JP2006038978A - Electrophotographic photoreceptor, method for manufacturing the same, image forming method using the same, image forming apparatus and process cartridge for image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which has high and stable wear and scuffing resistances and proper electrical characteristics and realizes high image quality over a prolonged period of time. <P>SOLUTION: In the electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, a surface layer of the photosensitive layer is a crosslinked layer formed, by curing at least a trifunctional or higher functionality radical polymerizable monomer having no charge transport structure and a radical polymerizable compound, having a charge transport structure by irradiation with light energy at an environmental temperature of 15-28°C at the time of starting the irradiation with light energy. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides an electronic device having high durability and high image quality over a long period of time by using a photosensitive layer having good film surface properties, high wear resistance, and good electrical characteristics. The present invention relates to a photographic 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 manufacturing, (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 property as the particle size of the toner particles is reduced. This also promotes wear of the photoreceptor. It is a factor. Such abrasion 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 (see, for example, Patent Document 1), and (2) using a polymeric charge transport material ( For example, refer patent document 2), (3) what dispersed the inorganic filler in the surface layer (for example, refer patent document 3), etc. are mentioned. Among these techniques, 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 a decrease in image density. Tends to occur. In addition, (2) using a polymer type charge transport material and (3) dispersed inorganic filler are required for organic photoreceptors, although they can improve wear resistance to some extent. The durability has not been fully satisfied. Further, in the case where the inorganic filler (3) is dispersed, the residual potential increases due to traps present on the surface of the inorganic filler, and the image density tends to decrease. 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.

  Furthermore, a photoreceptor containing a polyfunctional acrylate monomer cured product in order to improve the abrasion resistance and scratch resistance of (1) is also known (see Patent Document 4). However, in this photoreceptor, although there is a description that the polyfunctional acrylate monomer cured product is contained in the protective layer provided on the photosensitive layer, the protective layer may contain a charge transport material. However, when the surface layer contains a low-molecular charge transport material, there is a problem of compatibility with the cured product. In some cases, the molecular charge transport material is precipitated and the cloudiness phenomenon occurs, and the mechanical strength is also lowered. Furthermore, since this photoconductor specifically reacts with a monomer in a state containing a polymer binder, curing does not proceed sufficiently, and there is a problem of compatibility between the cured product and the binder resin. There was a tendency for surface irregularities due to phase separation to cause poor cleaning.

  As an alternative to the wear resistance technology of the photosensitive layer, a charge transport layer formed by using a coating solution comprising a monomer having a carbon-carbon double bond, a charge transport material having a carbon-carbon double bond, and a binder resin. The binder resin has a carbon-carbon double bond and is reactive with the charge transfer agent, and the double resin is known to be provided. Those having no bond and no reactivity are included. This photoconductor is remarkably compatible with wear resistance and good electrical properties, but when a non-reactive binder resin is used, the binder resin, the monomer and the charge transport agent are used. The compatibility with the cured product produced by this reaction was poor, and surface irregularities were generated during cross-linking from layer separation, and a tendency to cause poor cleaning was observed.

  Further, as described above, in this case, the binder resin prevents the curing of the monomer, and what is specifically described as the monomer used in the photoreceptor is a bifunctional one. The monomer has a small number of functional groups and a sufficient crosslinking density cannot be obtained, and these points have not yet been satisfactory in terms of wear resistance. Further, even when a reactive binder is used, it is difficult to achieve both the binding amount and the crosslinking density of the charge transport material due to the low number of functional groups contained in the monomer and the binder resin. The abrasion resistance was not sufficient.

  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 is also known (for example, see Patent Document 6). However, the manufacturing conditions, particularly the manufacturing method for crosslinking by light energy irradiation, is not described in detail, and if the actual film forming environment is not controlled, the surface unevenness becomes large, which may cause deterioration in cleaning properties. found.

  As a result of intensive studies, the inventors of the present invention cured the surface layer by irradiating light radicals with at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. It became clear that electrical characteristics and abrasion resistance were improved by using a crosslinked resin layer. However, this cross-linked resin layer also has a large change in surface properties depending on the coating conditions and cross-linking conditions, and the surface unevenness tends to increase. In particular, the environment at the time of light energy irradiation is very large and greatly affects the surface shape. If the surface smoothness of the photoreceptor is poor, cleaning failure is likely to occur. Further, the frictional force with the cleaning blade is large, and the blade may be turned over or the blade may squeal.

JP 56-48637 A JP-A 64-1728 JP-A-4-281461 Japanese Patent No. 3262488 Japanese Patent No. 3194392 JP 2000-66425 A

  An object of the present invention is to provide an electrophotographic photosensitive member that has high wear resistance and scratch resistance, is stable, has good electrical characteristics, and realizes high image quality over a long period of time. And providing 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 found that the purpose of the previous term can be achieved by using the photoreceptor according to claims (1) to (15), and have accomplished the present invention.
(1) In an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, the surface layer of the photosensitive layer has at least a trifunctional or higher functional radical polymerizable monomer having no charge transporting structure and a charge transporting structure. An electrophotographic photosensitive member, which is a crosslinked layer cured by irradiation with light energy under a condition that an ambient temperature at the start of irradiation with light energy is 15 to 28 ° C. on a mixture comprising a radical polymerizable compound having the above.
(2) The electrophotographic photosensitive member according to the above (1), wherein Rz (ten-point average surface roughness) of the surface layer of the photosensitive layer is 0.05 to 0.50 μm.
(3) The electrophotographic photosensitive member according to (1) or (2) above, wherein the radical polymerizable compound having the charge transporting structure is monofunctional.
(4) The electron according to (1) or (2) above, wherein the functional group of the tri- or higher functional radical polymerizable monomer having no charge transporting structure is an acryloyloxy group and / or a methacryloyloxy group. Photoconductor.
(5) The photoconductor for electrophotography according to (1) or (2) above, wherein the radical polymerizable compound having a charge transporting structure has an acryloyloxy group and / or a methacryloyloxy group as a functional group.
(6) The electrophotographic photosensitive member according to (1) or (2), wherein the radical polymerizable compound having a charge transporting structure has a triarylamine structure.
(7) The electrophotographic photosensitive material of the above (1) or (2), wherein the radical polymerizable compound having the charge transporting structure is a compound represented by the following general formula (1) or (2): body.

(In the formula, 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, Group, alkoxy group, —COOR ₇ (R ₇ is 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), halogen Carbonyl group or CONR ₈ R ₉ (R ₈ and R ₉ may 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. Ar ₁ and Ar ₂ each represent a substituted or unsubstituted arylene group, and may be the same or different.Ar ₃ , which may be the same or different from each other. Ar ₄ may be substituted Represents an unsubstituted aryl group, which 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 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 group, or an alkyleneoxycarbonyl group, and m and n represent an integer of 0 to 3.)
(8) The electrophotographic photosensitive member according to the above (1) or (2), wherein the radical polymerizable compound having the charge transporting structure is one or more kinds of compounds represented by 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. )
In addition, as a result of intensive studies, the present inventors have achieved the inventions described in the following (9) to (17) as a method for producing an electrophotographic photosensitive member that can achieve the purpose of the previous term.
(9) The electrophotographic photosensitive member according to the above (1) to (8), wherein the photosensitive layer has a laminated structure of a charge generation layer, a charge transport layer, and a surface layer from the support side.
(10) In a method for producing an electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizability having a charge transport structure. It is characterized by forming a crosslinked layer as a surface layer of the photosensitive layer by irradiating the mixture composed of the compound with light energy under the condition that the ambient temperature at the start of light energy irradiation is 15 to 28 ° C. A method for producing an electrophotographic photoreceptor.
(11) In a method for producing an electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizability having a charge transport structure. Rz (ten-point average surface roughness) as a surface layer of the photosensitive layer is cured by irradiating light energy to the mixture composed of the compounds under the condition that the environmental temperature at the start of light energy irradiation is 15 to 28 ° C. Forming a cross-linked layer having a thickness of 0.05 to 0.50 [mu] m.
(12) The method for producing an electrophotographic photosensitive member according to (10) or (11) above, wherein the radical polymerizable compound having the charge transporting structure is monofunctional.
(13) The electron according to (10) or (11) above, wherein the functional group of the trifunctional or higher radical polymerizable monomer having no charge transporting structure is an acryloyloxy group and / or a methacryloyloxy group. A method for producing a photographic photoreceptor.
(14) The production of the electrophotographic photosensitive member according to the above (10) or (11), wherein the radical polymerizable compound having the charge transporting structure has an acryloyloxy group and / or a methacryloyloxy group as a functional group. Method.
(15) The method for producing an electrophotographic photosensitive member according to (10) or (11) above, wherein the radical polymerizable compound having a charge transporting structure has a triarylamine structure.
(16) The electrophotographic photoconductor of (10) or (11) above, wherein the radical polymerizable compound having a charge transporting structure is a compound represented by the general formula (1) or (2) Body manufacturing method.
(17) The electrophotographic photosensitive member according to (10) or (11) above, wherein the radical polymerizable compound having the charge transporting structure is one or more of the compounds represented by the general formula (3). Manufacturing method.
Moreover, the said subject is solved by invention of following (18)-(20).
(18) An image forming method, wherein at least charging, image exposure, development, and transfer are repeated using the electrophotographic photosensitive member according to (1) to (8).
(19) An image forming apparatus comprising the electrophotographic photosensitive member according to the above (1) to (8).
(20) The electrophotographic photosensitive member according to the above (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 static elimination means, A process cartridge for an image forming apparatus, wherein the process cartridge is detachable from the main body of the image forming apparatus.

According to the present invention, in an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, the surface layer of the photosensitive layer has at least a trifunctional or higher functional radical polymerizable monomer having no charge transporting structure and charge transportability. A radically polymerizable compound having a structure is irradiated with light energy, and the environment at the start of light energy irradiation is a crosslinked layer cured at a temperature of 15 to 28 ° C. It is possible to obtain a highly durable and high performance photoreceptor having excellent electrical characteristics.
Further, in an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, a radical polymerization monomer having a charge transporting structure and a trifunctional or higher functional radical polymerizable monomer having a surface layer of the photosensitive layer at least having no charge transporting structure. By using a method for producing an electrophotographic photoreceptor, which is a cross-linked layer obtained by curing a photosensitive compound by light energy irradiation means, and the environment at the start of light energy irradiation is cured at a temperature of 15 to 28 ° C. A highly durable and high-performance photoreceptor having high wear characteristics and good electrical characteristics can be obtained.
Therefore, it is possible to provide a high-performance and highly reliable image forming process, an image forming apparatus, and a process cartridge for an image forming apparatus that can provide a good image over a long period of time by using this photoconductor.

Hereinafter, the present invention will be described in detail.
The present invention relates to 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 having no charge transporting structure and a charge transporting structure. Wear resistance by forming an electrophotographic photoreceptor characterized by being a cross-linked layer that is irradiated with light energy from a radical polymerizable compound having a cured environment at a temperature of 15 to 25 ° C. In addition, an electrophotographic photoreceptor that has high scratch resistance, excellent cleaning characteristics, and high image quality over a long period of time can be achieved.

The reasons for this are as follows.
The cross-linked surface layer of the present invention uses a tri- or higher-functional radically polymerizable monomer, thereby developing a three-dimensional network structure and obtaining a highly hard cross-linked surface layer having a very high degree of cross-linking, and having high wear resistance. Sex 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 polymer material is contained in the cross-linked surface layer, the development of the three-dimensional network structure is inhibited and the degree of cross-linking is lowered, so that 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 radical polymerizable compound having a charge transporting structure) is poor, resulting in localized from phase separation. Wears and appears as a scratch on the surface.

  Further, the crosslinked surface layer of the present invention contains a radical polymerizable compound having a charge transporting structure in addition to the trifunctional radical polymerizable monomer, which is crosslinked when the radical polymerizable monomer having the trifunctional or higher function is cured. Captured inside. 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 and white turbidity occur due to its low compatibility, and the cross-linked surface layer The mechanical strength also decreases.

  Furthermore, the crosslinked surface layer of the present invention irradiates a radical polymerizable compound having a trifunctional or higher functional group having no charge transporting structure and a radical polymerizable compound having a charge transporting structure with light energy, and the environment at the start of light energy irradiation. Is cured at a temperature of 15 to 28 ° C.

  When the temperature at the start of curing is less than 15 ° C., moisture tends to condense on the surface of the photoreceptor, and this moisture condensation inhibits the cross-linking reaction and makes it easy to make irregularities on the surface of the photoreceptor. On the other hand, when the temperature exceeds 28 ° C., the balance between volume shrinkage during crosslinking and thermal expansion of the film due to temperature is lost, the reaction on the surface tends to be uneven, and irregularities are generated on the surface of the photoreceptor. When unevenness occurs on the surface of the photoreceptor in this manner, cleaning failure is likely to occur, and a blade turning over phenomenon, a blade squealing phenomenon, etc. may occur. In particular, the influence of the environment at the initial stage of crosslinking is large. That is, if the reaction proceeds to some extent, even if the ambient temperature around the photosensitive member rises, unevenness on the surface is less likely to occur. Preferably, when the environment at the start of light energy irradiation is a temperature of 18 to 25 ° C., it is possible to form a film having a better surface.

  When the environment at the start of light energy irradiation is set to a temperature of 15 to 28 ° C., surface unevenness is less likely to occur. The ten-point average surface roughness (Rz value) of the photoreceptor surface layer thus produced is desirably 0.05 to 0.50 μm. As a measuring method of the Rz value of the surface layer, it is a ten-point average roughness measured according to JIS B0601-1994 standard. In the present invention, it is measured using Surfcom 1400D (manufactured by Tokyo Seimitsu). The value measured by any device having a performance equivalent to

Next, the constituent material of the crosslinked 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) 1-Substituted Ethylene Functional Group Examples of the 1-substituted ethylene functional group include functional groups represented by the following formulas.
CH ₂ = _{CH-X 2} -
(In the formula, X ₂ is an arylene group such as a phenylene group or a naphthylene group which may have a substituent, an alkenylene group which may have a substituent, a —CO— group, a —COO— group. , —CON (R ₃₆ ) — group (R ₃₆ 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 represents an —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) 1,1-Substituted Ethylene Functional Group Examples of the 1,1-substituted ethylene functional group include functional groups represented by the following formulas.
_{CH 2 = C (Y 4)} -X 3 -
(However, in the formula, Y ₄ 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, a naphthyl group, etc. Aryl group, halogen atom, cyano group, nitro group, alkoxy group such as methoxy group or ethoxy group, -COOR ₃₇ group (R ₃₇ is a hydrogen atom, an optionally substituted methyl group, ethyl group, etc. An alkyl group, an optionally substituted benzyl, an aralkyl group such as a phenethyl group, an optionally substituted phenyl group, an aryl group such as a naphthyl group, or -CONR ₃₈ R ₃₉ (R ₃₈ and R ₃₉ is a hydrogen atom, which may have a substituent an alkyl group such as methyl group and ethyl group, which may have a substituent group benzyl group, naphthylmethyl group, or a, such as a phenethyl group, Alkyl group or a substituent a phenyl group which may have a represents an aryl group such as phenyl or naphthyl, which may be the same or different from each other.) Further, X ₃ is the same as X ₂ in the formula 10 A substituent, a single bond, or an alkylene group, provided that at least one of Y ₄ and X ₃ is an oxycarbonyl group, 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 ₂ , X ₃ , and Y ₄ include, for example, an alkyl group such as a halogen atom, a nitro group, a cyano group, a methyl group, and an ethyl group, a methoxy group, and an ethoxy group. And aryloxy groups such as phenoxy group, aryl groups such as phenyl group and naphthyl group, and aralkyl groups such as benzyl group and phenethyl group.

  Among these radical polymerizable functional groups, acryloyloxy group and methacryloyloxy group are particularly useful, and a compound having three or more acryloyloxy groups is, for example, 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, HPA-modified trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, and PO-modified. Trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, HPA-modified trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate, ECH-modified glycerol triacrylate, EO-modified glycerol triacrylate , PO-modified glycerol triacrylate, Lith (acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate (DPHA), caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, alkyl-modified dipentaerythritol tetraacrylate, alkyl Modified dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, EO modified phosphoric acid triacrylate, 2,2,5,5-tetrahydroxymethylcyclopentanone tetraacrylate, etc. These may be used alone or in combination of two or more.

  In addition, the proportion of the trifunctional or higher functional radical polymerizable monomer having no charge transport structure used in the present invention is 20 to 80% by weight, preferably 30 to 70% by weight, based on the total amount of the crosslinked surface layer. 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 radical polymerizable compound having a charge transporting structure used in the present invention includes a hole transporting structure such as triarylamine, hydrazone, pyrazoline, carbazole, such as condensed polycyclic quinone, diphenoquinone, cyano group and nitro group. It refers to a compound having an electron transport structure such as an electron-withdrawing aromatic ring and 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.

  In addition, as the radical polymerizable compound having a charge transporting structure, a polyfunctional compound having two or more functional groups can be used, but a monofunctional compound is preferable in terms of film quality and electrostatic characteristics. This is because when a bifunctional or higher functional charge transport compound is used, it is fixed in the crosslinked structure by a plurality of bonds. However, since the charge transport structure is very bulky, distortion occurs in the cured resin, resulting in a crosslinked surface layer. The internal stress increases, and it becomes easy to cause cracks and scratches due to carrier adhesion and the like. In the case of a film thickness of 5 μm or less, there is no particular problem, but when a film exceeding 5 μm is formed, the internal stress of the crosslinked surface layer becomes very high and cracks are likely to occur immediately after crosslinking.

In addition, in terms of electrostatic characteristics, when a bifunctional or higher functional charge transporting compound is used, it is fixed in the crosslinked structure with a plurality of bonds, so that the intermediate structure (cation radical) during charge transport is stably maintained. In other words, the sensitivity is lowered due to charge trapping, and the residual potential is likely to increase. Such deterioration of the electrical characteristics appears as an image such as a decrease in image density and thinning of characters. For this reason, the radical polymerizable compound having a charge transporting structure uses a radical polymerizable compound having a monofunctional charge transporting structure and is fixed in a pendant shape between crosslinks, thereby causing cracks and scratches. And stabilization of electrostatic characteristics.
Further, the triarylamine structure is highly effective as a charge transporting structure. Moreover, what has one functional group is preferable, and when a compound shown by the structure of the following general formula 1 or 2 is used, electrical characteristics such as sensitivity and residual potential are favorably maintained.

(In the formula, 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, Group, alkoxy group, —COOR ₇ (R ₇ is 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), halogen Carbonyl group or CONR ₈ R ₉ (R ₈ and R ₉ may 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. Ar ₁ and Ar ₂ each represent a substituted or unsubstituted arylene group, and may be the same or different.Ar ₃ , which may be the same or different from each other. Ar ₄ may be substituted Represents an unsubstituted aryl group, which 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 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 group, or an alkyleneoxycarbonyl group, and 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-indacenyl group. , S-indacenyl group, fluorenyl group, acenaphthylenyl group, preadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, triphenylyl group, pyrenyl group , A chrycenyl group, a 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) Alkyl groups, preferably C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C ₄ linear or branched alkyl groups, further including fluorine atoms , a hydroxyl group, a cyano _group, an alkoxy group of C 1 -C _4, a phenyl group or a halogen _atom, which may have a phenyl group substituted by an alkoxy group C 1 -C ₄ alkyl or _C 1 -C ₄ Good. 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 ), and R ₂ represents the 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) An aryloxy group, and 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) Alkyl mercapto group or aryl mercapto group, and specific examples include methylthio group, ethylthio group, phenylthio group, p-methylphenylthio group and the like.
(6)

(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) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.
(8) A substituted or unsubstituted styryl group, a substituted or unsubstituted β-phenylstyryl group, a diphenylaminophenyl group, a ditolylaminophenyl group, and the like.

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.
The substituted or unsubstituted alkylene ether group represents ethyleneoxy, propyleneoxy, ethylene glycol, propylene glycol, diethylene glycol, tetraethylene glycol, tripropylene glycol, alkylene ether group alkylene group is hydroxyl group, methyl group, ethyl group, etc. You may have the substituent of.
The vinylene group is

Represented by
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, and b is 1 to 2 3 is represented.

Z represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkylene ether group, or an alkyleneoxycarbonyl group.
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 group include the alkylene ether group represented by X.
Examples of the alkyleneoxycarbonyl group include a caprolactone-modified group.
Further, the radical polymerizable compound having a monofunctional charge transport structure of the present invention is more preferably a compound having a structure 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. )
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 radically polymerizable compound having a monofunctional charge transport structure represented by the general formulas (1) and (2), particularly (3) used in the present invention is polymerized with the carbon-carbon double bond open on both sides. Therefore, in a polymer that is not a terminal structure but is incorporated in a chain polymer and crosslinked by polymerization with a tri- or higher functional radical polymerizable monomer, it exists in the main chain of the polymer, and Present in the cross-linked chain between the chain and the main chain (this cross-linked chain has an intermolecular cross-linked chain between one polymer and another polymer, and a site where the main chain is folded in one polymer. And other intramolecular cross-linked chains that are cross-linked with other sites derived from the polymerized monomer at positions away from this in the main chain), but even if they are present in the main chain, Even if present, the triarylamine structure suspended from the chain moiety is It has at least three aryl groups arranged in the radial 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 these triarylamine structures can be arranged adjacent to each other in the polymer, there is little structural distortion in the molecule, and the surface of the electrophotographic photosensitive member is also fixed. In the case of a layer, 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 radically polymerizable compound having a monofunctional charge transporting structure of the present invention are shown below, but are not limited to the compounds having these structures.

  Specific examples of the radically polymerizable compound having a bifunctional charge transporting structure of the present invention are shown below, but are not limited to compounds having these structures (Nos. 264, 346, and 358 are missing).

  Specific examples of the radical polymerizable compound having a trifunctional charge transporting structure of the present invention are shown below, but are not limited to the compounds having these structures.

  The radical polymerizable compound having a charge transport structure used in the present invention is important for imparting the charge transport performance of the crosslinked surface layer, and this component is preferably 20 to 80% by weight, preferably based on the total amount of the crosslinked surface layer. Is 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.

  The surface layer of the present invention is obtained by curing at least a trifunctional or higher-functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. Monofunctional and bifunctional radically polymerizable monomers and radically polymerizable oligomers can be used in combination for the purpose of adjustment, stress relaxation of the cross-linked surface layer, lower surface energy, and reduction of friction coefficient. 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, EO-modified bisphenol A diacrylate, EO-modified bisphenol F diacrylate, and neopentyl glycol diacrylate.

  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 addition, the surface layer of the present invention is obtained by curing at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure by irradiation with light energy. In order to advance the crosslinking reaction efficiently, a polymerization initiator may be used in the crosslinked surface layer.

  Examples of the polymerization 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-methyl Acetophenone-based or ketal-based photopolymerization initiators such as 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, 1 Benzophenone photopolymerization initiators such as 1,4-benzoylbenzene, thioxanthones such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone As photopolymerization initiators and other photopolymerization initiators, ethyl anthraquinone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl 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. Moreover, what has a photopolymerization acceleration effect can also be used individually or in combination with the said photoinitiator. Examples include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4,4'-dimethylaminobenzophenone, and the like.

  These polymerization initiators may be used alone or in combination of two or more. The content of the polymerization initiator is 0.5 to 40 parts by weight, preferably 1 to 20 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 formed by applying and curing a coating liquid containing at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. . 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, 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, light energy is given from the outside and it hardens | cures. As the energy of light, UV irradiation light sources such as high-pressure mercury lamps and metal halide lamps, which mainly have an emission wavelength in ultraviolet light, can be used, but a visible light source can also be selected according to the absorption wavelength of radically polymerizable substances and photopolymerization initiators. Is possible. Irradiation light amount 300 mW / cm ² or more, preferably 1000 mW / cm ² or less, it takes time for the curing reaction is less than 300 mW / cm ^2. If it is higher than 1000 mW / cm ^2, the progress of the reaction becomes non-uniform and the cross-linked surface layer becomes very rough.

  In the composition contained in the crosslinked surface layer coating solution, it is possible to contain a binder resin as long as the smoothness, electrical characteristics, or durability of the photoreceptor surface is not impaired. However, when a polymer material such as a binder resin is included in the coating liquid, it is in phase with the polymer formed by the curing reaction of the radical polymerizable composition (radical polymerizable monomer and radical polymerizable compound having a charge transporting structure). Phase separation occurs due to poor solubility, and the surface of the crosslinked surface layer becomes uneven. Therefore, it is preferable not to use a binder resin.

  In the cross-linked surface layer of the present invention, it is necessary to contain a bulky charge transporting structure in order to maintain electrical characteristics and to increase the cross-linking density in order to increase the strength. In such curing after application of the crosslinked surface layer, if very high energy is applied from the outside and the reaction proceeds rapidly, curing proceeds unevenly and the unevenness of the crosslinked film surface becomes severe. For this reason, light energy capable of controlling the reaction rate according to the light irradiation intensity and the amount of the polymerization initiator is used.

In the case of using the crosslinked surface layer forming material of the present invention, examples of the coating method include, for example, an acrylate monomer having three acryloyloxy groups and a triarylamine compound having one acryloyloxy group as a coating solution. When these are used, their use ratio is 7: 3 to 3: 7, and 3-20% by weight of a polymerization initiator is added to the total amount of these acrylate compounds, and a solvent is added to prepare a coating solution. To do. For example, in the case where the charge transport layer which is the lower layer of the cross-linked surface layer uses a triarylamine donor as the charge transport material and polycarbonate as the binder resin, and the cross-linked surface layer is formed by spray coating, the above coating solution As the solvent, tetrahydrofuran, 2-butanone, ethyl acetate and the like are preferable, and the use ratio thereof is 3 to 10 times the total amount of the acrylate compound.
Next, for example, the prepared coating solution is applied by spraying or the like on a photoreceptor in which an undercoat layer, a charge generation layer, and the charge transport layer are sequentially laminated on a support such as an aluminum cylinder. Then, it is dried at a relatively low temperature for a short time (25 to 80 ° C., 1 to 10 minutes) and cured by light irradiation.

For example, when irradiating UV light of 600 mW / cm ² , for example, at the time of curing, the drum may be rotated to uniformly irradiate all surfaces for about 45 to 360 seconds. At this time, the irradiation start temperature is set to 15 ° C. to 28 ° C., and the drum temperature during irradiation is controlled not to exceed 100 ° C.
After completion of curing, the photosensitive member of the present invention is obtained by heating at 100 to 150 ° C. for 10 to 30 minutes to reduce the residual solvent.

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, which is a single-layered photosensitive member in which a photosensitive layer having a charge generating function and a charge transporting function is provided on a conductive support. FIG. 1A shows the case where the cross-linked surface layer is the entire photosensitive layer, and FIG. 1B 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 having a charge generation function and a charge transport layer having a charge transport material function are laminated on a conductive support. FIG. 2A shows the case where the cross-linked surface layer is the entire charge transport layer, and FIG. 2B shows the case where the cross-linked surface layer is the surface portion of the charge transport layer.

<About conductive support>
Examples of the conductive support include those having a volume resistance of 10 ¹⁰ Ω · cm or less, such as metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, and platinum, tin oxide, and indium oxide. After metal oxide is deposited or sputtered, film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. Pipes that have been subjected to surface treatment such as cutting, super-finishing, and polishing can be used. Further, endless nickel belts and endless stainless steel belts disclosed in JP-A-52-36016 can also be used as the conductive support.
In addition, those obtained by dispersing and coating conductive powder in an appropriate binder resin on the support can also be used as the conductive support 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-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, Thermoplastic, thermosetting resin or photo-curing resin such as melamine resin, urethane resin, phenol resin, alkyd resin and the like can be mentioned. 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.

  Furthermore, it is electrically conductive by 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, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support 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 having a laminated structure>
(Charge generation layer)
The charge generation layer 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 fluorenone skeleton, azo pigments having oxadiazole skeleton, azo pigments having bis-stilbene skeleton, azo pigments having distyryl oxadiazole skeleton, azo pigments having 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.

  As a binder resin used as necessary for the charge generation layer, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, Examples include 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, No. 04-011627, No. 04-175337, No. 04-183719, No. 04-2225014, No. 04-230767, No. 04-320420, No. 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 08-252868, JP 08-269183, JP 09-062019, JP 09-038883, JP 09-71642, JP 09-87376. JP-A 09-104746, JP-A 09-110974, JP-A 09-110976, JP-A 09-157378, JP-A 09-221544, JP-A 09-227669. JP-A 09-228367, JP-A 09-241369 Charge transporting polymer materials described in JP 09-268226 A, JP 09-272728 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 may contain a low molecular charge transport material.
Low molecular charge transport materials that can be used in the charge generation layer 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 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 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, the radical polymerizable composition (radical polymerizable monomer having no charge transport structure) of the present invention is formed on the charge generation layer as described in the above cross-linked surface layer preparation method. And a radically polymerizable compound having a charge transporting structure; hereinafter the same) is applied, and if necessary, after drying, a curing reaction is initiated by light energy to form a crosslinked surface layer. 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.

  If the cross-linked surface layer is formed on the surface of the charge transport layer and the charge transport layer has a laminated structure, the lower charge transport layer dissolves the charge transport material having a charge transport function and the binder resin in an appropriate solvent. Or dispersed and formed on the charge generation layer by coating and drying, and a coating solution containing the radical polymerizable composition of the present invention is coated thereon and cured by crosslinking with light energy.

  As the charge transport material, the electron transport material, hole transport material and polymer charge transport material described in the charge generation layer 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 charge transport layer, the same solvent as 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 charge transport layer can be formed by the same coating method as that for the charge generation layer.
If necessary, a plasticizer and a leveling agent can be added.

As a plasticizer that can be used together with the lower 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 based on 100 parts by weight of the binder resin. 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.

  As described in the method for preparing a crosslinked surface layer, a coating liquid containing the radically polymerizable composition of the present invention is applied on the lower charge transport layer, and if necessary, the curing reaction is initiated by light energy after drying. 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 above method for forming the charge generation layer, the charge generation material is dispersed together with the coating solution containing the radical polymerizable composition, and the curing reaction is started by coating and light energy to form a crosslinked surface layer. Is done. 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 a suitable 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 and the charge transport layer.

  As the binder resin, in addition to the binder resin previously mentioned in the section of the charge transport layer, the binder resin mentioned in the charge generation layer 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. After drying as necessary, it is cured by light energy 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 generating 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. 10 to 70 parts by weight of the transport material is preferably used.

<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 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 the environmental resistance, in order to prevent a decrease in sensitivity and an increase in residual potential, in particular, a crosslinked surface layer, a charge generation layer, a charge transport layer, an undercoat layer, an intermediate layer, etc. Antioxidants can be added to each 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- (28-di-t-butyl-4-hydroxy Phenyl) 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-tert-butylphenyl) butane, 1,28-trimethyl-2,4,6-tris (28-di-tert-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] clico- Luester, tocopherols, etc.

(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 cross-linked surface layer. For example, at least after the photoconductor is subjected to charging, image exposure, and development processes, image holding is performed. 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.

  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 photoconductor (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. Be 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 the cross-linked surface layer and at least one of charging, developing, transferring, cleaning, and charge eliminating 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 Compound having Charge Transporting Structure>
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

(2) 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. 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. In this way, 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

  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]
An undercoat layer was formed on an Al support (outer diameter 30 mmφ) by dipping so that the film thickness after drying was 28 μm.
・ Coating liquid for undercoat layer 6 parts alkyd resin (Beckosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals, Inc.)
Melamine resin 4 parts (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.)
Titanium oxide 40 parts (CR-EL: Ishihara Sangyo)
50 parts of methyl ethyl ketone On this undercoat layer, a charge generation layer coating solution containing a bisazo pigment having the following structure was dip coated and dried by heating to form a 0.2 μm-thick charge generation layer.
-Coating solution for charge generation layer 2.5 parts of bisazo pigment with the following structure

Polyvinyl butyral (XYHL, manufactured by UCC) 0.5 parts Cyclohexanone 200 parts Methyl ethyl ketone 80 parts On this charge generation layer, dip-coating is performed using the coating liquid for charge transport layer having the following structure, followed by drying by heating. A charge transport layer of 22 μm was formed.
・ Coating solution for charge transport layer 10 parts of bisphenol Z type polycarbonate 10 parts of low molecular charge transport material with the following structure

Tetrahydrofuran 80 parts 1% silicone oil in tetrahydrofuran 0.2 parts (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.)

Spray coating was performed on the charge transport layer using a crosslinked surface layer coating solution having the following constitution. A drum was installed in the light energy irradiation tank, and light irradiation was performed under the conditions of irradiation light intensity (metal halide lamp): 650 mW / cm ² and irradiation time: 120 seconds. The temperature in the irradiation tank at the start of irradiation was 22.5 ° C. The irradiated photoreceptor was further dried at 130 ° C. for 30 minutes to provide a 5.2 μm cross-linked surface layer to obtain the electrophotographic photoreceptor of the present invention.
・ Crosslinking surface layer coating solution Trifunctional or higher functional radical polymerizable monomer 1 having no charge transporting structure 1 10 parts KAYARAD TMPTA (Nippon Kayaku)
(TMPTA: trimethylolpropane triacrylate)
10 parts of a radically polymerizable compound having a monofunctional charge transporting structure
(Exemplary Compound No. 54)
Photoinitiator 1 part 1-Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
80 parts of tetrahydrofuran

[Example 2]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 24.3 ° C.

[Example 3]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 26.2 ° C.

[Example 4]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 27.8 ° C.

[Example 5]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 18.2 ° C.

[Example 6]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 15.8 ° C.

[Comparative Example 1]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 29.3 ° C.

[Comparative Example 2]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 13.9 ° C.

[Example 8]
As the radical polymerizable compound having the charge transporting structure of Example 1, Exemplified Compound No. 1 was used. 360 was used, and an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 24.8 ° C. The film thickness of the crosslinked surface layer at this time was 4.9 μm.

[Example 9]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 16.2 ° C.

[Example 10]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 27.9 ° C.

[Comparative Example 3]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 29.5 ° C.

[Comparative Example 4]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 12.9 ° C.

[Example 11]
As the radical polymerizable compound having the charge transporting structure of Example 1, the exemplified compound NO. 148 was used, and an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 22.6 ° C. The film thickness of the crosslinked surface layer at this time was 4.7 μm.

[Comparative Example 5]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 13.1?

[Comparative Example 6]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 30.1 ° C.

[Example 12]
As the radical polymerizable compound having the charge transporting structure of Example 1, the exemplified compound NO. 150 was used, and an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 21.8 ° C. The film thickness of the crosslinked surface layer at this time was 4.7 μm.

[Comparative Example 7]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 13.2 ° C.

[Comparative Example 8]
It was produced in the same manner as in Example 1 except that the temperature in the irradiation tank at the start of irradiation was 31.2 ° C.

[Comparative Example 9]
It was produced in the same manner as Example 1 except that the cross-linked surface layer was not provided.

(Rz measurement)
The produced electrophotographic photosensitive member was measured using Surfcom 1400D (manufactured by Tokyo Seimitsu) according to JIS B0601-1994 standard, and the average value and standard deviation of Rz were obtained. The results are shown in Table 3.

(Real machine paper test)
The produced electrophotographic photosensitive member was tested for 100,000 sheets of actual paper (A4, MyPaper made by NBS Ricoh, charged potential at start-700V) using a modified imgio Neo270 made by Ricoh (655 nm semiconductor laser as an image exposure light source). ) To evaluate wear characteristics, in-machine potential, blade squeal evaluation, and image evaluation. The results are shown in Tables 4, 5, and 6.

  Since the electrophotographic photoreceptor of the present invention can provide a good image for a long period of time, it can be effectively used in an image forming process of a copying machine, a facsimile, a laser printer or the like.

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.

Explanation of symbols

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 101 Photosensitive drum 102 Charging device 103 Exposure 104 Developing device 105 Transfer body 106 Transfer device 107 Cleaning blade

Claims (20)

  In an electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, the surface layer of the photosensitive layer has at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerization having a charge transport structure. An electrophotographic photosensitive member, which is a cross-linked layer cured by irradiating light energy on a mixture comprising a functional compound under a condition that the environmental temperature at the start of light energy irradiation is 15 to 28 ° C.   2. The electrophotographic photosensitive member according to claim 1, wherein Rz (ten-point average surface roughness) of the surface layer of the photosensitive layer is 0.05 to 0.50 [mu] m.   3. The electrophotographic photoreceptor according to claim 1, wherein the radical polymerizable compound having a charge transporting structure is monofunctional.   3. The electrophotographic photoreceptor according to claim 1, wherein the functional group of the trifunctional or higher functional radical polymerizable monomer having no charge transport structure is an acryloyloxy group and / or a methacryloyloxy group.   3. The electrophotographic photoreceptor according to claim 1, wherein the radical polymerizable compound having a charge transporting structure has an acryloyloxy group and / or a methacryloyloxy group as a functional group.   3. The electrophotographic photosensitive member according to claim 1, wherein the radical polymerizable compound having a charge transporting structure has a triarylamine structure. The electrophotographic photosensitive member according to claim 1 or 2, wherein the radical polymerizable compound having a charge transporting structure is a compound represented by the following general formula (1) or (2).

(In the formula, 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, Group, alkoxy group, —COOR ₇ (R ₇ is 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), halogen Carbonyl group or CONR ₈ R ₉ (R ₈ and R ₉ may 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. Ar ₁ and Ar ₂ each represent a substituted or unsubstituted arylene group, and may be the same or different.Ar ₃ , which may be the same or different from each other. Ar ₄ may be substituted Represents an unsubstituted aryl group, which 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 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 group, or an alkyleneoxycarbonyl group, and m and n represent an integer of 0 to 3.) 3. The electrophotographic photosensitive member according to claim 1, wherein the radical polymerizable compound having the charge transporting structure is one or more compounds represented by 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. )   9. 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 surface layer from the support side.   In a method for producing an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, it comprises at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. An electrophotographic photosensitive film characterized by forming a crosslinked layer as a surface layer of the photosensitive layer by irradiating the mixture with light energy under the condition that the ambient temperature at the start of light energy irradiation is 15 to 28 ° C. Body manufacturing method.   In a method for producing an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, it comprises at least a trifunctional or higher functional radical polymerizable monomer having no charge transport structure and a radical polymerizable compound having a charge transport structure. The mixture is cured by irradiation with light energy under the condition that the ambient temperature at the start of irradiation with light energy is 15 to 28 ° C., and the Rz (10-point average surface roughness) as the surface layer of the photosensitive layer is 0. A method for producing an electrophotographic photoreceptor, comprising forming a crosslinked layer having a thickness of from 0.5 to 0.50 μm.   12. The method for producing an electrophotographic photosensitive member according to claim 10, wherein the radical polymerizable compound having a charge transporting structure is monofunctional.   12. The electrophotographic photosensitive member according to claim 10, wherein the functional group of the tri- or higher functional radical polymerizable monomer having no charge transport structure is an acryloyloxy group and / or a methacryloyloxy group. Method.   12. The method for producing an electrophotographic photoreceptor according to claim 10, wherein the radical polymerizable compound having a charge transporting structure has an acryloyloxy group and / or a methacryloyloxy group as a functional group.   12. The method for producing an electrophotographic photosensitive member according to claim 10, wherein the radical polymerizable compound having a charge transporting structure has a triarylamine structure. 12. The method for producing an electrophotographic photosensitive member according to claim 10, wherein the radical polymerizable compound having a charge transporting structure is a compound represented by the following general formula (1) or (2).

(In the formula, 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, Group, alkoxy group, —COOR ₇ (R ₇ is 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), halogen Carbonyl group or CONR ₈ R ₉ (R ₈ and R ₉ may 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. Ar ₁ and Ar ₂ each represent a substituted or unsubstituted arylene group, and may be the same or different.Ar ₃ , which may be the same or different from each other. Ar ₄ may be substituted Represents an unsubstituted aryl group, which 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 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 group, or an alkyleneoxycarbonyl group, and m and n represent an integer of 0 to 3.) 12. The method for producing an electrophotographic photosensitive member according to claim 10, wherein the radical polymerizable compound having a charge transporting structure is one or more compounds represented by 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. )   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 detachable from the forming apparatus main body.

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