermost surface layer is unevenly distributed (that is, segregated to a high concentration).
However, in the photoconductor according to the present embodiment, the lowermost second layer adjacent to the outermost surface layer (first layer) is used as a charge transporting cured film, and the outermost surface layer is provided on the second layer. Thereby, the transfer of the binder resin to the outermost surface layer is suppressed. For this reason. Even when the outermost surface layer contains fluorine-containing resin particles, uneven distribution of the fluorine-containing resin particles in the outermost surface layer is suppressed.
If the fluorine-containing resin particles are unevenly distributed (segregated at a high concentration) on the surface layer side of the outermost surface layer, for example, the ratio of the resin component in the surface layer portion of the outermost surface layer is decreased, and the wear resistance at the initial use is decreased. In addition, since the concentration of fluorine-containing resin particles inside the outermost surface layer (especially the lower layer side) is low, the outermost surface layer is scraped when the electrophotographic photosensitive member is used for a long period of time, resulting in a low concentration region of fluorine-containing resin particles. When the pressure reaches the value, the load (torque) applied to the cleaning blade increases, resulting in poor cleaning, which may deteriorate image quality.
On the other hand, in the electrophotographic photosensitive member according to this embodiment, the uneven distribution of fluorine-containing resin particles in the outermost surface layer is suppressed, so these phenomena are improved.

  Hereinafter, the electrophotographic photoreceptor according to the exemplary embodiment will be described in detail with reference to the drawings.

  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 a laminated photoreceptor), and an undercoat layer 1 is provided on a conductive substrate 4, on which charge generation layers 2, 2 are formed. The type has a structure in which the charge transport layers 3-1 and 3-2 are sequentially formed. In the electrophotographic photoreceptor 7A, the charge generation layer 2 and the charge transport layers 3-1 and 3-2 constitute a photosensitive layer, and the charge transport layers 3-1 and 3-2 include the first layer and the first layer, respectively. It corresponds to 2 layers.

The electrophotographic photosensitive member 7B shown in FIG. 2 has a function separated into the charge generation layer 2 and the charge transport layers 3-1, 3-2 and 3-3, like the electrophotographic photosensitive member 7A shown in FIG. This is a separate function photoreceptor.
An electrophotographic photoreceptor 7B shown in FIG. 2 is provided with an undercoat layer 1 on a conductive substrate 4, on which a charge generation layer 2, a non-curing charge transport layer 3-3, and a curing charge transport. It has a structure in which the layers 3-2 and 3-1 are sequentially formed. In the electrophotographic photoreceptor 7B, a photosensitive layer is constituted by the charge transport layers 3-1, 3-2 and 3-3 and the charge generation layer 2. The three types of charge transport layers in the electrophotographic photoreceptor 7B are configured such that the charge transport layers 3-1 and 3-2 are curable charge transport layers and the charge transport layer 3-3 is a non-curable charge transport layer. The charge transport layers 3-1 and 3-2 correspond to the first layer and the second layer, respectively.

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).
In the electrophotographic photoreceptor 7C shown in FIG. 3, the undercoat layer 1 is provided on the conductive support 4, and the monolayer type photosensitive layer 6 and the charge transport layers 3-2 and 3-1 are sequentially formed thereon. It has a structure. In the electrophotographic photoreceptor 7C, the photosensitive layer is constituted by the single-layer type photosensitive layer 6 and the charge transport layers 3-1 and 3-2, and the charge transport layers 3-1 and 3-2 are the first layer, respectively. And fall under the second layer.

  In the electrophotographic photosensitive member shown in FIGS. 1, 2, and 3, the undercoat layer 1 may or may not be provided.

Hereinafter, each layer will be described based on the electrophotographic photoreceptor 7B shown in FIG. 2 as a representative example. Note that. Reference numerals will be omitted.
However, the charge transport layer 3-1 is referred to as a “protective layer”, the charge transport layer 3-2 is referred to as a “curing charge transport layer”, and the charge transport layer 3-3 is referred to as a “non-curing charge transport layer”. explain.

(Conductive substrate)
Any conductive substrate may be used as long as it is conventionally used. For example, thin films (eg, metals such as aluminum, nickel, chromium, stainless steel, and films of aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, indium tin oxide (ITO), etc.) And a resin film coated or impregnated with a conductivity-imparting agent, a resin film coated or impregnated with a conductivity-imparting agent, and the like. The shape of the substrate is not limited to a cylindrical shape, and may be a sheet shape or a plate shape.
Note that the conductive substrate preferably has a conductivity of, for example, a volume resistivity of less than 10 ⁷ Ω · cm.

  When a metal pipe is used as the conductive substrate, the surface may be left as it is, and processing such as mirror cutting, etching, anodizing, rough cutting, centerless grinding, sand blasting, wet honing has been performed in advance. Also good.

(Undercoat layer)
The undercoat layer is provided as necessary for the purpose of preventing light reflection on the surface of the conductive substrate and preventing inflow of unnecessary carriers from the conductive substrate to the organic photosensitive layer.

The undercoat layer includes, for example, a binder resin and, if necessary, other additives.
Examples of the binder resin contained in the undercoat layer include acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, and 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, unsaturated urethane resin, polyester resin, alkyd resin, Examples thereof include known polymer resin compounds such as epoxy resins, charge transporting resins having a charge transporting group, and conductive resins such as polyaniline.
Among these, as the binder resin, a resin insoluble in the coating solvent of the upper layer (charge generation layer) is desirable, and in particular, urea resin, phenol resin, phenol-formaldehyde resin, melamine resin, urethane resin, unsaturated polyester resin, A thermosetting resin such as an alkyd resin or an epoxy resin, a polyamide resin, a polyester resin, a polyether resin, an acrylic resin, a polyvinyl alcohol resin, or a polyvinyl acetal resin and at least one resin selected from the group and a curing agent Resins obtained by reaction 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 a metal compound such as a silicone compound, an organic zirconium compound, an organic titanium compound, or an organic aluminum compound.

  The ratio between the metal compound and the binder resin is not particularly limited, and is set within a range in which desired electrophotographic photoreceptor characteristics can be obtained.

  Resin particles may be added to the undercoat layer in order to adjust the surface roughness. Examples of the resin particles include silicone resin particles and cross-linked polymethyl methacrylate (PMMA) resin particles. The surface may be polished after forming the undercoat layer for adjusting the surface roughness. As a polishing method, buffing, sandblasting, wet honing, grinding, or the like is used.

Here, the structure of the undercoat layer includes a structure containing at least a binder resin and conductive particles. Note that the conductive particles preferably have conductivity with a volume resistivity of less than 10 ⁷ Ω · cm, for example.

Examples of the conductive particles include metal particles (particles such as aluminum, copper, nickel, and silver), conductive metal oxide particles (particles such as antimony oxide, indium oxide, tin oxide, and zinc oxide), and conductive substance particles. (Carbon fiber, carbon black, particles of graphite powder) and the like. Among these, conductive metal oxide particles are preferable. You may mix and use 2 or more types of electroconductive particle.
In addition, the conductive particles may be subjected to a surface treatment with a hydrophobizing agent (for example, a coupling agent) or the like to adjust the resistance.
For example, the content of the conductive 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 formation of the undercoat layer is not particularly limited, and a well-known formation method is used. For example, a coating film of a coating solution for forming an undercoat layer 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.

  Examples of the method for applying the coating solution for forming the undercoat layer on the conductive substrate include dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating, curtain coating, and the like. Is mentioned.

  In the case of dispersing the particles in the coating solution for forming the undercoat layer, the dispersion method may be, for example, a media disperser such as a ball mill, a vibrating ball mill, an attritor, a sand mill, a horizontal sand mill, an agitator, an ultrasonic disperser, or the like. Medialess dispersers such as roll mills and high-pressure homogenizers are used. Here, examples of the high-pressure homogenizer include a collision method in which the 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. Can be 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.

  Here, although not shown, an intermediate layer may be further provided between the undercoat layer and the photosensitive layer. As the binder resin used for the intermediate layer, acetal resins such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl In addition to polymer resins such as acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, melamine resin, zirconium, titanium, aluminum, manganese, silicon atom, etc. An organometallic compound containing These compounds may be used alone or as a mixture or polycondensate of a plurality of compounds. Among these, an organometallic compound containing zirconium or silicon is preferable in that it has a low residual potential, a small potential change due to the environment, and a small potential change due to repeated use.

  The formation of the intermediate layer is not particularly limited, and a well-known formation method is used. For example, a coating film of the intermediate layer forming coating solution in which the above components are added to the solvent is formed, and the coating film is dried and necessary. It is performed by heating according to.

  Examples of the method for applying the intermediate layer forming coating solution onto the undercoat layer include dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating, and curtain coating. Conventional methods are used.

  In addition to improving the coatability of the upper layer, the intermediate layer also serves as an electrical blocking layer.However, if the film thickness is too large, the electrical barrier becomes too strong, leading to increased desensitization and potential increase due to repetition. It may happen. Therefore, when forming the intermediate layer, it is preferable to set the film thickness within the range of 0.1 μm to 3 μm. In this case, the intermediate layer may be used as the undercoat layer.

(Charge generation layer)
The charge generation layer includes, for example, a charge generation material and a binder resin. Note that the charge generation layer may be formed of, for example, a vapor generation film of a charge generation material.

  Examples of the charge generation material include phthalocyanine pigments such as metal-free phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, dichlorotin phthalocyanine, and titanyl phthalocyanine, and in particular, have a Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-rays. Chlorogallium phthalocyanine crystal having strong diffraction peaks at least at 7.4 °, 16.6 °, 25.5 ° and 28.3 °, Bragg angle (2θ ± 0.2 °) to CuKα characteristic X-ray of at least 7. Metal-free phthalocyanine crystals having strong diffraction peaks at 7 °, 9.3 °, 16.9 °, 17.5 °, 22.4 ° and 28.8 °, Bragg angle (2θ ± 0. 2 °) at least 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25 Hydroxygallium phthalocyanine crystals having strong diffraction peaks at 1 ° and 28.3 °, Bragg angles (2θ ± 0.2 °) with respect to CuKα characteristic X-rays of at least 9.6 °, 24.1 ° and 27.2 ° A titanyl phthalocyanine crystal having a strong diffraction peak can be mentioned. In addition, examples of the charge generation material include quinone pigments, perylene pigments, indigo pigments, bisbenzimidazole pigments, anthrone pigments, quinacridone pigments, and the like. These charge generation materials may be used alone or in combination of two or more.

Examples of the binder resin constituting the charge generation layer include polycarbonate resin (for example, polycarbonate resin such as bisphenol A or bisphenol Z type), acrylic resin, methacrylic resin, polyarylate resin, polyester resin, polyvinyl chloride resin, polystyrene. Resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene copolymer, polyvinyl acetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin, vinyl chloride-acetic acid Examples include vinyl-maleic anhydride resin, silicone resin, phenol-formaldehyde resin, polyacrylamide resin, polyamide resin, poly-N-vinylcarbazole resin. These binder resins may be used alone or in combination of two or more.
The mixing ratio of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10, for example.

  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. This is done by heating as necessary. The charge generation layer may be formed by vapor deposition of a charge generation material.

  Examples of the method for applying the charge generation layer forming coating liquid on the undercoat layer (or on the intermediate layer) include dip coating, push-up coating, wire bar coating, spray coating, blade coating, and knife coating. Method, curtain coating method and the like.

  In addition, as a method of dispersing particles (for example, charge generation material) in the coating solution for forming the charge generation layer, for example, a media dispersion machine such as a ball mill, a vibration ball mill, an attritor, a sand mill, a horizontal sand mill, agitation, ultrasonic Medialess dispersers such as dispersers, 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.

  The thickness of the charge generation layer is desirably set in the range of 0.01 μm to 5 μm, more desirably 0.05 μm to 2.0 μm.

(Non-curing charge transport layer)
The non-curing type charge transport layer includes, for example, a charge transport material and a binder resin.

  Examples of the charge transporting material include oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1- [Pyridyl- (2)]-3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazolin derivatives such as pyrazoline, triphenylamine, tris [4- (4,4-diphenyl-1,3- Aromatic tertiary amino such as butadienyl) phenyl] amine, N, N′-bis (3,4-dimethylphenyl) biphenyl-4-amine, tri (p-methylphenyl) aminyl-4-amine, dibenzylaniline Compounds, aromatic tertiary diamino compounds such as N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine, 3- (4′- 1,2,4-triazine derivatives such as methylaminophenyl) -5,6-di- (4'-methoxyphenyl) -1,2,4-triazine, 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, etc. Hydrazone derivatives, quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline, benzofuran derivatives such as 6-hydroxy-2,3-di (p-methoxyphenyl) benzofuran, p- (2,2-diphenylvinyl) -N Α-stilbene derivatives such as N-diphenylaniline, enamine derivatives, carbazole derivatives such as N-ethylcarbazole, hole transport materials such as poly-N-vinylcarbazole and its derivatives, quinone compounds such as chloranil and bromoanthraquinone, Tetracyanoquinodimethane compounds, 2,4,7-trini Polymers having a main chain or a side chain having a group consisting of an electron transport material such as trofluorenone, 2,4,5,7-tetranitro-9-fluorenone, an electron transport material such as a xanthone compound, a thiophene compound, and the above compound. Etc. These charge transport materials may be used alone or in combination of two or more.

Examples of the binder resin constituting the non-curing type charge transport layer include polycarbonate resin (for example, polycarbonate resin such as bisphenol A or bisphenol Z type), acrylic resin, methacrylic resin, polyarylate resin, polyester resin, polychlorinated resin. Vinyl resin, polystyrene resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene copolymer resin, polyvinyl acetate resin, polyvinyl formal resin, polysulfone resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin , Vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, phenol-formaldehyde resin, polyacrylamide resin, polyamide resin, chlorinated rubber insulating resin, and polyvinyl chloride Carbazole, polyvinyl anthracene, organic photoconductive polymers such as polyvinyl pyrene, and the like. These binder resins may be used alone or in combination of two or more.
Among these binder resins, polycarbonate is preferable, and in particular, a polycarbonate copolymer having a solubility parameter calculated by the Feders method of 11.40 or more and 11.75 or less is preferable.
The mixing ratio of the charge transport material and the binder resin is desirably a mass ratio of, for example, 10: 1 to 1: 5.

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

  The formation of the non-curing type charge transport layer is not particularly limited, and a known formation method is used. For example, a coating film of a coating liquid for forming a charge transport layer in which the above components are added to a solvent is formed. The coating is dried and heated as necessary.

  Examples of the method for applying the non-curing type charge transport layer forming coating solution on the charge generation layer include dip coating, push-up coating, wire bar coating, spray coating, blade coating, knife coating, A usual method such as a curtain coating method is used.

  In the case of dispersing the particles in the coating liquid for forming the non-curing charge transport layer, the dispersion method may be, for example, a media disperser such as a ball mill, a vibrating ball mill, an attritor, a sand mill, a horizontal sand mill, agitation, Medialess dispersers such as ultrasonic dispersers, 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.

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

(Curing type charge transport layer)
The curable charge transport layer is composed of a charge transport cured film.
The curable charge transport layer is not particularly limited as long as it is composed of a charge transportable cured film, and examples thereof include the layers shown in 1) or 2) below.
1) A layer composed of a cured film of a composition containing a reactive group-containing charge transporting material having a reactive group and a charge transporting skeleton in the same molecule (that is, a polymer or a crosslinked product of the reactive group-containing charge transporting material) Including layers)
2) A layer composed of a cured film of a composition comprising a non-reactive charge transport material and a reactive group-containing non-charge transport material having a reactive group and having no charge transport skeleton (that is, A layer comprising a non-reactive charge transport material and a polymer or a cross-linked product of the reactive group-containing non-charge transport material)

The reactive group of the reactive group-containing charge transport material includes a chain polymerizable group, an epoxy group, —OH, —OR [wherein R represents an alkyl group], —NH ₂ , —SH, —COOH, —SiR. ^Q1 _3-Qn (OR ^Q2 ) _Qn [wherein 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. _Qn represents an integer of 1 to 3], and the like, and other well-known reactive groups.
The chain polymerizable group is not particularly limited as long as it is a functional group capable of radical polymerization. For example, it is a functional group having a group containing at least 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 desirable.
The charge transporting skeleton of the reactive group-containing charge transporting material is not particularly limited as long as it is a known structure in an electrophotographic photoreceptor, and examples thereof include triarylamine compounds, benzidine compounds, hydrazone compounds, and the like. And a structure conjugated from a nitrogen-containing hole transporting compound and conjugated with a nitrogen atom. Among these, a triarylamine skeleton is desirable.

  The reactive group-containing charge transporting material having a reactive group and a charge transporting skeleton is selected from well-known materials, and specific reactive group-containing charge transporting materials (general formulas (I) and (II) described later) And a reactive compound represented by

Examples of the non-reactive charge transport material include the same materials as the charge transport material constituting the non-curable charge transport layer.
Examples of the reactive group-containing non-charge transport material include well-known heat- or photo-curable resins that do not have a charge transport skeleton.

Here, the curable charge transport layer is a layer composed of a cured film of a composition containing a reactive group-containing charge transport material having a styryl group, an acryloyl group, or a methacryloyl group (that is, the reactive group-containing charge transport layer). A layer containing a polymer or cross-linked material), and in particular, a composition containing a specific reactive group-containing charge transporting material (reactive compounds represented by the general formulas (I) and (II)). A layer composed of a cured film (a layer containing a polymer or a crosslinked product of a specific reactive group-containing charge transport material) is desirable.
That is, it is particularly desirable that the curable charge transport layer has the same configuration as the protective layer.

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

  In addition, since other additives, curing methods, and the like of the curable charge transport layer are the same as those of the protective layer, description thereof is omitted.

(Protective layer)
The protective layer is the outermost surface layer in the electrophotographic photosensitive member, and is composed of a cured film of a composition containing a specific reactive group-containing charge transport material.
That is, the protective layer includes a polymer or a cross-linked product of a specific reactive group-containing charge transport material.

  The cured film is cured by radical polymerization using heat, light, radiation, or the like. Adjusting the reaction so that it does not progress 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, so that radical generation is relatively slow. It is desirable to polymerize under the conditions that occur. 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.

-Specific reactive group-containing charge transport material-
The specific reactive group-containing charge transport material is at least one reactive compound selected from the 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, as the linking group represented by L ′ in the general formula (II),
* — (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, a group connected to the charge transporting skeleton represented by F of the 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 (IIA- It may be a group represented by 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 include an alkyloxy 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 include an alkyloxy group.

In general formulas (I) and (II), in the linking group represented by L or L ′, the alkyl group represented by R in “—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 is preferably 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 reactive compounds represented by) is preferred.
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 group-containing 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 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 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 formula (7), Z ′ is preferably represented by any one 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 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 a specific reactive group-containing charge transport material, wear of the protective layer (outermost surface layer) is suppressed and generation of density unevenness of the image is suppressed. It becomes easy to be done. 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 group-containing 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 group-containing charge transport material, film shrinkage accompanying the polymerization reaction or cross-linking reaction, charge transport structure and chain-polymerizable group periphery Aggregation of the structure is considered to occur. 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 a crosslinked product of the reactive compound represented by the general formula (Ic) is suppressed from deterioration in image quality due to repeated use. It is thought.
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, and 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 comprising one or more groups selected from the group consisting of a combination of —O—, —N (R) — or —S— (hereinafter referred to as “specific linking group”). It is.
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, desirably —N (R) —, —S—, —C (═O) —O—, —C (═O) —N (H) —, — C (= O) -O-, more preferably -C (= O) -O-.
The divalent linking group represented by L ^c includes, for example, a specific linking group, a saturated hydrocarbon (including any of linear, branched, and cyclic) or aromatic hydrocarbon residues, and an oxygen atom. And a divalent linking group formed by combining a specific linking group, a linear saturated hydrocarbon residue, and an oxygen atom. The linking group is preferable.
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 the chain polymerization reactivity, and desirably 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), * — (CH ₂ ) _cp —C (═O) —O—CH ₂ — is desirable as the divalent linking group represented by L ^c . 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 a specific reactive group-containing charge transporting material, wear of the protective layer (outermost surface layer) is suppressed and generation of uneven density in the image is suppressed. It becomes easy to be done. 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 desirably 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) (especially the general formula (II-a)) is applied as a specific reactive group-containing charge transport material, deterioration of electrical characteristics is suppressed even when used repeatedly over a long period of time. It becomes easy to be done. 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. Ark5 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, and 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 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 group-containing 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 reactive group-containing charge transport material (in particular, a reactive compound represented by the general formula (I)) is synthesized, for example, as follows.
That is, a specific reactive group-containing 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 the specific reactive group-containing charge transporting 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, Desirably 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 subjected to dehydration condensation using an acid catalyst, an arylamine compound carboxylic acid and a halogenated methylstyrene, A method of condensation using a base such as pyridine, piperidine, triethylamine, dimethylaminopyridine, trimethylamine, DBU, sodium hydride, sodium hydroxide, potassium hydroxide can be used, but a method using halogenated methylstyrene is a by-product. This is preferable because the object is suppressed.

The halogenated methylstyrene should be 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. .8 equivalents to 2.0 equivalents, preferably 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 -Aromatic solvents such as chloronaphthalene are effective, and in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight with respect to 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 should be added in an amount of 1 equivalent or more, preferably 1.2 equivalents or more, and more preferably 1.5 equivalents or more with respect to the alcohol of the arylamine compound alcohol. 8 equivalents or more and 2.0 equivalents or less, preferably 1.0 equivalents or more and 1.5 equivalents or less.
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 are used 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 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 reactive group-containing charge transport materials (especially the reactive compounds represented by the general formula (II)) are, 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.

  The content of the specific reactive group-containing charge transport 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 with respect to the total solid content in the composition for layer formation. % Or less.

-Fluorine-containing resin particles-
The film constituting the protective layer (outermost surface layer) may contain fluorine-containing 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. Examples thereof include non-perfluoroolefins such as vinyl, 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, Examples include vinyl esters such as “Oba” (trade name, vinyl ester manufactured by Shell), and alkyl vinyl ethers, allyl vinyl ethers, vinyl esters, and organosilicon compounds having a reactive α, β-unsaturated group are preferable.

  Of these, those having a high fluorination rate are desirable, 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. Of these, PTFE, FEP, and PFA are particularly desirable.

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 laser diffraction type particle size distribution measuring device LA-700 (made by Horiba Seisakusho).

  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. Further, block or branch polymers disclosed in US Pat. No. 5,637,142, Japanese Patent No. 4,251,662, Japanese Patent No. 4,251,662, etc. may be mentioned. 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.), Mega-Fac EXP, TF-1507, Mega-Fac EXP, TF-1535 (Dainippon Ink Co., Ltd.), FC-4430, FC-4432 (3M Co., Ltd.), 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 parts by mass or more and 0.1 parts by mass or less, and preferably 0 parts by mass with respect to 1 part by mass of the fluorine-containing resin particles. It is 0.05 parts by mass or less, and 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.
The compound having an unsaturated bond may be any of a monomer, an oligomer and a polymer, and may have a 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.

  Examples of the reactive polymer include JP-A-5-216249, JP-A-5-323630, JP-A-11-52603, JP-A-2000-264961, and JP-A-2005-2291. And the like.

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 preferably 60% by mass or less, for example, based on the total solid content of the composition used in forming the protective layer (outermost surface layer). It is preferably 55% by mass or less, more preferably 50% by mass or less.

On the other hand, examples of the compound having an unsaturated bond include those having a charge transport skeleton.
・ Chain polymerizable functional group (chain polymerizable functional group excluding styryl group) and compound having charge transporting skeleton in the same molecule Chain polymerization property in compound having chain polymerizable functional group and charge transporting skeleton in the same molecule The functional group is not particularly limited as long as it is a functional group capable of radical polymerization, and is, for example, a functional group having a group containing at least 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 desirable.
Further, the charge transporting skeleton in the compound having a chain polymerizable functional group and a charge transporting skeleton in the same molecule is not particularly limited as long as it is a known structure in an electrophotographic photosensitive member. For example, triarylamine Examples thereof include a skeleton derived from a nitrogen-containing hole transporting compound such as a benzene compound, a benzidine compound, or a hydrazone compound, and a structure conjugated with a nitrogen atom. Among these, a triarylamine skeleton is desirable.

-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 non-reactive charge transport materials do not have reactive groups that are not responsible for charge transport, when non-reactive charge transport materials are used for the protective layer (outermost surface layer), the concentration of the charge transport component is low. It is effective for further improving the electrical characteristics. 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 desirable from the viewpoint of charge mobility and compatibility.

  The non-reactive charge transport material is desirably used in an amount of 0% by mass to 30% by mass, and more desirably 1% by mass to 25% by mass with respect to the total solid content in the coating solution 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. desirable. 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 desirable to add a deterioration inhibitor to the film constituting the protective layer (outermost surface layer). As the degradation inhibitor, hindered phenols or hindered amines are desirable, 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 size is desirably 1 nm or more and 500 nm or less, and more desirably 10 nm or more and 100 nm or less.
The content of the silicone particles in the surface layer is desirably 0.1% by mass or more and 30% by mass or less, more desirably 0.5% by mass or more and 10% by mass or less, based on the total amount of 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 for forming the protective layer is preferably prepared as a coating solution for forming a protective layer obtained by dissolving or dispersing each component in a solvent.
Here, the solvent of the coating solution for forming the protective layer is charged from the viewpoint of suppressing the solubility of the charge transporting material, the dispersibility of the fluorine-containing resin particles, and the uneven distribution of the fluorine-containing resin particles on the surface layer side of the outermost surface layer. The difference (absolute value) in SP value (solubility parameter calculated by the Feders method) with the binder resin (specific polycarbonate copolymer) of the transport layer is 2.0 or more and 4.0 or less (preferably 2.5 or more and 3. 5 or less) ketone solvents or ester solvents may be used.
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, propionic acid Examples thereof include single solvents or mixed solvents such as esters such as butyl, 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 desirably room temperature (20 ° C.) to 100 ° C., more desirably 30 ° C. Heating is performed at a temperature of 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. It is also desirable to irradiate ultrasonic waves at this time.

-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 desirably 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, 1000 mW / cm ² or less is desirable, 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 in 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 formation of a high-strength film with suppressed unevenness can be achieved. More preferably, the molecular weight of the azo polymerization initiator is 250 or more, and more preferably 300 or more.

  The heating is performed in an inert gas atmosphere such as nitrogen or argon, and the oxygen concentration is desirably 1000 ppm or less, more desirably 500 ppm or less, desirably 50 ° C. or more and 170 ° C. or less, more desirably 70 ° C. or more and 150 ° C. or less. The heating is desirably performed for 10 minutes or more and 120 minutes or less, more desirably 15 minutes or more and 100 minutes or less.

  The total content of the photocuring catalyst or 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 desirable, and the range of 0.1 mass% or more and 5 mass% or less is especially desirable.

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 group-containing charge transport material and curing by heat, the structure relaxation of the coating film can be promoted, and a high protective layer (outermost surface layer) excellent in surface properties can be easily obtained. Become.

  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.

The structure of each layer in the function-separated type photosensitive layer has been described above with reference to the electrophotographic photoreceptor shown in FIG. 2, but this structure is also applied to each layer in the function-separated type electrophotographic photoreceptor shown in FIG. Can be adopted. However, in the case of the function separation type electrophotographic photosensitive member shown in FIG. 1, the film thickness of the curable charge transport layer is preferably set in the range of 5 μm to 50 μm, more preferably 10 μm to 30 μm. Is done.
On the other hand, 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 generation material is preferably 10% by mass or more and 85% by mass or less, and more 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, preferably from 5 μm to 50 μm, and more preferably from 10 μm to 40 μm.

[Image forming apparatus (and process cartridge)]
The image forming apparatus (and process cartridge) according to this embodiment will be described in detail below.

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 the present embodiment. A process cartridge 300 including the electrophotographic photoreceptor 7, an exposure device 9, a transfer device 40 (primary transfer device), and an intermediate transfer member 50 are provided. 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, a secondary transfer device that transfers the toner image transferred to the intermediate transfer member 50 to the transfer target member is also provided.

  The process cartridge 300 in FIG. 4 integrally supports the electrophotographic photoreceptor 7, the charging device 8, the developing device 11, and the cleaning device 13 in a housing. The cleaning device 13 has a cleaning blade (cleaning member), and the cleaning blade 131 is disposed so as to contact the surface of the electrophotographic photosensitive member 7.

  Moreover, although the fibrous member 132 (roll shape) which supplies the lubricant 14 to the surface of the electrophotographic photoreceptor 7 and the fibrous member 133 (flat brush shape) which assists cleaning are shown, these are shown. It may or may not be used.

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

-Charging device-
As the charging device 8, for example, a contact type charger using a conductive or semiconductive charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube or the like is used. Further, a non-contact type roller charger, a known charger such as a scorotron charger using a corona discharge or a corotron charger may be used.

  Although not shown, a photosensitive member heating member for raising the temperature of the electrophotographic photosensitive member 7 and reducing the relative temperature may be provided around the electrophotographic photosensitive member 7.

-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 in the spectral sensitivity region of the photoreceptor. As the wavelength of the semiconductor laser, near infrared having an oscillation wavelength near 780 nm is the mainstream. However, the present invention is not limited to this wavelength, and an oscillation wavelength laser in the 600 nm range or a laser having an oscillation wavelength 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-
As the developing device 11, for example, a general developing device that performs development by bringing a magnetic or non-magnetic one-component developer or a two-component developer into contact or non-contact may be used. The developing device 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 the one-component developer or the 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 desirable.

  The developer used in the developing device 11 may be a single component developer of toner alone, or may be a two component developer containing toner and carrier. A well-known thing is applied for these developers.

-Cleaning device-
As the cleaning device 13, a cleaning blade type device including a cleaning blade 131 is used.
In addition to the cleaning blade method, a fur brush cleaning method and a simultaneous development cleaning method may be employed.

-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) made of 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.

  The image forming apparatus 100 described above may include, for example, a known apparatus in addition to the above-described apparatuses.

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 process cartridge according to this embodiment may be any process cartridge that includes an electrophotographic photosensitive member and can be attached to and detached from the image forming apparatus.

  In the image forming apparatus (process cartridge) according to the present embodiment described above, the image forming apparatus to which the dry developer is applied has been described. However, the image forming apparatus (process cartridge) to which the liquid developer is applied may be used. . In particular, in an image forming apparatus (process cartridge) to which a liquid developer is applied, the liquid component of the liquid developer causes the outermost surface layer of the electrophotographic photoreceptor to swell, cracks, or cleaning scratches due to cleaning. However, by applying the electrophotographic photosensitive member according to the present embodiment, these can be improved, and as a result, a stable image can be obtained over a long period of time.

FIG. 6 is a schematic configuration diagram illustrating another example of the image forming apparatus according to the present embodiment. FIG. 7 is a schematic configuration diagram showing an image forming unit in the image forming apparatus shown in FIG.
The image forming apparatus 130 shown in FIG. 6 mainly includes a belt-shaped intermediate transfer member 401, color image forming units 481, 482, 483, 484, a heating unit 450 (an example of a layering unit), and a transfer fixing unit 460. And is composed of.

  As shown in FIG. 7, the image forming unit 481 includes an electrophotographic photosensitive member 410, a charging device 411 for charging the electrophotographic photosensitive member 410, and an electrostatic latent image on the surface of the charged electrophotographic photosensitive member 410 according to image information. An LED array head 412 (an example of an electrostatic latent image forming unit) that performs image exposure for forming, and a developing device 414 that develops the electrostatic latent image formed on the electrophotographic photosensitive member 410 using a liquid developer. And a developed image by a liquid developer formed on the electrophotographic photosensitive member 410 and disposed opposite to the electrophotographic photosensitive member 410 via a cleaner 415 for cleaning the surface of the photosensitive member, a static eliminator 416, and a belt-shaped intermediate transfer member 401. And a transfer roll 417 (an example of a primary transfer unit) to which a transfer bias for transferring the toner to the belt-shaped intermediate transfer member 401 is applied.

  As shown in FIG. 7, the developing device 414 includes a developing roll 4141, a liquid draining roll 4142, a developer cleaning roll 4143, a developer cleaning blade 4144, a developer cleaning brush 4145, and a circulation pump (not shown). 2), a liquid developer supply path 4146, and a developer cartridge 4147.

Examples of the liquid developer used here include a liquid developer in which particles mainly composed of a heat-melt fixing resin such as polyester and polystyrene are dispersed, and an excess dispersion medium (carrier liquid) is removed to remove the liquid developer in the liquid developer. A liquid developer that is layered (hereinafter referred to as film form) by increasing the solid content ratio is used. Details of the material for forming a film form are shown in USP 5,650,253 (Column 10 Line 8 to Column 13 Line 14) and USP 5,698,616.
A developer that forms a film form is a liquid developer in which a minute substance (such as a minute toner) having a glass transition temperature lower than room temperature (for example, 25 ° C.) is dispersed in a carrier liquid. It does not agglomerate in contact, but when the carrier liquid is removed, it becomes only the substance, and when attached in a film form, it binds at room temperature (for example, 25 ° C.) to form a film. This substance is obtained by blending ethyl alcohol and methyl methacrylate, and the glass transition temperature is set by the blending ratio.

  The other image forming units 482, 483, and 484 have the same configuration. The developing device of each image forming unit contains liquid developers of different colors (yellow, magenta, cyan, black). In each of the image forming units 481, 482, 483, and 484, an electrophotographic photosensitive member, a developing device, and the like are formed into a cartridge.

  In the above configuration, examples of the material of the belt-shaped intermediate transfer member 401 include a PET film (polyethylene terephthalate film) coated with silicon rubber coating or fluororesin, and a polyimide film.

  The electrophotographic photosensitive member 410 contacts the belt-shaped intermediate transfer member 401 on the upper surface thereof, and moves at the same speed as the belt-shaped intermediate transfer member 401.

  For example, a corona charger is used as the charging device 411. The electrophotographic photosensitive member 410 having the same circumference is used as the electrophotographic photosensitive member 410 in the image forming units 481, 482, 483, and 484. Further, the arrangement intervals of the transfer rolls 417 are different from each other. It is configured to be the same as the circumference of 410 or an integral multiple of the circumference.

  The heating unit 450 is disposed so as to rotate in contact with the inner surface of the belt-shaped intermediate transfer member 401 and to surround the outer surface of the belt-shaped intermediate transfer member 401 so as to face the heating roller 451. The storage tank 452 includes a carrier liquid recovery unit 453 that recovers carrier liquid vapor and carrier liquid from the storage tank 452. The carrier liquid recovery unit 453 includes a suction blade 454 that sucks the carrier liquid vapor in the storage tank 452, a condensing unit 455 that converts the carrier liquid vapor into a liquid state, a recovery cartridge 456 that recovers the carrier liquid from the condensing unit 455, Is installed.

  The transfer fixing unit 460 (an example of the secondary transfer unit) is configured to press the transfer support roll 461 that rotatably supports the belt-shaped intermediate transfer member 401 and the recording medium that passes through the transfer fixing unit 460 toward the belt-shaped intermediate transfer member 401. The transfer fixing roll 462 rotates, and both have a heating element inside.

  In addition to this, prior to color image formation on the belt-shaped intermediate transfer body 401, the cleaning roll 470 and the cleaning web 471 for cleaning the belt-shaped intermediate transfer body 401 and the belt-shaped intermediate transfer body 401 are driven to rotate. Support rolls 441 to 444 to support and support shoes 445 to 447 are provided.

  The belt-shaped intermediate transfer member 401 includes a transfer roll 417, a heating roll 451, a transfer support roll 461, support rolls 441 to 444, support shoes 445 to 447, a cleaning roll 470, and a cleaning web 471 of each color image forming unit. The intermediate unit 402 is configured so that the vicinity of the heating roll 451 moves up and down integrally with the vicinity of the heating roll 451 as a fulcrum.

The operation of the image forming apparatus using the liquid developer shown in FIG. 6 will be described below.
First, in the image forming unit 481, the electrophotographic photosensitive member 410 whose surface is charged by the charging device 411 is subjected to image exposure according to the yellow image information by the LED array head 412 to form an electrostatic latent image. This electrostatic latent image is developed with a yellow liquid developer by a developing device 414.

  The development here is performed in the following steps. The yellow liquid developer is supplied from the developer cartridge 4147 by the circulation pump through the liquid developer supply path 4146 to the vicinity where the developing roll 4141 and the electrophotographic photosensitive member 410 are close to each other. Due to the developing electric field formed between the electrostatic latent image on the electrophotographic photosensitive member 410 and the developing roll 4141, the colored solid content having a charge in the supplied liquid developer is changed to the image portion on the electrophotographic photosensitive member 410. To the electrostatic latent image portion side.

  Subsequently, the carrier liquid is removed from the electrophotographic photoreceptor 410 by the liquid draining roll 4142 so that the carrier liquid ratio required in the next transfer process is obtained. Thus, a yellow image is formed by the yellow liquid developer on the surface of the electrophotographic photosensitive member 410 that has passed through the developing device 414.

  In the developing device 414, the developer cleaning roll 4143 removes the liquid developer on the developing roll 4141 after the developing operation and the liquid developer attached on the squeeze roll by the squeeze operation, and the developer cleaning blade 4144 and the developer. The agent cleaning brush 4145 cleans the developer cleaning roll 4143 so that a stable developing operation is always performed. The configuration and operation of this developing device are described in detail in Japanese Patent Application Laid-Open No. 11-249444.

  Note that the solid content ratio concentration in the liquid developer is automatically controlled by at least one of the developing device 414 and the developer cartridge 4147 so that the liquid developer having a constant solid content ratio is supplied to the developing roll 4141. Has been done.

  The yellow developed image formed on the electrophotographic photosensitive member 410 is brought into contact with the belt-shaped intermediate transfer member 401 on the upper surface thereof by the rotation of the electrophotographic photosensitive member 410, and the electrophotographic photosensitive member is passed through the belt-shaped intermediate transfer member 401. Electrostatic transfer is performed on the belt-shaped intermediate transfer body 401 by a transfer roll 417 arranged in pressure-contact with the body 410 and applied with a transfer bias.

  After the contact electrostatic transfer, the electrophotographic photosensitive member 410 is removed from the residual liquid developer by the cleaner 415, and is neutralized by the static eliminator 416, and used for the next image formation.

  Similar operations are performed in the other image forming units 482, 483, and 484. The electrophotographic photoreceptor 410 having the same circumference is used as the electrophotographic photoreceptor in each image forming unit, and each color developed image formed on each photoreceptor is the same as the circumference of the photoreceptor. Alternatively, electrostatic transfer is sequentially performed on the belt-shaped intermediate transfer member 401 by transfer rolls arranged at integer multiple intervals, and therefore, each electrophotographic photosensitive member is considered in consideration of the overlapping position on the belt-shaped intermediate transfer member 401. The developed images of yellow, magenta, cyan, and black formed on the body 410 are sequentially superimposed on the belt-shaped intermediate transfer body 401 with high accuracy without misalignment even if the electrophotographic photosensitive member 410 is decentered. On the belt-like intermediate transfer member 401 that has undergone contact electrostatic transfer and has passed through the image forming unit 484, a developed image is formed with each color liquid developer.

  The developed image formed on the belt-shaped intermediate transfer member 401 is heated by the heating unit 450 from the back surface of the belt-shaped intermediate transfer member 401 by the heating roll 451, and the carrier liquid as a dispersion medium is almost evaporated, and the film form The resulting image is This is because when the liquid developer is a liquid developer in which particles mainly composed of a heat-melt fixing type resin are dispersed, the dispersed particles are melted by removal of excess dispersion medium and heating by the heating roll 451 to form a film foam. is there. Alternatively, it is a liquid developer that forms a film by removing excess dispersion medium (carrier liquid) and increasing the solid content ratio in the liquid developer.

  In the heating unit 450, the carrier liquid vapor in the storage tank 452 generated by being heated and evaporated by the heating roll 451 is introduced into the condensing unit 455 by the suction blade 454 in the carrier liquid recovery unit 453, and is liquefied and re-liquefied. Is guided to the recovery cartridge 456 and recovered.

  The belt-shaped intermediate transfer member 401 on which a film-like (layer-like) image is formed passing through the heating unit 450 has been conveyed at the transfer fixing unit 460 from the paper storage unit 490 at the lower part of the apparatus in time. A transfer body (for example, plain paper) is heated and pressed by a rotation support roll 461 and a transfer fixing roll 462, an image is formed on the transfer body, and output is discharged out of the apparatus by discharge rolls 491 and 492. Is done. In the transfer here, the adhesion force of the film-formed image formed on the belt-shaped intermediate transfer member 401 to the belt-shaped intermediate transfer member 401 is greater than the adhesion force of the film-formed image to the transfer target. The transfer is weak, and the transfer is performed on the transfer target due to the difference in adhesion, and no electrostatic force is applied during transfer. Note that the bonding force of the film-formed image as a film is larger than the adhesion force to the transfer target.

  The belt-shaped intermediate transfer body 401 that has passed through the transfer fixing unit 460 is included in the solid content of the transfer residue and the solid content by the cleaning roll 470 and the cleaning web 471 in which a heat source is disposed. The substance that inhibits is recovered and removed. Thereafter, the belt-shaped intermediate transfer member 401 is used for the next image formation.

  After the image formation as described above is performed, the intermediate body unit 402 moves integrally around the heating roll 451 and around the support roll 441, and the belt-like intermediate transfer body 401 is connected to each image forming unit. The electrophotographic photosensitive member 410 is separated. Similarly, the transfer fixing roll 462 is separated from the belt-shaped intermediate transfer member 401.

  When there is a request for image formation again, the intermediate unit 402 operates so that the belt-shaped intermediate transfer member 401 contacts the electrophotographic photosensitive member 410 of each image forming unit, and the transfer-fixing roll 462 is also belt-shaped. It operates so as to come into contact with the intermediate transfer member 401. This operation of the transfer fixing roll 462 may be performed in accordance with the timing of image transfer to the recording medium.

On the other hand, the image forming apparatus using the liquid developer is not limited to the image forming apparatus 130 shown in FIG. 6, and may be, for example, the image forming apparatus shown in FIG.
FIG. 8 is a schematic configuration diagram illustrating another example of the image forming apparatus according to the embodiment.

  Similar to the configuration of the image forming apparatus 130 shown in FIG. 6, the image forming apparatus 140 shown in FIG. 8 mainly includes a belt-shaped intermediate transfer member 401, color image forming units 485, 486, 487, and 488, and a heating unit. 450 and a transfer fixing unit 460.

  The image forming apparatus 140 shown in FIG. 8 is different from the image forming apparatus 130 shown in FIG. 6 in that the belt-shaped intermediate transfer member 401 travels in a substantially triangular manner and the color image forming units 485, 486, 487, and 488. The configuration of the developing device 420 in FIG. The heating unit 450 and the transfer fixing unit 460 are the same as those of the image forming apparatus 130 shown in FIG. The cleaning roll 470 and the cleaning web 471 are not shown.

  As the belt-shaped intermediate transfer member 401 rotates, the belt-shaped intermediate transfer member 401 bends. This bending operation affects the stable travel and life of the belt-shaped intermediate transfer member 401. The traveling form is a substantially triangular shape with little movement.

  The developing device 420 does not have a developing roll, a liquid draining roll, or the like, and a plurality of rows of recording heads 421 for selectively adhering the liquid developer to the electrostatic latent image formed on the electrophotographic photosensitive member 410 are arranged. Has been.

  Further, in each row of the recording heads 421, a large number of recording electrodes 422 are evenly arranged in the longitudinal direction of the electrophotographic photosensitive member 410, and the electrostatic latent image potential formed on the electrophotographic photosensitive member 410. And a flying bias potential applied to the recording electrode 422, a flying electric field is formed, and a colored solid having a charge in the liquid developer supplied to the recording electrode 422 becomes an image portion on the electrophotographic photoreceptor 410. The electrostatic latent image portion side is developed and developed.

  Around the recording electrode 422, a meniscus of liquid developer (a liquid holding form formed on or between members in contact with the liquid by liquid viscosity, surface tension, surface energy of the contact member surface) 424 is formed. The FIG. 9 shows the state. An electrostatic latent image serving as an image portion is formed on the electrophotographic photosensitive member 410A, which is the destination of the liquid developer droplets 423. At this time, for example, an electrostatic latent image potential of 50 V to 100 V is applied to the image portion 410B, and a potential of 500 V to 600 V is applied to the non-image portion 410C, for example. Here, when a flying bias potential of about 1000 V is applied to the recording electrode 422 via the bias voltage supply unit 425, the ratio is higher than the solid content ratio in the supplied liquid developer at the tip of the recording electrode 422 due to electric field concentration. That is, a high-concentration liquid developer is supplied, and the potential difference between the electrostatic latent image potential of the image portion 410C on the electrophotographic photosensitive member 410A and the flying bias potential of the recording electrode 422 (for example, 700 V to 800 V is flying). ) Is caused to fly and adhere to the electrostatic latent image portion (image portion) on the electrophotographic photoreceptor 410A. In the developing device 420, the developing device itself serves as a developer cartridge.

  The operation of the image forming apparatus 140 shown in FIG. 8 is the same as the operation of the belt-shaped intermediate transfer member 401 and the developing apparatus 420 except for the operation of the image forming apparatus 130 shown in FIG. Therefore, explanation is omitted.

Here, in the image forming apparatus using the liquid developer, the developing device is not limited to the above configuration, and may be, for example, the developing device shown in FIG.
FIG. 10 is a schematic configuration diagram showing another developing device in the image forming apparatus shown in FIG. 6 or FIG.

  The developing device 4150 shown in FIG. 10 is a developer cartridge when the electrostatic latent image formed on the electrophotographic photoreceptor 410 is developed by the developing roll 4151 in the image forming apparatuses 130 and 140 shown in FIG. A liquid developer layer having a solid content ratio higher than the solid content ratio in the liquid developer supplied from 4155 is formed on the developing roll 4151 and developed with the liquid developer layer having a high concentration.

  Liquid developer layer formation with a high solid content ratio on the developing roll 4151 is performed by forming an electric field by providing a potential difference between the supply roll 4152 and the developing roll 4151, so that the liquid from the developer cartridge 4155 is formed on the developing roll 4151. A liquid developer layer having a solid content ratio higher than the solid content ratio of the developer is formed. For the developing roll 4151 and the supply roll 4152, cleaning blades 4153 and 4154 for cleaning the respective roll surfaces are provided.

  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.

[Example 1]
(Preparation 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 is stirred and mixed with 500 parts by mass of toluene, and silane coupling agent (KBM503: manufactured by Shin-Etsu Chemical Co., Ltd.) 1.3 parts by mass Part 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 (ESLEC BM-1, manufactured by Sekisui Chemical Co., Ltd.) A solution obtained by mixing 38 parts by mass of a solution dissolved in 85 parts by mass of methyl ethyl ketone and 25 parts by mass of methyl ethyl ketone was dispersed for 2 hours in a sand mill using 1 mmφ glass beads.
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 support having a diameter of 30 mm, a length of 340 mm, and a thickness of 1 mm is prepared as a conductive support, and the resulting coating solution for forming the undercoat layer is applied onto the cylindrical aluminum support by a dip coating method. Then, dry curing at 170 ° C. for 40 minutes was performed to obtain an undercoat layer having a thickness of 18.7 μm.

(Preparation 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 support, dried at room temperature (25 ° C.), and a charge generation layer having a thickness of 0.2 μm. Formed.

(Preparation of non-curing charge transport layer)
Next, 40 parts by mass of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine (TPD), N, N-bis ( 3,4-dimethylphenyl) biphenyl-4-amine 10 parts by mass and 55 parts by mass of bisphenol Z polycarbonate resin (Mitsubishi Gas Co., Ltd .: viscosity average molecular weight: 60,000, weight average molecular weight 50,000) as a binder resin It melt | dissolved in addition to 560 mass parts of tetrahydrofuran and 240 mass parts of toluene, and obtained the coating liquid for charge transport layers. This coating solution was applied onto the charge generation layer and dried at 135 ° C. for 45 minutes to form a non-curing charge transport layer having a thickness of 25 μm.

(Preparation of curable charge transport layer (second layer))
As a reactive group-containing charge transport material, compound (a-1) [Exemplary compound (II) -50]: 100 parts by mass and VE-73 (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator 2 parts by mass Were added to 300 parts by mass of a cyclopentyl methyl ether (CPME) solvent and dissolved to prepare a coating liquid for forming a curable charge transport layer (second layer).
The obtained coating liquid for forming a curable charge transport layer (second layer) is pushed up by a ring coating method onto a non-curable charge transport layer previously formed on a cylindrical aluminum support at a speed of 50 mm / min. It was applied with. Thereafter, a curing reaction is carried out 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 curable charge transport layer (second layer). did. The film thickness of the curable charge transport layer was 2 μm.

(Preparation of protective layer (first layer))
As fluorine-containing resin particles, 5 parts by mass of Lubron L2 (manufactured by Daikin Industries, Ltd.) and 0.2 part by mass of a fluorine-based graft polymer (Aron GF300: manufactured by Toagosei Co., Ltd.) were mixed with a tetrahydrofuran (THF) / isobutyl acetate mixed solvent (mass). Ratio 7: 3) Along with 300 parts by mass, a dispersion treatment for 10 minutes was repeated 3 times with an ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusyo) in a constant temperature bath at 20 ° C. to obtain a suspension. In the suspension, 100 parts by mass of the compound (a-1) [Exemplary Compound (II) -50] as a reactive group-containing charge transport material and a polymerization initiator VE-73 (manufactured by Wako Pure Chemical Industries, Ltd.) 2 parts by mass was added and stirred and mixed at room temperature (25 ° C.) for 12 hours to prepare a coating solution for forming a protective layer (first layer).
The obtained coating liquid for forming the protective layer (first layer) was applied on the charge transport layer previously formed on the cylindrical aluminum support by a ring coating method at a push-up speed of 150 mm / min. Thereafter, in a nitrogen dryer having an oxygen concentration meter, a curing reaction was carried out at a temperature of 160 ± 5 ° C. for 60 minutes with an oxygen concentration of 200 ppm or less to form a protective layer (first layer). The film thickness of the protective layer was 7 μm.

  An electrophotographic photosensitive member was produced as described above.

[Examples 2-28, 31-36]
By the method described in Example 1, an undercoat layer and a charge generation layer were sequentially formed on a cylindrical aluminum support by coating. Then, according to Table 1 and Table 2 below, the composition of the coating solution for forming the protective layer (first layer) and the coating solution for forming the curable charge transport layer (second layer) was changed, as described in Example 1. By the method, a protective layer (first layer), a curable charge transport layer (second layer), charge transport layer 1 and charge transport layer 2 were formed to produce an electrophotographic photoreceptor.
However, in Tables 1 and 2, “Yes” in the column of fluorine-containing resin particles means that 5 parts by mass of Lubron L2 (manufactured by Daikin Industries, Ltd.) and fluorine-based graft polymer (Aron GF300: (Toa Gosei Co., Ltd.) 0.2 parts by mass is blended in the protective layer forming coating solution, and “none” indicates that this is not blended in the protective layer forming coating solution.

[Examples 29 to 30]
An electrophotographic photoreceptor of Example 29 was produced in the same manner as in Example 1 except that a curable charge transport layer (second layer) was formed as follows.
Then, in the same manner as in Example 29, except that Lubron L2 (produced by Daikin Industries, Ltd.) and fluorine-based graft polymer were not blended as the fluorine-containing resin particles in the protective layer (first layer) forming coating solution, The electrophotographic photosensitive member of Example 30 was produced.

-Preparation of curable charge transport layer (second layer)-
20 parts by mass of compound (a-14) as a non-reactive charge transport material and 80 parts by mass of compound (b-1) [FA-321M (manufactured by Hitachi Chemical Co., Ltd.)] as a non-reactive group-containing non-charge transport material Part and 2 parts by weight of a polymerization initiator VE-73 (manufactured by Wako Pure Chemical Industries, Ltd.) are added to 300 parts by weight of CPME solvent and dissolved to form a curable charge transport layer (second layer) coating. A liquid was prepared.
The obtained coating liquid for forming a curable charge transport layer (second layer) is pushed up by a ring coating method onto a non-curable charge transport layer previously formed on a cylindrical aluminum support at a speed of 50 mm / min. It was applied with. Thereafter, a curing reaction is carried out 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 curable charge transport layer (second layer). did. The film thickness of the curable charge transport layer was 2 μm.

[Comparative Examples 1-2]
In the composition of the coating liquid for forming the protective layer (first layer), the compound (a-4) [Exemplary Compound ((Ib) -23)] is blended as a reactive group-containing charge transport material, and a curable charge The electrophotography of Comparative Example 1 was made in the same manner as in Example 1 except that the transport layer (second layer) was not formed and the protective layer (first layer) was directly formed on the non-curable charge transport layer. A photoconductor was prepared.
Then, in the same manner as in Comparative Example 1, except that Lubron L2 (produced by Daikin Industries, Ltd.) and fluorine-based graft polymer were not blended as the fluorine-containing resin particles in the coating solution for forming the protective layer (first layer). An electrophotographic photosensitive member of Comparative Example 2 was produced.

[Comparative Examples 3 to 4]
Comparative Example 3 was performed in the same manner as in Example 1 except that a non-curable charge transport layer (second layer) was formed instead of the curable charge transport layer (second layer) as follows. An electrophotographic photoreceptor was prepared.
Then, except that Lubron L2 (produced by Daikin Industries, Ltd.) and a fluorine-based graft polymer are not blended as fluorine-containing resin particles in the protective layer (first layer) forming coating solution, An electrophotographic photosensitive member of Comparative Example 4 was produced.

-Production of non-curing type charge transport layer (second layer)-
20 parts by mass of the compound (a-14) as a non-reactive charge transport material and 80 parts by mass of (C-1) [Butyral resin (Esreck BM-1, manufactured by Sekisui Chemical Co., Ltd.)] as a CPME solvent It melt | dissolved in addition to 300 mass parts, and the coating liquid for non-hardening type charge transport layer (2nd layer) formation was created.
The obtained coating liquid for forming a non-curable charge transport layer (second layer) was applied on the charge transport layer previously formed on the cylindrical aluminum support by a ring coating method at a push-up speed of 50 mm / min. . Thereafter, drying was performed at 135 ° C. for 45 minutes to form a non-curing charge transport layer (second layer). The film thickness of the non-curing charge transport layer (second layer) was 2 μm.

[Comparative Examples 5-6]
In the composition of the coating liquid for forming the protective layer (first layer), the electrophotographic photosensitive film of Comparative Example 5 was prepared in the same manner as in Example 1 except that the compound (a-10) was blended as the reactive group-containing charge transport material. The body was made.
Then, except that Lubron L2 (produced by Daikin Industries, Ltd.) and fluorine-based graft polymer are not blended as fluorine-containing resin particles in the protective layer (first layer) forming coating solution, An electrophotographic photoreceptor of Comparative Example 6 was produced.

[Evaluation 1]
The electrophotographic photoreceptor obtained in each example is mounted on a DocuCenter Color 400CP (Fuji Xerox Co., Ltd.), and a solid image portion having an image density of 100% under an ordinary environment (20 ° C., 50% RH), an image density of 10 A printed image having a halftone image portion and a fine line image portion was output. Then, after continuously outputting 30000 black solid patterns, an image evaluation pattern was output again. The amount of light was adjusted using a filter depending on the sensitivity of the charge generation material.

―Evaluation of film thickness unevenness―
Before carrying out the evaluation 1, the surface charge transport layer 1 from a position advanced from the coating start position toward the 3 cm coating end position to a position advanced from the coating end position toward the 3 cm coating start position. The film thickness was measured at an interval of 90 ° in the circumferential direction using an eddy current film thickness meter, and the average value of the film thickness was used to determine the film thickness according to the following criteria.
A +: The difference in film thickness from the position proceeding from the coating start position toward the 3 cm coating end position to the position proceeding from the coating end position toward the 3 cm coating start position is 0.0 μm or more and smaller than 2.0 μm A: The difference in film thickness from the position advanced from the coating start position toward the 3 cm coating end position to the position advanced from the coating end position toward the 3 cm coating start position is 2.0 μm or more and smaller than 3.0 μm. B: The difference in film thickness from the position advanced from the coating start position toward the 3 cm coating end position to the position advanced from the coating end position toward the 3 cm coating start position is 3.0 μm or more and smaller than 5.0 μm. C: The film thickness difference from the position advanced from the coating start position toward the 3 cm coating end position to the position advanced from the coating end position toward the 3 cm coating start position is 5.0 μm or more.

―Evaluation of electrical property stability―
Before and after the evaluation 1, each photoconductor was negatively charged with a scorotron charger with a grid applied voltage of −700 V in a normal environment (20 ° C., 50% RH), and then the charged photoconductors. Using a 780 nm semiconductor laser, flash exposure was performed with a light amount of 10 mJ / m ² . The potential (V) on the surface of the photoconductor after 10 seconds after the exposure was measured, and this value was taken as the value of the residual potential. In any photoreceptor, the residual potential showed a negative value. For each of the photoreceptors, a value of (residual potential before evaluation 1) − (residual potential after evaluation 1) was calculated to evaluate electrical property stability. A ++ indicates the best characteristics.
A ++: Less than 10V A +: 10V or more and less than 20V A: 20V or more and less than 30V B: 30V or more and less than 50V C: 50V or more

―Evaluation of initial scratch resistance―
The degree of occurrence of scratches on the surface of the photoreceptor after the evaluation 1 was evaluated as follows.
A ++ indicates the best characteristics.
A ++: Scratches are not confirmed even by microscopic observation.
A +: Although scratches are not visually confirmed, small scratches are confirmed by microscopic observation.
A: Some scratches are visually confirmed (no problem in practical use).
B: Scratches are partially generated.
C: Scratches are generated on the entire surface.

-Long-term scratch resistance evaluation-
After outputting 50,000 black solid patterns under the same conditions as in Evaluation 1, the degree of scratches on the surface of the photoreceptor was evaluated as follows.
A ++ indicates the best characteristics.
A ++: Scratches are not confirmed even by microscopic observation.
A +: Although scratches are not visually confirmed, small scratches are confirmed by microscopic observation.
A: Some scratches are visually confirmed (no problem in practical use).
B: Scratches are partially generated.
C: Scratches are generated on the entire surface.

[Evaluation 2]
-Dispersibility evaluation of fluorine-containing resin particles-
The dispersibility of the fluorine-containing resin particles of the electrophotographic photoreceptor obtained in each example was evaluated by the following method. Using a single-edged trimming razor (manufactured by Nissin EM Co., Ltd.), a slice of the laminate from the undercoat layer to the surface charge transport layer 1 was cut out from the photoreceptor substrate, and a photocurable acrylic resin (product name D- 800: manufactured by JEOL Datum). Next, it was cut by a microtome method (microtome apparatus: manufactured by LEICA) using a diamond knife so that the cross section of the laminated section appeared. The cross section of the section was observed with a laser microscope OLS-1100 manufactured by Olympus Optical Co., Ltd. under the condition of a step amount of 0.01 μm and judged according to the following criteria.
A: Dispersed uniformly and no aggregation.
B: Some weak aggregation.
C: Strong aggregation.
In addition, this evaluation was not implemented about the photoreceptor which does not mix | blend a fluorine-containing resin particle with a protective layer (1st layer).

From the above results, it can be seen that in this example, better results were obtained in terms of evaluation of film thickness unevenness, electrical property stability, and scratch resistance compared to the comparative example.
Moreover, in a present Example, when a fluorine-containing resin particle is mix | blended with a protective layer (1st layer) compared with a comparative example, it turns out that it is excellent in the dispersibility.

Hereinafter, details such as abbreviations of materials used in the examples will be described.
[Charge transport materials (reactive group-containing charge transport materials, non-reactive charge transport materials]
(A-1): Exemplified compound (II) -50
(A-2): Exemplary compound (II) -58
(A-3): Exemplary compound (II) -33
(A-4): Exemplified compound (Ib) -23
(A-5): Exemplified compound (Ic) -30
(A-6): Exemplified compound (II) -13
(A-7): Exemplified compound (Ic) -15 (see the synthesis method below)
(A-8): Exemplified compound (Ib) -29
(A-9): Exemplified compound (Ic) -43 (see the synthesis method below)
(A-10): Compound represented by the following structural formula (a-11): Compound represented by the following structural formula (a-12): Compound represented by the following structural formula (a-13) ): A compound represented by the following structural formula: (a-14): a compound represented by the following structural formula: (a-15): exemplary compound (Ia) -25
(A-16): Exemplary compound (Id) -11
(A-17): Exemplary compound (II) -184

—Synthesis of Exemplary Compound (Ic) -15—
In a 500 ml three-necked flask, 68.3 g of 4,4′-bis (2-methoxycarbonylethyl) diphenylamine, 46.4 g of 4-iodoxylene, 30.4 g of potassium carbonate, 1.5 g of copper sulfate pentahydrate, 50 ml of n-tridecane Was added, and the system was stirred for 20 hours while heating at 220 ° C. while flowing nitrogen. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 20 g of sodium sulfate was added and stirred for 10 minutes, and then sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 65.1 g of (Ic) -15a (yield 73%).
59.4 g of (Ic) -15a and 450 ml of tetrahydrofuran were added to a 3 L three-necked flask, and an aqueous solution in which 11.7 g of sodium hydroxide was dissolved in 450 ml of water was added thereto, followed by stirring at 60 ° C. for 3 hours. Thereafter, the reaction solution was added dropwise to 1 L of water / 60 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. Further, 50 ml of an acetone / water mixed solvent (volume ratio 40/60) was added to this solid and stirred in a suspended state, then collected by suction filtration, dried in vacuo for 10 hours, and 46 of (Ic) -15b was obtained. 0.2 g was obtained (yield 83%).
To a 500 ml three-necked flask, 29.2 g of (Ic) -15b, 23.5 g of 4-chloromethylstyrene, 21.3 g of potassium carbonate, 0.17 g of nitrobenzene, 175 ml of DMF (N, N-dimethylformamide) were added, The system was stirred for 3 hours with nitrogen flowing and heated to 75 ° C. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 36.4 g of Exemplified Compound (Ic) -15 (yield 80%). .

—Synthesis of Exemplary Compound (Ic) -43—
In a 500 ml three-necked flask, 68.3 g of 4,4′-bis (2-methoxycarbonylethyl) diphenylamine, 43.4 g of 4,4′-diiodo 3,3′-dimethyl-1,1′-biphenyl, 30.4 g of potassium carbonate, Copper sulfate pentahydrate (1.5 g) and n-tridecane (50 ml) were added, and the system was stirred for 20 hours while heating at 220 ° C. with nitrogen flow. Thereafter, the temperature was lowered to room temperature, and 200 ml of toluene and 150 ml of water were added to carry out a liquid separation operation. The toluene layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by evaporating toluene under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 56.0 g of (Ic) -43a (yield 65%).
To a 3 L three-necked flask, 43.1 g of (Ic) -43a and 350 ml of tetrahydrofuran were added, an aqueous solution in which 8.8 g of sodium hydroxide was dissolved in 350 ml of water was added, and the mixture was stirred for 5 hours while heating to 60 ° C. did. Thereafter, the reaction solution was added dropwise to 1 L of water / 40 ml of concentrated hydrochloric acid, and the precipitated solid was collected by suction filtration. The solid was further added with 50 ml of an acetone / water mixed solvent (volume ratio 40/60), stirred in a suspended state, collected by suction filtration, dried in vacuo for 10 hours, and (Ic) -43b was replaced with 36. 0.6 g was obtained (yield 91%).
To a 500 ml three-necked flask, 28.2 g of (Ic) -43b, 23.5 g of 4-chloromethylstyrene, 21.3 g of potassium carbonate, 0.09 g of nitrobenzene, 175 ml of DMF (N, N-dimethylformamide) were added, The system was stirred for 5 hours while flowing nitrogen and heating to 75 ° C. Thereafter, the temperature was lowered to room temperature, and 200 ml of ethyl acetate / 200 ml of water was added to the reaction solution to carry out a liquid separation operation. The ethyl acetate layer was collected, 10 g of sodium sulfate was added and stirred for 10 minutes, and then the sodium sulfate was filtered. The crude product obtained by distilling off ethyl acetate under reduced pressure was purified by silica gel column chromatography using toluene / ethyl acetate as an eluent to obtain 37.8 g of Exemplified Compound (Ic) -43 (yield 85%). .

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

[Reactive group-containing non-charge transport material]
(B-1): FA-321M (manufactured by Hitachi Chemical Co., Ltd.)
[resin]
-(C-1): Butyral resin (ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.)

DESCRIPTION OF SYMBOLS 1 Undercoat layer, 2 Charge generation layer, 3-1 Charge transport layer, 3-2 Charge transport layer, 3-3 Charge transport layer, 4 Conductive substrate, 6 Single layer type photosensitive layer (Charge generation / charge transport layer ), 7A, 7B, 7C, 7 Electrophotographic photosensitive member, 8 Charging device, 9 Exposure device, 11 Developing device, 13 Cleaning device, 14 Lubricant, 40 Transfer device, 50 Intermediate transfer member, 100, 120, 130, 140 Image forming apparatus, 300 process cartridge

Claims (11)

A conductive substrate, and a photosensitive layer provided on the conductive substrate,
The first layer which is the outermost surface layer is composed of a cured film of a composition containing at least one selected from reactive compounds represented by the following general formulas (I) and (II),
An electrophotographic photosensitive member, wherein a second layer which is a lower layer adjacent to the outermost surface layer is formed of a charge transporting cured film.



[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 reactive compound represented by the general formula (I) is represented by the following general formula (Ia), the following general formula (Ib), the following general formula (Ic), or the following general formula (Id). The electrophotographic photoreceptor according to claim 1, which is at least one reactive compound selected from the reactive compounds represented by:



[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 linking divalent linked to a group represented by ^Ar a1 ^{to Ar a4} at * Indicates a group. an represents an integer of 1 or 2. ]



[In the general formula (Ib), Ar ^{b1 to} Ar ^b4 each independently represents 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 linkage linked to a group represented by Ar ^{b1 to} Ar ^b5 at *. Indicates a group. bn represents an integer of 3 to 6. ]



[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. ]



[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 is a divalent linkage linked to a group represented by Ar ^{d1 to} Ar ^d5 at *. Indicates a group. dn represents an integer of 1 to 6. ] The electrophotographic photosensitive member according to claim 2, wherein the group represented by the general formula (IA-c) is a group represented by the following general formula (IA-c1).



[In the general formula (IA-c1), cp1 represents an integer of 0 or more and 4 or less. ] The electrophotographic photoreceptor according to claim 1, wherein the reactive compound represented by the general formula (II) is a reactive compound represented by the following general formula (II-a).



[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- is shown. 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. ] The group linked to the charge transporting skeleton represented by F of the reactive compound represented by the general formula (II) is a group represented by the following general formula (IIA-a3) or (IIA-a4): The electrophotographic photosensitive member according to any one of -4.



[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 divalent linking group. kq4 represents an integer of 0 or 1. ] The group linked to the charge transporting skeleton represented by F of the reactive compound represented by the general formula (II) is a group represented by the following general formula (IIA-a1) or (IIA-a2): The electrophotographic photosensitive member according to any one of -4.



[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. ]   The electrophotographic photosensitive member according to claim 1, wherein the first layer as the outermost surface layer contains fluororesin particles.   The said 2nd layer is any one of Claims 1-7 comprised with the cured film of the composition containing at least 1 sort (s) selected from the reactive compound shown by the said general formula (I) and (II). The electrophotographic photoreceptor described in 1. The photosensitive layer includes a charge generation layer and a non-curing charge transport layer;
The electrophotographic photosensitive member according to claim 1, wherein the second layer is provided on the non-curing charge transport layer. The electrophotographic photosensitive member according to any one of claims 1 to 9 ,
A process cartridge that can be attached to and detached from an image forming apparatus. The electrophotographic photosensitive member according to any one of claims 1 to 9 ,
Charging means for charging 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;
Developing means for developing the electrostatic latent image formed on the surface of the electrophotographic photosensitive member with a developer containing toner to form a toner image;
Transfer means for transferring the toner image to a transfer medium;
An image forming apparatus comprising: