JP4844004B2 - Cured body, cured body forming composition, electrophotographic photosensitive member, outermost surface layer forming coating liquid, process cartridge, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cured body applicable to various kinds of molded articles exemplified by an electrophotographic photoreceptor, and achieving both of mechanical strength and oxidation-preventing properties in high level. <P>SOLUTION: The cured body is obtained by curing a composition comprising a polymerizable monomer containing at least one kind selected from the group consisting of a compound represented by general formula (1): F-[D-Si(R<SP>1</SP>)<SB>(3-a)</SB>Q<SB>a</SB>]<SB>b</SB>, and a compound represented by general formula (2): F-[(X)<SB>n</SB>R<SP>2</SP>-ZH]<SB>m</SB>, and/or a silicone resin composed of the polymerizable monomer and having a crosslinked structure, and a phenol resin and/or a phenoxy resin. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a cured body, a composition for forming a cured body, an electrophotographic photosensitive member, a coating solution for forming an outermost surface layer, a process cartridge, and an image forming apparatus.

  General-purpose polymer materials are generally susceptible to oxidative degradation. For example, polyesters widely used in molded articles such as beverage bottles are likely to be oxidized and deteriorated in the presence of heat and oxygen, thereby causing color fading and a decrease in mechanical strength, which is often a problem. Similarly, polycarbonate used for a substrate of a recording medium such as a CD-ROM or DVD is likely to be oxidized and deteriorated. For this reason, in order to use these polymer materials in a molded body, it is necessary to devise measures for preventing oxidative degradation.

  Known methods for preventing oxidative deterioration of the molded body include, for example, a method of containing an antioxidant such as phosphorus-based or hindered amine in the molded body, and a method of coating the molded body with a film having antioxidant properties. It has been.

  Further, there is an electrophotographic photosensitive member (hereinafter abbreviated as “photosensitive member” in some cases) used in an electrophotographic image forming apparatus using a polymer material. In recent years, the demand for extending the life of a photoreceptor is increasing. In a so-called xerographic image forming apparatus having a photoreceptor, a charging unit, an exposure unit, a developing unit, a transfer unit, and a fixing unit, each member In addition, due to the technological progress of the system, higher speed and longer life have been achieved. As a result, the demand for high-speed compatibility and high reliability of each subsystem is increasing. In particular, photoconductors used for image writing and cleaners that clean photoconductors are subject to a lot of stress due to sliding, so they tend to cause image defects due to scratches, wear, chipping, etc. The demand is even stronger.

  Furthermore, there is an increasing demand for higher image quality in image forming apparatuses. In order to satisfy this requirement, the toner is made smaller in particle size, made uniform in particle size distribution, spheroidized, and the like. There is a lot of toner development. As a result, a so-called photographic image quality has recently been obtained.

In order to realize a long life of the electrophotographic photosensitive member, it is extremely important to improve the mechanical strength of the outermost surface layer to reduce wear. For example, Patent Document 1 listed below discloses a photoconductor having improved mechanical strength by containing a specific silane compound in the outermost surface layer.
Japanese Patent Laid-Open No. 11-38656

  However, there is still room for improvement even if the molded body has been devised to prevent the above-described oxidation deterioration and the electrophotographic photosensitive member described in Patent Document 1 can be put to practical use.

  For example, the method of containing an antioxidant in a molded body has a drawback that the mechanical strength of the molded body is extremely reduced because a low molecular weight antioxidant is mixed into the molded body.

  In the case of a method of coating a molded article with an antioxidant film, it is possible to suppress a decrease in mechanical strength as a bulk of the molded article to some extent, but in order to obtain sufficient antioxidant properties, It is necessary to mix a large amount of antioxidant, and the mechanical strength of the coating is significantly reduced. Therefore, it is not suitable for applications that require surface wear resistance. Furthermore, since the antioxidant coating film may be mechanically peeled with the surface deterioration, there is a problem that it cannot withstand long-term use.

  In addition, regarding the electrophotographic photosensitive member, the electrophotographic photosensitive member described in Patent Document 1 can improve the mechanical strength of the outermost surface layer and reduce wear, but has an antioxidant property of the outermost surface layer. This is not always sufficient, and when an electrophotographic process including charging, exposure, development and transfer is repeated, image quality may be degraded. This deterioration in image quality is caused by the fact that discharge products such as NOx and ozone gas generated by charging stress in the electrophotographic process adhere to the surface of the photoconductor and penetrate into the photoconductor to generate oxidative degradation products. Caused by cause. At this time, if the antioxidant property of the outermost surface layer of the photoconductor is insufficient, an oxidized degradation product is easily generated, which adheres to the surface of the photoconductor and causes image quality deterioration such as white spots and density unevenness. . Further, when the discharge product penetrates into the outermost surface layer, it causes deterioration of the resin and the like, and the mechanical strength of the outermost surface layer is also lowered. That is, in order to obtain good image quality over a long period of time, it is important to improve the antioxidant properties of the outermost surface layer of the photoreceptor.

  The present invention has been made in view of the above-described problems of the prior art, and can be applied to various molded articles including an electrophotographic photosensitive member, and can achieve both mechanical strength and antioxidant properties at a high level. An object of the present invention is to provide a possible cured product and a composition for forming a cured product for forming the cured product.

  The present invention also provides an electrophotographic photosensitive member having sufficient mechanical strength, capable of sufficiently suppressing the occurrence of oxidative degradation, and capable of obtaining good image quality over a long period of time, and the electron An object of the present invention is to provide a coating solution for forming the outermost surface layer for forming the outermost surface layer of the photographic photoreceptor.

  It is another object of the present invention to provide a process cartridge and an image forming apparatus that include the electrophotographic photosensitive member and can obtain a good image quality over a long period of time.

In order to achieve the above object, the present invention provides a polymerizable monomer comprising at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). And / or a cured product obtained by curing a composition containing a silicon resin having a cross-linked structure composed of the polymerizable monomer and a phenol resin and / or a phenoxy resin. To do.
F- [D-Si (R ¹ ) _(3-a) Q _a ] _b (1)
[In Formula (1), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ¹ represents a hydrogen atom, an alkyl group, or A substituted or unsubstituted aryl group, Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4. ]
F-[(X) _n R ² -ZH] _m (2)
[In Formula (2), F represents an organic group derived from a compound having a hole transporting ability, R ² represents an alkylene group, Z represents an oxygen atom, a sulfur atom, NH, or CO ₂ ; X represents an oxygen atom or a sulfur atom, n represents 0 or 1, and m represents an integer of 1 to 4. ]

  According to such a cured product, excellent mechanical strength and excellent antioxidant properties can be obtained at the same time. The reason why the mechanical strength and the antioxidant property can be obtained simultaneously is not necessarily clear, but the present inventors infer as follows. That is, in the cured product obtained by curing the above composition, the phenolic hydroxyl group in the phenol resin and / or phenoxy resin is oxidized by itself, thereby preventing the surrounding oxidation and improving the antioxidant property of the cured product. Can be considered. Moreover, it is thought that the mechanical strength of the cured body can be increased by forming a siloxane cross-linked structure three-dimensionally from the cured silicon resin. When the specific silicon resin and the phenol resin and / or phenoxy resin are used in combination, the improvement in mechanical strength due to the siloxane cross-linking structure is hindered due to the high compatibility and the high reactivity with each other. It is thought that the outstanding antioxidant property by a phenol resin and / or a phenoxy resin can be obtained without this. In addition, the aromatic ring present in large numbers in the specific silicon resin stacks with the aromatic ring in the phenol resin and / or phenoxy resin, thereby further improving the mechanical strength and antioxidant properties of the cured product. It is thought that you can.

  Moreover, when the silicon resin is composed of the specific polymerizable monomer, the cured body can obtain an excellent antistatic effect. Furthermore, since such a cured product can exhibit excellent antioxidant properties without using an antioxidant, it is possible to obtain better mechanical strength by not mixing the antioxidant.

  Here, it is preferable that the composition which forms the said hardening body contains a resole resin as a phenol resin. Moreover, it is also preferable that the composition which forms the said hardening body contains novolak resin as a phenol resin. Furthermore, the composition forming the cured body preferably contains a phenoxy resin.

  When a resole resin is used, the mechanical strength of the cured body can be further improved. Moreover, when a novolac resin is used, the insulation of a hardening body can be improved and a hardening body can be used conveniently for the use as which electrical neutrality is calculated | required. Furthermore, when a phenoxy resin is used, the flexibility and flexibility of the cured product can be improved.

  Moreover, it is preferable that the cured body of the present invention has a structure in which the silicon resin and the phenol resin and / or the phenoxy resin are chemically bonded.

  When the silicon resin and the phenol resin and / or the phenoxy resin are chemically bonded to form a cured body, the cured body can obtain better mechanical strength and better antioxidant properties.

Further, the cured product of the present invention preferably has a color difference Δb ^* of 0.10 or less before and after exposure for 8 hours in an 80 ° C. thermostatic layer into which 400 ppm of ozone is introduced.

The present invention also provides a polymerizable monomer containing at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and / or Provided is a composition for forming a cured body, comprising a silicon resin having a crosslinked structure composed of a polymerizable monomer, a phenol resin and / or a phenoxy resin, and an organic solvent.
F- [D-Si (R ¹ ) _(3-a) Q _a ] _b (1)
[In Formula (1), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ¹ represents a hydrogen atom, an alkyl group, or A substituted or unsubstituted aryl group, Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4. ]
F-[(X) _n R ² -ZH] _m (2)
[In Formula (2), F represents an organic group derived from a compound having a hole transporting ability, R ² represents an alkylene group, Z represents an oxygen atom, a sulfur atom, NH, or CO ₂ ; X represents an oxygen atom or a sulfur atom, n represents 0 or 1, and m represents an integer of 1 to 4. ]

  According to such a composition for forming a cured product, the cured product of the present invention excellent in both mechanical strength and antioxidant property can be efficiently formed. Here, when the cured body is manufactured as, for example, an antioxidant film, it is extremely advantageous to manufacture by a dip coating method because of high film thickness accuracy and low cost. According to the composition for forming a cured product of the present invention, the pot life of the coating solution can be extremely increased as compared with a conventional coating solution using a crosslinkable polymer, Manufacturing can be performed easily.

  Here, it is preferable that the said hardening body formation composition contains a resole resin as said phenol resin. Moreover, it is also preferable that the said composition for hardening body contains novolak resin as said phenol resin. Furthermore, it is preferable that the said composition for hardening body formation contains the said phenoxy resin.

  When the said composition for hardening body formation contains a resole resin, the hardening body which has the more outstanding mechanical strength can be obtained. Moreover, when the said composition for hardening body formation contains a novolak resin, the hardening body which has the outstanding insulation and can be used suitably for the use by which electrical neutrality is calculated | required can be obtained. . Furthermore, when the said composition for hardening body formation contains a phenoxy resin, the hardening body which has the outstanding softness | flexibility and flexibility can be obtained.

The present invention is also an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer provided on the conductive support, wherein the photosensitive layer is on the side farthest from the conductive support. The outermost surface layer, and the outermost surface layer is a polymerizable unit containing at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). It is a layer formed by curing a composition containing a silicon resin having a crosslinked structure composed of a monomer and / or the polymerizable monomer, and a phenol resin and / or a phenoxy resin. An electrophotographic photoreceptor is provided.
F- [D-Si (R ¹ ) _(3-a) Q _a ] _b (1)
[In Formula (1), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ¹ represents a hydrogen atom, an alkyl group, or A substituted or unsubstituted aryl group, Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4. ]
F-[(X) _n R ² -ZH] _m (2)
[In Formula (2), F represents an organic group derived from a compound having a hole transporting ability, R ² represents an alkylene group, Z represents an oxygen atom, a sulfur atom, NH, or CO ₂ ; X represents an oxygen atom or a sulfur atom, n represents 0 or 1, and m represents an integer of 1 to 4. ]

  According to such an electrophotographic photosensitive member, sufficient mechanical strength can be obtained, generation of oxidation degradation products can be sufficiently suppressed, and good image quality can be obtained over a long period of time. The reason why such an effect is obtained is not necessarily clear, but the present inventors infer as follows. That is, in the outermost surface layer obtained by curing the above composition, the phenolic hydroxyl group in the phenolic resin and / or phenoxy resin is oxidized by itself to prevent the surrounding oxidation, and the outermost surface layer has an antioxidant property. It is thought that it can raise. In addition, the cured product of the silicon resin forms a siloxane cross-linked structure in three dimensions, so that the mechanical strength of the outermost surface layer can be increased and the generation of oxidative degradation products associated with the electrophotographic process can be further suppressed I think it can be done. When the specific silicon resin and the phenol resin and / or phenoxy resin are used in combination, the improvement in mechanical strength due to the siloxane cross-linking structure is hindered due to the high compatibility and the high reactivity with each other. It is thought that the outstanding antioxidant property by a phenol resin and / or a phenoxy resin can be obtained without this. In addition, the mechanical strength of the outermost surface layer can be further improved by stacking a large number of aromatic rings in the specific silicon resin with the aromatic rings in the phenol resin and / or phenoxy resin. , It is possible to suppress the discharge product generated in the electrophotographic process from penetrating into the outermost surface layer, and to sufficiently reduce the mechanical strength due to the generation of the oxidized deterioration product and the deterioration of the outermost surface layer. It is thought that it can be suppressed. Suppressing the generation of oxidative degradation products can reduce the amount of deposits on the surface of the photoconductor, so that good image quality can be obtained, and the decrease in mechanical strength of the outermost surface layer is also suppressed. According to the electrophotographic photosensitive member of the present invention, good image quality can be obtained over a long period of time.

  Further, deposits on the surface of the photosensitive member are scraped off by a cleaning means such as a cleaning blade. At this time, the surface of the photosensitive member is mechanically worn to improve the removal of the deposits. However, in the conventional photoconductor, when the mechanical strength of the outermost surface layer is increased, the amount of mechanical wear decreases, and the removal of deposits tends to be insufficient. On the other hand, according to the electrophotographic photosensitive member of the present invention, the amount of the deposit itself can be reduced and the removal property of the deposit can be improved, and a good image quality can be obtained over a long period of time. Can do.

  Moreover, when the silicon resin is composed of the specific polymerizable monomer, the outermost surface layer can obtain an excellent antistatic effect. Further, in such an electrophotographic photosensitive member, the outermost surface layer can exhibit excellent antioxidant properties without using an antioxidant, and therefore, better mechanical strength can be obtained by not mixing an antioxidant. It can also be obtained.

  Here, in the electrophotographic photoreceptor, the composition forming the outermost surface layer preferably contains a resole resin as a phenol resin. Moreover, it is also preferable that the said composition which forms the said outermost surface layer contains a novolak resin as a phenol resin. Further, the composition forming the outermost surface layer preferably contains a phenoxy resin.

  When a resole resin is used, the mechanical strength of the outermost surface layer can be further improved. Moreover, when novolac resin is used, the insulation of the outermost surface layer can be enhanced. Furthermore, when a phenoxy resin is used, the flexibility and flexibility of the outermost surface layer can be improved.

  In the electrophotographic photoreceptor of the present invention, the outermost surface layer preferably has a structure in which the silicon resin and the phenol resin and / or the phenoxy resin are chemically bonded.

  The silicon resin and the phenolic resin and / or phenoxy resin are chemically combined to form the outermost surface layer, thereby improving the mechanical strength of the outermost surface layer and suppressing the generation of oxidative degradation products associated with the electrophotographic process. Can be achieved at a higher level, and as a result, the electrophotographic photosensitive member can obtain good image quality for a longer period of time.

Furthermore, the electrophotographic photoreceptor of the present invention preferably has a color difference Δb ^* of the outermost surface layer of 0.10 or less before and after exposure for 8 hours in a constant temperature layer at 80 ° C. into which 400 ppm of ozone has been introduced.

The present invention also provides an electrophotographic photosensitive member comprising: a conductive support; and a photosensitive layer provided on the conductive support and having an outermost surface layer disposed on the side farthest from the conductive support. A coating solution for forming the outermost surface layer of the body, comprising at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) An outermost surface characterized by containing a polymerizable monomer and / or a silicon resin having a cross-linked structure composed of the polymerizable monomer, a phenol resin and / or a phenoxy resin, and an organic solvent A coating liquid for layer formation is provided.
F- [D-Si (R ¹ ) _(3-a) Q _a ] _b (1)
[In Formula (1), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ¹ represents a hydrogen atom, an alkyl group, or A substituted or unsubstituted aryl group, Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4. ]
F-[(X) _n R ² -ZH] _m (2)
[In Formula (2), F represents an organic group derived from a compound having a hole transporting ability, R ² represents an alkylene group, Z represents an oxygen atom, a sulfur atom, NH, or CO ₂ ; X represents an oxygen atom or a sulfur atom, n represents 0 or 1, and m represents an integer of 1 to 4. ]

  According to the coating solution for forming the outermost surface layer, the outermost surface layer in the electrophotographic photosensitive member of the present invention described above can be efficiently formed. Here, it is extremely advantageous to form the outermost surface layer of the electrophotographic photosensitive member by a dip coating method because of high film thickness accuracy and low cost. According to the coating solution for forming the outermost surface layer of the present invention, the pot life of the coating solution can be made extremely long as compared with the conventional coating solution using a crosslinkable polymer, and the outermost surface by the dip coating method. It becomes possible to easily form the layer. By forming the outermost surface layer in the electrophotographic photosensitive member using the coating solution for forming the outermost surface layer, the obtained electrophotographic photosensitive member can obtain sufficient mechanical strength and sufficiently generate oxidative degradation products. And good image quality can be obtained over a long period of time.

  Here, the outermost surface layer forming coating solution preferably contains a resol resin as the phenol resin. Moreover, it is also preferable that the coating solution for forming the outermost surface layer contains a novolac resin as the phenol resin. Furthermore, it is preferable that the coating solution for forming the outermost surface layer contains the phenoxy resin.

  When the coating solution for forming the outermost surface layer contains a resol resin, an outermost surface layer having better mechanical strength can be formed. Moreover, when the said outermost surface layer forming coating liquid contains a novolak resin, the outermost surface layer which has the outstanding insulating property can be formed. Furthermore, when the coating solution for forming the outermost surface layer contains a phenoxy resin, an outermost surface layer having excellent flexibility and flexibility can be formed.

  The present invention also provides the electrophotographic photosensitive member of the present invention, charging means for charging the electrophotographic photosensitive member, and developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image. There is provided a process cartridge comprising: a developing unit for forming; and at least one selected from the group consisting of a cleaning unit for removing toner remaining on the surface of the electrophotographic photosensitive member.

  The present invention further includes the electrophotographic photosensitive member of the present invention, a charging unit for charging the electrophotographic photosensitive member, an exposure unit for forming an electrostatic latent image on the charged electrophotographic photosensitive member, And developing means for developing the electrostatic latent image with toner to form a toner image, and transfer means for transferring the toner image from the electrophotographic photosensitive member to a transfer target. An image forming apparatus is provided.

  These process cartridges and image forming apparatuses can obtain good image quality over a long period of time by including the electrophotographic photosensitive member of the present invention.

  According to the present invention, a cured body that can be applied to various molded bodies including an electrophotographic photosensitive member and can achieve both mechanical strength and antioxidant properties at a high level, and the cured body is formed. It is possible to provide a composition for forming a cured body.

  Further, according to the present invention, an electrophotographic photosensitive member having sufficient mechanical strength, capable of sufficiently suppressing the occurrence of oxidative degradation, and capable of obtaining good image quality over a long period of time, and A coating solution for forming the outermost surface layer for forming the outermost surface layer of the electrophotographic photosensitive member can be provided.

  Furthermore, according to the present invention, it is possible to provide a process cartridge and an image forming apparatus capable of obtaining good image quality over a long period of time by including the electrophotographic photosensitive member.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

(Curing body and composition for forming cured body)
The cured product of the present invention is a polymerizable monomer containing at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and / or A composition containing a silicon resin having a cross-linked structure composed of the polymerizable monomer and a phenol resin and / or a phenoxy resin is cured.
F- [D-Si (R ¹ ) _(3-a) Q _a ] _b (1)
[In Formula (1), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ¹ represents a hydrogen atom, an alkyl group, or A substituted or unsubstituted aryl group, Q represents a hydrolyzable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4. ]
F-[(X) _n R ² -ZH] _m (2)
[In Formula (2), F represents an organic group derived from a compound having a hole transporting ability, R ² represents an alkylene group, Z represents an oxygen atom, a sulfur atom, NH, or CO ₂ ; X represents an oxygen atom or a sulfur atom, n represents 0 or 1, and m represents an integer of 1 to 4. ]

  Hereinafter, each constituent material of the cured body will be described.

  The silicon resin having a crosslinked structure is composed of a polymerizable monomer containing at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2). It is. Here, specific examples of the compounds represented by the general formulas (1) and (2) will be described later in the description of the electrophotographic photosensitive member below.

  The silicon resin having such a crosslinked structure and / or the above polymerizable monomer constituting the silicon resin can be used alone or in combination of two or more.

  As the phenol resin, known resins can be used without particular limitation. For example, phenol resins such as resol type, novolak type, cresol type, xylenol type, pt-butylphenol type, p-phenylphenol type, resorcinol type, etc. Can be used. These phenol resins can be used alone or in combination of two or more.

A phenoxy resin is a compound having in its molecule a structure in which a group represented by the following general formula (A) is bonded to a constituent carbon atom of a phenyl group. For example, a structure in which an alkyl alcohol is introduced into a phenolic hydroxyl group in a phenol resin. It is what has.
-O-R-OH (A)
[Wherein, R represents an alkylene group. ]

  As such a phenoxy resin, a known one can be used without particular limitation, and for example, a phenoxy resin such as a bisethoxyphenylpropane type or a bisethoxyphenylisopropane type can be used. These phenoxy resins can be used alone or in combination of two or more.

  The cured body of the present invention can be obtained by curing the composition containing each of the above constituent materials. For example, it can be obtained by curing the composition for forming a cured body of the present invention. Here, the composition for forming a cured body of the present invention is polymerizable containing at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2). It is comprised including the silicon resin which has a crosslinked structure which consists of a monomer and / or this polymerizable monomer, the said phenol resin and / or the said phenoxy resin, and the organic solvent.

  Here, the organic solvent is not particularly limited as long as it can dissolve or disperse the constituent material of the cured body. For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cell Usable organic solvents such as sorb, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene and toluene can be used alone or in admixture of two or more.

  In the composition for forming a cured body, the content of the silicon resin having the crosslinked structure and / or the polymerizable monomer constituting the silicon resin is 20 to 80% by mass based on the total solid content in the coating solution. It is preferable to be 30 to 70% by mass. When the blending amount is less than 20% by mass, the viscosity of the coating solution tends to be low and the film formability tends to be poor. On the other hand, if the blending amount exceeds 70% by mass, the pot life of the coating solution tends to be shortened.

  In the composition for forming a cured body, the content of the phenol resin and / or phenoxy resin is preferably 10 to 80% by mass, based on the total solid content in the coating solution, and preferably 20 to 70% by mass. More preferably. If the blending amount is less than 10% by mass, the viscosity of the coating solution tends to be low and the film formability tends to be poor. On the other hand, when the blending amount exceeds 80% by mass, the pot life of the coating solution tends to be shortened.

  The method for dispersing each of these constituent materials is not particularly limited, and usual methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used.

  For example, when the cured body of the present invention is formed as an antioxidant film, the cured film-forming composition described above is applied onto a substrate to form a coating film, and then the obtained coating film is thermally cured. Can be formed. Here, as a coating method of the coating solution, for example, die coating method, casting method, blade coating method, wire bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method, etc. The usual method can be used.

  Moreover, thermosetting can be performed on the conditions for 0.1 to 20 hours at the temperature of 80-250 degreeC. Thereby, a hardening body can be obtained.

  The cured product of the present invention thus obtained can be applied to the outermost surface layer of an electrophotographic photosensitive member, and has antioxidant properties and mechanical strength such as PET bottles, optical disk substrates, IC cards, and carport corrugated plates. It can be applied to required polymer moldings. The cured body of the present invention may be used as the molded body itself or as an antioxidant film of the molded body.

(Electrophotographic photosensitive member and outermost surface layer forming coating solution)
FIG. 1 is a schematic cross-sectional view showing a first embodiment of the electrophotographic photosensitive member of the present invention. The electrophotographic photoreceptor 100 shown in FIG. 1 is a so-called function-separated photoreceptor (or laminated photoreceptor), and has an undercoat layer 4, a charge generation layer 1, and a charge transport layer 2 on a conductive support 3. And the protective layer 5 are sequentially laminated. In the electrophotographic photoreceptor 100, a photosensitive layer 6 is constituted by the charge generation layer 1, the charge transport layer 2, and the protective layer 5. In the electrophotographic photosensitive member 100, the outermost surface layer located on the side farthest from the conductive support 3 is the protective layer 5, and as will be described later, the protective layer 5 is represented by the general formula (1). A polymerizable monomer containing at least one compound selected from the group consisting of a compound and a compound represented by the above general formula (2), and / or a silicon resin having a cross-linked structure consisting of the polymerizable monomer , A phenol resin and / or a phenoxy resin.

  Hereinafter, each element constituting the electrophotographic photoreceptor 100 will be described.

  First, the conductive support 3 will be described. Examples of the conductive support 3 include a metal plate, a metal drum, a metal belt, or a conductive material using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Examples thereof include paper, plastic film, belt and the like coated, vapor-deposited, or laminated with a conductive polymer, a conductive compound such as indium oxide, or a metal or alloy such as aluminum, palladium, or gold.

  Further, when the electrophotographic photoreceptor 100 is used in a laser printer, the surface of the conductive support 3 has a center line average roughness Ra of 0.04 in order to prevent interference fringes generated when laser light is irradiated. It is preferable that the surface is roughened to be ~ 0.5 μm. As a roughening method, wet honing is performed by suspending an abrasive in water and spraying the conductive support 3, and the conductive support 3 is pressed against a rotating grindstone to continuously grind. Centerless grinding, anodic oxidation, etc. are preferred. If Ra is less than 0.04 μm, the effect of preventing interference tends to be insufficient because it is close to a mirror surface, and if Ra exceeds 0.5 μm, the image quality tends to be coarse. When non-interfering light is used as a light source, roughening for preventing interference fringes is not particularly necessary, and generation of defects due to irregularities on the surface of the substrate can be prevented, which is suitable for longer life.

  Here, the roughening treatment by anodization is a treatment for forming an oxide film on the aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the porous anodic oxide film formed by anodic oxidation is chemically active as it is, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the pores in the anodized film are sealed with pressurized water vapor or boiling water (a metal salt such as nickel may be added) by volume expansion due to a hydration reaction, and a sealing process is performed to change to a more stable hydrated oxide. It is preferable.

  The thickness of the anodized film is preferably 0.3 to 15 μm. When the film thickness is less than 0.3 μm, the barrier property against implantation tends to be insufficient. On the other hand, if the film thickness exceeds 15 μm, the residual potential tends to increase due to repeated use.

  Further, the conductive support 3 may be subjected to treatment with an acidic aqueous solution or boehmite treatment. The treatment with an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid is carried out as follows. First, an acidic treatment liquid is prepared. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10 to 11% by mass, chromic acid is in the range of 3 to 5% by mass, and hydrofluoric acid is in the range of 0.5 to 2% by mass. The concentration of these acids is preferably in the range of 13.5 to 18% by mass. The treatment temperature is preferably 42 to 48 ° C., but by keeping the treatment temperature high, a thicker film can be formed faster. The film thickness is preferably 0.3 to 15 μm. If it is less than 0.3 μm, the barrier property against injection tends to be poor and the effect tends to be insufficient. On the other hand, when it exceeds 15 μm, there is a tendency that the residual potential increases due to repeated use.

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

  Next, the undercoat layer 4 will be described. The undercoat layer 4 includes, for example, an organometallic compound and a binder resin.

  As organometallic compounds, zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organotitanium compounds such as titanate coupling agents, aluminum chelate compounds, aluminum coupling agents In addition to organoaluminum compounds such as antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, And aluminum zirconium alkoxide compounds. . As the organometallic compound, in particular, an organozirconium compound, an organotitanyl compound, and an organoaluminum compound are preferably used because of their low residual potential and good electrophotographic characteristics.

  As binder resin, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenol resin , Vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, polyacrylic acid, and other known binder resins can be used. These mixing ratios can be appropriately set as necessary.

  The undercoat layer 4 includes vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxy. Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, Silane coupling agents such as β-3,4-epoxycyclohexyltrimethoxysilane can also be included.

  In the undercoat layer 4, an electron transport pigment can also be mixed / dispersed. Examples of the electron transport pigment include organic pigments such as perylene pigment, bisbenzimidazole perylene pigment, polycyclic quinone pigment, indigo pigment, and quinacridone pigment described in JP-A-47-30330, cyano group, nitro group, Examples thereof include organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as nitroso groups and halogen atoms, and inorganic pigments such as zinc oxide and titanium oxide. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments, zinc oxide, and titanium oxide are preferably used because of their high electron mobility.

  Further, the surface of these pigments may be surface-treated with the above coupling agent, binder resin or the like for the purpose of controlling dispersibility and charge transport property. If the amount of the electron transporting pigment is too large, the strength of the undercoat layer is lowered and a coating film defect is caused. Therefore, the amount is preferably 95% by mass or less, more preferably 90% by mass or less.

  In the undercoat layer 4, various organic compound fine powders or inorganic compound fine powders can be added for the purpose of improving electrical characteristics and light scattering properties. In particular, white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white, lithopone, and inorganic pigments such as alumina, calcium carbonate, barium sulfate, polytetrafluoroethylene resin particles, benzoguanamine resin particles, Styrene resin particles and the like are effective. The added fine powder preferably has a particle size of 0.01 to 2 μm. The fine powder is added as necessary, but the addition amount is preferably 10 to 90% by mass, and 30 to 80% by mass with respect to the total mass of the solid content of the undercoat layer 4. More preferably.

  In addition, it is also effective in the undercoat layer 4 to contain an electron transporting substance, an electron transporting pigment or the like from the viewpoint of lowering the residual potential and environmental stability.

  The undercoat layer 4 is formed using a coating solution for forming an undercoat layer containing the above constituent materials.

  As a method for mixing / dispersing the coating solution for forming the undercoat layer, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent. The organic solvent dissolves a periodical metal compound and a binder resin, and does not cause gelation or aggregation when an electron transporting pigment is mixed / dispersed. I just need it. Examples of the organic solvent include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. Ordinary organic solvents such as chloroform, chlorobenzene and toluene. These can be used individually by 1 type or in mixture of 2 or more types.

  The coating method used when providing the undercoat layer 4 is a normal method such as a blade coating method, a Mayer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method. Can be used.

  After coating, the coating film is dried to obtain an undercoat layer. Usually, the drying is performed at a temperature at which the solvent can be evaporated and a film can be formed. In particular, the conductive support 3 subjected to the acidic solution treatment and the boehmite treatment is preferably formed with the undercoat layer 4 because its defect concealing power tends to be insufficient.

  The thickness of the undercoat layer 4 is preferably 0.01 to 30 μm, more preferably 0.05 to 25 μm.

  Next, the charge generation layer 1 will be described. The charge generation layer 1 includes a charge generation material or a charge generation material and a binder resin.

  Charge generation materials include azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, organic pigments such as perylene pigments, pyrrolopyrrole pigments, and phthalocyanine pigments, and inorganic pigments such as trigonal selenium and zinc oxide. All known ones can be used. As the charge generation material, an inorganic pigment is preferable when a light source with an exposure wavelength of 380 nm to 500 nm is used, and a metal and a metal-free phthalocyanine pigment are preferable when a light source with an exposure wavelength of 700 nm to 800 nm is used. Among them, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472 and special Dichlorotin phthalocyanine disclosed in Kaihei 5-140473 or titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 is particularly preferable.

  The binder resin can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polymers such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin. Insulating resins such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be mentioned, but are not limited thereto. These binder resins can be used individually by 1 type or in mixture of 2 or more types.

  The charge generation layer 1 is formed by vapor deposition using the charge generation material or using a charge generation layer forming coating solution containing the charge generation material and a binder resin.

  In the charge generation layer forming coating solution, the mixing ratio (mass ratio) of the charge generation material and the binder resin is preferably 10: 1 to 1:10. Further, as a method for dispersing them, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. At this time, a condition that the crystal type does not change due to dispersion is required. Incidentally, it has been confirmed that the crystal form is not changed before dispersion in any of the above dispersion methods.

  Further, in this dispersion, it is effective that the particles have a particle size of preferably 0.5 μm or less, more preferably 0.3 μm or less, and still more preferably 0.15 μm or less.

  Moreover, as a solvent used for these dispersions, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, Examples include ordinary organic solvents such as tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene. These can be used individually by 1 type or in mixture of 2 or more types.

  In addition, as a coating method used when the charge generation layer 1 is provided, a normal method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like. Can be used.

  The film thickness of the charge generation layer 1 is preferably 0.1 to 5 μm, more preferably 0.2 to 2.0 μm.

  Next, the charge transport layer 2 will be described. The charge transport layer 2 includes a charge transport material and a binder resin, or includes a polymer charge transport material.

  Charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds , Electron transport compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include pore transporting compounds. These charge transport materials can be used singly or in combination of two or more, but are not limited thereto.

  Moreover, as a charge transport material, the compound represented by the following general formula (3-1), (3-2), or (3-3) from a mobility viewpoint is preferable.

In the above formula (3-1), R ¹⁴ represents a hydrogen atom or a methyl group, and n ¹ represents 1 or 2. Ar ¹¹ and Ar ¹² represent a substituted or unsubstituted aryl group, —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), or —CH═CH—CH═C (Ar) ₂ ; Examples of the substituent include a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms. R ¹⁸ , R ¹⁹ , and R ²⁰ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group.

In said formula (3-2), R < ¹⁵ >, R < ¹⁵ '> may be same or different and shows a hydrogen atom, a halogen atom, a C1-C5 alkyl group, and a C1-C5 alkoxy group. R ¹⁶ , R ¹⁶ ′, R ¹⁷ and R ¹⁷ ′ may be the same or different, and are a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. An amino group substituted with an alkyl group, a substituted or unsubstituted aryl group, —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), or —CH═CH—CH═C (Ar) ₂ is shown. , R ¹⁸ , R ¹⁹ and R ²⁰ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group. n ² and ^{n 3} represents an integer of 0 to 2.

In the above formula (3-3), R ²¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH—CH═. C (Ar) ₂ is shown. Ar represents a substituted or unsubstituted aryl group. R ²² and R ²³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group substituted with an alkyl group having 1 to 2 carbon atoms, or A substituted or unsubstituted aryl group is shown.

  As the binder resin, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, Vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polysilane, Polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used individually by 1 type or in mixture of 2 or more types. The blending ratio (mass ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  A polymer charge transport material can also be used alone. As the polymer charge transport material, known materials having charge transport properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. The polymer charge transport material alone can be used as the charge transport layer, but it may be formed by mixing with the binder resin.

  The charge transport layer 2 is configured using a charge transport layer forming coating solution containing the above-described constituent materials. Solvents used in the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride. Examples include ordinary organic solvents such as aliphatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether, and linear ethers. These can be used individually by 1 type or in mixture of 2 or more types. Moreover, a well-known method can be used as a dispersion | distribution method of said each constituent material.

  Coating methods for applying the charge transport layer forming coating solution onto the charge generation layer 1 include blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain A usual method such as a coating method can be used.

  The film thickness of the charge transport layer 2 is preferably 5 to 50 μm, more preferably 10 to 30 μm.

  Next, the protective layer 5 that is the outermost surface layer in the electrophotographic photoreceptor 100 will be described. The protective layer 5 is a layer provided in order to give resistance to abrasion and scratches on the surface layer and to increase toner transfer efficiency. The protective layer 5 is a polymerizable monomer containing at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2), and / or It has the structure formed by hardening the composition containing the silicon resin which has this crosslinked structure which consists of this polymeric monomer, and a phenol resin and / or a phenoxy resin.

  Hereinafter, each constituent material of the protective layer 5 will be described.

  The silicon resin having a crosslinked structure contains at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2).

  Here, it is preferable that the protective layer 5 has a charge transporting property. From this viewpoint, the organic group F in the general formula (1) and the general formula (2) is represented by the following general formula (4). It is particularly preferred that

[Wherein, Ar ^{1 to} Ar ⁴ each independently represents a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group, and 2 to 4 of Ar ^{1 to} Ar ⁵ In the compound represented by the above formula (1), -D-Si (R ¹ ) _(3-a) Q _a or _a- (X in the compound represented by the above formula (2) ) _n R having the moiety capable of binding a bond represented by ² -ZH. ]

Ar ¹ to Ar ⁴ in the general formula (4) each independently represent a substituted or unsubstituted aryl group, specifically, the structural unit shown in Table 1 are preferred.

  Here, Ar is preferably a structural unit selected from Table 2.

  Z ′ is preferably a structural unit selected from Table 3.

Here, R ⁶ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, an unsubstituted phenyl group, or And an aralkyl group having 7 to 10 carbon atoms. R ^{7 to} R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or unsubstituted. A phenyl group, a C7-10 aralkyl group, or a halogen is shown. r and s represent 0 or 1, g and h represent an integer of 1 to 10, and t and t ′ represent an integer of 1 to 3. X ¹ is a group represented by —D—Si (R ² ) _(3-a) Q _a in the general formula (1), or Z— (R ¹ ) in the general formula (2). _The group represented by _p (X) _q- is shown.

  W is preferably a structural unit shown in Table 4.

  Here, i represents an integer of 0 to 3.

In the general formula (4), Ar ⁵ is preferably an aryl group exemplified in the description of Ar ^{1 to} Ar ⁴ when k is 0, and when k is 1, the aryl group is selected from the aryl group. An arylene group in which a hydrogen atom is removed is preferable.

As a specific example of the compound represented by the general formula (1), Ar ^{1 to} Ar ⁵ and k in the general formula (4) are the compounds (1-1) to ( 1-61), but not limited thereto. In Tables 5 to 10, S represented by a structure representing Ar ^{1 to} Ar ⁵ represents the structure in the right column of the same row. In Tables 5 to 10, Me represents a methyl group, Et represents an ethyl group, and iPr represents an isopropyl group.

  Specific examples of the compound represented by the general formula (2) include compounds (2-1) to (2-26) shown in the following Tables 11 to 16. In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

  In the present invention, as the phenol resin, known resins can be used without particular limitation. For example, resol type, novolak type, cresol type, xylenol type, pt-butylphenol type, p-phenylphenol type, resorcinol type A phenolic resin such as can be used. These phenol resins can be used alone or in combination of two or more.

  Further, the phenoxy resin is a compound having in its molecule a structure in which the group represented by the general formula (A) is bonded to the constituent carbon atom of the phenyl group, and any known one can be used without any particular limitation. A phenoxy resin such as bishydroxyethoxyphenylpropane type or bishydroxyethoxyphenylisopropane type can be used. These phenoxy resins can be used alone or in combination of two or more.

  In addition, a compound represented by the following general formula (5) can also be added to the protective layer 5 in order to control various physical properties such as strength and film resistance of the protective layer 5.

Si (R ³⁰ ) _(4-c) Q _c (5)
In the formula (5), R ³⁰ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q is shown a hydrolyzable group, c is an integer of 1-4.

  Specific examples of the compound represented by the general formula (5) include the following silane coupling agents. Examples of silane coupling agents include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl L) Triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H , 1H, 2H, 2H-perfluorodecyltriethoxysilane, trifunctional alkoxysilanes such as 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (c = 3); dimethyldimethoxysilane, diphenyldimethoxysilane, methyl And bifunctional alkoxysilanes such as phenyldimethoxysilane (c = 2); monofunctional alkoxysilanes such as trimethylmethoxysilane (c = 1), and the like. Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and monofunctional and bifunctional alkoxysilanes are preferable for improving the flexibility and film formability.

  In addition, a silicon-based hard coat agent produced mainly from these coupling agents can also be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Etc.) can be used.

  In addition, in order to increase the strength of the protective layer 5, it is also preferable to use a compound having two or more silicon atoms as shown in the following general formula (6).

B- (Si (R ² ) _(3-a) Q _a ) ₂ (6)
In the above formula (6), B represents a divalent organic group, R ² represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and a represents 1 to 3 Indicates an integer.

  Specific examples of the compound represented by the general formula (6) include the following compounds (6-1) to (6-16).

  Further, in order to extend pot life, control film properties, and reduce torque, the protective layer 5 contains at least one of a cyclic compound having a repeating structural unit represented by the following general formula (7) or a derivative thereof. It is preferable.

In the above formula (7), A ¹ and A ² each independently represent a monovalent organic group.

  Examples of the cyclic compound having a repeating structural unit represented by the general formula (7) include commercially available cyclic siloxanes. Specifically, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5-trimethyl-1,3,5- Triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7 , 9-pentaphenylcyclopentasiloxane and other cyclic methylphenylcyclosiloxanes, hexaphenylcyclotrisiloxane and other cyclic phenylcyclosiloxanes, and 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane and other fluorine Atom-containing cyclosiloxanes, methylhydrosiloxa Mixture, pentamethylcyclopentasiloxane, mention may be made of phenyl hydrosilyl group-containing cyclosiloxanes of hydrocyclosiloxane like, cyclic siloxanes and vinyl group-containing cyclosiloxanes such as penta vinyl pentamethylcyclopentasiloxane like. These cyclic siloxane compounds may be used alone or in combination of two or more.

  Furthermore, various fine particles can also be added to the protective layer 5 in order to improve the contamination resistance adhesion and lubricity on the surface of the electrophotographic photosensitive member. They can be used alone or in combination. Examples of the fine particles include silicon-containing fine particles. Silicon-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon-containing fine particles is selected from acidic or alkaline aqueous dispersions having an average particle diameter of 1 to 100 nm, preferably 10 to 30 nm, or those dispersed in organic solvents such as alcohols, ketones and esters. A commercially available product can be used. The solid content of the colloidal silica in the outermost surface layer is not particularly limited, but is 0.1 to 50% by mass in the total solid content of the protective layer 5 in terms of film forming properties, electrical characteristics, and strength. Is used, preferably in the range of 0.1 to 30% by mass.

  Silicone fine particles used as silicon-containing fine particles are spherical and have an average particle diameter of 1 to 500 nm, preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and are generally commercially available. Can be used. Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain sufficient characteristics is low, the electron does not hinder the crosslinking reaction, The surface properties of the photographic photoreceptor can be improved. In other words, in a state in which it is uniformly incorporated into a strong cross-linked structure, it improves the lubricity and water repellency of the surface of the electrophotographic photosensitive member, and maintains good wear resistance and contamination resistance adhesion over a long period of time. Can do. The content of the silicone fine particles in the protective layer 5 in the electrophotographic photosensitive member of the present invention is in the range of 0.1 to 30% by mass, preferably 0.5 to 10% by mass in the total solid content of the protective layer 5. Range.

Other fine particles include fluorine-based fine particles such as ethylene tetrafluoride, trifluoride ethylene, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Material Forum Lecture Proceedings p89. Fine particles made of a resin obtained by copolymerizing the fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , Examples thereof include semiconductive metal oxides such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. For the same purpose, an oil such as silicone oil can be added. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3, 5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrafe Cyclic methylphenylcyclosiloxanes such as lucyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane, and cyclic phenyls such as hexaphenylcyclotrisiloxane Hydrosilyl group-containing cyclosiloxanes such as cyclosiloxanes, fluorine-containing cyclosiloxanes such as 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane, methylhydrosiloxane mixtures, pentamethylcyclopentasiloxane and phenylhydrocyclosiloxane Examples thereof include cyclic siloxanes such as siloxanes and vinyl group-containing cyclosiloxanes such as pentavinylpentamethylcyclopentasiloxane.

  Further, additives such as a plasticizer, a surface modifier, an antioxidant, and a photodegradation inhibitor can be used for the protective layer 5. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons. An antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure can be added to the protective layer 5, which is effective in improving the potential stability and image quality when the environment changes.

  Examples of the antioxidant include the following compounds. For example, hindered phenols include “Sumilizer BHT-R”, “Sumizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW”, “Sumizer BP-76”, Sumilizer BP-101 "," Sumilizer GA-80 "," Sumilizer GM "," Sumilizer GS "or more manufactured by Sumitomo Chemical Co., Ltd.," IRGANOX1010 "," IRGANOX1035 "," IRGANOX1076 "," IRGANOX1098 "," IRGANOX1098 "," IRGANOX1098 "," IRGANOX1098 " ”,“ IRGANOX1222 ”,“ IRGANOX1330 ”,“ IRGANOX1425WL ”,“ IRGANOX1 20L "," IRGANOX 245 "," IRGANOX 259 "," IRGANOX 3114 "," IRGANOX 3790 "," IRGANOX 5057 "," IRGANOX 565 "or more manufactured by Ciba Specialty Chemicals," ADK STAB AO-20 "," ADK STAB AO-30 "," ADEKA STAB " "AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", "ADK STAB AO-330" or more manufactured by Asahi Denka. As the hindered amine system, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744” or more manufactured by Sankyo Lifetech Co., Ltd. “Mark LA57”, “Mark LA67”, “Mark LA62”, “Mark LA68”, “Mark LA63” or more, manufactured by Asahi Denka Co., Ltd., “Sumilyzer TPS” or more, manufactured by Sumitomo Chemical Co., Ltd. “D” or more, manufactured by Sumitomo Chemical Co., Ltd., and the phosphite system includes “Mark 2112”, “Mark PEP · 8”, “Mark PEP · 24G”, “Mark PEP · 36”, “Mark 329K”, “Mark HP · 10” As mentioned above, those manufactured by Asahi Denka Co., Ltd. are mentioned. Dirt amine antioxidants are preferred. Furthermore, these may be modified with a substituent such as an alkoxysilyl group capable of undergoing a crosslinking reaction with the material forming the crosslinked film.

  The protective layer 5 can be formed by curing the composition containing each constituent material described above, for example, by curing the outermost surface layer forming coating solution (protective layer forming coating solution) of the present invention. Can be formed. Here, the coating solution for forming the outermost surface layer of the present invention is a polymerization containing at least one compound selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2). And / or a silicon resin having a cross-linked structure composed of the polymerizable monomer, a phenol resin and / or a phenoxy resin, and an organic solvent.

  As the organic solvent, for example, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran; ethers such as diethyl ether and dioxane; Good. As such a solvent, those having a boiling point of 100 ° C. or less are preferable, and they can be arbitrarily mixed and used. When the amount of the solvent in the coating solution is too small, a silicon resin having a crosslinked structure is likely to be precipitated. Therefore, the amount is preferably 0.5 to 30 parts by mass with respect to 1 part by mass of the silicon resin having a crosslinked structure. More preferably, it is part by mass. The protective layer 5 can be formed without adding an organic solvent if the coating solution is liquid.

  In the coating solution for forming the outermost surface layer, the content of the silicon resin having the cross-linked structure and / or the polymerizable monomer constituting the silicon resin is 20 to 80% by mass based on the total solid content in the coating solution. It is preferable that it is, and it is more preferable that it is 30-70 mass%. If the blending amount is less than 20% by mass, the charge transporting ability of the outermost surface layer obtained tends to decrease. On the other hand, when the blending amount exceeds 80% by mass, the pot life of the coating solution tends to be shortened.

  Moreover, in the coating liquid for outermost surface layer formation, it is preferable that content of the said phenol resin and / or phenoxy resin is 10-80 mass% on the basis of the solid content whole quantity in a coating liquid, 20-70 mass%. It is more preferable that If the amount is less than 10% by mass, the mechanical strength tends to be low. On the other hand, if the blending amount exceeds 80% by mass, the charge transporting ability tends to decrease.

  Moreover, it is preferable to add or use a catalyst when forming the outermost surface layer forming coating solution or the outermost surface layer forming coating solution. Such catalysts include inorganic acids such as hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, potassium hydroxide, hydroxide Examples include alkali catalysts such as sodium, calcium hydroxide, ammonia, triethylamine.

Furthermore, a solid catalyst insoluble in the system as shown below can also be used. As the solid catalyst, Amberlite 15, Amberlite 200C, Amberlist 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Company); Lebatit SPC-108, Lebatit SPC-118 (above, Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433 Duolite-464 (above, manufactured by Sumitomo Chemical Co., Ltd.); Cation exchange resin such as Nafion-H (made by DuPont); Amberlite IRA-400, Amberlite IRA-45 (above, Rohm and Haas) Ltd.) anion exchange resin such _{as; Zr (O 3 PCH 2 CH} 2 SO 3 H Polyorgano containing protonic acid group of the polyorganosiloxane having a sulfonic acid _{group; 2, Th (O 3 PCH} 2 CH 2 COOH) groups containing protonic acid group of ₂ such as inorganic solids are bonded to the surface Siloxane; heteropolyacids such as cobalt tungstic acid and phosphomolybdic acid; isopolyacids such as niobic acid, tantalum acid and molybdic acid; unitary metal oxides such as silica gel, alumina, chromia, zirconia, CaO and MgO; silica-alumina, Composite metal oxides such as silica-magnesia, silica-zirconia, zeolites; clay minerals such as acid clay, activated clay, montmorillonite, kaolinite; metal sulfates such as LiSO ₄ , MgSO ₄ ; zirconia phosphate, lanthanum phosphate metal phosphate and the _{like; LiNO 3, Mn (NO 3} ) _2, etc. Metal nitrate; inorganic solid obtained by reacting aminopropyltriethoxysilane on silica gel with a group containing amino group such as solid; polyorgano containing amino group such as amino-modified silicone resin Examples thereof include siloxane.

  In addition, when preparing the coating solution for forming the outermost surface layer, it is preferable to use a solid catalyst that is insoluble in a photofunctional compound, a reaction product, water, a solvent, etc., because the stability of the coating solution tends to be improved. . The solid catalyst insoluble in the system is not particularly limited as long as the catalyst component is insoluble in a material for forming a resin having a crosslinked structure, other additives, water, a solvent and the like. Although the usage-amount of these solid catalysts is not restrict | limited in particular, 0.1-100 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group. Further, as described above, these solid catalysts are insoluble in raw material compounds, reaction products, solvents and the like, and therefore can be easily removed after the reaction according to a conventional method. The reaction temperature and reaction time are appropriately selected according to the type and amount of the raw material compound or solid catalyst, but the reaction temperature is usually 0 to 100 ° C, preferably 10 to 70 ° C, more preferably 15 to 50. The reaction time is preferably 10 minutes to 100 hours. When the reaction time exceeds the above upper limit, gelation tends to occur.

  When a coating solution for forming the outermost surface layer is used, when a catalyst that is insoluble in the system is used, it is preferable to use a catalyst that is further dissolved in the system for the purpose of improving strength, liquid storage stability, and the like. Such catalysts include, in addition to those described above, aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate), mono (sec-butoxy) aluminum diisopropylate, diisopropoxyaluminum (ethyl acetoacetate). ), Aluminum tris (ethyl acetoacetate), aluminum bis (ethyl acetoacetate) monoacetylacetonate, aluminum tris (acetylacetonate), aluminum diisopropoxy (acetylacetonate), aluminum isopropoxy-bis (acetylacetonate) Organic aluminum compounds such as aluminum tris (trifluoroacetylacetonate) and aluminum tris (hexafluoroacetylacetonate) It is possible to use.

  In addition to organoaluminum compounds, organotin compounds such as dibutyltin dilaurate, dibutyltin dioctiate, dibutyltin diacetate; titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis Organic titanium compounds such as (isopropoxy) bis (acetylacetonate); zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate), etc. Zirconium compounds; etc. can also be used, but from the viewpoints of safety, low cost, and pot life length, it is preferable to use an organoaluminum compound, particularly an aluminum chelate compound. It is more preferable. Although the usage-amount in particular of these catalysts is not restrict | limited, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group, and 0.3-10 mass parts is especially preferable.

In the present invention, when an organometallic compound is used as a catalyst, it is preferable to add a multidentate ligand from the viewpoint of pot life and curing efficiency. Examples of such multidentate ligands include those shown below and those derived therefrom, but the present invention is not limited to these. Specifically, β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, and dipivaloylmethylacetone; acetoacetates such as methyl acetoacetate and ethyl acetoacetate; bipyridine and derivatives thereof; glycine and its Derivatives; ethylenediamine and derivatives thereof; 8-oxyquinoline and derivatives thereof; salicylaldehyde and derivatives thereof; catechol and derivatives thereof; bidentate ligands such as 2-oxyazo compounds; diethyltriamine and derivatives thereof; nitrilotriacetic acid and derivatives thereof And tridentate ligands such as ethylenediaminetetraacetic acid (EDTA) and derivatives thereof. In addition to the organic ligands as described above, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be exemplified. As the multidentate ligand, a bidentate ligand is particularly preferable, and a bidentate ligand represented by the following general formula (8) is more preferable, and R ⁴⁰ and R ^{41 in the following} general formula (8) are more preferable. Are particularly preferred. By making R ⁴⁰ and R ^{41 the} same, the coordination power of the ligand near room temperature becomes strong, and further stabilization of the coating solution for forming the protective layer can be achieved.

In the formula (8), R ⁴⁰ and R ⁴¹ each independently represent an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, or an alkoxy group having 1 to 10 carbon atoms.

  The compounding amount of the polydentate ligand can be arbitrarily set, but is 0.01 mol or more, preferably 0.1 mol or more, more preferably 1 mol or more, with respect to 1 mol of the organometallic compound used. It is preferable to do this.

  When the coating solution for forming the outermost surface layer is applied onto the charge transport layer 2, the coating methods are blade coating method, Meyer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain A usual method such as a coating method can be used. And after application | coating, the protective layer 5 forms by thermosetting a coating film.

  Here, the reaction temperature and reaction time when the coating film is thermally cured are not particularly limited, but the reaction temperature is preferably 60 ° C. or higher from the viewpoint of the mechanical strength and chemical stability of the protective layer 5 to be formed. More preferably, it is 80-200 degreeC, and reaction time becomes like this. Preferably it is 10 minutes-5 hours. In addition, keeping the protective layer 5 obtained by curing the coating film in a high humidity state is effective in stabilizing the characteristics of the protective layer 5. Furthermore, depending on the application, the protective layer 5 can be subjected to a surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like to make it hydrophobic.

  In addition, in the case of application | coating, when a required film thickness cannot be obtained by one application | coating, a required film thickness can be obtained by apply | coating several times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application.

  The thickness of the protective layer 5 formed as described above is preferably 0.5 to 15 μm, more preferably 1 to 10 μm, and further preferably 1 to 5 μm.

  The photosensitive layer 6 may be added with an antioxidant, a light stabilizer, a heat stabilizer, etc. for the purpose of preventing deterioration of the photoreceptor due to ozone, an oxidizing gas, or light or heat generated in the image forming apparatus. An agent can be added. These additives can be added to at least one of the charge generation layer 1, the charge transport layer 2 and the protective layer 5 constituting the photosensitive layer 6.

  Examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds.

  Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine.

In addition, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use. Examples of the electron acceptor include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, Examples include chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, and phthalic acid. Of these, benzene derivatives having an electron-withdrawing substituent such as fluorenone, quinone, Cl, CN, and NO ₂ are particularly preferable.

  The preferred embodiments of the electrophotographic photoreceptor of the present invention have been described above, but the electrophotographic photoreceptor of the present invention is not limited to the above. For example, the electrophotographic photoreceptor 100 shown in FIG. 1 has a structure in which an undercoat layer 4, a charge generation layer 1, a charge transport layer 2 and a protective layer 5 are sequentially laminated on a conductive support 3. However, the electrophotographic photosensitive member of the present invention does not have to have an undercoat layer like the electrophotographic photosensitive member 110 shown in FIG. Further, the electrophotographic photoreceptor 120 shown in FIG. 2A may not have a protective layer, and the undercoat layer and the protective layer may be protected like the electrophotographic photoreceptor 130 shown in FIG. It is not necessary to have both layers. When the electrophotographic photosensitive member does not have a protective layer like the electrophotographic photosensitive members 120 and 130, the charge transporting layer 2 becomes the outermost surface layer. Therefore, the charge transporting layer 2 has the general formula (1). A polymerizable monomer containing at least one compound selected from the group consisting of a compound represented by formula (2) and a compound represented by the above general formula (2), and / or a crosslinked structure comprising the polymerizable monomer. It is necessary to have a structure obtained by curing a composition containing a silicon resin and a phenol resin and / or a phenoxy resin.

  Further, the electrophotographic photoreceptor of the present invention may be a so-called single layer type photoreceptor such as the electrophotographic photoreceptor 140 shown in FIG. In this case, the photosensitive layer has a single-layer type photosensitive layer formed containing a charge generating material and a binder resin. The charge generation material is the same as that used for the charge generation layer in the function separation type photosensitive layer, and the binder resin is a binder resin used for the charge generation layer and the charge transport layer in the function separation type photosensitive layer. Similar ones can be used. The content of the charge generating material in the single-layer type photosensitive layer is preferably 10 to 85% by mass, more preferably 20 to 50% by mass, based on the total solid content in the single-layer type photosensitive layer. In addition, a charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer for the purpose of improving photoelectric characteristics. The addition amount is preferably 5 to 50% by mass based on the total solid content in the single-layer type photosensitive layer. Moreover, the solvent and coating method used for coating can be the same as those for the above layers. The thickness of the single-layer type photosensitive layer is preferably about 5 to 50 μm, more preferably 10 to 40 μm.

  When the single-layer type photoreceptor does not have a protective layer as shown in FIG. 2C, the photosensitive layer 6 is the outermost surface layer, and therefore the photosensitive layer 6 is represented by the general formula (1). A polymerizable monomer containing at least one compound selected from the group consisting of a compound and a compound represented by the above general formula (2), and / or a silicon resin having a cross-linked structure consisting of the polymerizable monomer It is necessary to have a configuration obtained by curing a composition containing a phenol resin and / or a phenoxy resin.

(Image forming apparatus and process cartridge)
Next, an image forming apparatus and a process cartridge equipped with the electrophotographic photosensitive member of the present invention will be described.

  FIG. 3 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 200 shown in FIG. 3 includes an electrophotographic photosensitive member 7, a non-contact charging unit 8 for charging the electrophotographic photosensitive member 7, a power source 9 connected to the charging unit 8, and a charging unit 8. An exposure unit 10 that exposes the charged electrophotographic photosensitive member 7 to form an electrostatic latent image; a developing unit 11 that develops the formed electrostatic latent image with toner to form a toner image; and The image forming apparatus includes a transfer unit 12 for transferring from the photoconductor 7 to a transfer medium, a cleaning unit 13, a static eliminator 14, and a fixing unit 15.

  FIG. 4 is a cross-sectional view schematically showing a basic configuration of another embodiment of the image forming apparatus of the present invention shown in FIG. An image forming apparatus 210 shown in FIG. 4 has the same configuration as that of the image forming apparatus 200 shown in FIG. 3 except that the image forming apparatus 210 includes a charging unit 8 that charges the electrophotographic photoreceptor 7 by a contact charging method. At this time, as the charging means 8, a contact-type charging means in which an AC voltage is superimposed on a DC voltage can be preferably used because it has excellent wear resistance. In this case, the static eliminator 14 may not be provided.

  Examples of the non-contact charging type charging means 8 used in the present invention include a corotron and a scorotron using corona discharge. Moreover, as the charging means 8 of the contact charging system, a charger using a contact charging member such as a charging roller or a charging brush can be cited.

Contact charging members include metals such as aluminum, iron and copper, conductive polymer materials such as polyacetylene, polypyrrole and polythiophene, polyurethane rubber, silicone rubber, epichlorohydrin rubber, ethylene propylene rubber, acrylic rubber, fluorine rubber, styrene A material obtained by dispersing metal oxide particles such as carbon black, copper iodide, silver iodide, zinc sulfide, silicon carbide, and metal oxide in an elastomer material such as butadiene rubber or butadiene rubber can be used. Examples of this metal oxide include ZnO, SnO ₂ , TiO ₂ , In ₂ O ₃ , MoO _{3 and the} like, or a composite oxide thereof. Further, as the contact charging member, a material obtained by adding perchlorate to an elastomer material and imparting conductivity may be used.

  Further, a coating layer may be provided on the surface of the contact charging member. As a material for forming the coating layer, N-alkoxymethylated nylon, cellulose resin, vinyl pyridine resin, phenol resin, polyurethane, polyvinyl butyral, melamine and the like are used alone or in combination. Also, emulsion resin-based materials such as acrylic resin emulsion, polyester resin emulsion, polyurethane, particularly emulsion resin synthesized by soap-free emulsion polymerization can be used. In these resins, in order to further adjust the resistivity, conductive agent particles may be dispersed, or an antioxidant may be contained in order to prevent deterioration. In addition, in order to improve the film formability when forming the coating layer, the emulsion resin may contain a leveling agent or a surfactant. Examples of the shape of the contact charging member include a roller type, a blade type, a belt type, and a brush type.

Electrical resistance of the contact charging member is preferably ^{1 × 10 2 ~1 × 10 14} Ωcm, more preferably ^{1 × 10 2 ~1 × 10 12} Ωcm. Further, as the voltage applied to the contact charging member, either direct current or alternating current can be used. It can also be applied in the form of direct current + alternating current (direct voltage and alternating voltage superimposed).

  As the exposure means 10, an optical system device that can expose a light source such as a semiconductor laser, an LED (light emitting diode), a liquid crystal shutter, or the like on the surface of the electrophotographic photoreceptor 7 in a desired image-like manner can be used. Among these, when an exposure apparatus capable of exposing non-interference light is used, interference fringes between the conductive support of the electrophotographic photosensitive member 7 and the photosensitive layer can be prevented.

  When laser light is used as the exposure light source, the oscillation wavelength is preferably 350 to 850 nm, and the shorter wavelength is preferable because the resolution is excellent.

  As the developing means 11, a conventionally known developing device or the like can be used. Further, the type of developer used and the method for producing the same are not particularly limited. For example, a kneading and pulverizing method for kneading, pulverizing, and classifying a binder resin and a colorant, a release agent, and a charge control agent as necessary, A method of changing the shape of the particles obtained by the kneading and pulverization method by mechanical impact force or thermal energy, an emulsion polymerization of a polymerizable monomer of a binder resin, a formed dispersion, a colorant, a release agent Emulsion polymerization aggregation method to obtain a toner particle by mixing a mold agent and, if necessary, a dispersion of a charge control agent, and agglomerating and heat-fusing, a polymerizable monomer and a colorant for obtaining a binder resin A suspension polymerization method in which a solution of a release agent, if necessary, a charge control agent or the like is suspended in an aqueous solvent and polymerized, a binder resin and a colorant, a release agent, and a charge control agent if necessary A solution suspension method in which a solution is suspended in an aqueous solvent and granulated can be used. In addition, a known method such as a production method in which the toner obtained by the above method is used as a core and agglomerated particles are further adhered and heat-fused to have a core-shell structure can be used. From the viewpoint, a suspension polymerization method, an emulsion polymerization aggregation method, and a dissolution suspension method produced with an aqueous solvent are preferable, and an emulsion polymerization aggregation method is particularly preferable.

The toner is composed of a binder resin, a colorant, and a release agent. If necessary, silica or a charge control agent may be used. The volume average particle diameter of the toner is preferably 3 to 9 μm. Further, the average shape index (ML ² / A) of the toner is preferably 100 to 140, more preferably 115 to 140, since a high development, transferability, and high quality image can be obtained. .

  Binder resins used in the toner include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate. , Α-methylene aliphatic monocarboxylic such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Examples of homopolymers and copolymers of acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl butyl ether, and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropenyl ketone Particularly typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene. -Maleic anhydride copolymer, polyethylene, polypropylene and the like. Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.

  In addition, toner colorants include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, and malachite green oxa. Rate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.

  Typical examples of the release agent include low molecular weight polyethylene, low molecular weight polypropylene, Fischer tropic wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  Further, a charge control agent may be added to the toner as necessary. As the charge control agent, known ones can be used. For example, an azo metal complex compound, a metal complex compound of salicylic acid, a resin type charge control agent containing a polar group, or the like can be used.

  When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  When an external additive is added, it can be produced by mixing the toner and the external additive with a Henschel mixer or a V blender. Further, when the toner is manufactured by a wet method, it can be externally added by a wet method.

  Lubricating particles added to the toner used in the present invention include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids, fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene, and polybutene, and heating. Aliphatic amides such as silicones with softening point, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil, etc. Mineral waxes, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc., petroleum wax, and their modified products can be used. Has one kind It can be used or in combination of two or more Germany. The volume average particle size of the lubricious particles is preferably 0.1 to 10 μm, and may be pulverized to make the particle sizes uniform as necessary. The amount added to the toner is preferably 0.05 to 2.0 parts by mass, and more preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the toner.

  To the toner used in the present invention, inorganic fine particles, organic fine particles, composite fine particles obtained by adhering inorganic fine particles to the organic fine particles, and the like may be added for the purpose of removing deposits and deteriorated matters on the surface of the electrophotographic photoreceptor 7. Although it is possible, inorganic fine particles having excellent polishing properties are particularly preferable. Inorganic fine particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used. Further, titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecyl benzene sulfonyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, γ- (2-amino) Ethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane Hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxy The treatment may be performed with a silane coupling agent such as silane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane. Moreover, it is also preferable to hydrophobize with higher fatty acid metal salts, such as silicone oil, aluminum stearate, zinc stearate, calcium stearate.

  Examples of the organic fine particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles.

  If the particle size of the inorganic or organic fine particles is too small, the polishing ability is insufficient, and if it is too large, the surface of the electrophotographic photosensitive member 7 is likely to be damaged. Therefore, the average particle size is preferably 5 to 1000 nm. 5 to 800 nm is more preferable, and 5 to 700 nm is particularly preferable. The addition amount of inorganic and organic fine particles to the toner is preferably 0.6 parts by mass or more as the sum of the addition amount of the slippery particles with respect to 100 parts by mass of the toner.

  As other inorganic oxides added to the toner, small-diameter inorganic oxides having an average primary particle size of 40 nm or less are used for powder fluidity, charge control, etc. It is preferable to add a larger-diameter inorganic oxide. These inorganic oxide fine particles may be known ones, but it is preferable to use silica and titanium oxide in combination in order to perform precise charge control. Further, the surface treatment of the small-diameter inorganic fine particles increases the dispersibility and increases the powder flowability.

  The color toner for electrophotography is used by mixing with a carrier. As the carrier, iron powder, glass beads, ferrite powder, nickel powder or those having a resin coating on the surface thereof are used. The mixing ratio with the carrier can be set as appropriate.

  Examples of the transfer unit 12 include a roller-type contact charging member, a contact-type transfer charger using a belt, a film, a rubber blade, or the like, or a scorotron transfer charger or a corotron transfer charger using corona discharge. .

  Although untransferred toner may remain on the surface of the electrophotographic photosensitive member 7 after the transfer, the remaining toner can be removed by the cleaning means 13. As the cleaning means 13, those provided with a cleaning member such as a blade, a magnetic brush, or a conductive fiber brush are preferably used. Hereinafter, a cleaning apparatus including a blade member as an example of the cleaning unit 13 will be described in detail.

  The material of the blade is not particularly limited. For example, a urethane prepolymer composed of a polyol such as a polyester polyol such as polyethylene adipate and polycaprolactone and an isocyanate such as diphenylmethane diisocyanate, and 1,4-butanediol, trimethylolpropane, ethylene glycol, Those using a cross-linking agent such as a mixture thereof as a raw material are preferable because the obtained blade member is excellent in wear resistance and has high mechanical strength. Moreover, as a urethane prepolymer which is a constituent material of a blade member, for example, an NCO group content of about 4 to 10% by mass and a viscosity at 70 ° C. of about 1000 to 3000 cP are preferably used.

  The thickness of the blade member is not particularly limited as long as it has sufficient strength to remove the residual toner on the surface of the photoreceptor, and is usually preferably about 1 to 3 mm. For example, when an adhesive that is reactively cured by irradiating ultraviolet rays or the like is used to obtain a cleaning blade by bonding a blade member and a mounting bracket, which will be described later, the blade member is transparent, ultraviolet rays, etc. It is preferable to have a thickness that can pass through. The rubber hardness of the blade member is not particularly limited as long as it has a strength sufficient to remove the residual toner on the surface of the electrophotographic photosensitive member 7, but is usually 65 to 80 (JIS K6253 A It is preferable that the measured value is about a value measured with a type hardness meter.

  In manufacturing the blade member, for example, the following method can be employed. First, the raw material of the blade material adjusted so as to have a desired blending amount is stirred and mixed for about 1 to 3 minutes using, for example, a mixing stirrer such as agitator to obtain a mixed solution, which is about 120 to 160 ° C. Rotating at about 100 to 300 rpm, for example, after being injected into a forming drum mold of a centrifugal molding machine, the number of rotations of the forming drum mold is increased to about 600 to 1200 rpm, and the injected mixed liquid is applied to the inner surface of the forming drum mold. The blade material is in a state in which bubbles that are uniformly spread and entrained at the time of injection float on the surface. Here, the amount of the liquid mixture injected into the molding drum mold may be adjusted so that, for example, a blade member having a desired thickness as described above can be obtained. Next, while maintaining the rotational speed of the forming drum mold at about 600 to 1200 rpm and the temperature at about 120 to 160 ° C., before the blade material is cross-linked and cured, for example, the abrasive fine particles are uniformly distributed using a spray gun or the like. After spraying the dispersed suspension onto the blade material, the blade material is cured while rotating the molding drum mold so that abrasive fine particles are present at least on the cleaning surface. The medium for obtaining the suspension in which the abrasive fine particles are uniformly dispersed is not particularly limited as long as it does not exhibit an interaction between the abrasive fine particles and the blade material. For example, when obtaining the blade material When silicone oil such as dimethylpolysiloxane, methylphenylpolysiloxane, trifluoropropylmethylpolysiloxane, etc., which is normally used for foaming, promotes defoaming, is used, the abrasive particles are uniformly distributed in the blade material. This is preferable because it can be transferred to the surface. Although it is sufficient that the abrasive fine particles are uniformly dispersed in the abrasive, the amount of the abrasive fine particles to be present on the cleaning surface can be adjusted by the blending amount of the abrasive fine particles in the suspension. The abrasive fine particles are preferably blended in an amount of about 1 to 20 parts by mass with respect to 100 parts by mass of the medium. Further, the desired amount of abrasive fine particles can be directly mixed and dispersed in the raw material of the blade material, and then molded.

A spray gun or the like is used to spray the suspension onto the blade material. The air pressure and spray amount during spraying may be adjusted according to the amount of abrasive fine particles to be present on the cleaning surface. Usually, the air pressure is about 1 to 10 kg / cm ² and the spray amount is It is preferably about 0.5 to ⁵ mg / cm ² . The time when the suspension material is sprayed onto the blade material may be any time as long as the blade material is spread uniformly in the molding drum mold and before the blade material is cured in a state where air bubbles emerge on the surface of the blade material. For example, since it varies depending on the target depth when impregnating the abrasive fine particles into the blade member, it cannot be determined unconditionally. However, after the blade material is put into the molding drum mold, it is usually 2-10. It is preferable that about a minute pass. In the blade member thus obtained, the abrasive fine particles are firmly adhered at least to the cleaning surface or immersed therein, so that the physical properties such as tensile strength and tear strength and the adhesion to the mounting bracket are reduced. It has excellent durability. Further, since the abrasive fine particles are present at least on the cleaning surface by centrifugal force, the degree of polishing performance can be adjusted by adjusting the spray amount of the suspension of the fine abrasive particles, the timing of spraying, the rotational speed of the molding drum mold, etc. The durability of polishing performance can be controlled.

  The blade member is integrated with the mounting bracket by using, for example, a hot melt adhesive, double-sided tape, etc. to form a cleaning blade, and is used by being mounted on an image forming apparatus such as for PPC, PPP, or PPF. it can. The mounting bracket is not particularly limited. For example, a mounting bracket made of a rigid metal, an elastic metal, plastic, ceramic, or the like, which is usually used for a cleaning blade, can be used. A mounting bracket made of a treated steel plate, a steel plate that has been subjected to a surface treatment such as zinc phosphate treatment or chromate treatment, or a steel plate that has been subjected to plating treatment is particularly preferred from the standpoint that it does not change over time such as corrosion. Further, the blade member may be a single layer or a laminate in which a plurality of materials are bonded together.

  FIG. 5 is a cross-sectional view schematically showing a basic configuration of another embodiment of the image forming apparatus of the present invention. An image forming apparatus 220 shown in FIG. 5 is an image forming apparatus that forms a color image by a tandem method. In the housing 400, four electrophotographic photosensitive members 401a to 401d (for example, the electrophotographic photosensitive member 401a is yellow and the electrophotographic photosensitive member is formed. The body 401b can form an image of magenta, the electrophotographic photoreceptor 401c can be cyan, and the electrophotographic photoreceptor 401d can be formed of a black color.) Are arranged in parallel with each other along the intermediate transfer belt 409.

  Here, the electrophotographic photoreceptors 401a to 401d mounted on the image forming apparatus 220 are the electrophotographic photoreceptors of the present invention.

  Each of the electrophotographic photosensitive members 401a to 401d can be rotated in a predetermined direction (counterclockwise on the paper surface), and the charging rolls 402a to 402d, the developing devices 404a to 404d, and the primary transfer roll 410a along the rotation direction. To 410d and cleaning blades 415a to 415d are arranged. Each of the developing devices 404a to 404d can be supplied with toner of four colors of black, yellow, magenta and cyan accommodated in the toner cartridges 405a to 405d, and the primary transfer rolls 410a to 410d are respectively intermediate transfer belts. 409 is in contact with the electrophotographic photoreceptors 401a to 401d.

  Further, a laser light source (exposure means) 403 is disposed at a predetermined position in the housing 400, and the surface of the electrophotographic photoreceptors 401a to 401d after charging is irradiated with laser light emitted from the laser light source 403. Is possible. Accordingly, charging, exposure, development, primary transfer, and cleaning are sequentially performed in the rotation process of the electrophotographic photosensitive members 401a to 401d, and the toner images of the respective colors are transferred onto the intermediate transfer belt 409 in an overlapping manner.

  The intermediate transfer belt 409 is supported with a predetermined tension by a drive roll 406, a backup roll 408, and a tension roll 407, and can rotate without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to contact the backup roll 408 via the intermediate transfer belt 409. The intermediate transfer belt 409 passing between the backup roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed in the vicinity of the drive roll 406 and then repeatedly used for the next image forming process. Is done.

  A tray (transfer medium tray) 411 is provided at a predetermined position in the housing 400, and the transfer medium 500 such as paper in the tray 411 is transferred to the intermediate transfer belt 409 and the secondary transfer roll by the transfer roll 412. Then, the paper is sequentially transferred between the two fixing rolls 414 that are in contact with each other and the two fixing rolls 414, and then discharged to the outside of the housing 400.

  In the above description, the case where the intermediate transfer belt 409 is used as the intermediate transfer member has been described. However, the intermediate transfer member may have a belt shape like the intermediate transfer belt 409 or a drum shape. Also good. In the case of a belt shape, a conventionally known resin can be used as the resin material used as the base material of the intermediate transfer member. For example, polyimide resin, polycarbonate resin (PC), polyvinylidene fluoride (PVDF), polyalkylene terephthalate (PAT), ethylenetetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, PC / PAT blend material, polyester Resin materials such as polyether ether ketone and polyamide, and resin materials using these as main raw materials. Furthermore, a resin material and an elastic material can be blended and used.

  As an elastic material, polyurethane, chlorinated polyisoprene, NBR, chloropyrene rubber, EPDM, hydrogenated polybutadiene, butyl rubber, silicone rubber, or the like can be used, or a material obtained by blending two or more kinds can be used. If necessary, a conductive agent imparting electronic conductivity or a conductive agent having ionic conductivity is added to the resin material and elastic material used for these base materials in combination of one kind or two or more kinds. Among these, it is preferable to use a polyimide resin in which a conductive agent is dispersed from the viewpoint of excellent mechanical strength. As the conductive agent, a conductive polymer such as carbon black, metal oxide, or polyaniline can be used. When a belt-shaped configuration such as the intermediate transfer belt 409 is adopted as the intermediate transfer member, generally the thickness of the belt is preferably 50 to 500 μm, more preferably 60 to 150 μm, but the hardness of the material It can be selected as appropriate according to the conditions.

  For example, a belt made of a polyimide resin in which a conductive agent is dispersed is 5 to 20 mass as a conductive agent in a polyamic acid solution which is a polyimide precursor, as described in JP-A-63-311263. % Of carbon black is dispersed, the dispersion is cast on a metal drum and dried, and then the film peeled off from the drum is stretched at a high temperature to form a polyimide film. It can be manufactured by forming a belt.

  The film molding is generally performed by injecting a polyamic acid solution film-forming stock solution in which a conductive agent is dispersed into a cylindrical mold and, for example, heating at 100 to 200 ° C. at a rotational speed of 500 to 2000 rpm. The film was formed into a film by a centrifugal molding method while rotating, and then the obtained film was demolded in a semi-cured state and covered with an iron core. It can be carried out by proceeding a ring-closing reaction) and carrying out main curing. In addition, the stock solution is cast on a metal sheet to a uniform thickness and heated to 100 to 200 ° C. to remove most of the solvent in the same manner as described above, and then gradually raised to a high temperature of 300 ° C. or higher. There is also a method of forming a polyimide film. Further, the intermediate transfer member may have a surface layer.

  When a drum-shaped configuration is adopted as the intermediate transfer member, it is preferable to use a cylindrical substrate formed of aluminum, stainless steel (SUS), copper, or the like as the substrate. If necessary, an elastic layer can be coated on the cylindrical substrate, and a surface layer can be formed on the elastic layer.

  The transfer medium according to the present invention is not particularly limited as long as it is a medium that transfers a toner image formed on an electrophotographic photosensitive member. For example, when transferring directly from an electrophotographic photosensitive member to a transfer medium such as paper, paper or the like is the transfer medium. When an intermediate transfer member is used, the intermediate transfer member is a transfer medium.

  FIG. 6 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the process cartridge of the present invention. The process cartridge 300 is obtained by combining the electrophotographic photosensitive member 7 with the charging unit 8, the developing unit 11, the cleaning unit 13, the opening 18 for exposure, and the static eliminator 14 using the mounting rail 16. is there. The process cartridge 300 is detachable from the main body of the image forming apparatus including the transfer unit 12, the fixing unit 15, and other components (not shown). It constitutes. Such a process cartridge 300 can be applied to any of the image forming apparatuses shown in FIGS.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Example 1]
16 parts by mass of a compound represented by the following formula (9) and 16 parts by mass of methanol are placed in a 100 ml sample bottle, and 1.6 parts by mass of an ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) are added. Stir at room temperature for about 3 hours. Next, 35 parts by mass of n-butanol and 8 parts by mass of water were added, stirred for 5 minutes at room temperature, and quickly filtered. In the obtained solution, 0.3 parts by mass of aluminum trisacetylacetonate (Al (aqaq) ₃ ), 0.3 parts by mass of acetylacetonate (aqaq), and 3,5-di-t-butyl-4-hydroxy Toluene (BHT) 0.3 part by mass was added and stirred at room temperature for 1 hour. 16 parts by mass of a resole resin (Resitop PL-4852, manufactured by Gunei Chemical Co., Ltd.), which is a phenol resin, was added to this liquid, and the mixture was further stirred at room temperature for 1 hour. Then, it filtered with a 5-micrometer membrane filter, and obtained the composition for hardening body formation.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Example 2]
Curing was conducted in the same manner as in Example 1 except that 16 parts by mass of resole resin (BLS-3135, manufactured by Showa Polymer Co., Ltd.) was used instead of 16 parts by mass of resol resin (Resitop PL-4852, manufactured by Gunei Chemical Co., Ltd.). A body-forming composition was obtained.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Example 3]
In place of 16 parts by mass of resole resin (Resitop PL-4852, manufactured by Gunei Chemical Co., Ltd.) 16 parts by mass, curing was carried out in the same manner as in Example 1 except that 16 parts by mass of resol resin (BLS-356, manufactured by Showa Polymer Co., Ltd.) was used. A body-forming composition was obtained.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Example 4]
Curing was carried out in the same manner as in Example 1 except that 16 parts by mass of resole resin (BLS-722, manufactured by Showa Polymer) was used instead of 16 parts by mass of resol resin (Resitop PL-4852, manufactured by Gunei Chemical Co., Ltd.). A body-forming composition was obtained.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Example 5]
Curing was carried out in the same manner as in Example 1 except that 16 parts by mass of resole resin (BLS-3122, manufactured by Showa Polymer Co., Ltd.) was used instead of 16 parts by mass of resol resin (Resitop PL-4852, manufactured by Gunei Chemical Co., Ltd.). A body-forming composition was obtained.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Example 6]
Curing was conducted in the same manner as in Example 1 except that 16 parts by mass of novolac resin (PR-54869, manufactured by Sumitomo Bakelite Co., Ltd.) was used instead of 16 parts by mass of Resole resin (Resitop PL-4852, manufactured by Gunei Chemical Co., Ltd.). A body-forming composition was obtained.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Example 7]
Instead of 16 parts by mass of resole resin (Resitop PL-4852, manufactured by Gunei Chemical Co., Ltd.), the same procedure as in Example 1 was carried out except that 16 parts by mass of novolak resin (PR-HF-3, manufactured by Showa Polymer) was used. A composition for forming a cured body was obtained.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Example 8]
A composition for forming a cured body was obtained in the same manner as in Example 1 except that the amount of the resole resin (Resitop PL-4852, manufactured by Gunei Chemical Co., Ltd.) was changed from 16 parts by mass to 10 parts by mass.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Comparative Example 1]
10 parts by mass of a resole resin (Resitop PL-4857, manufactured by Gunei Chemical Co., Ltd.) is dissolved in 20 parts by mass of n-butanol, and 0.05 parts by mass of a silicone coupling agent (KBM7802, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to room temperature. Was stirred for 1 hour and filtered through a 5 μm membrane filter to obtain a composition for forming a cured product.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Comparative Example 2]
A cured product-forming composition was obtained in the same manner as in Example 1 except that 16 parts by mass of a resole resin (Resitop PL-4857, manufactured by Gunei Chemical Co., Ltd.) was not added.

  The obtained coating solution was die-coated on a polyester sheet (Lumirror # 125, manufactured by Toray Industries, Inc.) and heat-cured at 130 ° C. for 40 minutes to prepare a cured body as an antioxidant film having a thickness of 10 μm.

[Evaluation of antioxidant properties]
The antioxidant films obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were placed in a constant temperature layer at 80 ° C., and 400 ppm of ozone was introduced into the constant temperature layer and exposed for 8 hours. The chromaticity (b ^* ) before and after the exposure was measured with a color difference meter (SQ2000, manufactured by Mysec Co., Ltd.), and the color difference (Δb ^* ) was calculated. Note that the greater the color difference Δb ^* , the greater the oxidation degradation.

[Evaluation of mechanical strength]
Using the compositions for forming a cured body obtained in Examples 1 to 8 and Comparative Examples 1 and 2, cured films having a thickness of 20 μm were obtained by a casting method under curing conditions of 175 ° C. and 3 hours, respectively. This film was cut into 30 mm × 200 mm, and the bending strength was measured with a strograph V50 (manufactured by Toyo Seiki Co., Ltd.). The results are shown in Table 18.

  As is clear from the results shown in Table 18, the cured bodies of Examples 1 to 8 have superior antioxidant properties and high mechanical strength as compared with the cured bodies of Comparative Examples 1 and 2. Was confirmed.

[Example 9]
The cylindrical aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness was set to Rz = 0.6 μm. In order to clean the aluminum substrate subjected to the centerless polishing treatment, a degreasing treatment, an etching treatment with a 2% by mass sodium hydroxide solution for 1 minute, a neutralization treatment, and a pure water washing were performed in this order. Next, an anodic oxide film (current density: 1.0 A / dm ² ) was formed on the surface of the base material with a 10% by mass sulfuric acid solution with respect to the aluminum base material. After washing with water, sealing treatment was performed by dipping in a 1 mass% nickel acetate solution at 80 ° C. for 20 minutes. Further, pure water washing and drying treatment were performed. In this way, an aluminum base material having an anodized film of about 7 μm formed on the surface was obtained.

  Next, 1 mass of chlorogallium phthalocyanine having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum of 7.4 °, 16.6 °, 25.5 °, and 28.3 °. Part is mixed with 1 part by weight of polyvinyl butyral (S-Rec BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by weight of n-butyl acetate, and dispersed by treatment with a glass bead for 1 hour with a paint shaker. A coating solution was obtained. The obtained coating solution was dip-coated on the aluminum base material on which the anodic oxide film was formed and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts by mass of a charge transporting compound represented by the following general formula (10) and 3 parts by mass of a polymer compound (viscosity average molecular weight 39,000) having a structural unit represented by the following general formula (11) It was made to melt | dissolve in 20 mass parts of chlorobenzene, and the coating liquid for charge transport layer formation was obtained.

  The obtained coating solution was applied onto the charge generation layer by a dip coating method and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, the composition for forming a cured body obtained in Example 1 was applied on the charge transport layer by a ring dip coating method and thermally cured at 130 ° C. for 40 minutes to obtain a film thickness of 3.5 μm as the outermost surface layer. A protective layer was formed. As a result, an intended electrophotographic photosensitive member was obtained.

[Examples 10 to 16]
It replaced with the composition for hardening body formation obtained in Example 1, and it carried out similarly to Example 9 except having formed the protective layer using the composition for hardening body formation obtained in Examples 2-8, respectively. The electrophotographic photoreceptors of Examples 10 to 16 were obtained.

[Example 17]
In the same procedure as in Example 9, an aluminum base material having an anodized film of about 7 μm formed on the surface was obtained.

  Next, 1 part by mass of titanyl phthalocyanine having a strong diffraction peak with a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum of 27.2 ° is obtained from polyvinyl butyral (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.). 1 part by mass and 100 parts by mass of n-butyl acetate were mixed and treated with a glass shaker with a paint shaker for 1 hour to disperse to obtain a coating solution for forming a charge generation layer. The obtained coating solution was dip-coated on the aluminum base material on which the anodic oxide film was formed and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, a charge transport layer having a thickness of about 20 μm was formed on the charge generation layer in the same procedure as in Example 9.

  Next, a protective layer having a thickness of 4.5 μm was formed on the charge transport layer in the same procedure as in Example 9. As a result, an intended electrophotographic photosensitive member was obtained.

[Example 18]
First, the cylindrical aluminum base material which gave the honing process was prepared. Next, 100 parts by mass of a zirconium compound (Olgatix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts by mass of a silane compound (A1100, manufactured by Nihon Unicar Co., Ltd.), 400 parts by mass of isopropanol, and 200 parts by mass of butanol are mixed, and an undercoat layer A forming coating solution was obtained. This coating solution was applied by dip coating on the above aluminum substrate and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of about 0.1 μm.

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, 1 part by mass of hydroxygallium phthalocyanine having a strong diffraction peak at 28.3 ° is mixed with 1 part by mass of polyvinyl butyral (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by mass of n-butyl acetate, together with glass beads A coating shaker was applied for 1 hour to disperse, and a charge generation layer forming coating solution was obtained. The obtained coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts by mass of a charge transporting compound represented by the following general formula (12) and 3 parts by mass of a polymer compound having a structural unit represented by the above general formula (11) (viscosity average molecular weight 39,000) It was made to melt | dissolve in 20 mass parts of chlorobenzene, and the coating liquid for charge transport layer formation was obtained.

  The obtained coating solution was applied onto the charge generation layer by a dip coating method and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, a protective layer having a thickness of 3.8 μm was formed on the charge transport layer in the same procedure as in Example 9. As a result, an intended electrophotographic photosensitive member was obtained.

[Example 19]
100 parts by mass of zinc oxide (SMZ-017N, manufactured by Teica) was mixed with 500 parts by mass of toluene, and 2 parts by mass of a silane coupling agent (A1100, manufactured by Nihon Unicar) was added and stirred for 5 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the ratio of Si element strength to zinc element strength was 1.8 × 10 ⁻⁴ .

  35 parts by mass of zinc oxide subjected to the above surface treatment, 15 parts by mass of blocked isocyanate (Sumijoule 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.) as a curing agent, 6 parts by mass of butyral resin (BM-1, manufactured by Sekisui Chemical Co., Ltd.) And 44 parts by mass of methyl ethyl ketone were mixed and dispersed for 2 hours with a sand mill using 1 mmφ glass beads to obtain a dispersion. To the obtained dispersion, 0.005 parts by mass of dioctyltin dilaurate as a catalyst and 17 parts by mass of Tospearl 130 (manufactured by GE Toshiba Silicone) were added to obtain a coating solution for forming an undercoat layer. This coating solution was applied onto an aluminum substrate by a dip coating method, followed by drying and curing at 160 ° C. for 100 minutes to form an undercoat layer having a thickness of 20 μm. The surface roughness of the undercoat layer was measured using a surface roughness shape measuring instrument (Surfcom 570A, manufactured by Tokyo Seimitsu Co., Ltd.) at a measurement distance of 2.5 mm and a scanning speed of 0.3 mm / sec. .24.

  Next, a charge generation layer having a thickness of about 0.15 μm was formed on the undercoat layer in the same procedure as in Example 17.

  Next, a charge transport layer having a thickness of about 20 μm was formed on the charge generation layer in the same procedure as in Example 9.

  Next, a 3.7 μm-thick protective layer was formed on the charge transport layer by the same procedure as in Example 9. As a result, an intended electrophotographic photosensitive member was obtained.

[Comparative Example 3]
10 parts by mass of a resole resin (Resitop PL-4852, manufactured by Gunei Chemical Co., Ltd.) and 7 parts by mass of a compound represented by the following formula (13) are dissolved in 20 parts by mass of n-butanol, and silicone oil (KB340, Shin-Etsu Chemical Co., Ltd.) is dissolved. 0.01 parts by mass) and 0.01 parts by mass of a silicone coupling agent (KBM7802, manufactured by Shin-Etsu Chemical Co., Ltd.) are added and stirred at room temperature for 1 hour, and filtered through a 5 μm membrane filter for forming the outermost surface layer. A coating solution was obtained.

  The electrophotographic photosensitive member of Comparative Example 3 was prepared in the same manner as in Example 9 except that a protective layer was formed using the above coating solution for forming the outermost surface layer instead of the composition for forming a cured body obtained in Example 1. Got.

[Comparative Example 4]
Comparative Example 4 was conducted in the same manner as in Example 9 except that a protective layer was formed using the composition for forming a cured body obtained in Comparative Example 2 instead of the composition for forming a cured body obtained in Example 1. An electrophotographic photosensitive member was obtained.

[Preparation of Developer 1]
In the following description regarding the developer, each physical property value was measured by the following method. That is, the particle size distribution of the toner and composite particles was measured using a multisizer (manufactured by Nikka Kisha Co., Ltd.) with an aperture diameter of 100 μm. Further, the average shape factor ML ² / A of the toner and the composite particles is expressed by the following formula:
ML ² / A = (maximum length) ² × π × 100 / (area × 4)
In the case of a true sphere, ML ² / A = 100. As a specific method for obtaining the average shape factor, a toner image is taken from an optical microscope into an image analyzer (LUZEX III, manufactured by Nireco), the equivalent circle diameter is measured, and the maximum length and area are 50 or more. For the toner particles, the value of ML ² / A in the above formula was determined, and the average value was calculated.

<Manufacture of toner base particles>
(Adjustment of resin fine particle dispersion)
A solution prepared by mixing 370 g of styrene, 30 g of n-butyl acrylate, 8 g of acrylic acid, 24 g of dodecanethiol and 4 g of carbon tetrabromide, 6 g of a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and an anion A solution obtained by dissolving 10 g of a surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in 550 g of ion-exchanged water was mixed to start emulsion polymerization in a flask. Was added 50 g of ion-exchanged water in which 4 g of ammonium persulfate was dissolved. After carrying out nitrogen substitution in the flask, the mixed solution was heated with an oil bath until the temperature of the mixed solution reached 70 ° C. while stirring, and emulsion polymerization was continued for 5 hours. As a result, a resin fine particle dispersion in which resin fine particles having a volume average particle size of 150 nm, a glass transition temperature (Tg) of 58 ° C., and a weight average molecular weight (Mw) of 11,500 is obtained. The solid content concentration of this dispersion was 40% by mass.

(Preparation of colorant dispersion (1))
Carbon black (Mogal L, manufactured by Cabot Corp.) 60 g, nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) 6 g and ion-exchanged water 240 g were mixed, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used. Stir for 10 minutes. Thereafter, a colorant dispersion (1) in which colorant (carbon black) particles having a volume average particle diameter of 250 nm were dispersed was prepared by dispersing with an optimizer.

(Adjustment of colorant dispersion (2))
Cyan pigment (B15: 3, manufactured by Dainichi Seika Co., Ltd.) 60 g, nonionic surfactant (Nonipol 400, manufactured by Sanyo Kasei Co., Ltd.) 5 g and ion-exchanged water 240 g were mixed together, and a homogenizer (Ultra Turrax T50, manufactured by IKA). And stirred for 10 minutes. Thereafter, a colorant dispersion liquid (2) in which colorant (Cyan pigment) particles having a volume average particle diameter of 250 nm were dispersed was prepared by dispersing with an optimizer.

(Adjustment of colorant dispersion (3))
60 g of Magenta pigment (R122, manufactured by Dainichi Seika Co., Ltd.), 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Kasei Co., Ltd.) and 240 g of ion-exchanged water are mixed, and a homogenizer (Ultra Turrax T50, manufactured by IKA) is used. And stirred for 10 minutes. Thereafter, a colorant dispersion liquid (3) in which colorant (Magenta pigment) particles having a volume average particle diameter of 250 nm were dispersed was prepared by dispersing with an optimizer.

(Adjustment of colored dispersion (4))
90 g of Yellow pigment (Y180, manufactured by Dainichi Seika Co., Ltd.), 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Kasei Co., Ltd.) and 240 g of ion-exchanged water are mixed, and a homogenizer (Ultra Turrax T50, manufactured by IKA) is used. And stirred for 10 minutes. Thereafter, a colorant dispersion liquid (4) in which colorant (Yellow pigment) particles having a volume average particle diameter of 250 nm were dispersed was prepared by dispersing with an optimizer.

(Preparation of release agent dispersion)
100 g of paraffin wax (HNP0190, manufactured by Nippon Seiwa Co., Ltd., melting point 85 ° C.), 5 g of a cationic surfactant (Sanisol B50, manufactured by Kao Corporation) and 240 g of ion-exchanged water were mixed, and a homogenizer ( The dispersion was carried out for 10 minutes using an ultra turrax T50 (manufactured by IKA). Thereafter, a dispersion treatment was performed using a pressure discharge type homogenizer to prepare a release agent dispersion liquid in which release agent particles having a volume average particle diameter of 550 nm were dispersed.

(Preparation of toner mother particles K1)
234 parts by mass of the resin fine particle dispersion, 30 parts by mass of the colorant dispersion (1), 40 parts by mass of the release agent dispersion, and 0.5 parts by mass of polyaluminum hydroxide (Pho2S, manufactured by Asada Chemical Co., Ltd.) And 600 parts by mass of ion-exchanged water were respectively added to a round stainless steel flask, and mixed and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the mixed liquid in the flask was heated to 40 ° C. while stirring in an oil bath for heating, and kept at 40 ° C. for 30 minutes. At this time, it was confirmed that aggregated particles having a volume average particle diameter D50 of 4.5 μm were generated in the mixed solution. Further, when the temperature of the heating oil bath was raised and held at 56 ° C. for 1 hour, D50 was 5.3 μm. After adding 26 parts by mass of the resin fine particle dispersion to the dispersion containing the aggregate particles, the mixture was held at 50 ° C. for 30 minutes using a heating oil bath. After adding 1N sodium hydroxide to the dispersion containing the aggregate particles to adjust the pH of the dispersion to 7.0, the flask is sealed and heated to 80 ° C. while continuing stirring using a magnetic seal. Hold for 4 hours. After the dispersion was cooled, the toner base particles produced in the dispersion were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K1. The volume average particle diameter D50 of the toner base particles K1 is 5.9 μm, and the average shape factor ML ² / L is 132.

(Preparation of toner base particles C1)
Toner base particles C1 were obtained in the same manner as the preparation of toner base particles K1, except that the color particle dispersion (2) was used instead of the color particle dispersion (1). The toner base particle C1 has a volume average particle diameter D50 of 5.8 μm and an average shape factor ML ² / A of 131.

(Preparation of toner mother particles M1)
Toner base particles M1 were obtained in the same manner as the preparation of toner base particles K1, except that the color particle dispersion (3) was used instead of the color particle dispersion (1). The toner base particle M1 has a volume average particle diameter D50 of 5.5 μm and an average shape factor ML ² / A of 135.

(Preparation of toner mother particles Y1)
Toner base particles Y1 were obtained in the same manner as the preparation of toner base particles K1, except that the color particle dispersion (4) was used instead of the color particle dispersion (1). The volume average particle diameter D50 of the toner base particles Y1 is 5.9 μm, and the average shape factor ML ² / A is 130.

<Manufacture of carriers>
14 parts by mass of toluene, 2 parts by mass of a styrene-methacrylate copolymer (component ratio: 90/10) and 0.2 parts by mass of carbon black (R330, manufactured by Cabot Corporation) are mixed and dispersed by stirring with a stirrer for 10 minutes. A coating solution was prepared. Next, the coating solution and 100 parts by mass of ferrite particles (volume average particle size: 50 μm) are put in a vacuum degassing kneader, stirred at 60 ° C. for 30 minutes, and then degassed by further reducing pressure while heating. And dried to obtain a carrier. This carrier had a volume resistivity of 10 ¹¹ Ω · cm when an applied electric field of 1000 V / cm was applied.

<Preparation of K, C, M, Y color toner 1>
1 part by mass of rutile type titanium oxide (particle size: 20 nm, treated with n-decyltrimethoxysilane), silica (particle size: 40 nm) with respect to 100 parts by mass of each of the toner base particles K1, C1, M1, Y1. 2.0 parts by mass prepared by a gas phase oxidation method and treated with silicone oil), 1 part by mass of cerium oxide (volume average particle size: 0.7 μm), and higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) And a mixture of zinc stearate at a ratio of 5: 1 (mass ratio) is pulverized by a jet mill, 0.3 parts by mass of a mixed material having a volume average particle size of 8.0 μm is added, and a 5 L Henschel mixer is used. Blending was performed at a peripheral speed of 30 m / s for 15 minutes. Thereafter, coarse particles are removed using a sieve having an opening of 45 μm, and K (black), C (cyan), M (magenta) and Y (yellow) color toners 1 having additives added to the surface are obtained. It was.

<Preparation of Developer 1>
For each of the K, C, M, and Y color toners 1 to which the additive is externally added to the surface, 5 parts by mass of the toner and 100 parts by mass of the carrier are mixed at 40 rpm for 20 minutes using a V-blender. The developer 1 was obtained by stirring and sieving with a sieve having an opening of 212 μm.

[Preparation of Developer 2]
(Preparation of toner mother particles K2)
234 parts by mass of the resin fine particle dispersion, 30 parts by mass of the colorant dispersion (1), 40 parts by mass of the release agent dispersion, and 0.5 parts by mass of polyaluminum hydroxide (Pho2S, manufactured by Asada Chemical Co., Ltd.) And 600 parts by mass of ion-exchanged water were respectively added to a round stainless steel flask, and mixed and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the mixed liquid in the flask was heated to 40 ° C. while stirring in an oil bath for heating, and kept at 40 ° C. for 30 minutes. At this time, it was confirmed that aggregated particles having a volume average particle diameter D50 of 4.5 μm were generated in the mixed solution. Further, when the temperature of the heating oil bath was raised and held at 56 ° C. for 1 hour, D50 was 5.3 μm. After adding 26 parts by mass of the resin fine particle dispersion to the dispersion containing the aggregate particles, the mixture was held at 50 ° C. for 30 minutes using a heating oil bath. After adding 1N sodium hydroxide to the dispersion containing the aggregate particles and adjusting the pH of the dispersion to 5.0, the flask is sealed and heated to 95 ° C. while continuing stirring using a magnetic seal. Hold for 4 hours. After the dispersion was cooled, the toner base particles produced in the dispersion were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K2. The volume average particle diameter D50 of the toner base particles K2 is 5.8 μm, and the average shape factor ML ² / L is 109.

(Preparation of toner base particles C2)
Toner base particles C2 were obtained in the same manner as in the adjustment of toner base particles K2, except that the colored particle dispersion liquid (2) was used instead of the colored particle dispersion liquid (1). The volume average particle diameter D50 of the toner base particles C2 is 5.7 μm, and the average shape factor ML ² / A is 110.

(Preparation of toner mother particles M2)
Toner base particles M2 were obtained in the same manner as the adjustment of toner base particles K2, except that the colored particle dispersion (3) was used instead of the colored particle dispersion (1). The volume average particle diameter D50 of the toner base particles M2 is 5.6 μm, and the average shape factor ML ² / A is 114.

(Preparation of toner mother particle Y2)
Toner base particles Y2 were obtained in the same manner as in the adjustment of toner base particles K2, except that the colored particle dispersion (4) was used instead of the colored particle dispersion (1). The volume average particle diameter D50 of the toner base particles Y2 is 5.8 μm, and the average shape factor ML ² / A is 108.

<Preparation of K, C, M, Y color toner 2 and developer 2>
Instead of toner base particles K1, C1, M1, and Y1, toner base particles K2, C2, M2, and Y2 are used, and aluminum oxide (volume) is used instead of 1 part by mass of cerium oxide (volume average particle size: 0.7 μm). K, C, M, Y color toner 2 was obtained in the same manner as in the preparation of K, C, M, Y color toner 1 except that 1 part by mass was used (average particle size: 0.1 μm).

  Further, a developer 2 was obtained in the same manner as in the preparation of the developer 1 except that K, C, M, and Y color toners 2 were used instead of the K, C, M, and Y color toners 1.

[Preparation of Developer 3]
(Preparation of toner mother particles K3)
100 parts by mass of polyester resin (linear polyester obtained from terephthalic acid-bisphenol A ethylene oxide adduct-cyclohexanedimethanol, Tg: 62 ° C., Mn: 12000, Mw: 32000), carbon black (Mogal L, manufactured by Cabot Corporation) ) A mixture of 4 parts by mass and 5 parts by mass of carnauba wax was kneaded with an extruder, pulverized with a jet mill, and then classified with an air classifier to obtain toner mother particles K3. The volume average particle diameter D50 of the toner base particles K3 is 5.9 μm, and the average shape factor ML ² / L is 145.

(Preparation of toner base particles C3)
Toner base particles C3 were obtained in the same manner as the preparation of toner base particles K3 except that Cyan pigment (B15: 3, manufactured by Dainichi Seika Co., Ltd.) was used instead of carbon black (Mogal L, manufactured by Cabot Corp.). . The volume average particle diameter D50 of the toner base particles C3 is 5.6 μm, and the average shape factor ML ² / A is 141.

(Preparation of toner mother particles M3)
Toner base particles M3 were obtained in the same manner as toner base particles K3 except that Magenta pigment (R122, manufactured by Dainichi Seika Co., Ltd.) was used instead of carbon black (Mogal L, manufactured by Cabot Corp.). The toner mother particles M3 had a volume average particle diameter D50 of 5.9 μm and an average shape factor ML ² / A of 149.

(Preparation of toner mother particles Y3)
Toner base particles Y3 were obtained in the same manner as the adjustment of toner base particles K3 except that Yellow pigment (Y180, manufactured by Dainichi Seika Co., Ltd.) was used instead of carbon black (Mogal L, manufactured by Cabot Corp.). The volume average particle diameter D50 of the toner base particles Y3 is 5.8 μm, and the average shape factor ML ² / A is 144.

<Preparation of K, C, M, Y color toner 3 and developer 3>
The toner base particles K3, C3, M3, and Y3 are used instead of the toner base particles K1, C1, M1, and Y1, and aluminum oxide (volume) is used instead of 1 part by mass of cerium oxide (volume average particle size: 0.7 μm). K, C, M, Y color toner 3 was obtained in the same manner as in the preparation of K, C, M, Y color toner 1 except that 1 part by mass was used (average particle size: 0.1 μm).

  Further, a developer 3 was obtained in the same manner as in the preparation of the developer 1 except that the K, C, M, and Y color toners 3 were used instead of the K, C, M, and Y color toners 1.

[Image formation test]
The electrophotographic photoreceptors obtained in Examples 9 to 19 and Comparative Examples 3 to 4 and the developers 1 to 3 described above were mounted on a printer (DocuCenter Color 400CP, manufactured by Fuji Xerox Co., Ltd.) in the combinations shown in Table 19. The image forming apparatuses of Examples 20 to 32 and Comparative Examples 5 to 6 were produced. Using this image forming apparatus, an image forming test of 10,000 sheets was conducted in an environment of high temperature and high humidity (28 ° C., 75% RH), and then 10,000 sheets of paper was used in an environment of low temperature and low humidity (10 ° C., 20% RH). An image formation test was conducted. Thereafter, the presence or absence of deposits such as oxidative degradation on the surface of the photoreceptor after the image formation test was visually evaluated. Also, the presence or absence of image quality defects (deletion defects due to oxidative degradation of the photoreceptor) after the image formation test was visually evaluated. Further, the amount of wear of the photoreceptor after the image formation test was measured. These results are shown in Table 19.

  As is apparent from the results shown in Table 19, according to the image forming apparatuses of Examples 20 to 32, the generation of deposits such as oxidation degradation products is sufficient as compared with the image forming apparatuses of Comparative Examples 5 to 6. The amount of wear is sufficiently reduced due to excellent mechanical strength, and there is no oxidative degradation of the photoreceptor, and good image quality is obtained by suppressing the occurrence of image quality defects over a long period of time. It was confirmed that

(A)-(b) is a schematic cross section which shows 1st-2nd embodiment of the electrophotographic photoreceptor of this invention, respectively. (A)-(c) is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention, respectively. 1 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of an image forming apparatus of the present invention. It is sectional drawing which shows schematically the basic composition of other suitable one Embodiment of the image forming apparatus of this invention. It is sectional drawing which shows schematically the basic composition of other suitable one Embodiment of the image forming apparatus of this invention. 1 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of a process cartridge of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Charge generating layer, 2 ... Charge transport layer, 3 ... Conductive support body, 4 ... Undercoat layer, 5 ... Protective layer, 6 ... Photosensitive layer, 7 ... Electrophotographic photoreceptor, 8 ... Charging means, 9 ... Power supply DESCRIPTION OF SYMBOLS 10 ... Exposure means, 11 ... Developing means, 12 ... Transfer means, 13 ... Cleaning means, 14 ... Static eliminator, 15 ... Fixing means, 16 ... Mounting rail, 18 ... Opening for exposure, 20 ... Transfer object 100, 110, 120, 130, 140 ... electrophotographic photosensitive member, 200, 210, 220 ... image forming apparatus, 300 ... process cartridge, 500 ... medium to be transferred.

Claims (6)

A polymerizable monomer represented by the following formula (9) , and / or a silicon resin having a cross-linked structure composed of the polymerizable monomer;
Phenol resins of the resol type or novolak type,
A cured product obtained by curing a composition comprising

A polymerizable monomer represented by the following formula (9) , and / or a silicon resin having a cross-linked structure composed of the polymerizable monomer;
Phenol resins of the resol type or novolak type,
An organic solvent,
A composition for forming a cured body, comprising:

An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer provided on the conductive support,
The photosensitive layer has an outermost surface layer on the side farthest from the conductive support,
2. The electrophotographic photosensitive member, wherein the outermost surface layer comprises the cured body according to claim 1 . The outermost surface of the electrophotographic photoreceptor comprising: a conductive support; and a photosensitive layer provided on the conductive support and having a topmost surface layer disposed on the side farthest from the conductive support. A coating solution for forming a layer,
A coating solution for forming the outermost surface layer, comprising the composition for forming a cured body according to claim 2 . The electrophotographic photosensitive member according to claim 3 ,
A charging means for charging the electrophotographic photosensitive member; a developing means for developing a latent electrostatic image formed on the electrophotographic photosensitive member with toner to form a toner image; and At least one selected from the group consisting of cleaning means for removing toner remaining on the surface;
A process cartridge comprising: The electrophotographic photosensitive member according to claim 3 ,
Charging means for charging the electrophotographic photosensitive member;
Exposure means for forming an electrostatic latent image on the charged electrophotographic photosensitive member;
Developing means for developing the electrostatic latent image with toner to form a toner image;
Transfer means for transferring the toner image from the electrophotographic photosensitive member to a transfer target;
An image forming apparatus comprising: