JP5102852B2 - Electrophotographic photosensitive member, image forming method using the same, image forming apparatus, and process cartridge for image forming apparatus - Google Patents

Description

  The present invention provides an electrophotographic film having high durability and high image quality over a long period of time by using a photosensitive layer having high wear resistance, smooth surface properties and good electrical characteristics. The present invention relates to a photoreceptor. The present invention also relates to an image forming method, an image forming apparatus, and a process cartridge for the image forming apparatus using the long-life, high-performance photoconductor.

In recent years, organic photoreceptors (OPC) have been widely used in copying machines, facsimile machines, laser printers, and composite machines in place of inorganic photoreceptors because of their good performance and various advantages. This is because, for example, (1) optical characteristics such as the light absorption wavelength range and the amount of absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, and (3) material selection range (4) Ease of production, (5) Low cost, (6) Non-toxicity, and the like.
On the other hand, the diameter of the photoconductor has recently been reduced due to the downsizing of the image forming apparatus, and the high speed of the machine and the maintenance-free movement have been added to increase the durability of the photoconductor. From this point of view, organophotoreceptors are generally soft because the surface layer is mainly composed of low-molecular charge transport materials and inert polymers, and when used repeatedly in electrophotographic processes, they are mechanically driven by development systems and cleaning systems. There is a drawback that wear is likely to occur due to a typical load. In addition, due to the demand for higher image quality, the cleaning blade is required to increase its rubber hardness and contact pressure for the purpose of improving the cleaning properties as the particle size of the toner particles is reduced. This also promotes the wear of the photoreceptor. Is a factor. Such wear of the photoreceptor deteriorates electrical characteristics such as sensitivity deterioration and chargeability, and causes abnormal images such as image density reduction and background stains. Further, scratches where wear is locally generated cause streak-like stain images due to poor cleaning. Under the present circumstances, the wear and scratches are rate-determined and the life of the photoconductor has been replaced.

Therefore, it is indispensable to reduce the above-mentioned wear amount in order to increase the durability of the organic photoreceptor, and this is the most pressing issue in this field.
Techniques for improving the abrasion resistance of the photosensitive layer include (1) using a curable binder for the surface layer (for example, see Patent Document 1), and (2) using a polymeric charge transport material (for example, , Patent Document 2), (3) Those in which an inorganic filler is dispersed in the surface layer (for example, see Patent Document 3), and the like. Among these technologies, those using the curable binder (1) have poor compatibility with the charge transport material, and the residual potential increases due to impurities such as polymerization initiators and unreacted residues, resulting in decreased image density. Tends to occur. In addition, although the polymer charge transport material (2) can improve the abrasion resistance to some extent, the durability required for the organic photoreceptor is not fully satisfied. Not reached. In addition, polymer charge transport materials are difficult to polymerize and purify, and it is difficult to obtain a high-purity material. Therefore, it is difficult to stabilize electrical characteristics between materials. Furthermore, production problems such as high viscosity of the coating solution may occur. The dispersion of the inorganic filler (3) exhibits higher wear resistance than a photoconductor in which a normal low molecular charge transport material is dispersed in an inert polymer, but traps present on the surface of the inorganic filler. As a result, the residual potential rises and the image density tends to decrease. In addition, when the unevenness of the inorganic filler and the binder resin on the surface of the photoconductor is large, defective cleaning may occur, which may cause toner filming and image flow. These technologies (1), (2), and (3) are sufficient to satisfy the overall durability including the electrical durability and mechanical durability required for the organic photoreceptor. Has not reached.

  As a photoreceptor for the purpose of improving these electrical characteristics, wear resistance and surface smoothness, a technique using a cured resin in which a charge transporting structure is incorporated in a polymerization bond is known. Examples of this include a charge transport layer formed using a coating liquid comprising a monomer having a carbon-carbon double bond, a charge transport agent having a carbon-carbon double bond, and a binder resin (see, for example, Patent Document 4). ), And a photosensitive layer containing a compound obtained by curing a hole transporting compound having two or more chain polymerizable functional groups in the same molecule (see, for example, Patent Document 5). In the former, the amount of the crosslink in the charge transport layer cannot be increased because the monomer having a large amount of binder resin and the monomer having a carbon-carbon double bond that is specifically used is bifunctional. It did not have good wear resistance. The latter is an example of a charge transport layer that has been electron beam cured using a hole transporting compound having a bifunctional acryloyloxy group and a trifunctional acrylic monomer. Further, since the bulky hole transporting compound is fixed in the cross-linked bond by a plurality of bonds, there is a problem that distortion is large and unevenness of the surface layer, cracks, and film peeling tend to occur. In order to avoid these problems, it is necessary to finely control the composition material, its proportion and curing conditions, and this not only restricts the freedom of materials and conditions but also has the same quality. It was difficult to stably produce

In addition, regarding a photocuring protective layer photoreceptor, as a technique for improving slipperiness, abrasion resistance and scratch resistance, a technique using a photopolymerization initiator having a morpholino group or a dialkylamino group is mentioned (for example, Patent Documents). 6). Although these photopolymerization initiators have a high curing rate and a smooth cured film can be obtained, when used in a charge transport layer, this site has a tertiary amine structure substituted with a dialkyl group in the structure, and this site causes charge trapping. Thus, the residual potential increases with repeated use.
Even in a photoreceptor having a cross-linked photosensitive layer chemically bonded to a charge transporting structure in these prior arts, it cannot be said that it has sufficient comprehensive properties at present, and a photopolymerization initiator that improves the curability of the film. Adoption of this also caused deterioration of electrical characteristics.

  Accordingly, an object of the present invention is to provide an electrophotographic photosensitive member having high wear resistance and excellent surface smoothness and having a low exposed area potential among electrical characteristics, and being stable for a long period of time. Another object of the present invention is to provide an image forming method, an image forming apparatus and a process cartridge for the image forming apparatus using the long-life, high-performance photoconductor.

  As a result of intensive studies, the present inventors have photopolymerized a radically polymerizable monomer having a trifunctional or higher functional group in which the surface layer of the photosensitive layer does not have a charge transporting structure and a charge transporting compound having a radically polymerizable functional group. It has been found that the above object can be achieved by a photoreceptor having an acylphosphine oxide compound as an initiator and having a cross-linked layer cured by light energy irradiation.

  That is, the above-described problem is (1) “an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the surface layer of the photosensitive layer has at least a trifunctional or higher functional structure. A crosslinked layer cured by light energy irradiation using an acylphosphine oxide compound as a photopolymerization initiator with a radically polymerizable monomer and a charge transporting compound having a radically polymerizable functional group, and having the radically polymerizable functional group The electrophotographic photoreceptor, wherein the charge transporting compound is one or more of the following general formula (1) or (2):

〔式中、Ｒ_１は水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基、シアノ基、ニトロ基、アルコキシ基、−ＣＯＯＲ_７（Ｒ_７は水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基又は置換基を有してもよいアリール基を表す。）、ハロゲン化カルボニル基若しくはＣＯＮＲ_８Ｒ_９（Ｒ_８及びＲ_９は水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基又は置換基を有してもよいアリール基を示し、互いに同一であっても異なっていてもよい。）を表わし、Ａｒ_１、Ａｒ_２は置換もしくは未置換のアリーレン基を表わし、同一であっても異なってもよい。Ａｒ_３、Ａｒ_４は置換もしくは未置換のアリール基を表わし、同一であっても異なってもよい。Ｘは単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル２価基、酸素原子、硫黄原子、ビニレン基を表わす。Ｚは置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキレンエーテル２価基、アルキレンオキシカルボニル２価基を表わす。ｍ、ｎは０〜３の整数を表わす。〕」、（２）「前記表面層に用いられる電荷輸送性構造を有しない３官能以上のラジカル重合性モノマーの官能基が、アクリロイルオキシ基及び／又はメタクリロイルオキシ基であることを特徴とする前記第（１）項に記載の電子写真感光体」、
（３）「前記表面層に用いられる電荷輸送性構造を有しない３官能以上のラジカル重合性モノマーにおける官能基数に対する分子量の割合（分子量／官能基数）が、２５０以下であることを特徴とする前記第（１）項または第（２）項に記載の電子写真感光体」、
（４）「前記表面層に用いられるラジカル重合性官能基を有する電荷輸送性化合物が、下記一般式（３）の一種以上であることを特徴とする前記第（１）項乃至第（３）項のいずれかに記載の電子写真感光体；

[Wherein, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a cyano group, a nitro group, A group, an alkoxy group, —COOR ₇ (R ₇ represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent. ), A halogenated carbonyl group or CONR ₈ R ₉ (R ₈ and R ₉ have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an aryl group which may be the same or different, and Ar ₁ and Ar ₂ represent a substituted or unsubstituted arylene group, which may be the same or different. . Ar ₃ and Ar ₄ represent a substituted or unsubstituted aryl group, and may be the same or different. X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether divalent group, an oxygen atom, a sulfur atom, or a vinylene group. Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether divalent group, or an alkyleneoxycarbonyl divalent group. m and n represent an integer of 0 to 3. ], (2) "The functional group of the tri- or higher functional radical polymerizable monomer having no charge transport structure used for the surface layer is an acryloyloxy group and / or a methacryloyloxy group" The electrophotographic photosensitive member according to item (1),
(3) “The ratio of the molecular weight to the number of functional groups (molecular weight / number of functional groups) in a trifunctional or higher functional polymerizable monomer having no charge transport structure used for the surface layer is 250 or less” The electrophotographic photosensitive member according to item (1) or (2) ",
(4) “The charge transporting compound having a radical polymerizable functional group used in the surface layer is one or more of the following general formula (3)”: (1) to (3) The electrophotographic photosensitive member according to any one of the items;

（式中、ｏ、ｐ、ｑはそれぞれ０又は１の整数、Ｒａは水素原子、メチル基を表わし、Ｒｂ、Ｒｃは水素原子以外の置換基で炭素数１〜６のアルキル基を表わし、複数の場合は異なっても良い。ｓ、ｔは０〜３の整数を表わす。Ｚａは単結合、メチレン基、エチレン基、

(Wherein, o, p and q are each an integer of 0 or 1, Ra represents a hydrogen atom or a methyl group, Rb and Rc represent a substituent other than a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, And s and t each represents an integer of 0 to 3. Za is a single bond, a methylene group, an ethylene group,

を表わす。）」、（５）「前記表面層に用いられるアシルホスフィンオキサイド化合物は、吸収極大波長が４００ｎｍ以上であることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載の電子写真感光体」、（６）「前記表面層に用いられるアシルホスフィンオキサイド化合物が下記構造式（Ｐ−１）で表される化合物であることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載の電子写真感光体」、

Represents. ) ”, (5)“ Acylphosphine oxide compound used in the surface layer has an absorption maximum wavelength of 400 nm or more, according to any one of (1) to (4) ”above. Electrophotographic photosensitive member ”, (6)“ Acylphosphine oxide compound used for the surface layer is a compound represented by the following structural formula (P-1) ”: 4) the electrophotographic photosensitive member according to any one of items

」、
（７）「前記表面層に用いられるアシルホスフィンオキサイド化合物が下記構造式（Ｐ−３）で表される化合物であることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載の電子写真感光体」、

"
(7) Any one of the above items (1) to (4), wherein the acylphosphine oxide compound used for the surface layer is a compound represented by the following structural formula (P-3) The electrophotographic photoreceptor described in "

」、
（８）「前記感光層が支持体側から電荷発生層、電荷輸送層、電荷輸送性架橋表面層の積層構成であることを特徴とする前記第（１）項乃至第（７）項のいずれかに記載の電子写真感光体」により達成される。
また、上記課題は、本発明の（９）「前記第（１）項乃至第（８）項のいずれかに記載の電子写真感光体を用いて、少なくとも帯電、画像露光、現像、転写を繰り返し行なうことを特徴とする画像形成方法」により達成される。
また、上記課題は、本発明の（１０）「前記第（１）項乃至第（８）項のいずれかに記載の電子写真感光体を有することを特徴とする画像形成装置」により達成される。
また、上記課題は、本発明の（１１）「前記第（１）項乃至第（８）項のいずれかに記載の電子写真感光体と、帯電手段、現像手段、転写手段、クリーニング手段および除電手段よりなる群から選ばれた少なくとも一つの手段を有するものであって、画像形成装置本体に着脱可能としたことを特徴とする画像形成装置用プロセスカートリッジ」により達成される。

"
(8) Any one of the above items (1) to (7), wherein the photosensitive layer has a laminated structure of a charge generation layer, a charge transport layer, and a charge transport crosslinkable surface layer from the support side. It is achieved by the electrophotographic photosensitive member described in 1).
In addition, the above-mentioned problem is that at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to any one of (9) and (1) to (8) of the present invention. The image forming method is characterized in that it is achieved.
Further, the above object is achieved by (10) “an image forming apparatus comprising the electrophotographic photosensitive member according to any one of (1) to (8)” of the present invention. .
In addition, the above-mentioned problems are solved by (11) “the electrophotographic photosensitive member according to any one of (1) to (8)”, a charging unit, a developing unit, a transfer unit, a cleaning unit, It is achieved by an image forming apparatus process cartridge having at least one means selected from the group consisting of means and detachable from the main body of the image forming apparatus.

  As will be apparent from the following detailed and specific description, according to the present invention, a trifunctional or higher-functional radical polymerizable monomer having no charge transporting structure and a charge transporting compound having a radical polymerizable functional group are optically converted. By using an acylphosphine oxide compound as a polymerization initiator and providing a crosslinked surface layer cured by light energy irradiation, a photoreceptor having excellent surface smoothness and electrical characteristics, high durability and long life can be obtained. Further, by using this photoreceptor, it is possible to provide a highly reliable and high-performance image forming process, an image forming apparatus, and a process cartridge for the image forming apparatus that can maintain a good image for a long period of time.

1 is an example of a cross-sectional view of an electrophotographic photosensitive member of the present invention. It is another example of sectional drawing of the electrophotographic photosensitive member of this invention. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention. FIG. 2 is a schematic diagram illustrating an example of a process cartridge for an image forming apparatus according to the present invention.

Hereinafter, the present invention will be described in detail.
In the present invention, an acylphosphine oxide compound is prepared by using a photopolymerization initiator as a photopolymerization initiator with a radical polymerizable monomer having a trifunctional or higher functional group whose surface layer of the photosensitive layer does not have a charge transporting structure and a radical transporting functional group. An electrophotographic photosensitive member that has high abrasion resistance and excellent surface smoothness, and has a low exposed area potential and is stable over a long period of time due to the photosensitive member having a crosslinked layer cured by light energy irradiation. Is achieved.

The effect of the present invention is considered to be based on the following principle.
In the formation of the outermost surface layer of the photoreceptor of the present invention, a radically polymerizable monomer having three or more functional groups is used, whereby a three-dimensional network structure is developed and a high hardness surface layer having a very high degree of crosslinking is obtained. And high wear resistance is achieved. On the other hand, when only monofunctional and bifunctional radically polymerizable monomers are used, the cross-linking bond in the cross-linked surface layer becomes dilute, and a dramatic improvement in wear resistance cannot be achieved. When a large amount of polymer material is contained in the cross-linked surface layer, the development of the three-dimensional network structure is inhibited or the cross-linking bond is dilute, and sufficient wear resistance cannot be obtained as compared with the present invention. Furthermore, the compatibility between the polymer material and the cured product resulting from the reaction of the radical polymerizable composition (radical polymerizable monomer or charge transporting compound having a radical polymerizable functional group) is poor, and the surface is separated from the phase separation. Smoothness and local wear and damage are likely to occur. In addition, in the formation of the outermost surface phase of the present invention, in addition to the trifunctional radically polymerizable monomer, a charge transporting compound having a radically polymerizable functional group is contained, and this is a radical polymerization having the above trifunctional or higher functionality. Is incorporated into the cross-linking during curing of the functional monomer. On the other hand, when a low molecular charge transport material having no functional group is contained in the cross-linked surface layer, precipitation of the low molecular charge transport material or white turbidity occurs due to its low compatibility. The mechanical strength of is reduced.

  Furthermore, the photoreceptor of the present invention has good electrical characteristics, and thus high image quality can be realized over a long period of time. This is due to the use of a charge transporting compound having a radical polymerizable functional group and immobilization between the crosslinks. When a charge transport material having no functional group is used as described above, precipitation and clouding phenomenon occur, which causes a decrease in sensitivity, an increase in residual potential, and the like. In the output image, it appears as a phenomenon such as a decrease in image density or background contamination.

  Further, in the present invention, an acylphosphine oxide compound is used as a polymerization initiator for photocuring a tri- or higher functional radical polymerizable monomer having no charge transport structure and a charge transport compound having a radical polymerizable functional group. As a result, the surface smoothness is improved, the potential of the exposed area is low, and it can be stabilized over a long period of time. The reason is considered as follows. Since a charge transporting compound having a radical polymerizable functional group is included as a constituent component in the formation of the cross-linked surface layer, the amount of light absorbed by a normal photopolymerization initiator is extremely reduced due to absorption of this charge transporting site. , Radical generation amount is reduced. For this reason, in order to cure the surface layer, it is necessary to irradiate light with a long time or high intensity, which causes decomposition of the electrified transport structure and deterioration of characteristics. In order to increase the amount of radical generation, a method of increasing the content of the photopolymerization initiator is also possible, but this substantially reduces the content of the radically polymerizable monomer and charge transporting compound in the crosslinked surface layer. This causes a decrease in wear resistance and an increase in residual potential. On the other hand, since the acylphosphine oxide compound has absorption in a visible region of 400 nm or more, it efficiently absorbs light transmitted through the charge transporting compound having a radical polymerizable functional group and generates radicals. In addition, since the acylphosphine oxide compound has a light bleaching effect that eliminates its own light absorption upon decomposition, it is excellent in internal curability. For this reason, it is hardly affected by light irradiation unevenness in the surface direction and light transmission unevenness inside the film, and uniform curing proceeds instantaneously in the film surface direction and film thickness direction. Therefore, the unevenness | corrugation resulting from the difference in the hardness and volume shrinkage of a hardening part and an unhardened part does not generate | occur | produce, and the crosslinked film excellent in smoothness is obtained. In addition, the reason for not causing deterioration of electrical characteristics such as increase in residual potential is that it has a tertiary amino group such as a dialkylamino group or a morpholino group used as a structure for sensitizing radical generation of a photopolymerization initiator. Due to not. Further, it is considered that the decomposition of light itself disappears due to the decomposition, so that the decomposition progresses to the inside of the film and is taken into the polymerized structure as an electrically inactive group.

Next, the constituent material of the surface layer coating solution of the present invention will be described.
The trifunctional or higher functional radical polymerizable monomer having no charge transporting property used in the present invention is a hole transporting structure such as triarylamine, hydrazone, pyrazoline, carbazole, such as condensed polycyclic quinone, diphenoquinone, cyano group. And a monomer having no electron transport structure such as an electron-withdrawing aromatic ring having a nitro group and having three or more radical polymerizable functional groups. The radical polymerizable functional group may be any group as long as it has a carbon-carbon double bond and is capable of radical polymerization.
Examples of these radical polymerizable functional groups include 1-substituted ethylene functional groups and 1,1-substituted ethylene functional groups shown below.
(1) Examples of the 1-substituted ethylene functional group include functional groups represented by the following formulas.

〔ただし、式中、Ｘ_１は、置換基を有していてもよいフェニレン基、ナフチレン基等のアリーレン基、置換基を有していてもよいアルケニレン基、−ＣＯ−基、−ＣＯＯ−基、−ＣＯＮ（Ｒ_１０）−基（Ｒ_１０は、水素、メチル基、エチル基等のアルキル基、ベンジル基、ナフチルメチル基、フェネチル基等のアラルキル基、フェニル基、ナフチル基等のアリール基を表す。）、または−Ｓ−基を表わす。〕
これらの置換基を具体的に例示すると、ビニル基、スチリル基、２−メチル−１，３−ブタジエニル基、ビニルカルボニル基、アクリロイルオキシ基、アクリロイルアミド基、ビニルチオエーテル基等が挙げられる。
（２）１，１−置換エチレン官能基としては、例えば以下の式で表わされる官能基が挙げられる。

[Wherein, X ₁ is an arylene group such as a phenylene group or a naphthylene group optionally having a substituent, an alkenylene group optionally having a substituent, a —CO— group, a —COO— group. , —CON (R ₁₀ ) — group (R ₁₀ represents an alkyl group such as hydrogen, methyl group or ethyl group, an aralkyl group such as benzyl group, naphthylmethyl group or phenethyl group, or an aryl group such as phenyl group or naphthyl group. Or -S- group. ]
Specific examples of these substituents include a vinyl group, a styryl group, a 2-methyl-1,3-butadienyl group, a vinylcarbonyl group, an acryloyloxy group, an acryloylamide group, and a vinyl thioether group.
(2) Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following formulas.

〔ただし、式中、Ｙは、置換基を有していてもよいアルキル基、置換基を有していてもよいアラルキル基、置換基を有していてもよいフェニル基、ナフチル基等のアリール基、ハロゲン原子、シアノ基、ニトロ基、メトキシ基あるいはエトキシ基等のアルコキシ基、−ＣＯＯＲ_１１基（Ｒ_１１は、水素原子、置換基を有していてもよいメチル基、エチル基等のアルキル基、置換基を有していてもよいベンジル、フェネチル基等のアラルキル基、置換基を有していてもよいフェニル基、ナフチル基等のアリール基を表す。）、または−ＣＯＮＲ_１２Ｒ_１３（Ｒ_１２およびＲ_１３は、水素原子、置換基を有していてもよいメチル基、エチル基等のアルキル基、置換基を有していてもよいベンジル基、ナフチルメチル基、あるいはフェネチル基等のアラルキル基、または置換基を有していてもよいフェニル基、ナフチル基等のアリール基を表わし、互いに同一または異なっていてもよい。）、
また、Ｘ_２は上記式１０のＸ_１と同一の置換基及び単結合、アルキレン基を表わす。ただし、Ｙ，Ｘ_２の少なくとも何れか一方がオキシカルボニル基、シアノ基、アルケニレン基、及び芳香族環である。〕

[Wherein Y represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a phenyl group which may have a substituent, an aryl such as a naphthyl group, etc. Group, halogen atom, cyano group, nitro group, alkoxy group such as methoxy group or ethoxy group, -COOR ₁₁ group (R ₁₁ is a hydrogen atom, an alkyl such as an optionally substituted methyl group or ethyl group) A benzyl group optionally having a substituent, an aralkyl group such as a phenethyl group, an aryl group such as a phenyl group or a naphthyl group optionally having a substituent), or -CONR ₁₂ R ₁₃ ( R ₁₂ and R ₁₃ are hydrogen atom, an optionally substituted methyl group, an alkyl group such as ethyl group, optionally substituted benzyl group, naphthylmethyl group or phenethyl, Aralkyl or phenyl group which may have a substituent, etc., an aryl group such as a naphthyl group, which may be the same or different from each other.)
X ₂ represents the same substituent, single bond, and alkylene group as X _{1 in the} formula 10. However, Y, at least one oxycarbonyl group in X _2, a cyano group, an alkenylene group, and an aromatic ring. ]

Specific examples of these substituents include an α-acryloyloxy chloride group, a methacryloyloxy group, an α-cyanoethylene group, an α-cyanoacryloyloxy group, an α-cyanophenylene group, and a methacryloylamino group.
In addition, examples of the substituent further substituted with the substituent for X ₁ , X ₂ , and Y include, for example, a halogen atom, a nitro group, a cyano group, a methyl group, an alkyl group such as an ethyl group, a methoxy group, an ethoxy group, and the like And an aryloxy group such as a phenoxy group, an aryl group such as a phenyl group and a naphthyl group, and an aralkyl group such as a benzyl group and a phenethyl group.
Among these radically polymerizable functional groups, acryloyloxy group and methacryloyloxy group are particularly useful. For example, a compound having three or more acryloyloxy groups is a compound having three or more hydroxyl groups in the molecule and an acrylic group. It can be obtained by using an acid (salt), an acrylic acid halide, or an acrylic ester to cause an ester reaction or a transesterification reaction. A compound having three or more methacryloyloxy groups can be obtained in the same manner. Further, the radical polymerizable functional groups in the monomer having three or more radical polymerizable functional groups may be the same or different.

Specific examples of the trifunctional or higher functional radical polymerizable monomer having no charge transporting structure include the following, but are not limited to these compounds.
That is, examples of the radical polymerizable monomer used in the present invention include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, trimethylolpropane alkylene-modified triacrylate, trimethylolpropane ethyleneoxy-modified (hereinafter referred to as EO modification). ) Triacrylate, trimethylolpropane propyleneoxy modified (hereinafter PO modified) triacrylate, trimethylolpropane caprolactone modified triacrylate, trimethylolpropane alkylene modified trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate Glycerol epichlorohydrin modified (ECH modified) tria Relate, glycerol EO-modified triacrylate, glycerol PO-modified triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol caprolactone-modified hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkylated di Pentaerythritol pentaacrylate, alkylated dipentaerythritol tetraacrylate, alkylated dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, phosphoric acid EO-modified triacrylate, 2, 2, 5, 5 , -Tetrahydroxymethylcyclopentanone tetraacrylate And the like, which can be used in combination either alone or in combination.

  The trifunctional or higher functional radical polymerizable monomer having no charge transport structure used in the present invention is a ratio of molecular weight to the number of functional groups in the monomer in order to form a dense crosslink in the cross-linked surface layer. (Molecular weight / functional group number) is preferably 250 or less. When this ratio is larger than 250, the crosslinked surface layer is soft and wear resistance is somewhat lowered. Therefore, among the monomers exemplified above, monomers having a modifying group such as EO, PO, and caprolactone are extremely long. It is not preferable to use one having a modifying group alone. In addition, the proportion of the trifunctional or higher functional radical polymerizable monomer having no charge transporting structure used for the surface layer is 20 to 80% by weight, preferably 30 to 70% by weight, based on the total amount of the crosslinked surface layer. The content in the coating liquid solid content is adjusted. When the monomer component is less than 20% by weight, the three-dimensional cross-linking density of the cross-linked surface layer is small, and a drastic improvement in wear resistance is not achieved as compared with the case of using a conventional thermoplastic binder resin. On the other hand, if it exceeds 80% by weight, the content of the charge transporting compound is lowered, and the electrical characteristics are deteriorated. Since the required wear resistance and electrical characteristics differ depending on the process used, it cannot be said unconditionally, but considering the balance of both characteristics, the range of 30 to 70% by weight is most preferable.

  The charge transporting compound having a radical polymerizable functional group used in the present invention is a hole transporting structure such as triarylamine, hydrazone, pyrazoline, carbazole, such as condensed polycyclic quinone, diphenoquinone, cyano group or nitro group. A compound having an electron transport structure such as an electron-withdrawing aromatic ring having a radical polymerizable functional group. Examples of the radical polymerizable functional group include those shown in the above radical polymerizable monomer, and acryloyloxy group and methacryloyloxy group are particularly useful. The number of radically polymerizable functional groups in one molecule may be one or more, but it is easy to obtain a smooth surface property by suppressing the internal stress of the crosslinked surface layer, and in order to maintain good electrical characteristics. It is preferable that the number of radical polymerizable functional groups is one. In the present invention, a cross-linked surface layer having smooth and good electrical characteristics is achieved by using an acylphosphine oxide compound as a photopolymerization initiator. However, the charge transporting compound has two or more radical polymerizable functional groups. In some cases, the margin may decrease due to large distortion due to the bulky hole-transporting compound being fixed in the cross-linking by a plurality of bonds, and unevenness, cracks, film peeling may occur due to the charge-transporting structure and the number of functional groups. May happen. In addition, the intermediate structure (cation radical) at the time of charge transport cannot be stably maintained due to the large strain, and the sensitivity is lowered and the residual potential is easily increased due to charge trapping. As the charge transporting structure of the charge transporting compound having a radical polymerizable functional group, a triarylamine structure is preferable because of its high mobility, and among them, a compound represented by the following general formula (1) or (2) is used. If so, electrical characteristics such as sensitivity and residual potential are favorably sustained.

〔式中、Ｒ_１は水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基、シアノ基、ニトロ基、アルコキシ基、−ＣＯＯＲ_７（Ｒ_７は水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基又は置換基を有してもよいアリール基を表す。）、ハロゲン化カルボニル基若しくはＣＯＮＲ_８Ｒ_９（Ｒ_８及びＲ_９は水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基又は置換基を有してもよいアリール基を示し、互いに同一であっても異なっていてもよい。）を表わし、Ａｒ_１、Ａｒ_２は置換もしくは未置換のアリーレン基を表わし、同一であっても異なってもよい。Ａｒ_３、Ａｒ_４は置換もしくは未置換のアリール基を表わし、同一であっても異なってもよい。Ｘは単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル２価基、酸素原子、硫黄原子、ビニレン基を表わす。Ｚは置換もしくは無置換のアルキレン基、置換もしくは無置換のアルキレンエーテル２価基、アルキレンオキシカルボニル２価基を表わす。ｍ、ｎは０〜３の整数を表わす。〕

[Wherein, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a cyano group, a nitro group, A group, an alkoxy group, —COOR ₇ (R ₇ represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent. ), A halogenated carbonyl group or CONR ₈ R ₉ (R ₈ and R ₉ have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an aryl group which may be the same or different, and Ar ₁ and Ar ₂ represent a substituted or unsubstituted arylene group, which may be the same or different. . Ar ₃ and Ar ₄ represent a substituted or unsubstituted aryl group, and may be the same or different. X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether divalent group, an oxygen atom, a sulfur atom, or a vinylene group. Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether divalent group, or an alkyleneoxycarbonyl divalent group. m and n represent an integer of 0 to 3. ]

Specific examples of general formulas (1) and (2) are shown below.
In the general formulas (1) and (2), in the substituent of R ₁ , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the aryl group include a phenyl group and a naphthyl group. The aralkyl group includes a benzyl group, a phenethyl group, and a naphthylmethyl group, and the alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, and the like. These include a halogen atom, a nitro group, a cyano group, and a methyl group. Substituted with an alkyl group such as an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, an aryl group such as a phenyl group or a naphthyl group, an aralkyl group such as a benzyl group or a phenethyl group, etc. May be.
Of the substituents for R ₁ , particularly preferred are a hydrogen atom and a methyl group.
Substituted or unsubstituted Ar ₃ and Ar ₄ are aryl groups, and examples of the aryl group include condensed polycyclic hydrocarbon groups, non-fused cyclic hydrocarbon groups, and heterocyclic groups.
The condensed polycyclic hydrocarbon group preferably has 18 or less carbon atoms forming a ring, for example, a pentanyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group, an as (asym) -Indacenyl group, s (sym) -indacenyl group, fluorenyl group, acenaphthylenyl group, preadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrylenyl group, aceanthrylenyl group , Triphenylyl group, pyrenyl group, chrycenyl group, naphthacenyl group and the like.

  Examples of the non-fused cyclic hydrocarbon group include monovalent groups of monocyclic hydrocarbon compounds such as benzene, diphenyl ether, polyethylene diphenyl ether, diphenyl thioether and diphenyl sulfone, or biphenyl, polyphenyl, diphenylalkane, diphenylalkene, diphenylalkyne, Monovalent groups of non-condensed polycyclic hydrocarbon compounds such as triphenylmethane, distyrylbenzene, 1,1-diphenylcycloalkane, polyphenylalkane, and polyphenylalkene, or ring assemblies such as 9,9-diphenylfluorene And monovalent groups of hydrocarbon compounds.

Examples of the heterocyclic group include monovalent groups such as carbazole, dibenzofuran, dibenzothiophene, oxadiazole, and thiadiazole.
The aryl group represented by Ar ₃ or Ar ₄ may have a substituent as shown below, for example.
(1) Halogen atom, cyano group, nitro group and the like.
(2) an alkyl group;
_Preferably, C 1 _{-C 12} especially _C 1 -C _8, more preferably a straight or branched alkyl group of _C 1 -C _4, in the alkyl group a fluorine atom, a hydroxyl group, a cyano group, C ₁ -C ₄ alkoxy group which may have a phenyl group or a halogen _atom, C 1 -C ₄ alkyl or _C 1 -C ₄ phenyl group substituted with an alkoxy group. Specifically, methyl group, ethyl group, n-butyl group, i-propyl group, t-butyl group, s-butyl group, n-propyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-ethoxyethyl Group, 2-cyanoethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-phenylbenzyl group and the like.
(3) an alkoxy group (—OR ₂ );
R ₂ represents an alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, benzyloxy group And a trifluoromethoxy group.
(4) aryloxy group;
Examples of the aryl group include a phenyl group and a naphthyl group. It _may contain an alkoxy group having C 1 -C _4, alkyl group, or a halogen atom C 1 -C ₄ as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methoxyphenoxy group, and a 4-methylphenoxy group.
(5) an alkyl mercapto group or an aryl mercapto group;
Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.
(6) Substituent represented by the following formula

（式中、Ｒ_３及びＲ_４は各々独立に水素原子、前記（２）で定義したアルキル基、またはアリール基を表わす。アリール基としては、例えばフェニル基、ビフェニル基又はナフチル基が挙げられ、これらはＣ_１〜Ｃ_４のアルコキシ基、Ｃ_１〜Ｃ_４のアルキル基またはハロゲン原子を置換基として含有してもよい。Ｒ_３及びＲ_４は共同で環を形成してもよい）
具体的には、アミノ基、ジエチルアミノ基、Ｎ−メチル−Ｎ−フェニルアミノ基、Ｎ，Ｎ−ジフェニルアミノ基、Ｎ，Ｎ−ジ（トリール）アミノ基、ジベンジルアミノ基、ピペリジノ基、モルホリノ基、ピロリジノ基等が挙げられる。
（７）メチレンジオキシ基、又はメチレンジチオ基等のアルキレンジオキシ基又はアルキレンジチオ基
（８）置換又は無置換のスチリル基、置換又は無置換のβ−フェニルスチリル基、ジフェニルアミノフェニル基、ジトリルアミノフェニル基等。

(In the formula, R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group defined in (2) above, or an aryl group. Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. these may form a ring _C 1 -C ₄ alkoxy _groups, C 1 -C a alkyl group or a halogen atom ₄ which may contain as substituents .R ₃ and _{R 4} jointly)
Specifically, amino group, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (tolyl) amino group, dibenzylamino group, piperidino group, morpholino group And pyrrolidino group.
(7) alkylenedioxy group or alkylenedithio group such as methylenedioxy group or methylenedithio group (8) substituted or unsubstituted styryl group, substituted or unsubstituted β-phenylstyryl group, diphenylaminophenyl group, di A tolylaminophenyl group and the like.

On the other hand, the arylene group represented by Ar ₁ and Ar ₂ is a divalent group derived from the aryl group represented by Ar ₃ and Ar ₄ .

X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group.
The substituted or unsubstituted alkylene group is a C ₁ -C ₁₂ , preferably C ₁ -C ₈ , more preferably C ₁ -C ₄ linear or branched alkylene group, and these alkylene groups include a fluorine atom, a hydroxyl group, a cyano _group, an alkoxy group of C 1 -C _4, a phenyl group or a halogen _atom, a phenyl group substituted with an alkyl group or a _C 1 -C ₄ alkoxy group C 1 -C ₄ It may be. Specifically, methylene group, ethylene group, n-butylene group, i-propylene group, t-butylene group, s-butylene group, n-propylene group, trifluoromethylene group, 2-hydroxyethylene group, 2-ethoxyethylene Group, 2-cyanoethylene group, 2-methoxyethylene group, benzylidene group, phenylethylene group, 4-chlorophenylethylene group, 4-methylphenylethylene group, 4-biphenylethylene group and the like.
The substituted or unsubstituted cycloalkylene _group, a cyclic alkylene group of C 5 -C _7, these are the cyclic alkylene group fluorine atom, a hydroxyl _group, an alkyl group of C 1 -C _4, a C 1 -C ₄ It may have an alkoxy group. Specific examples include a cyclohexylidene group, a cyclohexylene group, and a 3,3-dimethylcyclohexylidene group.
Examples of the substituted or unsubstituted alkylene ether divalent group include an alkyleneoxy divalent group such as an ethyleneoxy group and a propyleneoxy group, an alkylenedioxy divalent group derived from ethylene glycol, propylene glycol, and the like, or diethylene glycol, tetra Examples include di- or poly (oxyalkylene) oxy divalent groups derived from ethylene glycol, tripropylene glycol, etc. The alkylene group of the alkylene ether divalent group has a substituent such as a hydroxyl group, a methyl group, or an ethyl group. You may have.
The vinylene group is

で表わされ、
〔式中、Ｒ_５は水素、アルキル基（前記（２）で定義されるアルキル基と同じ）、アリール基（前記Ａｒ_３、Ａｒ_４で表わされるアリール基と同じ）、ａは１または２、ｂは１〜３を表わす。〕

Represented by
[Wherein, R ₅ is hydrogen, an alkyl group (same as the alkyl group defined in (2) above), an aryl group (same as the aryl group represented by Ar ₃ or Ar ₄ above), a is 1 or 2, b represents 1-3. ]

Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether divalent group, or an alkyleneoxycarbonyl group divalent.
Examples of the substituted or unsubstituted alkylene group include the same alkylene groups as those described above for X.
Examples of the substituted or unsubstituted alkylene ether divalent group include the alkylene ether divalent group of X.
Examples of the alkyleneoxycarbonyl divalent group include a caprolactone-modified divalent group.

  Further, the charge transporting compound having a radical polymerizable functional group of the present invention is more preferably a compound having the structure of the following general formula (3).

（式中、ｏ、ｐ、ｑはそれぞれ０又は１の整数、Ｒａは水素原子、メチル基を表わし、Ｒｂ、Ｒｃは水素原子以外の置換基で炭素数１〜６のアルキル基を表わし、複数の場合は異なっても良い。ｓ、ｔは０〜３の整数を表わす。Ｚａは単結合、メチレン基、エチレン基、

(Wherein, o, p and q are each an integer of 0 or 1, Ra represents a hydrogen atom or a methyl group, Rb and Rc represent a substituent other than a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, And s and t each represents an integer of 0 to 3. Za is a single bond, a methylene group, an ethylene group,

を表わす。）
上記一般式で表わされる化合物としては、Ｒｂ、Ｒｃの置換基として、特にメチル基、エチル基である化合物が好ましい。

Represents. )
As the compound represented by the above general formula, a compound having a methyl group or an ethyl group as a substituent for Rb and Rc is particularly preferable.

The charge transporting compound having the radically polymerizable functional group represented by the general formulas (1) and (2), particularly (3) used in the present invention is polymerized because the double bond between carbon and carbon is opened on both sides. In a polymer that does not become a terminal structure, is incorporated in a chain polymer, and is crosslinked by polymerization with a radically polymerizable monomer having three or more functions, it exists in the main chain of the polymer, and the main chain- Present in the cross-linked chain between the main chains (this cross-linked chain includes an inter-molecular cross-linked chain between one polymer and another polymer, a site with a main chain folded in one polymer, and a main chain. There are intramolecular cross-linked chains that are cross-linked with other sites derived from the polymerized monomer at positions away from this in the chain), but they are also present in the cross-linked chain even if they are present in the main chain Even if the triarylamine structure suspended from the chain moiety is released from the nitrogen atom, It has at least three aryl groups arranged in the shape direction and is bulky, but is not directly bonded to the chain part, but is suspended from the chain part via a carbonyl group etc. Since they are fixed in a certain state, these triarylamine structures can be arranged spatially adjacent to each other in the polymer, so there is little structural distortion in the molecule, and the surface layer of the electrophotographic photoreceptor In this case, it is presumed that an intramolecular structure that is relatively free from interruption of the charge transport pathway can be adopted.
Specific examples of the charge transporting compound having a radical polymerizable functional group of the present invention are shown below, but are not limited to compounds having these structures.

  The charge transporting compound having a radical polymerizable functional group used in the present invention is important for imparting the charge transport performance of the crosslinked surface layer, and this component is 20 to 80% by weight based on the total amount of the crosslinked surface layer, Preferably, the content of the coating liquid component is adjusted to 30 to 70% by weight. When this component is less than 20% by weight, the charge transport performance of the crosslinked surface layer cannot be maintained sufficiently, and deterioration of electrical characteristics such as a decrease in sensitivity and an increase in residual potential appears with repeated use. On the other hand, if it exceeds 80% by weight, the content of the trifunctional monomer having no charge transport structure is lowered, and the crosslink density is lowered, so that high wear resistance is not exhibited. The required electrical characteristics and wear resistance differ depending on the process to be used, so it cannot be said unconditionally, but considering the balance of both characteristics, the range of 30 to 70% by weight is most preferable.

Next, the acylphosphine oxide compound used as a photopolymerization initiator in the present invention will be described.
The acylphosphine oxide compound used in the present invention is represented by general formula (4) or general formula (5).

（式中、Ｒ_２１〜Ｒ_２３はそれぞれ独立してアルキル基、アリール基、アラルキル基、アルケニル基またはアルキニル基を示す。）
（式中、Ｒ_２２およびＲ_２３は、それぞれ独立して、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、又は複素環基を表し、Ｒ_２１はアルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基、若しくは複素環基を表す。）
上記アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アルコキシ基としては炭素数１〜３０の置換基が好ましく、アリール基としては、フェニル基、ナフチル基、あるいはビフェニル基等が、アリールオキシ基としては、フェノキシ基、ナフトキシ基等が、また複素環基としては、ピリジル基、フリル基、チエニル基、イミダゾリル基等がそれぞれ挙げられる。
上記Ｒ_２１〜_２３のアルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基又は複素環基はそれぞれ置換されていてもよく、該置換基としては、例えばアルキル基、、アリール基、アルコキシ基、アリールオキシ基、ヒドロキシ基、ハロゲン原子、ニトロ基、シアノ基、アルキルスルホニル基、アリールスルホニル基、アルキルチオ基、アリールチオ基、アルキル置換アミノ基、アシルアミノ基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基等が挙げられる。

_(Wherein, R 21 _{to R 23} independently represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group or alkynyl group.)
(Wherein R ₂₂ and R ₂₃ each independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R ₂₁ represents an alkyl group, an alkenyl group, or an alkynyl group) Represents a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group.)
The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and alkoxy group are preferably a substituent having 1 to 30 carbon atoms, and the aryl group includes a phenyl group, a naphthyl group, a biphenyl group, and the like as an aryloxy group. Includes a phenoxy group, a naphthoxy group, and the like, and examples of the heterocyclic group include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, and the like.
The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group or heterocyclic group of R ₂₁ to ₂₃ may be substituted, and examples of the substituent include an alkyl group. , Aryl group, alkoxy group, aryloxy group, hydroxy group, halogen atom, nitro group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkyl-substituted amino group, acylamino group, carbamoyl group, alkoxy A carbonyl group, an aryloxycarbonyl group, an acyl group, etc. are mentioned.

（式中、Ｒ_２４〜Ｒ_２６はそれぞれ独立してアルキル基、アリール基、アラルキル基、アルケニル基、アルキニル基または複素環基を示す。）
（式中、Ｒ_２４及びＲ_２６は、それぞれ独立してアルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基又は複素環基を表し、Ｒ_２５は、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アラルキル基、アリール基、又は複素環基を表す。）
上記アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アルコキシ基としては炭素数１〜３０の置換基が好ましく、アリール基としては、フェニル基、ナフチル基あるいはビフェニル基等が、アリールオキシ基としては、フェノキシ基、ナフトキシ基等が、また、複素環基としては、ピリジル基、フリル基、チエニル基、イミダゾリル基等がそれぞれ挙げられる。
上記アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基又は複素環基は、それぞれ置換基を有していてもよく、この置換基としては、上記Ｒ_２１〜_２３のアルキル基、アルケニル基、アルキニル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基又は複素環基の置換基として示したものが挙げられる。

(Wherein R _{24 to} R ₂₆ each independently represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group or a heterocyclic group)
(Wherein R ₂₄ and R ₂₆ each independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group or a heterocyclic group, and R ₂₅ represents an alkyl group) Represents an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a heterocyclic group.)
As the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and alkoxy group, a substituent having 1 to 30 carbon atoms is preferable. As the aryl group, a phenyl group, a naphthyl group, a biphenyl group, etc. , A phenoxy group, a naphthoxy group, and the like, and examples of the heterocyclic group include a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, and the like.
The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group or heterocyclic group each may have a substituent, and examples of the substituent include R ₂₁ to Examples of the substituents for the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group or heterocyclic group of ₂₃ .

  These polymerization initiators are more sensitive in the longer wavelength region than the UV initiators used in the past (visible light region of 400 nm or more), have excellent light transmission, and are cleaved by light irradiation. Since an acyl radical and a phosphino radical are generated, the polymerization initiation efficiency is higher than that of conventionally used UV initiators.

  Specific examples of the bisacylphosphine oxide compound of the general formula (4) used in the present invention include bis (2,6-dichlorobenzoyl) phenylphosphine oxide and bis (2,6-dichlorobenzoyl) -2,5 dimethyl. Phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-biphenylphosphine oxide, bis (2,6-dichlorobenzoyl)- 4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) ) -4-Chlorophenylphosphine oxa Bis (2,6-dichlorobenzoyl) -2,2-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -dodecylphosphine oxide, bis (2,6-dichlorobenzoyl) -4- Octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, Bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-phenylphosphine oxide, bis (2-methyl) -1-naphthoyl) -4-biphenylphosphine oxa Bis (2-methyl-1-naphthoyl) -4-ethoxybiphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2-ethoxybiphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4 -Propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-methoxyphenylphosphine oxide, bis (2,6- And dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

Specific examples of the acylphosphine oxide compound of the general formula (5) used in the present invention include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-diphenylbenzoyl-diphenylphosphine oxide, and 2,6-dimethoxy. Benzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2-phenyl -6-methylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,8-dimethylnaphthalene-1-carbonyl-diphenylphosphine oxy 1,3-dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-di And chlorobenzoyl-phenylphosphinic acid methyl ester.
Among the acylphosphine compounds used as the photopolymerization initiator of the present invention, P-1, P-2 and P-3 represented by the following structural formula are particularly useful.

  The acylphosphine oxide compound used in the present invention can be used alone or in admixture of two or more, and its content is 0 with respect to 100 parts by weight of the total content having radical polymerizability in the solid content of the coating liquid. 0.5 to 40 parts by weight, preferably 0.5 to 10 parts by weight.

The crosslinked surface layer of the present invention was cured using an acyl phosphine oxide compound using at least a trifunctional or higher radical polymerizable monomer having no charge transport structure and a charge transport compound having a radical polymerizable functional group as a photopolymerization initiator. In addition to this, monofunctional and bifunctional radically polymerizable monomers and radical polymerization for the purpose of imparting functions such as viscosity adjustment during coating, stress relaxation of the crosslinked surface layer, lower surface energy and reduced friction coefficient, etc. Can be used in combination. Known radical polymerizable monomers and oligomers can be used.
Examples of the monofunctional radical monomer include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-ethylhexyl carbitol acrylate, 3-methoxybutyl acrylate, benzyl acrylate, and cyclohexyl acrylate. , Isoamyl acrylate, isobutyl acrylate, methoxytriethylene glycol acrylate, phenoxytetraethylene glycol acrylate, cetyl acrylate, isostearyl acrylate, stearyl acrylate, styrene monomer, and the like.
Examples of the bifunctional radical polymerizable monomer include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1, Examples include 6-hexanediol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, bisphenol A-EO modified diacrylate, bisphenol F-EO modified diacrylate, neopentyl glycol diacrylate, and the like.
Examples of the functional monomer include those substituted with a fluorine atom such as octafluoropentyl acrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluoroisononylethyl acrylate, No. 60503, JP-B-6-45770, siloxane repeating units: 20-70 acryloyl polydimethylsiloxane ethyl, methacryloyl polydimethylsiloxane ethyl, acryloyl polydimethylsiloxane propyl, acryloyl polydimethylsiloxane butyl, diacryloyl polydimethylsiloxane Examples include vinyl monomers having a polysiloxane group such as diethyl, acrylates and methacrylates.
Examples of the radical polymerizable oligomer include epoxy acrylate, urethane acrylate, and polyester acrylate oligomers. However, when a large amount of monofunctional and bifunctional radically polymerizable monomers and radically polymerizable oligomers are contained, the three-dimensional cross-linking density of the cross-linked surface layer is substantially reduced, resulting in a decrease in wear resistance. For this reason, the content of these monomers and oligomers is limited to 50 parts by weight or less, preferably 30 parts by weight or less, with respect to 100 parts by weight of the tri- or higher functional radical polymerizable monomer.

In the present invention, an acylphosphine oxide compound is used as a photopolymerization initiator, but other photopolymerization initiators and photopolymerization accelerators may be used alone or in combination.
Examples of the photopolymerization initiator include diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Acetophenone-based or ketal-based photopolymerization initiators such as methyl-2-morpholino (4-methylthiophenyl) propan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether Benzoin ether photopolymerization initiators such as benzoin isopropyl ether, benzophenone, 4-hydroxybenzophenone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoylphenyl ether, acrylated benzophenone, Benzophenone photopolymerization initiators such as 1,4-benzoylbenzene, thioxanthones such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Examples of photopolymerization initiators and other photopolymerization initiators include ethyl anthraquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoic acid. Phenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, methylphenylglyoxyester, 9,10 -Phenanthrene, an acridine type compound, a triazine type compound, an imidazole type compound is mentioned.

In the present invention, as the photopolymerization initiator, an acylphosphine oxide compound alone or a combination of other photopolymerization initiators as described above is used, and commercially available photopolymerization initiators are used as these. it can. Specifically, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur-1173, manufactured by Ciba Specialty Chemicals) and bis (2,6-dimethoxybenzoyl-2) , 4,4-trimethylpentylphosphine oxide (Ciba Specialty Chemicals Co., Ltd.) mixed at a ratio of 75% / 25% "Irgacure 1700" (Ciba Specialty Chemicals Co., Ltd.), 1 -Hydroxy-cyclohexyl-phenyl ketone (trade name: “Irgacure 184”, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (Ciba Specialty) 75% / 25% for Tea Chemicals) Trade name “Irgacure 1800” (manufactured by Ciba Specialty Chemicals) mixed with 50% / 50% trade name “Irgacure 1850” (manufactured by Ciba Specialty Chemicals), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name “Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd.”), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Lucirin TPO BASF 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxy Oxide (trade name: Lu There is a trade name: “Darocur 4265” in which cirin TPO BASF Co., Ltd.) is mixed at a ratio of 50% / 50%.
Moreover, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples thereof include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4′-dimethylaminobenzophenone, and the like. These contents are 0.5 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total content having radical polymerizability.

  Furthermore, the coating liquid of the present invention can contain additives such as various plasticizers (for the purpose of stress relaxation and adhesion improvement), leveling agents, and low molecular charge transport materials having no radical reactivity as required. As these additives, known additives can be used, and as plasticizers, those used in general resins such as dibutyl phthalate and dioctyl phthalate can be used, and the amount used is the total solid content of the coating liquid. To 20% by weight or less, preferably 10% or less. As leveling agents, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the side chain can be used, and the amount used is based on the total solid content of the coating liquid. 3% by weight or less is appropriate.

  The crosslinked surface layer of the present invention is a coating containing at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure, a charge transportable compound having a radical polymerizable functional group, and an acylphosphine oxide compound as a photopolymerization initiator. It is formed by applying a liquid and photocuring. When the radically polymerizable monomer is a liquid, such a coating liquid can be applied by dissolving other components in the liquid, but if necessary, it is diluted with a solvent and applied. Solvents used at this time include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran, dioxane and propyl ether. And ethers such as dichloromethane, dichloroethane, trichloroethane, and chlorobenzene, aromatics such as benzene, toluene, and xylene, and cellosolves such as methyl cellosolve, ethyl cellosolve, and cellosolve acetate. These solvents may be used alone or in combination of two or more. The dilution ratio with the solvent varies depending on the solubility of the composition, the coating method, and the target film thickness, and is arbitrary. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.

In this invention, after apply | coating this coating liquid, hardening reaction is advanced by irradiating light energy, and a crosslinked surface layer is formed. As the energy of light used at this time, a UV irradiation light source such as a high-pressure mercury lamp or a metal halide lamp having an emission wavelength mainly in ultraviolet light can be used. It is also possible to select a longer wavelength light source. Irradiation light amount is 50 mW / cm ² or more, preferably 1000 mW / cm ² or less, it takes time for the curing reaction is less than 50 mW / cm ^2. If it is higher than 1000 mW / cm ² , the reaction progresses unevenly, and the unevenness of the cross-linked surface layer and the deterioration of the electrical characteristics become severe.

  Since the film thickness of the crosslinked surface layer of the present invention varies depending on the layer structure of the photoreceptor in which the crosslinked surface layer is used, it will be described later together with the layer structure.

Hereinafter, the present invention will be described according to the layer structure.
<About the layer structure of the electrophotographic photoreceptor>
The electrophotographic photosensitive member used in the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing an electrophotographic photosensitive member of the present invention, in which a single layer structure in which a photosensitive layer (33) having a charge generating function and a charge transporting function is provided on a conductive support (31). This is a photoreceptor. FIG. 1A shows the case where the cross-linked surface layer is the entire photosensitive layer, and FIG. 1-B shows the case where the cross-linked surface layer is the surface portion of the photosensitive layer.
FIG. 2 shows a photoreceptor having a laminated structure in which a charge generation layer (35) having a charge generation function and a charge transport layer (37) having a charge transport material function are laminated on a conductive support (31). is there. FIG. 2-A shows the case where the cross-linked surface layer is the entire charge transport layer, and FIG. 2-B shows the case where the cross-linked surface layer is the surface portion of the charge transport layer.

<About conductive support>
As the conductive support (31), a material having a volume resistance of 10 ¹⁰ Ω · cm or less, for example, a metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation Metal oxide such as indium is deposited or sputtered to form film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. After conversion, a tube that has been subjected to surface treatment such as cutting, superfinishing, or polishing can be used. Further, an endless nickel belt and an endless stainless steel belt disclosed in Japanese Patent Application Laid-Open No. 52-36016 can be used as the conductive support (31).
In addition, the conductive support dispersed in a suitable binder resin and coated on the support can also be used as the conductive support (31) of the present invention.

  Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. Can be mentioned. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Further, a heat shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, polytetrafluoroethylene-based fluororesin on a suitable cylindrical substrate. Those provided with a conductive layer can be used favorably as the conductive support (31) of the present invention.

<About photosensitive layer>
Next, the photosensitive layer will be described. The photosensitive layer may have a laminated structure or a single layer structure.
In the case of a laminated structure, the photosensitive layer is composed of a charge generation layer having a charge generation function and a charge transport layer having a charge transport function. In the case of a single layer structure, the photosensitive layer is a layer having a charge generation function and a charge transport function at the same time.
Hereinafter, each of the photosensitive layer having a laminated structure and the photosensitive layer having a single layer structure will be described.

<Photosensitive layer comprising a charge generation layer and a charge transport layer>
(Charge generation layer)
The charge generation layer (35) is a layer mainly composed of a charge generation material having a charge generation function, and a binder resin can be used in combination as necessary. As the charge generation material, inorganic materials and organic materials can be used.
Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms, phosphorus atoms, or the like are preferably used.
On the other hand, a known material can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having carbazole skeleton, azo pigments having triphenylamine skeleton, azo pigments having diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having a fluorenone skeleton, azo pigments having an oxadiazole skeleton, azo pigments having a bis-stilbene skeleton, azo pigments having a distyryl oxadiazole skeleton, azo pigments having a distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, Goido based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  The binder resin used as necessary for the charge generation layer (35) is polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-. Examples thereof include vinyl carbazole and polyacrylamide. These binder resins can be used alone or as a mixture of two or more. In addition to the binder resin described above as a binder resin for the charge generation layer, a polymer charge transport material having a charge transport function, such as an arylamine skeleton, benzidine skeleton, hydrazone skeleton, carbazole skeleton, stilbene skeleton, pyrazoline skeleton, etc. Polymer materials such as polycarbonate, polyester, polyurethane, polyether, polysiloxane, and acrylic resin, polymer materials having a polysilane skeleton, and the like can be used.

Specific examples of the former include JP-A-01-001728, JP-A-01-009964, JP-A-01-013061, JP-A-01-019049, JP-A-01-241559, Japanese Unexamined Patent Publication Nos. 04-011627, 04-175337, 04-183719, 04-2225014, 04-230767, 04-320420, 05 -232727, JP-A 05-310904, JP-A 06-234836, JP-A 06-234837, JP-A 06-234838, JP-A 06-234839, JP-A 06-234840. No. 1, JP-A 06-234841, JP-A 06-239049, Japanese Unexamined Patent Publication Nos. 06-236050, 06-236051, 06-295077, 07-0756374, 08-176293, 08-208820, 08 No. -21640, JP 08-253568, JP 08-269183, JP 09-062019, JP 09-043883, JP 09-71642, JP 09-87376. No. 1, JP-A 09-104746, JP 09-110974, JP 09-110976, JP 09-157378, JP 09-221544, JP 09-227669. JP 09-235367 A, JP 09-241369 A Charge transporting polymer materials described in JP 09-268226 A, JP 09-272735 A, JP 09-302084 A, JP 09-302085 A, JP 09-328539 A, etc. Can be mentioned.
Specific examples of the latter include polysilylene polymers described in, for example, JP-A No. 63-285552, JP-A No. 05-19497, JP-A No. 05-70595, JP-A No. 10-73944, and the like. Illustrated.

The charge generation layer (35) may contain a low molecular charge transport material.
Low molecular charge transport materials that can be used in combination with the charge generation layer (35) include hole transport materials and electron transport materials.
Examples of the electron transporting material include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and diphenoquinone derivatives. These electron transport materials can be used alone or as a mixture of two or more.

  Examples of the hole transporting material include the electron donating materials shown below and are used favorably. As hole transport materials, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triaryls Other known materials such as methane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and the like can be given. These hole transport materials can be used alone or as a mixture of two or more.

Methods for forming the charge generation layer (35) include a vacuum thin film preparation method and a casting method from a solution dispersion system.
As the former method, a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-described inorganic materials and organic materials can be satisfactorily formed.
In addition, in order to provide a charge generation layer by the casting method described later, if necessary, the inorganic or organic charge generation material together with a binder resin, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclohexane. Can be formed by dispersing with a ball mill, attritor, sand mill, bead mill, etc. using a solvent such as pentanone, anisole, xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, etc. . Moreover, leveling agents, such as a dimethyl silicone oil and a methylphenyl silicone oil, can be added as needed. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.
The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, preferably 0.05 to 2 μm.

(About charge transport layer)
The charge transport layer (37) is a layer having a charge transport function, and the crosslinked surface layer having the charge transport structure of the present invention is useful as a charge transport layer. When the cross-linked surface layer is the entire charge transport layer (37), the radical polymerizable composition (charge transport structure of the present invention is formed on the charge generation layer (35) as described in the above cross-linked surface layer preparation method. A coating liquid containing a radically polymerizable monomer and a charge transporting compound having a radically polymerizable functional group (the same applies hereinafter) is applied, and if necessary, after drying, a curing reaction is initiated by external energy to form a crosslinked surface layer. Is formed. At this time, the film thickness of the crosslinked surface layer is 10 to 30 μm, preferably 10 to 25 μm. If it is thinner than 10 μm, a sufficient charging potential cannot be maintained, and if it is thicker than 30 μm, peeling from the lower layer tends to occur due to volume shrinkage during curing.
When the cross-linked surface layer is formed on the surface portion of the charge transport layer (37) and the charge transport layer (37) has a laminated structure, the lower layer portion of the charge transport layer has a charge transport material having a charge transport function and a binder. The resin is dissolved or dispersed in a suitable solvent, and this is formed on the charge generation layer (35) by coating and drying, and a coating solution containing the radical polymerizable composition of the present invention is coated thereon. Then, it is crosslinked and cured by external energy.
As the charge transport material, the electron transport material, hole transport material and polymer charge transport material described in the charge generation layer (35) can be used. As described above, the use of the polymer charge transport material can reduce the solubility of the lower layer when the surface layer is applied, and is particularly useful.

As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin And thermoplastic or thermosetting resins such as phenol resins and alkyd resins.
The amount of the charge transport material is appropriately 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. However, when a polymer charge transport material is used, it can be used alone or in combination with a binder resin.
As the solvent used for coating the lower layer portion of the charge transport layer, the same solvent as that for the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin well is suitable. These solvents may be used alone or in combination of two or more. The lower layer portion of the charge transport layer can be formed by a coating method similar to that for the charge generation layer (35).

If necessary, a plasticizer and a leveling agent can be added.
As a plasticizer that can be used in combination with the lower layer portion of the charge transport layer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is 100 parts by weight of the binder resin. On the other hand, about 0 to 30 parts by weight is appropriate.
As a leveling agent that can be used in combination with the lower layer portion of the charge transport layer, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain are used. About 0 to 1 part by weight is appropriate for 100 parts by weight of the binder resin.
The thickness of the lower layer portion of the charge transport layer is appropriately about 5 to 40 μm, preferably about 10 to 30 μm.

  When the cross-linked surface layer is the surface portion of the charge transport layer (37), the radical polymerizable composition of the present invention is contained on the lower layer portion of the charge transport layer as described in the method for preparing a cross-linked surface layer. After the coating liquid is applied and dried as necessary, a curing reaction is initiated by external energy such as heat or light to form a crosslinked surface layer. At this time, the film thickness of the crosslinked surface layer is 1 to 20 μm, preferably 2 to 10 μm. If the thickness is less than 1 μm, the durability varies due to uneven film thickness. If the thickness is more than 20 μm, the entire thickness of the charge transport layer is increased, and the reproducibility of the image is reduced due to the diffusion of charges.

<Single photosensitive layer>
The photosensitive layer having a single layer structure is a layer having a charge generation function and a charge transport function at the same time, and the crosslinked surface layer having the charge transport structure of the present invention contains a charge generation material having a charge generation function, thereby providing a single layer structure. It is useful as a photosensitive layer. As described in the method for forming a charge generation layer, the charge generation material is dispersed together with a coating solution containing a radical polymerizable composition, applied onto the charge generation layer (35), and dried if necessary. The curing reaction is initiated by external energy, and a crosslinked surface layer is formed. In addition, you may add the liquid in which the charge generation material was previously disperse | distributed with the solvent to this coating material for bridge | crosslinking surface layers. At this time, the film thickness of the crosslinked surface layer is 10 to 30 μm, preferably 10 to 25 μm. If the thickness is less than 10 μm, a sufficient charging potential cannot be maintained. If the thickness is more than 30 μm, peeling from the conductive substrate or the undercoat layer tends to occur due to volume shrinkage during curing.

  Further, when the crosslinked surface layer is a surface portion of a photosensitive layer having a single layer structure, the lower layer portion of the photosensitive layer is composed of a charge generating material having a charge generating function, a charge transporting material having a charge transport function, and a binder resin in an appropriate solvent. It can be formed by dissolving or dispersing in, coating and drying. Moreover, a plasticizer, a leveling agent, etc. can also be added as needed. As the charge generation material dispersion method, the charge generation material, the charge transport material, the plasticizer, and the leveling agent may be the same as those already described in the charge generation layer (35) and the charge transport layer (37). As the binder resin, in addition to the binder resin previously mentioned in the section of the charge transport layer (37), the binder resin mentioned in the charge generation layer (35) may be mixed and used. In addition, the above-described polymer charge transport materials can also be used, which is useful in that contamination of the lower photosensitive layer composition into the crosslinked surface layer can be reduced. The thickness of the lower layer portion of the photosensitive layer is suitably about 5 to 30 μm, preferably about 10 to 25 μm.

  When the cross-linked surface layer is the surface portion of the photosensitive layer having a single layer structure, the coating solution containing the radical polymerizable composition of the present invention and the charge generating material is applied onto the lower layer portion of the photosensitive layer as described above. If necessary, after drying, it is cured by external energy such as heat or light to form a crosslinked surface layer. At this time, the film thickness of the crosslinked surface layer is 1 to 20 μm, preferably 2 to 10 μm. When the thickness is less than 1 μm, the durability varies due to the film thickness unevenness.

  The charge generation material contained in the photosensitive layer having a single layer structure is preferably 1 to 30% by weight based on the total amount of the photosensitive layer, and the binder resin contained in the lower layer portion of the photosensitive layer is 20 to 80% by weight of the total amount. The transport material is preferably used in an amount of 10 to 70 parts by weight.

<About the intermediate layer>
In the photoreceptor of the present invention, when the crosslinked surface layer is the surface portion of the photosensitive layer, it is possible to provide an intermediate layer for the purpose of suppressing mixing of lower layer components into the crosslinked surface layer or improving adhesion with the lower layer. is there. This intermediate layer prevents inhibition of the curing reaction and unevenness of the crosslinked surface layer caused by mixing of the lower photosensitive layer composition in the outermost surface layer containing the radical polymerizable composition. It is also possible to improve the adhesion between the lower photosensitive layer and the surface cross-linked layer.
In the intermediate layer, a binder resin is generally used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a generally used coating method is employed as described above. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.

<About the undercoat layer>
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support (31) and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.
These undercoat layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, in the undercoat layer of the present invention, Al ₂ O ₃ is provided by anodization, organic substances such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.

<Addition of antioxidant to each layer>
In the present invention, in order to improve environmental resistance, in order to prevent a decrease in sensitivity and an increase in residual potential, a surface cross-linked layer, a photosensitive layer, a charge generation layer, a charge transport layer, an undercoat layer, an intermediate layer An antioxidant can be added to each layer such as a layer.

The following are mentioned as antioxidant which can be used for this invention.
(Phenolic compounds)
2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4, 4'-thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4 -Hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene- -(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid ] Cryol ester, tocopherols and the like.

(Paraphenylenediamines)
N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N, N'- Di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.

(Hydroquinones)
2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- (2-octadecenyl) ) -5-methylhydroquinone and the like.

(Organic sulfur compounds)
Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.

(Organic phosphorus compounds)
Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.

These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
The addition amount of the antioxidant in the present invention is 0.01 to 10% by weight based on the total weight of the layer to be added.

<Image Forming Method and Apparatus>
Next, the image forming method and the image forming apparatus of the present invention will be described in detail with reference to the drawings.
The image forming method and the image forming apparatus of the present invention use a photoconductor having a smooth charge transporting surface cross-linked layer. For example, at least after the photoconductor is charged, exposed to an image, and developed, the image is held. An image forming method and an image forming apparatus including a process of transferring a toner image onto a body (transfer paper), fixing, and cleaning of the surface of a photoreceptor.
In some cases, an image forming method or the like in which an electrostatic latent image is directly transferred to a transfer member and developed does not necessarily have the above-described process arranged on a photosensitive member.

FIG. 3 is a schematic diagram illustrating an example of an image forming apparatus. A charging charger (3) is used as a means for charging the photoconductor on average. As the charging means, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, or the like is used, and a known system can be used.
In particular, the configuration of the present invention is effective when a charging unit such as a contact charging method or a non-contact proximity arrangement charging method is used in which the photosensitive composition is decomposed by proximity discharge from the charging unit. Here, the contact charging method is a charging method in which a charging roller, a charging brush, a charging blade or the like is in direct contact with the photosensitive member. On the other hand, the proximity charging method is, for example, a type in which the charging roller is arranged in a non-contact state so as to have a gap of 200 μm or less between the surface of the photoreceptor and the charging means. If this gap is too large, the charging tends to become unstable, and if it is too small, the surface of the charging member may be contaminated when toner remaining on the photoreceptor exists. is there. Accordingly, the gap is suitably 10 to 200 μm, preferably 10 to 100 μm.
Next, the image exposure unit (5) is used to form an electrostatic latent image on the uniformly charged photoreceptor (1). As the light source, all luminescent materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
Next, the developing unit (6) is used to visualize the electrostatic latent image formed on the photoreceptor (1). Development methods include a one-component development method using a dry toner, a two-component development method, and a wet development method using a wet toner. When the photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.
Next, a transfer charger (10) is used to transfer the toner image visualized on the photoconductor onto the transfer body (9). In addition, a pre-transfer charger (7) may be used for better transfer. As these transfer means, a transfer charger, an electrostatic transfer method using a bias roller, a mechanical transfer method such as an adhesive transfer method and a pressure transfer method, and a magnetic transfer method can be used. As the electrostatic transfer method, the charging means can be used.
Next, a separation charger (11) and a separation claw (12) are used as means for separating the transfer body (9) from the photoreceptor (1). As other separation means, electrostatic adsorption induction separation, side end belt separation, tip grip conveyance, curvature separation, and the like are used. As the separation charger (11), the charging means can be used.
Next, a fur brush (14) and a cleaning blade (15) are used to clean the toner remaining on the photoreceptor after transfer. Further, a pre-cleaning charger (13) may be used in order to perform cleaning more efficiently. Other cleaning means include a web method, a magnet brush method, and the like, but each may be used alone or in combination.
Next, a neutralizing unit is used for the purpose of removing the latent image on the photoreceptor as required. As the charge removal means, a charge removal lamp (2) and a charge removal charger are used, and the exposure light source and the charging means can be used respectively.
In addition, known processes can be used for reading, feeding, fixing, paper discharge and the like that are not close to the photoconductor.

The present invention is an image forming method and an image forming apparatus using the electrophotographic photoreceptor according to the present invention for such image forming means.
The image forming means may be fixedly incorporated in a copying apparatus, facsimile, or printer, but may be incorporated in these apparatuses in the form of a process cartridge and detachable. An example of the process cartridge is shown in FIG.
The process cartridge for the image forming apparatus includes a photoreceptor (101), and in addition, a charging unit (102), a developing unit (104), a transfer unit (106), a cleaning unit (107), and a discharging unit (not shown). ), And an apparatus (part) that can be attached to and detached from the image forming apparatus main body.

Referring to the image forming process by the apparatus illustrated in FIG. 4, the surface of the photoreceptor (101) is exposed by charging by the charging means (102) and exposure by the exposure means (103) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed, and the electrostatic latent image is developed with toner by the developing means (104). The toner development is transferred to the transfer body (105) by the transfer means (106), and printed. Out. Next, the surface of the photoconductor after the image transfer is cleaned by a cleaning unit (107), and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.
The present invention provides a process cartridge for an image forming apparatus in which a photosensitive member having a smooth charge transporting surface cross-linked layer and at least one of charging, developing, transferring, cleaning, and neutralizing means are integrated.
As is apparent from the above description, the electrophotographic photosensitive member of the present invention is not only used in electrophotographic copying machines, but also in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making. Can also be used widely.

<Synthesis Example of Charge Transporting Compound Compound Having Radical Polymerizable Functional Group>
The compound having a charge transporting structure in the present invention is synthesized, for example, by the method described in Japanese Patent No. 3164426. An example of this is shown below.
(1) Synthesis of hydroxy group-substituted triarylamine compound (the following structural formula B) 113.85 g (0.3 mol) of a methoxy group-substituted triarylamine compound (the following structural formula A) and 138 g (0.92 mol) of sodium iodide To this, 240 ml of sulfolane was added and heated to 60 ° C. in a nitrogen stream. In this solution, 99 g (0.91 mol) of trimethylchlorosilane was added dropwise over 1 hour and stirred at a temperature of about 60 ° C. for 4 and a half hours to complete the reaction. About 1.5 L of toluene was added to the reaction solution, cooled to room temperature, and washed repeatedly with water and an aqueous sodium carbonate solution. Thereafter, the solvent was removed from the toluene solution and purified by column chromatography (adsorption medium: silica gel, developing solvent: toluene: ethyl acetate = 20: 1). Cyclohexane was added to the obtained pale yellow oil to precipitate crystals. In this way, 88.1 g (yield = 80.4%) of white crystals of the following structural formula B was obtained.
Melting point: 64.0-66.0 ° C
Elemental analysis value (%)

(2) Synthesis of Triarylamino Group-Substituted Acrylate Compound (Exemplary Compound No. 54 in Table 1) 82.9 g (0.227 mol) of the hydroxy group-substituted triarylamine compound (Structural Formula B) obtained in (1) above ) Was dissolved in 400 ml of tetrahydrofuran, and an aqueous sodium hydroxide solution (NaOH: 12.4 g, water: 100 ml) was added dropwise in a nitrogen stream. The solution was cooled to 5 ° C., and 25.2 g (0.272 mol) of acrylic acid chloride was added dropwise over 40 minutes. Then, it stirred at 5 degreeC for 3 hours, and reaction was complete | finished. The reaction solution was poured into water and extracted with toluene. This extract was repeatedly washed with an aqueous sodium bicarbonate solution and water. Thereafter, the solvent was removed from the toluene solution and purified by column chromatography (adsorption medium: silica gel, developing solvent: toluene). N-Hexane was added to the obtained colorless oil to precipitate crystals. Thus, Exemplified Compound No. As a result, 80.73 g (yield = 84.8%) of 54 white crystals were obtained.
Melting point: 117.5-119.0 ° C
Elemental analysis value (%)

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. Note that “parts” used in the examples all represent parts by weight.
<Example 1>
By coating and drying an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution in the following order on a φ30 mm aluminum cylinder in sequence, an undercoat layer of 3.5 μm A 0.2 μm charge generation layer and an 18 μm charge transport layer were formed. A coating solution for a crosslinked surface layer having the following composition is spray-coated on the charge transport layer, and light irradiation is performed under the conditions of a metal halide lamp: 120 W / cm, irradiation intensity: 350 mW / cm ² , irradiation time: 15 seconds, Further, drying was performed at 130 ° C. for 20 minutes to provide a 6 μm surface cross-linked layer to obtain an electrophotographic photosensitive member of the present invention.
[Coating liquid for undercoat layer]
Alkyd resin 6 parts (Beckosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.)
Melamine resin 4 parts (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.)
Titanium oxide 40 parts Methyl ethyl ketone 50 parts [Coating liquid for charge generation layer]
Bisazo pigment pigment of the following structural formula (I) 2.5 parts Polyvinyl butyral (XYHL, manufactured by UCC) 0.5 part Cyclohexanone 200 parts Methyl ethyl ketone 80 parts

〔電荷輸送層用塗工液〕
ビスフェノールＺポリカーボネート １０部
（パンライトＴＳ−２０５０、帝人化成製）
下記構造式（II）の低分子電荷輸送物質（Ｄ−１） ７部
テトラヒドロフラン １００部
１％シリコーンオイルのテトラヒドロフラン溶液 ０．２部
（ＫＦ５０−１００ＣＳ、信越化学工業製）

[Coating liquid for charge transport layer]
Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals)
Low molecular charge transport material (D-1) having the following structural formula (II) 7 parts Tetrahydrofuran 100 parts 1% silicone oil tetrahydrofuran solution 0.2 part (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

〔架橋表面層用塗工液〕
電荷輸送性構造を有さない３官能以上のラジカル重合性モノマー １０部
トリメチロールプロパントリアクリレート
（ＫＡＹＡＲＡＤ ＴＭＰＴＡ、日本化薬製）
分子量：２９６、官能基数：３官能
ラジカル重合性官能基を有する電荷輸送性化合物 ７．５部
（例示化合物Ｎｏ．５４）
光重合開始剤
イルガキュア８１９（チバスペシャリティーケミカルズ製） ０．６部
《アシルホスフィンオキサイド化合物》
ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド

[Coating liquid for cross-linked surface layer]
Trifunctional or higher-functional radical polymerizable monomer having no charge transporting structure 10 parts Trimethylolpropane triacrylate (KAYARAD TMPTA, Nippon Kayaku)
Molecular weight: 296, number of functional groups: trifunctional 7.5 parts of charge transporting compound having radical polymerizable functional group (Exemplary Compound No. 54)
Photopolymerization initiator Irgacure 819 (manufactured by Ciba Specialty Chemicals) 0.6 parts << Acylphosphine oxide compound >>
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide

テトラヒドロフラン １００部

Tetrahydrofuran 100 parts

<Example 2>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator of Example 1 was replaced with an acylphosphine oxide compound having the following structure.
Photopolymerization initiator Lucirin TPO (manufactured by BASF) 0.6 parts << Acylphosphine oxide compound >>
2,4,6-trimethylbenzoyl-diphenylphosphine oxide

<Example 3>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator of Example 1 was changed to a mixture of acylphosphine oxide compounds having the following structure.
Mixed photopolymerization initiator Irgacure 1700 (manufactured by Ciba Specialty Chemicals)
0.6 part << acylphosphine oxide compound >>
Bis (2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide 25%

《その他の光重合開始剤》
２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン ７５％

<< Other photoinitiators >>
2-Hydroxy-2-methyl-1-phenylpropan-1-one 75%

<Example 4>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator of Example 1 was changed to a mixture of acylphosphine oxide compounds having the following structure.
Mixed photopolymerization initiator Irgacure 1800 (manufactured by Ciba Specialty Chemicals)
0.6 part << acylphosphine oxide compound >>
Bis (2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide 25%

《その他の光重合開始剤》
１−ヒドロキシ−シクロヘキシル−フェニルケトン ７５％

<< Other photoinitiators >>
1-hydroxy-cyclohexyl-phenyl ketone 75%

<Example 5>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator of Example 1 was changed to a mixture of acylphosphine oxide compounds having the following structure.
Mixed photopolymerization initiator Irgacure 1850 (Ciba Specialty Chemicals)
0.6 part << acylphosphine oxide compound >>
Bis (2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide 50%

《その他の光重合開始剤》
１−ヒドロキシ−シクロヘキシル−フェニルケトン ５０％

<< Other photoinitiators >>
1-hydroxy-cyclohexyl-phenyl ketone 50%

<Example 6>
The electrophotographic photoreceptor as in Example 1 except that the trifunctional or higher functional radical polymerizable monomer having no charge transporting structure contained in the crosslinked surface layer coating solution of Example 1 was replaced with the following monomer. Was made.
Trifunctional or higher radical polymerizable monomer having no charge transport structure 10 parts Dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayaku)
Average molecular weight: 536, number of functional groups: 5.5 functional

<Example 7>
Electrons in the same manner as in Example 1 except that the trifunctional or higher functional radical polymerizable monomer having no charge transporting structure contained in the crosslinked surface layer coating liquid of Example 1 was replaced with the following two mixed monomers. A photographic photoreceptor was prepared.
Trifunctional or higher functional radical polymerizable monomer having no charge transport structure 5 parts Trimethylolpropane triacrylate (KAYARAD TMPTA, Nippon Kayaku)
Molecular weight: 296, number of functional groups: trifunctional, trifunctional or higher radical polymerizable monomer having no charge transport structure 5 parts caprolactone-modified dipentaerythritol hexaacrylate (KAYARAD DPCA-120, manufactured by Nippon Kayaku Co., Ltd.)
Molecular weight: 1947, number of functional groups: 6 functions

<Example 8>
The charge transporting compound having a radical polymerizable functional group contained in the coating solution for the crosslinked surface layer of Example 1 is exemplified by Compound No. 1. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amount was changed to 25 and 7.5 parts.

<Example 9>
The charge transporting compound having a radical polymerizable functional group contained in the coating solution for the crosslinked surface layer of Example 1 is exemplified by Compound No. 1. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amount was changed to 184 and 7.5 parts.

<Comparative Example 1>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator of Example 1 was changed to the compound (I-1) having the following structure.
Photopolymerization initiator 4,4'-bis (dimethylamino) benzophenone [Michler's ketone]
(Tokyo Chemical) 0.6 parts

<Comparative example 2>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator of Example 1 was changed to the compound (I-2) having the following structure.
Photopolymerization initiator Carbazole / phenone initiator, Adekaoptomer N-1414
(Asahi Denka Kogyo) 0.6 parts

<Comparative Example 3>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator in Example 1 was changed to the compound (I-3) having the following structure.
Photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-oneylgure 907 (manufactured by Ciba Specialty Chemicals) 0.6 parts

<Comparative example 4>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator of Example 1 was changed to the compound (I-4) having the following structure.
Photopolymerization initiator 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-ylgacure 369 (manufactured by Ciba Specialty Chemicals) 0.6 parts

<Comparative Example 5>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator of Example 1 was changed to the compound (I-5) having the following structure.
Photopolymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one Darocur 1173 (manufactured by Ciba Specialty Chemicals) 0.6 parts

<Comparative Example 6>
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the photopolymerization initiator of Example 1 was changed to the compound (I-6) having the following structure.
Photopolymerization initiator Benzoin (manufactured by Tokyo Chemical Industry) 0.6 parts

<Comparative Example 7>
The photopolymerization initiator of Example 1 was replaced with 2 parts of the compound (I-5) of Comparative Example 5, and the light irradiation conditions of Example 1 were the metal halide lamp: 160 W / cm, irradiation intensity: 700 mW / cm ² , and irradiation time. : An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the time was 120 seconds.

<Comparative Example 8>
The trifunctional or higher functional radical polymerizable monomer having no charge transporting structure contained in the crosslinked surface layer coating solution of Example 1 is converted into the following bifunctional radical polymerizable monomer 10 having no charge transporting structure: An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the parts were changed.
Bifunctional radical polymerizable monomer having no charge transporting structure 10 parts 1,6-hexanediol diacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
Molecular weight: 226, number of functional groups: bifunctional

<Comparative Example 9>
The amount of the charge transporting compound having a radical polymerizable functional group without containing a trifunctional or higher functional radical polymerizable monomer having no charge transporting structure which is the composition of the coating solution for the crosslinked surface layer of Example 1 An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amount was changed to 17.5 parts.

<Comparative Example 10>
16. The amount of the trifunctional or higher functional radical polymerizable monomer having no transporting structure without containing the radically polymerizable compound having the transporting structure which is the composition of the coating solution for the crosslinked surface layer of Example 1 is 17. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amount was changed to 5 parts.

<Comparative Example 11>
The structural formula used in the charge transporting layer coating solution instead of containing the charge transporting compound having a radical polymerizable functional group, which is the composition of the coating solution for the crosslinked surface layer of Example 1, An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 7.5 parts of the low molecular charge transport material (D-1) of II) was added.

<Comparative Example 12>
An electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the cross-linked surface layer of Example 1 was not provided and the thickness of the charge transport layer was 24 μm.

<Surface smoothness test>
Surfcom 1400D (manufactured by Tokyo Seimitsu) was used as a method for evaluating the smoothness of the surface of the photoreceptor. Measure for 5 mm. Measurement points are 50 mm from both ends of the drum in the axial direction, three points in the center of the drum, and four ways of 90 degrees in the circumferential direction.
<Curing test>
A solubility test for an organic solvent is performed as an index of the curing progress of the crosslinked surface layer. One drop of tetrahydrofuran (hereinafter abbreviated as THF) and dichloromethane (hereinafter abbreviated as MDC) are dropped on the photoreceptor, and the change in the surface shape after natural drying is visually observed. In the case where the curing has not progressed, a part of the surface is dissolved, and ring-shaped unevenness and cloudiness occur.
<Durability test>
The photosensitive member is mounted on a process cartridge for an electrophotographic apparatus, and the initial dark portion potential is set to −700 V by a Ricoh imago Neo Neo 270 remodeling machine using a 655 nm semiconductor laser as an image exposure light source. Thereafter, a paper passing test is started, and image evaluation is performed at the initial stage and every 5000 sheets, and a maximum of 30,000 sheets of A4 size paper is passed. Note that when the image quality becomes extremely poor, the paper feeding is stopped and the processing is terminated. As the electrical characteristics, the dark part and the exposure part potential at the initial stage and at the end of paper passing are measured. Further, the film thickness at the initial stage and at the end of paper passing is measured, and the film thickness reduction amount is calculated from this difference.

The electrophotographic photosensitive members of Examples 1 to 9 and Comparative Examples 1 to 10 were measured for surface roughness Rz at the time of preparation, after the end of the durability test, and after completion, and the results are shown in Table 2.
Table 2 shows the results of solubility in organic solvents for the electrophotographic photoreceptors of Examples 1 to 9 and Comparative Examples 1 to 10.

  It can be seen that the photoreceptors of Examples 1 to 9 of the present invention have good surface smoothness before and after the durability test and high durability against scratches. In addition, the photoconductors of Examples 1 to 9 of the present invention are insoluble in an organic solvent, and curing proceeds to form a dense three-dimensional network structure. On the other hand, a photoreceptor using a general initiator having a short absorption wavelength in Comparative Examples 5 and 6 for the crosslinked surface layer, a photoreceptor using the bifunctional monomer of Comparative Example 8 for the crosslinked surface layer, and Comparative Example 9 The photoreceptor using only the charge transport compound having a radical polymerizable group for the crosslinked surface layer and the photoreceptor using the low molecular charge transport material of Comparative Example 11 for the crosslinked surface layer are soluble in organic solvents and insufficiently cured. It is. Further, since the photoconductors of Comparative Examples 5 and 6 are slow to cure, the photoconductor of Comparative Example 11 has poor surface smoothness during production due to precipitation of a low molecular charge transport material. In addition, the photoreceptors of Comparative Examples 5, 6, 8, 9, and 11 in which the network structure of the crosslinked surface layer is insufficient and Comparative Example 12 that does not use the crosslinked surface layer have poor surface smoothness after the durability test.

  Durability tests were performed on the electrophotographic photoreceptors of Examples 1 to 9 and Comparative Examples 1 to 10, and the results are shown in Tables 3 and 4.

  The photoreceptors of Examples 1 to 9 of the present invention have a low electrical potential at the initial stage and before and after the durability test of 30,000 sheets, and have good electrical characteristics. On the other hand, the photosensitive material using a long-wavelength absorption photopolymerization initiator other than the acylphosphine oxides of Comparative Examples 1 to 4 in the cross-linked surface layer and the content of the photopolymerization initiator of Comparative Example 7 were increased to increase the light irradiation energy. The photoreceptor having the crosslinked surface layer and the photoreceptor using the crosslinked surface layer of only the radically polymerizable monomer having no charge transporting group of Comparative Example 10 are significantly deteriorated in electrical characteristics.

  In the photoconductors of Examples 1 to 9 of the present invention, in the durability test of 30,000 sheets, the amount of decrease in film thickness was small, and good images were obtained. On the other hand, a photoconductor using a long-wavelength absorption photopolymerization initiator other than the acylphosphine oxides of Comparative Examples 1 to 4 as a cross-linked surface layer, and a cross-linked surface layer of only a radical polymerizable monomer having no charge transporting group of Comparative Example 10 Since the image density of the photoconductor using the toner was remarkably lowered, the durability test was stopped at the initial stage or during the process. Further, the image density of the photosensitive member having a crosslinked surface layer in which the content of the photopolymerization initiator in Comparative Example 7 was increased and the light irradiation energy was increased was also observed from the beginning. A photoreceptor using a general initiator having a short absorption wavelength in Comparative Examples 5 and 6 for the crosslinked surface layer, a photoreceptor using the bifunctional monomer of Comparative Example 8 for the crosslinked surface layer, and a radical polymerizable group of Comparative Example 9 The photoconductor using only the charge transporting compound having a cross-linked surface layer and the photoconductor using the low molecular charge transporting material of Comparative Example 11 for the cross-linked surface layer have a non-uniform and insufficient three-dimensional network structure of the cross-linked surface layer. Thus, the amount of wear was large and the surface unevenness due to wear increased, causing background stains and streak-like stains. The photoconductor not provided with the cross-linked surface layer of Comparative Example 12 has a large amount of wear and has a background stain, and is less durable than the photoconductor having the cross-linked surface layer of the present invention.

  Therefore, an acylphosphine oxide compound is used as a photopolymerization initiator for the trifunctional or higher functional radical polymerizable monomer having no charge transport structure of the present invention and a charge transportable compound having a radical polymerizable functional group. It has been found that a photoconductor provided with a cured cross-linked surface layer can provide a photoconductor with excellent surface smoothness, low exposed area potential, high durability and long life. Further, it has been found that the image forming process, the image forming apparatus, and the process cartridge for the image forming apparatus using the photoconductor of the present invention have high performance and high reliability.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger 4 Eraser 5 Image exposure part 6 Developing unit 7 Pre-transfer charger 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation charger 12 Separation claw 13 Pre-cleaning charger 14 Fur brush 15 Cleaning blade 31 Conductivity Support 33 Photosensitive layer 35 Charge generation layer 37 Charge transport layer 101 Photosensitive drum 102 Charging device 103 Exposure device 104 Development device 105 Transfer body 106 Transfer device 107 Cleaning blade

JP 56-48637 A JP-A 64-1728 JP-A-4-281461 Japanese Patent No. 3194392 JP 2000-66425 A Japanese Patent No. 3126889

Claims (11)

An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the surface layer of the photosensitive layer has at least a trifunctional or higher-functional radical polymerizable monomer and a radical polymerizable functional group not having a charge transporting structure. The charge transporting compound is a cross-linked layer cured by light energy irradiation using an acylphosphine oxide compound as a photopolymerization initiator, and the charge transporting compound having the radical polymerizable functional group is represented by the following general formula (1) or An electrophotographic photosensitive member characterized by being one or more of (2).

[Wherein, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, a cyano group, a nitro group, A group, an alkoxy group, —COOR ₇ (R ₇ represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent. ), A halogenated carbonyl group or CONR ₈ R ₉ (R ₈ and R ₉ have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a substituent. Represents an aryl group which may be the same or different, and Ar ₁ and Ar ₂ represent a substituted or unsubstituted arylene group, which may be the same or different. . Ar ₃ and Ar ₄ represent a substituted or unsubstituted aryl group, and may be the same or different. X represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether divalent group, an oxygen atom, a sulfur atom, or a vinylene group. Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether divalent group, or an alkyleneoxycarbonyl divalent group. m and n represent an integer of 0 to 3. ]   2. The electrophotography according to claim 1, wherein a functional group of a trifunctional or higher-functional radical polymerizable monomer having no charge transport structure used in the surface layer is an acryloyloxy group and / or a methacryloyloxy group. Photoconductor.   The ratio of the molecular weight to the number of functional groups (molecular weight / number of functional groups) in a trifunctional or higher-functional radical polymerizable monomer having no charge transport structure used for the surface layer is 250 or less. The electrophotographic photoreceptor described in 1. 4. The electrophotographic photosensitive member according to claim 1, wherein the charge transporting compound having a radical polymerizable functional group used in the surface layer is one or more of the following general formula (3). .

(Wherein, o, p and q are each an integer of 0 or 1, Ra represents a hydrogen atom or a methyl group, Rb and Rc represent a substituent other than a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, And s and t each represents an integer of 0 to 3. Za is a single bond, a methylene group, an ethylene group,

Represents. ) The electrophotographic photosensitive member according to claim 1, wherein the acylphosphine oxide compound used for the surface layer has an absorption maximum wavelength of 400 nm or more. The electrophotographic photoreceptor according to any one of claims 1 to 4, wherein the acylphosphine oxide compound used for the surface layer is a compound represented by the following structural formula (P-1).

The electrophotographic photoreceptor according to claim 1, wherein the acylphosphine oxide compound used for the surface layer is a compound represented by the following structural formula (P-3).

8. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a laminated structure of a charge generation layer, a charge transport layer, and a charge transport cross-linked surface layer from the support side.   An image forming method, wherein at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to claim 1. An image forming apparatus comprising the electrophotographic photosensitive member according to claim 1.   An electrophotographic photosensitive member according to any one of claims 1 to 8, and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, a cleaning means, and a charge eliminating means, A process cartridge for an image forming apparatus, wherein the process cartridge is removable from a main body of the forming apparatus.

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