JP4696866B2 - Electrophotographic photosensitive member, method for manufacturing the same, process cartridge, and image forming apparatus - Google Patents

Description

The present invention relates to an electrophotographic photosensitive member, a method for manufacturing the same , a process cartridge , and an image forming apparatus.

  A common issue with general-purpose polymer materials is weather resistance. For example, polyesters widely used for molded articles such as beverage bottles are often problematic because they undergo oxidative degradation in the presence of heat and oxygen, causing coloration and lowering of mechanical strength. The same problem occurs in polycarbonate used for a substrate of a recording medium such as a CD-ROM or DVD. Furthermore, when a polymer material is used for the spectacle lens, deterioration discoloration due to ultraviolet rays becomes a big problem. In order to use these polymer materials in a molded product, it is necessary to improve weather resistance, particularly to improve antioxidant properties.

  The polymer material is also used for a gas barrier film, and the gas barrier film is widely used, for example, as a protective film for waterproofing an electroluminescent (EL) panel or a liquid crystal panel, or as a food protective wrap. It is used. Such a gas barrier film can be formed as a film alone, which can be affixed on, for example, the above-mentioned EL panel, or a gas barrier film coating liquid is applied to the surface of a molded body to be given gas barrier properties and dried. Thus, a gas barrier layer can also be formed. In addition, since there is little fear of gas leakage at the interface with the molded body, the method of forming a gas barrier layer by the latter coating is particularly preferably used in recent years. As a material for the gas barrier film, for example, polyvinyl alcohol, polyvinylidene chloride, polyamide or the like is frequently used. And also about the molded object using these polymeric materials, the improvement of antioxidant property is desired.

  One of the means for improving the antioxidant property is a method of kneading a phosphorus-based, hindered amine-based antioxidant or the like in the molded body. There is also a method of coating the molded body with a film having antioxidant properties. Furthermore, as a method for preventing deterioration due to ultraviolet rays, a method in which an ultraviolet absorbent is mixed into a molded body is common.

  By the way, there is a field of electrophotographic photoreceptors in the field of using the polymer material as described above, and in recent years, there is an increasing demand for extending the life of the electrophotographic photoreceptor. A so-called xerographic image forming apparatus including a charging unit, an exposure unit, a developing unit, a transfer unit, a fixing unit, and the like has been further improved in speed and life due to technical progress of each member and system. As a result, the demand for high-speed compatibility and high reliability of each subsystem is increasing. In particular, the electrophotographic photosensitive member used for image writing and the cleaner that cleans the electrophotographic photosensitive member are subject to a lot of stress due to mutual sliding, and image defects due to scratches, wear, chipping, etc. are likely to occur and can be handled at high speed. There is a strong demand for reliability and high reliability. On the other hand, there is a strong demand for high image quality, and the toner has been made in a solvent mainly composed of water as a method for producing a toner that satisfies the quality by reducing the particle size of the toner, making the particle size distribution uniform, and making it spherical. Toners, so-called chemical toners, have been actively developed. As a result, recently, so-called photographic image quality has been obtained.

In order to extend the life of the electrophotographic photosensitive member, it is extremely important to increase the mechanical strength in order to reduce the wear of the outermost surface layer. For example, in the following Patent Document 1, it is reported that an electrophotographic photoreceptor having a cross-linked structure and a structural unit having a charge transporting ability has a very long life.
Japanese Patent No. 3264218

  However, although the electrophotographic photosensitive member described in Patent Document 1 has high mechanical strength of the outermost surface layer and is less likely to be worn, another problem has occurred because it is less likely to be worn. That is, the phenomenon in which oxidative degradation products caused by charging stress or the like adhere to the outermost surface layer is no longer negligible. Such an adhesion phenomenon causes a decrease in image quality such as white spots and density unevenness depending on the type and degree of adhesion. In the conventional photoconductor, the outermost surface layer is mechanically worn by the cleaning stress, but at that time, the above-mentioned deposits are scraped off and can be removed. However, since the mechanical strength of the outermost surface layer is increased and the amount of mechanical wear is reduced, the deposits cannot be sufficiently removed.

  In order to improve such problems, it is desired to improve the antioxidation property of the outermost surface layer of the electrophotographic photosensitive member and reduce the generation of oxidative degradation products due to charging stress or the like.

  However, in the method of kneading an antioxidant or the like in a molded body such as an electrophotographic photoreceptor, a problem arises in that the mechanical strength of the molded body is extremely reduced due to the incorporation of a low molecular weight antioxidant. . In addition, in the method of forming an antioxidant film on the surface of the molded body, this surface film becomes an antioxidant-rich film, so that the mechanical strength of the surface is significantly reduced and the surface wear resistance is reduced. Cannot be used for applications that require. Moreover, since the antioxidant film may be mechanically peeled off due to surface deterioration, there is a problem that it cannot withstand long-term use.

  The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide an electrophotographic photosensitive member, a process cartridge, and an image forming apparatus in which both mechanical strength and oxidation resistance are achieved at a high level. And

In order to achieve the above object, the present invention provides an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer disposed on the conductive support, wherein the photosensitive layer is formed from the conductive support. On the farthest side, the following compounds (II-4), (II-6), (II-11), (II-12), (II-13), (III-1), (III-3), ( A curable resin composition containing III-5) or (III-11) is cured, and the following compounds (II-4), (II-6), (II-11), (II-12) , (II-13), ( III-1), (III-3), (III-5), or (III-11) is an epoxy group of the hydroxyl group and reaction with other molecules of the same compound The electrophotographic photosensitive member is characterized by having an outermost surface layer including a three-dimensional cross-linked structure formed as described above.
Further, the present invention provides a method for producing an electrophotographic photoreceptor, wherein the curable resin composition containing the epoxy compound is cured to form an outermost surface layer of the photosensitive layer.

  The epoxy compound used in the present invention has a functional group having a hydroxyl group at the terminal (hereinafter referred to as “phenolic hydroxyl group”) bonded to an aromatic ring in the main chain and / or side chain, so that at the time of curing. Bonding of epoxy compounds occurs through this phenolic hydroxyl group, and it becomes possible to form a strong and dense three-dimensional crosslinked structure. And according to the electrophotographic photoreceptor of the present invention, by forming the outermost surface layer using the curable resin composition containing the specific epoxy compound, the mechanical strength and antioxidant properties of the outermost surface layer can be improved. Both can be achieved at a high level. Therefore, even when image formation is performed for a long time using this electrophotographic photosensitive member, it is possible to sufficiently suppress the occurrence of abrasion and scratches on the outermost surface layer, and to prevent oxidation degradation products due to charging stress or the like. Occurrence can be sufficiently suppressed, and an image with good image quality can be stably obtained.

Upper disappeared epoxy compound has the structure of a special epoxy compound having an aromatic ring having a phenolic hydroxyl group in the main chain. The phenolic hydroxyl group contained in such an epoxy compound forms a strong hydrogen bond by acting with the aromatic hydrogen directly bonded in the adjacent epoxy compound, and dramatically increases the density of the resulting cured film (outermost surface layer). be able to. At this time, it is important that the main chain contains an aromatic ring having a phenolic hydroxyl group, and the three-dimensional density can be further improved because the main chain has a small free volume. A three-dimensional crosslinked structure such as a conventional epoxy resin is known to have high mechanical strength and high heat resistance, but generally the gap volume becomes large and the gas barrier property is lowered. On the other hand, by using a special epoxy compound containing an aromatic ring having a phenolic hydroxyl group in the main chain, the cured film has a sufficient gap volume despite the fact that it is a three-dimensional crosslinked structure for the above reasons. In particular, a particularly excellent gas barrier property can be obtained while achieving both a high mechanical strength and an antioxidant property at a high level, and an excellent heat resistance can be obtained.

A polyvinyl alcohol film that has been widely used as a conventional gas barrier film is excellent in gas barrier properties, but has extremely low heat resistance and causes deformation in an atmosphere of about 50 ° C. In order to prevent this, a polyvinyl alcohol-polyethylene copolymer film is used, but it still has the disadvantages that it is deformed at about 70 ° C., has a low mechanical strength, is easily scraped, and is very easily damaged. Polyvinylidene chloride film has relatively high heat resistance and does not deform up to around 100 ° C, but its mechanical strength is low and its solubility in organic solvents is poor. Have difficulty. Furthermore, although the polyamide film is excellent in heat resistance and mechanical strength, its use is extremely limited because of its poor gas barrier properties. Thus, in the conventional gas barrier film, in particular but compatible with other properties such as gas barrier properties and mechanical strength has not been fully achieved, in the electrophotographic photoreceptor of the present invention, using the above disappeared epoxy compound The outermost surface layer formed in this way can sufficiently achieve both gas barrier properties and mechanical strength.

Upper disappeared epoxy compound has the structure of a special epoxy compound having an aromatic ring having a phenolic hydroxyl group in the side chain. In the epoxy compound having such a structure, the epoxy group exhibits good reactivity with the phenolic hydroxyl group at a temperature of 100 ° C. or higher. In other words, an epoxy compound having a phenolic hydroxyl group in the side chain alone reacts with an epoxy group at a certain molecular end and a phenolic hydroxyl group at another molecular side chain, and this is repeated, resulting in an extremely tough three-dimensional crosslinked structure. Can be formed. As a result, the resulting cured film (outermost surface layer) can achieve both high mechanical strength and anti-oxidation properties at a high level, and can also achieve excellent heat resistance and excellent chemical stability, Excellent weather resistance can be obtained.

Here, in the electrophotographic photoreceptor of the present invention, the curable resin composition for forming the outermost surface layer is represented by the following general formula (IV), (V), (VI), (VII) or (VIII). It is preferred to further contain one or more of the charge transporting compounds represented.
F [-D-Si (R ⁶¹ ) _(3-a) Q _a ] _b (IV)
[In Formula (IV), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ⁶¹ represents a hydrogen atom, a substituted or unsubstituted group. 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 1) n1}} R 62 -Z 1 H] m1 (V)
[In Formula (V), F represents an organic group derived from a compound having a hole transporting ability, R ⁶² represents an alkylene group, Z ¹ represents an oxygen atom, a sulfur atom, NH or COO, and X ¹ Represents an oxygen atom or a sulfur atom, m1 represents an integer of 1 to 4, and n1 represents 0 or 1. ]
_{^{F [- (X 2) n2}} - (R 63) n3 - (Z 2) n4 G] n5 (VI)
[In Formula (VI), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ⁶³ represents an alkylene group, Z ² represents an oxygen atom, S represents a sulfur atom, NH or COO, G represents an epoxy group, n2, n3 and n4 each independently represents 0 or 1, and n5 represents an integer of 1 to 4. ]


[In Formula (VII), F represents an organic group derived from a compound having a hole-transport property, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁶⁴ , R ⁶⁵ and R ⁶⁶ independently represents a hydrogen atom or a monovalent organic group, R ⁶⁷ represents a monovalent organic group, m 2 represents 0 or 1, and n 6 represents an integer of 1 to 4. However, R ⁶⁶ and R ⁶⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]


[In Formula (VIII), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, R ⁶⁸ represents a monovalent organic group, and m3 represents 0 or 1 N7 represents an integer of 1 to 4. ]

  Since the epoxy compound used in the present invention described above and the charge transporting compound are extremely compatible, when a curable resin composition containing them is cured, a good interpolymer network is formed, Stability is enhanced and excellent mechanical strength can be obtained. In particular, by forming the outermost surface layer of the electrophotographic photoreceptor using the curable resin composition containing the charge transporting compound, both the mechanical strength and electrical characteristics of the photoreceptor are achieved at a high level. Can do.

  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.

  According to the process cartridge and the image forming apparatus of the present invention, since the electrophotographic photoreceptor of the present invention having excellent characteristics as described above is used, high image quality and long life can be achieved.

  According to the present invention, by forming the outermost surface layer of the electrophotographic photoreceptor using a curable resin composition containing a specific epoxy compound, both the mechanical strength and the antioxidant property of the outermost surface layer are at a high level. To provide an electrophotographic photosensitive member capable of stably obtaining an image having a good image quality even when image formation is performed for a long time, and a process cartridge and an image forming apparatus using the same. it can.

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

(Epoxy compound)
The epoxy compound used in the present invention has a structure represented by the following general formula (I).

[In the above formula (I), R ¹ is an s-valent organic group, R ² is a trivalent hydrocarbon group having 1 to 12 carbon atoms, and R ³ is a divalent hydrocarbon group having 1 to 12 carbon atoms. R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a halogen atom or a silicon-containing group, L ¹ and L ² each independently represent a divalent organic group, f is an integer of 0 to 4, g is an integer of 0 to 5, h and i are each independently 0 or 1, p is an integer of 0 to 4 selected such that p + q ≧ 1, q is p represents an integer of 0 to 5 selected so that p + q ≧ 1, r represents an integer of 0 to 12, and s represents an integer of 1 to 6, respectively. However, when p is 0, r represents an integer of 1 to 12. ]

In the general formula (I), when there are a plurality of R ² , R ³ , R ⁴ , R ⁵ , L ¹ and L ² , such as when s is 2 or more, a plurality of R ² , R ³ , R ^{2 4} , R ⁵ , L ¹ and L ² may be the same or different. Moreover, in the said general formula (I), when r is 0, p shows the integer of 1-4. In the general formula (I), f + p is preferably 4 or less, and g + q is preferably 5 or less.

The epoxy compound used in the present invention, Among the epoxy compound represented by the general formula (I), compounds represented by the following general formula (II) or the following general formula (III) is used.

[In the formula ^{(II), R 11} and ^{R 21} each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group, an aralkyl group, a halogen atom or a silicon-containing ^{group, R 14} And R ²⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a halogen atom or a silicon-containing group, and R ¹³ and R ²³ each independently represents a divalent hydrocarbon having 1 to 12 carbon atoms. L ¹¹ and L ²¹ are each independently a divalent organic group, f 1 and f 2 are each independently an integer of 0 to 3, h 1 and h 2 are each independently 0 or 1, and p 1 and p 2 are each Each independently represents an integer of 1 to 4. However, R ¹¹ and R ²¹ may be bonded to each other to form a ring. ]

[In the formula ^{(III), R 11} and ^{R 21} each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group, an aralkyl group, a halogen atom or a silicon-containing ^{group, R 14} , R ²⁴ , R ¹⁵ and R ²⁵ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, a halogen atom or a silicon-containing group, and R ¹² and R ²² each independently represent 1 to 12 carbon atoms. R ¹³ and R ²³ are each independently a divalent hydrocarbon group having 1 to 12 carbon atoms, and L ¹¹ , L ²¹ , L ¹² and L ²² are each independently a divalent hydrocarbon group. F3, f4, g1, g2, p3 and p4 are each independently an integer of 0 to 4, h1, h2, i1 and i2 are each independently 0 or 1, q1 and q2 are each independently 1 An integer of ~ 5, r1 and r2 are each 1-12 of integers to stand, respectively. However, R ¹¹ and R ²¹ may be bonded to each other to form a ring. ]

In the above general formulas (II) and (III), when f1, f2, f3, f4, g1, g2, p1, p2, p3, p4, q1, q2, r1, and r2 are 2 or more, etc. , R ¹² , R ²² , R ¹⁴ , R ²⁴ , R ¹⁵ , R ²⁵ , L ¹¹ , L ²¹ , L ¹² and a plurality of L ²² , a plurality of R ¹² , R ²² , R ¹⁴ , R ²⁴ , R ¹⁵ , R ²⁵ , L ¹¹ , L ²¹ , L ¹² and L ²² may be the same or different. In the general formula (II), f1 + p1 and f2 + p2 are each preferably 4 or less. Further, in the general formula (III), f3 + p3 and f4 + p4 are each preferably 4 or less, and g1 + i1 and g2 + i2 are each preferably 5 or less.

In the general formula (II) and ^(III), it is preferred that ^{R 11} and ^{R 21} are each independently a methyl group or a phenyl group. R ¹⁴ , R ²⁴ , R ¹⁵ and R ²⁵ are preferably each independently a methyl group or a phenyl group. R ¹² and R ²² are preferably each independently a trivalent hydrocarbon group having 2 or 3 carbon atoms. L ¹¹ , L ²¹ , L ¹² and L ²² are preferably each independently a methylene group, an ethylene group or a propylene group.

  More specific examples of the epoxy compound represented by the general formula (II) include the following compounds (II-1) to (II-13).

  Specific examples of the epoxy compound represented by the general formula (III) include the following compounds (III-1) to (III-11).

  Next, the method for synthesizing the epoxy compound represented by the general formula (I) will be described by taking as an example the case of synthesizing the epoxy compound represented by the general formula (II).

  The synthesis | combination of the epoxy compound represented by the said general formula (II) is performed in the following procedures, for example. First, as shown in the following reaction formula (A), a phenol and a ketone having a desired structure are dissolved in a solvent such as tetrahydrofuran, and heated and stirred at 100 to 200 ° C. together with a catalyst such as triethylamine. Bisphenol is obtained.

  Next, as shown in the following reaction formula (B), the obtained bisphenol and epichloroalkane are heated to 200 to 300 ° C. together with the metal oxide catalyst to thereby obtain the desired formula represented by the general formula (II). The epoxy compound can be obtained.

  The epoxy compound represented by the above general formula (III) is synthesized by using the epoxy compound represented by the above general formula (II) except that a pendant type phenol represented by the following general formula (C) is used as the starting phenol. It can carry out like the synthesis | combination of.

(Curable resin composition)
The curable resin composition used in the present invention contains the above-described epoxy compound.

  The curable resin composition preferably further contains one or more charge transporting compounds represented by the following general formula (IV), (V), (VI), (VII) or (VIII). .

F [-D-Si (R ⁶¹ ) _(3-a) Q _a ] _b (IV)
[In Formula (IV), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ⁶¹ represents a hydrogen atom, a substituted or unsubstituted group. 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 1) n1}} R 62 -Z 1 H] m1 (V)
[In Formula (V), F represents an organic group derived from a compound having a hole transporting ability, R ⁶² represents an alkylene group, Z ¹ represents an oxygen atom, a sulfur atom, NH or COO, and X ¹ Represents an oxygen atom or a sulfur atom, m1 represents an integer of 1 to 4, and n1 represents 0 or 1. ]

^{_{F [- (X 2) n2}} - (R 63) n3 - (Z 2) n4 G] n5 (VI)
[In Formula (VI), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ⁶³ represents an alkylene group, Z ² represents an oxygen atom, S represents a sulfur atom, NH or COO, G represents an epoxy group, n2, n3 and n4 each independently represents 0 or 1, and n5 represents an integer of 1 to 4. ]

[In Formula (VII), F represents an organic group derived from a compound having a hole-transport property, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁶⁴ , R ⁶⁵ and R ⁶⁶ independently represents a hydrogen atom or a monovalent organic group, R ⁶⁷ represents a monovalent organic group, m 2 represents 0 or 1, and n 6 represents an integer of 1 to 4. However, R ⁶⁶ and R ⁶⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (VIII), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, R ⁶⁸ represents a monovalent organic group, and m3 represents 0 or 1 N7 represents an integer of 1 to 4. ]

(Electrophotographic photoreceptor)
The electrophotographic photosensitive member of the present invention includes a conductive support and a photosensitive layer disposed on the conductive support, and the photosensitive layer is on the side farthest from the conductive support. It has an outermost surface layer formed by curing a curable resin composition containing an epoxy compound.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the electrophotographic photosensitive member of the present invention. An electrophotographic photoreceptor 100 shown in FIG. 1 is a function-separated type photoreceptor in which a charge generation layer 1 and a charge transport layer 2 are separately provided. The photosensitive layer 6 is subtracted in order from the side close to the conductive support 3. The layer 4, the charge generation layer 1, the charge transport layer 2 and the protective layer 5 are laminated. The outermost surface layer in the electrophotographic photoreceptor 100 shown in FIG. 1 is a protective layer 5, and this protective layer 5 is a layer formed by curing the curable resin composition described above.

  Hereinafter, each element of the electrophotographic photoreceptor 100 shown in FIG. 1 will be described.

  Examples of the conductive support 3 include a metal plate, a metal drum, and a metal belt formed using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Etc. Examples of the conductive support 3 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.

  When the photosensitive member 100 is used in a laser printer, the laser oscillation wavelength is preferably 350 nm to 850 nm, and the shorter wavelength is preferable because the resolution is excellent. The surface of the conductive support 3 is preferably roughened to a center line average roughness Ra of 0.04 μm to 0.5 μm in order to prevent interference fringes generated when laser light is irradiated. If Ra is less than 0.04 μm, it tends to be close to a mirror surface, so that the effect of preventing interference tends not to be obtained. On the other hand, if Ra exceeds 0.5 μm, the image quality tends to be rough even if a film is formed. . Further, when non-interfering light is used as a light source, it is not particularly necessary to roughen the interference fringes, and defects due to irregularities on the surface of the conductive support 3 can be prevented.

  As a roughening method, a wet honing process in which an abrasive is suspended in water and sprayed on a support, a centerless grinding process in which a support is pressed against a rotating grindstone, and grinding is continuously performed, an anode Examples thereof include an oxidation treatment or a method of forming a layer containing organic or inorganic semiconductive fine particles.

  Anodizing treatment is to form an oxide film on an 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 as it is after the treatment is chemically active, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the anodic oxide film is treated with pressurized steam or boiling water (a metal salt such as nickel may be added), blocked by volume expansion due to micropore hydration reaction, and converted into a more stable hydrated oxide. It is preferable to perform a hole treatment.

  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 is poor and the effect tends to be insufficient. On the other hand, if it 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 treatment liquid or boehmite treatment. The treatment with the acidic treatment liquid is carried out as follows using an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid. 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 processing temperature is 42 to 48 ° C., but by keeping the processing temperature high, a thicker film can be formed faster. The film thickness is preferably 0.3 to 15 μm. When the film thickness is less than 0.3 μm, the barrier property against implantation is poor and the effect tends to be insufficient. On the other hand, if it exceeds 15 μm, the residual potential tends to increase due to repeated use.

  The boehmite treatment can be performed by immersing the conductive support 3 in pure water at 90 to 100 ° C. for 5 to 60 minutes, or by contacting it 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.

  The undercoat layer 4 is configured to contain 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, an organic zirconium compound, an organic titanyl compound, and an organoaluminum compound are particularly preferably used since they have 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 addition, it is preferable to add various kinds of fine powders of organic compounds or fine powders of inorganic compounds to the undercoat layer 4 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 mass%, more preferably 30 to 80 mass%, based on the total solid content of the undercoat layer 4. .

  The undercoat layer 4 is configured 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 the undercoat layer 4. 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 0.1 to 30 μm, more preferably 0.2 to 25 μm.

  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.

  As the charge generation material, Bragg angles (2θ ± 0.2 °) with respect to CuKα characteristic X-rays of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25 Hydroxygallium phthalocyanine having diffraction peaks at .1 ° and 28.3 °, titanyl phthalocyanine having a strong diffraction peak at 27.2 ° with a Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray, CuKα characteristic X Also preferred are chlorogallium phthalocyanines with strong diffraction peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° of the Bragg angle to the line (2θ ± 0.2 °).

  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 resins, polyarylate resins (for example, polycondensates of bisphenols and aromatic divalent carboxylic acids such as polycondensates of bisphenol A and phthalic acid), polycarbonate resins, polyester resins, Insulating resins such as phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin It can be mentioned, but is not limited to these. 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. According to these dispersion methods, it is possible to prevent a change in the crystal form of the charge generation material due to the dispersion.

  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.

  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 shown by the following general formula (a-1), (a-2) or (a-3) from a mobility viewpoint is preferable.

In the above formula (a-1), R ³⁴ represents a hydrogen atom or a methyl group, and k10 represents 1 or 2. Ar ⁶ and Ar ⁷ are each a substituted or unsubstituted aryl group, —C ₆ H ₄ —C (R ³⁸ ) ═C (R ³⁹ ) (R ⁴⁰ ), or —C ₆ H ₄ —CH═CH—. CH = C (Ar) ₂ represents a substituted amino substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms Groups. R ³⁸ , R ³⁹ and R ⁴⁰ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and Ar is a substituted or unsubstituted aryl group.

In the above formula (a-2), R ³⁵ and R ³⁵ ′ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, R ³⁶ , R ³⁶ ′. R ³⁷ and R ³⁷ ′ are each independently 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, A substituted aryl group, —C (R ³⁸ ) ═C (R ³⁹ ) (R ⁴⁰ ), or —CH═CH—CH═C (Ar) ₂ , R ³⁸ , R ³⁹ and R ⁴⁰ are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, Ar represents a substituted or unsubstituted aryl group. M4 and m5 each independently represents an integer of 0 to 2.

In the above formula (a-3), R ⁴¹ is 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 ⁴² , R ⁴² ′, R ⁴³ , and R ⁴³ ′ 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, or an alkyl having 1 to 2 carbon atoms. An amino group substituted with a group, 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.

  In addition, the charge generation layer 1 and / or the charge transport layer 2 may be provided with an antioxidant, a light stabilizer 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 additive such as an agent and a heat stabilizer can be contained.

  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.

  The charge generation layer 1 and / or the charge transport layer 2 may contain at least one electron accepting substance for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, and the like. .

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, fluorenone-based, quinone-based, and benzene derivatives having an electron-withdrawing substituent such as Cl, CN, NO ₂ are particularly preferable.

  The protective layer 5 is an outermost surface layer formed by curing the curable resin composition containing the epoxy compound described above.

  The protective layer 5 cures a curable resin composition further containing one or more charge transporting compounds represented by the general formula (IV), (V), (VI), (VII) or (VIII). Preferably, the layer is Thereby, the protective layer 5 can obtain better mechanical strength and a good charge transport function.

  Here, from the viewpoint of obtaining charge transport properties and electrical characteristics desired for the protective layer of the electrophotographic photosensitive member, the F in the charge transport compounds represented by the general formulas (IV) to (VIII) is represented by the following general formula. A group represented by (IX) is preferred.

[In formula (IX), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group, and Ar 1-4 of ^{1 to} Ar ⁵ are the site represented by the following general formula (X) in the compound represented by the above general formula (IV), the following general formula (XI) in the compound represented by the above general formula (V) ), A moiety represented by the following general formula (XII) in the compound represented by the above general formula (VI), a moiety represented by the following general formula (XIII) in the compound represented by the above general formula (VII), Or it has the bond for couple | bonding with the site | part shown by the following general formula (XIV) in the compound represented by the said general formula (VIII). K represents 0 or 1. ]

-D-Si (R ⁶¹ ) _(3-a) Q _a (X)
_{^{- (X 1) n1 R 62}} -Z 1 H (XI)
_{^{- (X 2) n2 - (}} R 63) n3 - (Z 2) n4 G (XII)

In addition, as the substituted or unsubstituted aryl group represented by Ar ^{1 to} Ar ⁴ in the general formula (IX), specifically, aryl groups represented by the following general formulas (1) to (7) are preferable. .

In said formula (1)-(7), ^R69 is a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, phenyl substituted by them. A group or an unsubstituted phenyl group, or an aralkyl group having 7 to 10 carbon atoms, wherein R ^{70 to} R ⁷² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a carbon number, respectively. 1 to 4 alkoxy groups, phenyl or unsubstituted phenyl groups substituted therewith, aralkyl groups having 7 to 10 carbon atoms or halogen atoms, Ar represents a substituted or unsubstituted arylene group, and X represents the above One of the structures represented by general formulas (X) to (XIV) is shown, c and s each represent 0 or 1, and t represents an integer of 1 to 3.

  Moreover, as Ar in the aryl group represented by the above formula (7), an arylene group represented by the following formula (8) or (9) is preferable.

In the above formulas (8) and (9), R ⁷³ and R ⁷⁴ are each substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. A phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, and t represents an integer of 1 to 3.

  Moreover, as Z 'in the aryl group represented by the above formula (7), divalent groups represented by the following formulas (10) to (17) are preferable.

In formulas (10) to (17), R ⁷⁵ and R ⁷⁶ are each substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. A phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom; W represents a divalent group; v and w each represents an integer of 1 to 10; Each represents an integer of 1 to 3.

  In the above formulas (16) to (17), W is preferably a divalent group represented by the following formulas (18) to (26). In formula (25), u represents an integer of 0 to 3.

Further, the specific structure of Ar ⁵ in the general formula (IX) is as follows. When k = 0, the structure of c = 1 in the specific structure of Ar ^{1 to} Ar ⁴ is described above, and when k = 1, the structure of Ar 5 is described above. ^The structure of c = 0 in the specific structure of ^{1 to} Ar ⁴ is given.

Specific examples of the compound represented by the general formula (IV) include the following compounds (IV-1) to (IV-61). The following compounds (IV-1) to (IV-61) are prepared by combining Ar ^{1 to} Ar ⁵ and k of the compound represented by the general formula (IX) as shown in the following table, and an alkoxysilyl group. (S) is the specific one shown in the table below.

  Specific examples of the compound represented by the general formula (V) include the following compounds (V-1) to (V-37). In addition, in the following table | surface, although the bond is described, the thing in which the substituent is not described shows a methyl group.

  Specific examples of the compound represented by the general formula (VI) include the following compounds (VI-1) to (VI-47). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (VII) include the following compounds (VII-1) to (VII-40). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (VIII) include the following compounds (VIII-1) to (VIII-55). In the following table, Me or a bond is described but a substituent is not described indicates a methyl group.

  Further, a compound represented by the following general formula (XV) is added to the curable resin composition for forming the protective layer 5 in order to control various physical properties such as strength and film resistance of the protective layer 5. You can also.

Si (R ⁵⁰ ) _(4-c) Q _c (XV)
[In the formula (XV), R ⁵⁰ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and c represents an integer of 1 to 4. ]

  Specific examples of the compound represented by the general formula (XV) 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.

  Moreover, in order to raise the intensity | strength of the protective layer 5, the compound which has a 2 or more silicon atom as shown to the following general formula (XVI) is used for the curable resin composition for forming the protective layer 5 Is also preferable.

B- (Si (R ⁵¹ ) _(3-d) Q _d ) ₂ (XVI)
[In the above formula (XVI), B represents a divalent organic group, R ⁵¹ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and d represents an integer of 1 to 3. Indicates. ]

  More specific examples of the compound represented by the general formula (XVI) include the following compounds (XVI-1) to (XVI-16).

  Further, for the purpose of extending the pot life and controlling the film properties, it is preferable to contain a cyclic compound having a repeating structural unit represented by the following general formula (XVII) or a derivative thereof.

[In the above formula (XVII), 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 (XVII) 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 be added to the curable resin composition for forming the protective layer 5 in order to control the contamination resistance adhesion, lubricity, hardness, etc. of the electrophotographic photoreceptor surface.

  Examples of the fine particles include silicon atom-containing fine particles. The silicon atom-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 atom-containing fine particles preferably has a volume average particle diameter of 1 to 100 nm, more preferably 10 to 30 nm, in an acidic or alkaline aqueous dispersion, or an organic solvent such as alcohol, ketone or ester. It is selected from those dispersed in, and commercially available products can be used. The solid content of colloidal silica in the curable resin composition is not particularly limited, but is preferably based on the total solid content in the curable resin composition in terms of film formability, electrical characteristics, and strength. Is used in the range of 0.1 to 50% by mass, more preferably in the range of 0.1 to 30% by mass.

  Silicone fine particles used as silicon atom-containing fine particles are spherical and preferably have a volume average particle diameter of 1 to 500 nm, more preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles. A commercially available product 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 curable resin composition is preferably in the range of 0.1 to 30% by mass, more preferably 0.5 to 10% by mass based on the total solid content in the curable resin composition. % 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 composed of a resin obtained by copolymerizing a 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 , ZnO Examples thereof include semiconductive metal oxides such as —TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO.

  In addition, oil such as silicone oil can be added in order to control the contamination resistance adhesion, lubricity, hardness and the like of the surface of the electrophotographic photosensitive member. 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. Examples include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes. These may be added in advance to the curable resin composition for forming the protective layer 5, or may be impregnated under reduced pressure or increased pressure after producing the photoreceptor.

  Moreover, the curable resin composition for forming the protective layer 5 can also contain additives, such as a plasticizer, a surface modifier, antioxidant, and a photodegradation inhibitor. 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 curable resin composition for forming the protective layer 5, and the potential stability during environmental changes It is effective for improving image quality.

  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, "Sumilyzer TPS" or more manufactured by Sumitomo Chemical Co., Ltd. As a phosphite system manufactured by Sumitomo Chemical Co., Ltd., "Mark 2112", "Mark PEP 8", "Mark PEP 24G", "Mark PEP 36", "Mark 329K", "Mark HP 10" or more Asahi Denka products, especially hindered phenol, hindert Min 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 a curable resin composition containing the above-described constituent materials. Here, the curable resin composition may be used as a solution by adding 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. These can be used individually by 1 type or in mixture of 2 or more types. 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 solution of the curable resin composition is too small, when the charge transporting compounds represented by the general formulas (IV) to (VIII) are contained, they are likely to be precipitated. It is preferable to set it as 0.5-30 mass parts with respect to 1 mass part of compounds, and it is more preferable to set it as 1-20 mass parts. The protective layer 5 can be formed without adding an organic solvent if the curable resin composition is liquid.

  Further, as a mixing / dispersing method for preparing the curable resin composition, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like can be applied.

  The content of the epoxy compound represented by the general formula (I) in the curable resin composition is preferably 5 to 80 mass% based on the total solid content in the curable resin composition, and preferably 30 to 70 mass%. % Is more preferable. When the content of the epoxy compound is less than the above lower limit value, the gas barrier properties and weather resistance tend to be lowered, and when the content exceeds the above upper limit value, the film tends to become brittle.

  In addition, the content of the charge transporting compound in the curable resin composition is preferably 20 to 95% by mass, and preferably 30 to 70% by mass based on the total solid content in the curable resin composition. More preferred. If the content of the charge transporting compound is less than the above lower limit value, the charge transporting property and antistatic property tend to decrease, and if the content exceeds the above upper limit value, the gas barrier property and weather resistance tend to decrease. .

  It is preferable to add or use a catalyst when the curable resin composition or the preparation thereof is made. 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 preparing the curable resin composition, it is preferable to use a solid catalyst that is insoluble in a photofunctional compound, a reaction product, water, a solvent, or the like because the stability of the composition tends to be improved. The solid catalyst insoluble in the system is not particularly limited as long as the catalyst component is insoluble in an epoxy compound, a charge transporting compound, 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 curable resin composition 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 (XVIII) is more preferable, and R ⁸⁰ and R ^{81 in the following} general formula (XVIII) are more preferable. Are particularly preferred. By making R ⁸⁰ and R ^{81 the} same, the coordination power of the ligand near room temperature becomes strong, and further stabilization of the curable resin composition can be achieved.

[In the formula (XVIII), R ⁸⁰ and R ⁸¹ each independently represents 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 curable resin composition is applied onto the charge transport layer 2, the application methods are blade coating method, Meyer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method. A usual method such as can be used. And after application | coating, the protective layer 5 can be formed 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 electrophotographic photosensitive member of the present invention is not limited to the above embodiment. For example, in the electrophotographic photosensitive member of the present invention, the undercoat layer 4 is not necessarily provided.

  The electrophotographic photosensitive member shown in FIG. 1 includes a protective layer 5 made of a cured product of the curable resin composition, but the curable resin composition contains a charge transporting compound. In this case, since the obtained cured product has excellent mechanical strength and sufficient photoelectric characteristics, it can be used as it is as a charge transport layer of a multilayer photoreceptor. An example of such an electrophotographic photoreceptor is shown in FIG. An electrophotographic photoreceptor 100 shown in FIG. 2 has a structure in which an undercoat layer 4, a charge generation layer 1, and a charge transport layer 2 are sequentially laminated on a conductive support 3, and the charge transport layer 2 is cured as described above. It is the outermost surface layer formed by curing the conductive resin composition. The conductive support 3, the undercoat layer 4, and the charge generation layer 1 are the same as those of the electrophotographic photosensitive member shown in FIG. 1 (hereinafter the same).

  Further, the order of stacking the charge generation layer 1 and the charge transport layer 2 may be reversed from that in the above embodiment. An example of such an electrophotographic photoreceptor is shown in FIG. The electrophotographic photoreceptor shown in FIG. 3 has a structure in which an undercoat layer 4, a charge transport layer 2, a charge generation layer 1 and a protective layer 5 are sequentially laminated on a conductive support 3. Is the outermost surface layer formed by curing the curable resin composition.

  In addition, the electrophotographic photoreceptor of the present invention may be a single-layer photoreceptor having a layer (charge generation / charge transport layer) containing both a charge generation material and a charge transport material. Examples of single-layer type photoreceptors are shown in FIGS.

  An electrophotographic photoreceptor 100 shown in FIG. 4 has a structure in which an undercoat layer 4 and a charge generation / charge transport layer 7 are sequentially laminated on a conductive support 3. It is an outermost surface layer formed by curing a curable resin composition. The charge generation / charge transport layer 7 is formed by adding the charge generation material and, if necessary, a binder resin other than the epoxy compound represented by the general formula (I), a charge transport material, and the like to the curable resin composition. It can form using the coating liquid which mix | blended these additives. The charge generation material is the same as that used for the charge generation layer in the function-separated type photosensitive layer, and other binder resins include polyvinyl butyral resin, polyvinyl formal resin, and part of butyral formal, acetoacetal, etc. Acetal-modified polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins (for example, Sleksui B and K manufactured by Sekisui Chemical Co., Ltd.), polyamide resins, cellulose resins, and the like can be used. The content of the charge generation material in the charge generation / charge transport layer 7 is preferably 10 to 85% by mass, more preferably 20 to 50% by mass, based on the total solid content in the charge generation / charge transport layer 7. A charge transport material or a polymer charge transport material may be added to the charge generation / charge transport layer 7 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 charge generation / charge transport layer 7. Moreover, the solvent and coating method used for coating can be the same as those for the above layers. The film thickness of the charge generation / charge transport layer 7 is preferably about 5 to 50 μm, and more preferably 10 to 40 μm.

  The electrophotographic photoreceptor 100 shown in FIG. 5 has a structure in which an undercoat layer 4, a charge generation / charge transport layer 7 and a protective layer 5 are sequentially laminated on a conductive support 3. Is the outermost surface layer formed by curing the curable resin composition.

(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. 6 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. 6 includes an electrophotographic photosensitive member 100, a non-contact charging type charging unit 8 that charges the electrophotographic photosensitive member 100, 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 100 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, a cleaning unit 13, a static eliminator 14, and a fixing unit 15 that transfer from the photoconductor 100 to a transfer medium.

  FIG. 7 is a cross-sectional view schematically showing a basic configuration of another embodiment of the image forming apparatus of the present invention. The image forming apparatus 210 shown in FIG. 7 has the same configuration as the image forming apparatus 200 shown in FIG. 6 except that the image forming apparatus 210 includes a charging unit 8 that charges the electrophotographic photosensitive member 100 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 unit 10, an optical system device that can expose a light source such as a semiconductor laser, an LED (light emitting diode), and a liquid crystal shutter on the surface of the electrophotographic photoreceptor 100 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 photoreceptor 100 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 size of the toner is preferably 2 to 12 μm, and more 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 100. 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. Moreover, titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzene 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.

  As the particle size of the inorganic or organic fine particles, if the particle size is too small, the polishing ability is insufficient. If the particle size is too large, the surface of the electrophotographic photosensitive member 100 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 100 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 residual toner on the surface of the electrophotographic photosensitive member 100, 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. 8 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. 8 is an image forming apparatus that forms a color image by a tandem method. In the housing 400, four electrophotographic photoreceptors 100a to 100d (for example, the electrophotographic photoreceptor 100a is yellow and the electrophotographic photoreceptor is used. The body 100b can form an image of magenta, the electrophotographic photoreceptor 100c can be cyan, and the electrophotographic photoreceptor 100d can be formed of a black color.) Are arranged in parallel with each other along the intermediate transfer belt 409.

  Here, the electrophotographic photoreceptors 100a to 100d mounted on the image forming apparatus 220 are the electrophotographic photoreceptors of the present invention.

  Each of the electrophotographic photoreceptors 100a to 100d 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 100a to 100d.

  Further, a laser light source (exposure means) 403 is arranged at a predetermined position in the housing 400, and the surfaces of the electrophotographic photoreceptors 100a to 100d after charging are 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 photoreceptors 100a to 100d, 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, followed by a polyimide reaction (polyamic acid at a high temperature of 300 ° C. or higher. Can be carried out by carrying out a main ring curing reaction. 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 an outermost 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. 9 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 formed by combining the electrophotographic photosensitive member 100 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.

[Synthesis Example 1]
100 parts by weight of m-hydroxyphenol and 20 parts by weight of acetone were dissolved in 500 parts by weight of tetrahydrofuran and placed in a 1 L flask. 0.01 parts by weight of triethylamine was added thereto, and the mixture was stirred at 100 ° C. for 24 hours while refluxing. 100 parts by weight of the obtained reaction solution was gradually dropped into 2000 parts by weight of methanol. The resulting white solid was separated by filtration through a 10 μm membrane filter.

  Next, 10 parts by weight of the obtained white solid and 60 parts by weight of epichloropropane were dissolved in 200 parts by weight of tetrahydrofuran, 0.1 parts by weight of metallic sodium was added, and the mixture was stirred in a 1 L flask for 2 hours. Thereafter, the mixture was heated to reflux at 100 ° C. and stirred for 20 hours. The obtained reaction solution was dropped into 1000 parts by weight of methanol, and the resulting white solid was separated by filtration through a 10 μm membrane filter. As a result, 9 parts by mass (yield: 65%) of the epoxy compound (II-12) was obtained.

[Experimental Example 1]
16 parts by mass of a compound represented by the following formula (XIX) and 16 parts by mass of methanol are placed in a 100 ml sample bottle, and 1.6 parts by mass of ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) is added. And stirred 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 the epoxy compound (II-12) was added to this solution, and the mixture was further stirred at room temperature for 1 hour. Then, it filtered with the 0.5 micrometer membrane filter, and obtained the filtrate as a solution of curable resin composition.

  The solution of the obtained curable resin composition was dip-coated on a mirror-finished aluminum plate and dried and cured at 150 ° C. for 1 hour, and then the obtained film was peeled off from the aluminum plate to be 60 × 60 mm and 10 μm thick. A cured film was obtained.

[Experimental Examples 2 to 5]
Instead of the epoxy compound (II-12), the epoxy compounds (II-11), (II-6), (II-4), and (II-13) were used for each of Experimental Examples 2, 3, 4, and 5. Except that, a solution of the curable resin composition of Experimental Examples 2 to 5 and a cured film of 60 × 60 mm and a thickness of 10 μm were obtained in the same manner as in Experimental Example 1.

[Experimental Examples 6-7]
The curable resin compositions of Experimental Examples 6 and 7 were the same as Experimental Example 1 except that the amount of the epoxy compound (II-12) was 10 parts by mass for Experimental Example 6 and 24 parts by mass for Experimental Example 7. And a cured film of 60 × 60 mm and a thickness of 10 μm were obtained.

[Experimental Examples 8 to 9]
The curable resin compositions of Experimental Examples 8 and 9 were the same as in Experimental Example 1, except that the drying and curing conditions were set at 130 ° C. for 40 minutes for Experimental Example 8 and 1 hour at 170 ° C. for Experimental Example 9. And a cured film of 60 × 60 mm and a thickness of 10 μm were obtained.

[Comparative Experiment Example 1]
10 parts by mass of polyvinyl alcohol resin (Poval PVA117, manufactured by Kuraray Co., Ltd.) was dissolved in 90 parts by mass of distilled water. This solution was filtered through a 0.5 μm membrane filter, and the filtrate was obtained as a solution of the curable resin composition.

  The obtained curable resin composition solution was dip-coated on a mirror-finished aluminum plate, dried at 70 ° C. for 2 hours, and further dried and cured at 100 ° C. for 8 hours. Peeling was performed to obtain a cured film having a size of 60 × 60 mm and a thickness of 10 μm.

[Comparative Experiment Example 2]
10 parts by mass of an ethylene-vinyl alcohol copolymer (Eval 105B, manufactured by Kuraray Co., Ltd.) was completely dissolved in a mixed solvent of 45 parts by mass of distilled water and 45 parts by mass of isopropyl alcohol. This solution was filtered through a 0.5 μm membrane filter, and the filtrate was obtained as a solution of the curable resin composition.

  The obtained curable resin composition solution was dip-coated on a mirror-finished aluminum plate, dried at 70 ° C. for 2 hours, and further dried and cured at 100 ° C. for 8 hours. Peeling was performed to obtain a cured film having a size of 60 × 60 mm and a thickness of 10 μm.

[Comparative Experiment 3]
10 parts by mass of a polyamide resin (CM-4001, manufactured by TORAY) was completely dissolved in 90 parts by mass of isopropyl alcohol. This solution was filtered through a 0.5 μm membrane filter, and the filtrate was obtained as a solution of the curable resin composition.

  The obtained curable resin composition solution is dip-coated on a mirror-finished aluminum plate, dried and cured at 150 ° C. for 1 hour, and the obtained film is peeled off from the aluminum plate to give a cured film of 60 × 60 mm and a thickness of 10 μm. Got.

[Comparison Experiment 4]
A comparative experiment was conducted in the same manner as in Experimental Example 1 except that 16 parts by mass of an epoxy resin having no phenolic hydroxyl group (Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.) was used instead of 16 parts by mass of the epoxy compound (II-12). A solution of the curable resin composition of Example 4 and a cured film of 60 × 60 mm and a thickness of 10 μm were obtained.

[Comparative Experimental Example 5]
Instead of 16 parts by mass of the epoxy compound (II-12), 16 parts by mass of an epoxy resin having no phenolic hydroxyl group (Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.) and an antioxidant (Irganox 1010, Nikka Chemical Co., Ltd.) (Manufactured) A solution of the curable resin composition of Comparative Experimental Example 5 and a cured film of 60 × 60 mm and a thickness of 10 μm were obtained in the same manner as in Experimental Example 1 except that 0.5 part by mass was used.

(Characteristic evaluation test of cured film)
The oxygen permeability coefficient at 23 ° C. of the cured films obtained in Experimental Examples 1 to 9 and Comparative Experimental Examples 1 to 5 was measured with a gas permeability measuring device (BT-3, manufactured by Toyo Seiki Co., Ltd.). Further, the cured films obtained in Experimental Examples 1 to 9 and Comparative Experimental Examples 1 to 5 were cut out to 10 × 30 mm, and the tensile strength was measured with Instron (Strograph VE10D, manufactured by Toyo Seiki Co., Ltd.). Further, the cured films obtained in Experimental Examples 1 to 9 and Comparative Experimental Examples 1 to 5 were fixed to the SUS support, and the deflection temperature under load was measured with a deflection temperature measuring device (HDT-E model, manufactured by Toyo Seiki Co., Ltd.). It was measured. These results are shown in Table 59.

  As is clear from the results shown in Table 59, the cured films (cured bodies) obtained in Experimental Examples 1 to 9 have sufficient gas barrier properties, and exhibit excellent mechanical strength while being heat resistant. Also confirmed to be excellent. On the other hand, the cured films obtained in Comparative Experimental Examples 1 and 2 were confirmed to have low mechanical strength and extremely poor heat resistance. Moreover, it was confirmed that the cured film obtained in Comparative Experimental Examples 3 to 5 is inferior in gas barrier properties.

(Preparation of base photoreceptor 1)
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 benzidine compound represented by the following general formula (XX) 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 (XXI) It was made to melt | dissolve in a mass part 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. Thereby, the base photosensitive member 1 was obtained.

(Preparation of base photoreceptor 2)
In the same manner as the production of the base photoreceptor 1, an aluminum base material on which an anodized film was formed 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, in the same manner as the production of the base photoconductor 1, a charge transport layer was formed on the charge generation layer to obtain a base photoconductor 2.

(Preparation of base photoreceptor 3)
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 (XXII) and 3 parts by mass of a polymer compound (viscosity average molecular weight 39,000) having a structural unit represented by the above general formula (XXI) 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. Thereby, the base photoreceptor 3 was obtained.

(Preparation of base photoconductor 4)
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 was formed on the undercoat layer in the same manner as the production of the base photoreceptor 2. Further, in the same manner as the production of the base photoreceptor 1, a charge transport layer was formed on the charge generation layer, and the base photoreceptor 4 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. The ML ² / A value of the above formula was determined for 100 toner particles (in this example), 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.

[Examples 1 to 9]
On the base photoreceptor 1, the solution of the curable resin composition obtained in Experimental Examples 1 to 9 was applied by a ring dip coating method, and dried under the conditions when a cured film was prepared in each of Experimental Examples 1 to 9. Curing was performed to form a protective layer having a thickness of 10 μm. This obtained the electrophotographic photoreceptor of Examples 1-9.

  In addition, the obtained electrophotographic photosensitive member and developer 1 were combined and mounted on a printer (DocuCenter Color 400CP, manufactured by Fuji Xerox Co., Ltd.) to produce image forming apparatuses of Examples 1-9.

[Examples 10 to 12]
On the base photoreceptors 2 to 4, the solution of the curable resin composition obtained in Experimental Example 1 was applied by a ring dip coating method, and was dried and cured under the conditions when a cured film was prepared in Experimental Example 1, and the film A protective layer having a thickness of 10 μm was formed. This obtained the electrophotographic photoreceptor of Examples 10-12.

  The obtained electrophotographic photosensitive member and developer 1 were combined and mounted on a printer (DocuCenter Color 400CP, manufactured by Fuji Xerox Co., Ltd.) to produce image forming apparatuses of Examples 10-12.

[Examples 13 to 14]
Image forming apparatuses of Examples 13 to 14 were produced in the same manner as in Example 1 except that the electrophotographic photosensitive member obtained in Example 1 and developers 2 to 3 were used in combination.

[Comparative Example 1]
16 parts by mass of the compound represented by the above formula (XIX) and 16 parts by mass of methanol are placed in a 100 ml sample bottle, and 1.6 parts by mass of ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) is added. And stirred 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. 10 parts by mass of a resole resin (Resitop PL-2211, manufactured by Gunei Chemical Co., Ltd.) is added to this solution, and after stirring and completely dissolved, the solution is filtered through a 0.5 μm membrane filter. Obtained as a solution of the composition.

  The solution of the obtained curable resin composition was applied onto the base photoreceptor 1 by a ring dip coating method, and dried and cured at 150 ° C. for 40 minutes to form a protective layer having a thickness of 10 μm. As a result, an electrophotographic photosensitive member of Comparative Example 1 was obtained.

  The obtained electrophotographic photosensitive member and developer 1 were combined and mounted on a printer (DocuCenter Color 400CP, manufactured by Fuji Xerox Co., Ltd.) to produce an image forming apparatus of Comparative Example 1.

[Comparative Example 2]
A solution of a curable resin composition was obtained in the same manner as in Comparative Example 1 except that 10 parts by mass of an alicyclic epoxy resin (Adeka Resin EP4088S, manufactured by Asahi Denka Kogyo Co., Ltd.) was used instead of 10 parts by mass of the resole resin. . An electrophotographic photosensitive member and an image forming apparatus of Comparative Example 2 were obtained in the same manner as in Comparative Example 1 except that this curable resin composition solution was used.

[Comparative Examples 3 to 4]
A comparative example was carried out in the same manner as in Example 1 except that the curable resin composition solution obtained in Comparative Experimental Examples 4 to 5 was used instead of the curable resin composition solution obtained in Experimental Example 1. 3 to 4 electrophotographic photoreceptors and image forming apparatuses were obtained.

(Print test)
Using the image forming apparatuses obtained in Examples 1 to 14 and Comparative Examples 1 to 4, 10,000 sheets of image forming tests were performed in an environment of high temperature and high humidity (28 ° C., 75% RH), and then low temperature and low humidity ( The image formation test for 10,000 sheets was performed in an environment of 10 ° C. and 20% RH. Thereafter, the occurrence of deletion defects due to oxidative degradation on the surface of the photoreceptor was visually evaluated. The print image quality was evaluated visually. Further, the wear amount of the protective layer after the image formation test was measured using a laser film thickness meter. These results are shown in Table 60.

  As is clear from the results shown in Table 60, the electrophotographic photoreceptors and image forming apparatuses of Examples 1 to 14 of the present invention do not generate deletion due to oxidative deterioration of the surface even during long-term use including environmental changes. It was confirmed that the print image quality was good and the wear resistance was excellent. On the other hand, it was confirmed that the electrophotographic photosensitive member and the image forming apparatus of Comparative Example 1 caused a slight amount of deletion due to oxidative deterioration of the surface, which adversely affected the print image quality. In addition, it was confirmed that the electrophotographic photosensitive member and the image forming apparatus of Comparative Example 2 had a large number of deletions, had an adverse effect on print image quality, and had extremely poor wear resistance. Further, it was confirmed that the electrophotographic photoreceptors and image forming apparatuses of Comparative Examples 3 to 4 had a large number of deletions, had an adverse effect on print image quality, and were inferior in wear resistance.

[Experimental Example 10]
16 parts by mass of the compound represented by the above formula (XIX) and 16 parts by mass of methanol are placed in a 100 ml sample bottle, and 1.6 parts by mass of ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) is added. And stirred 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 the epoxy compound (III-1) was added to this solution, and the mixture was further stirred at room temperature for 1 hour. Then, it filtered with the 0.5 micrometer membrane filter, and obtained the filtrate as a solution of curable resin composition.

  The solution of the obtained curable resin composition was dip-coated on a mirror-finished aluminum plate and dried and cured at 150 ° C. for 1 hour, and then the obtained film was peeled off from the aluminum plate to be 60 × 60 mm and 10 μm thick. A cured film was obtained.

[Experimental Examples 11 to 13]
Similar to Experimental Example 10, except that the epoxy compounds (III-3), (III-5), and (III-11) were used for Experimental Examples 11, 12, and 13 instead of the epoxy compound (III-1), respectively. Thus, a solution of the curable resin composition of Experimental Examples 11 to 13 and a cured film of 60 × 60 mm and a thickness of 10 μm were obtained.

[Experimental Examples 14 to 15]
The curable resin compositions of Experimental Examples 14 and 15 were the same as Experimental Example 10 except that the compounding amount of the epoxy compound (III-1) was 10 parts by mass for Experimental Example 14 and 6 parts by mass for Experimental Example 15. And a cured film of 60 × 60 mm and a thickness of 10 μm were obtained.

[Experimental Examples 16 to 17]
The curable resin compositions of Experimental Examples 16 and 1740 were the same as in Experimental Example 10 except that the conditions for dry curing were 130 ° C. for 1 hour for Experimental Example 16 and 1 hour at 170 ° C. for Experimental Example 17. And a cured film of 60 × 60 mm and a thickness of 10 μm were obtained.

[Comparative Experimental Example 6]
A curable resin composition was obtained by kneading 5 parts by mass of an epoxy resin (Epicoat 828, manufactured by Japan Epoxy Resin) and 1 part by mass of a curing agent (Epicure U, manufactured by Japan Epoxy Resin). The obtained curable resin composition was applied onto a mirror-finished aluminum plate with an applicator and thermally cured at 150 ° C. for 1 hour. The obtained film was peeled off from the aluminum plate, and a cured film having a thickness of 60 × 60 mm and a thickness of 10 μm. Got.

[Comparative Experimental Example 7]
Using a weather-resistant polyethylene naphthalate resin (Teonex Q81, manufactured by Teijin Limited), a film of 60 × 60 mm and a thickness of 10 μm was formed.

(Characteristic evaluation test of cured film)
The cured films obtained in Experimental Examples 10 to 17 and Comparative Experimental Examples 6 to 7 and 4 to 5 were set in a weatherometer (Ci5000, manufactured by Atlas Co.), and were irradiated with 2000 nm at 350 nm light and 100 W / m ² illuminance. A weather resistance test was performed, and the chromaticity difference ΔL ^* before and after the test and the rate of decrease in tensile strength were evaluated. The results are shown in Table 61.

  As is clear from the results shown in Table 61, the cured films (cured bodies) used in the present invention obtained in Experimental Examples 10 to 17 are less susceptible to color change and mechanical strength reduction even in the accelerated weather resistance test. It was confirmed that it has extremely excellent weather resistance (antioxidation property). On the other hand, it was confirmed that the cured films obtained in Comparative Experimental Examples 6 to 7 and 4 to 5 were severe in both color change and mechanical strength reduction and inferior in weather resistance.

[Examples 15 to 22]
On the base photoreceptor 1, the solution of the curable resin composition obtained in Experimental Examples 10 to 17 was applied by a ring dip coating method, and dried under the conditions when a cured film was prepared in each of Examples 10 to 17. Curing was performed to form a protective layer having a thickness of 10 μm. This obtained the electrophotographic photoreceptor of Examples 15-22.

  The obtained electrophotographic photosensitive member and developer 1 were combined and mounted on a printer (DocuCenter Color 400CP, manufactured by Fuji Xerox Co., Ltd.) to produce image forming apparatuses of Examples 15-22.

[Examples 23 to 25]
On the base photoreceptors 2 to 4, the solution of the curable resin composition obtained in Example 10 was applied by a ring dip coating method, and was dried and cured under the conditions when a cured film was produced in Example 10 to form a film. A protective layer having a thickness of 10 μm was formed. This obtained the electrophotographic photoreceptor of Examples 23-25.

  The obtained electrophotographic photosensitive member and developer 1 were combined and mounted on a printer (DocuCenter Color 400CP, manufactured by Fuji Xerox Co., Ltd.) to produce image forming apparatuses of Examples 23 to 25.

[Examples 26 to 27]
Image forming apparatuses of Examples 26 to 27 were produced in the same manner as in Example 15 except that the electrophotographic photosensitive member obtained in Example 15 and developers 2 to 3 were used in combination.

(Print test)
Using the image forming apparatuses obtained in Examples 10 to 27 and Comparative Examples 1 to 4, an image forming test for 10,000 sheets was performed in an environment of high temperature and high humidity (28 ° C., 75% RH), and then low temperature and low humidity ( The image formation test for 10,000 sheets was performed in an environment of 10 ° C. and 20% RH. Thereafter, in order to evaluate the mechanical strength of the photoreceptor, the wear amount of the protective layer was measured using a laser film thickness meter. The print image quality was evaluated visually. Further, the residual potential after static elimination was measured for the photoconductor at the initial stage of the print test and after the test, and the difference (ΔRp) between the initial residual potential and the residual potential after the test was calculated. These results are shown in Table 62.

  As is apparent from the results shown in Table 62, the electrophotographic photoreceptors and image forming apparatuses of Examples 15 to 27 of the present invention have excellent surface resistance even when used for a long period of time including environmental changes. It was confirmed that the film exhibited wearability, print quality was good, and deterioration of electrical characteristics was sufficiently suppressed. On the other hand, it was confirmed that the electrophotographic photosensitive member and the image forming apparatus of Comparative Example 1 had image quality defects due to oxidative degradation of the surface, and electrical characteristics were also degraded. In addition, it was confirmed that the electrophotographic photoreceptors and image forming apparatuses of Comparative Examples 2 to 4 have low wear resistance, image quality defects, and further deterioration of electrical characteristics.

  As is clear from the above results, it was confirmed that the epoxy compound used in the present invention can provide a cured product that achieves both mechanical strength and antioxidant properties at a high level. And according to the electrophotographic photosensitive member and the image forming apparatus of the present invention using such an epoxy compound as the constituent material of the outermost surface layer, both the mechanical strength and the antioxidant property of the outermost surface layer are achieved at a high level, It was confirmed that an image with good image quality can be stably obtained even when the period image formation is performed.

1 is a schematic cross-sectional view showing a preferred embodiment of an electrophotographic photoreceptor of the present invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. 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 generation layer, 2 ... Charge transport layer, 3 ... Conductive support body, 4 ... Undercoat layer, 5 ... Protective layer, 6 ... Photosensitive layer, 7 ... Charge generation / charge transport layer, 8 ... Charging means, 9 DESCRIPTION OF SYMBOLS ... Power supply, 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 ... Covered Transfer body, 100, 100a to 100d, electrophotographic photosensitive member, 200, 210, 220, image forming apparatus, 300, process cartridge, 500, medium to be transferred.

Claims (5)

An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer disposed on the conductive support,
The photosensitive layer has the following compounds (II-4), (II-6), (II-11), (II-12), (II-13), (III) on the side farthest from the conductive support. -1), (III-3), (III-5), or (III-11), which is obtained by curing a curable resin composition, the following compounds (II-4), (II-6), (II-11), (II -12), the (II-13), (III -1), (III-3), an epoxy group of the (III-5), or (III-11), the same other electrophotographic photoreceptor molecule characterized by having a top surface layer comprising a three-dimensional crosslinked structure formed by reaction with hydroxyl groups of the compound.

The curable resin composition further contains one or more charge transporting compounds represented by the following general formula (IV), (V), (VI), (VII) or (VIII). The electrophotographic photosensitive member according to claim 1.
F [-D-Si (R ⁶¹ ) _(3-a) Q _a ] _b (IV)
[In the formula (IV), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ⁶¹ represents a hydrogen atom, a substituted or unsubstituted group. 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 1) n1}} R 62 -Z 1 H] m1 (V)
[In Formula (V), F represents an organic group derived from a compound having a hole transporting ability, R ⁶² represents an alkylene group, Z ¹ represents an oxygen atom, a sulfur atom, NH or COO, and X ¹ Represents an oxygen atom or a sulfur atom, m1 represents an integer of 1 to 4, and n1 represents 0 or 1. ]
_{^{F [- (X 2) n2}} - (R 63) n3 - (Z 2) n4 G] n5 (VI)
[In the formula (VI), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ⁶³ represents an alkylene group, Z ² represents an oxygen atom, S represents a sulfur atom, NH or COO, G represents an epoxy group, n2, n3 and n4 each independently represents 0 or 1, and n5 represents an integer of 1 to 4. ]

[In formula (VII), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁶⁴ , R ⁶⁵ and R ⁶⁶ independently represents a hydrogen atom or a monovalent organic group, R ⁶⁷ represents a monovalent organic group, m 2 represents 0 or 1, and n 6 represents an integer of 1 to 4. However, R ⁶⁶ and R ⁶⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (VIII), F represents an organic group derived from a compound having a hole transporting property, T represents a divalent group, R ⁶⁸ represents a monovalent organic group, and m3 represents 0 or 1 N7 represents an integer of 1 to 4. ] The electrophotographic photosensitive member according to claim 1 or 2,
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 1 or 2,
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: A method for producing an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer disposed on the conductive support,
On the side farthest from the conductive support, the following compounds (II-4), (II-6), (II-11), (II-12), (II-13), (III-1), ( A curable resin composition containing III-3), (III-5), or (III-11) is cured to produce the following compounds (II-4), (II-6), (II-11), (II-12), (II-13), (III-1), (III-3), (III-5), or (III-11) having an epoxy group, other molecules of the same compound A method for producing an electrophotographic photoreceptor , comprising forming an outermost surface layer of the photosensitive layer including a three-dimensional cross-linked structure formed by reacting with a hydroxyl group .