JP2010128458A - Image holder for image forming apparatus, process cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image holder for an image forming apparatus having excellent stability in repeated use. <P>SOLUTION: In the image holder for an image forming apparatus, a photosensitive layer containing a compound represented by general formula (I) is formed on a support, wherein a plurality of symbols Ar each independently represent H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted monovalent aromatic group or a substituted or unsubstituted monovalent aromatic group containing an aromatic heterocycle, and n represents an integer of 1-3. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an image carrier for an image forming apparatus, a process cartridge, and an image forming apparatus.

  A photoreceptor having a photosensitive layer containing an organic photoconductive compound as a main component is compared with a photoreceptor containing an inorganic photoconductor (such as selenium, zinc oxide, cadmium sulfide or silicon), which has been conventionally used, as a main component. Therefore, it has been actively researched with many advantages such as being relatively easy to manufacture, inexpensive, easy to handle, and excellent thermal stability.

  In particular, the charge generation function and the charge transport function of the photoconductor are assigned to separate functional layers, the former material having the generation function is used as the charge generation layer, and the latter material having the transport function is used as the charge transport layer. A photoreceptor having a laminated type function separation type photosensitive layer to be contained has already been put into practical use.

Among them, as a photoconductive compound, a tetraarylbenzidine compound has been actively studied because of its high charge mobility. (For example, refer patent document 1, patent document 2, patent document 3, patent document 4, and patent document 5).
Further, organic photoreceptors using phenothiazine derivatives have been proposed (see, for example, Patent Document 6 and Patent Document 7).
U.S. Pat. No. 4,047,948 US Pat. No. 4,299,897 Japanese Patent Laid-Open No. 61-132955 Japanese Patent Laid-Open No. 62-26749 JP-A-3-138654 Japanese Patent Laid-Open No. 10-59952 Japanese Patent Laid-Open No. 11-158165

  An object of the present invention is to provide an image carrier for an image forming apparatus in which a change in residual potential due to repeated use is low as compared with the invention described in Patent Document 1.

The above problem is solved by the following means. That is,
The invention according to claim 1 is an image carrier for an image forming apparatus having a support and a photosensitive layer containing a compound represented by the following general formula (I) on the support.

  In general formula (I), each Ar independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted monovalent aromatic group, or a substituted or unsubstituted 1 containing an aromatic heterocyclic ring. Represents a valent aromatic group, and n represents an integer of 1 to 3.

  According to a second aspect of the present invention, there is provided an image forming apparatus for an image forming apparatus according to the first aspect, a charging unit for charging the image holding body for the image forming apparatus, and exposing the charged image holding body for the image forming apparatus. An exposure unit that forms an electrostatic latent image; a developing unit that develops the electrostatic latent image to form a toner image; a transfer unit that transfers the toner image to a transfer target; and an image carrier for the image forming apparatus. And a process cartridge having at least one selected from cleaning means for cleaning.

  According to a third aspect of the present invention, the image forming apparatus image holding body according to the first aspect, charging means for charging the image forming apparatus image holding body, and the charged image forming apparatus image holding body are exposed. An image forming apparatus comprising: an exposure unit that forms an electrostatic latent image; a developing unit that develops the electrostatic latent image to form a toner image; and a transfer unit that transfers the toner image to a transfer target. is there.

According to the first aspect of the present invention, there is provided an image carrier for an image forming apparatus in which the variation of the residual potential due to repeated use is lower than that of the invention described in Patent Document 1.
According to the second aspect of the present invention, there is provided a process cartridge having an image carrier for an image forming apparatus in which the variation of the residual potential due to repeated use is low as compared with the invention described in Patent Document 1.
According to the third aspect of the present invention, an image forming apparatus having an image carrier for an image forming apparatus in which the variation of the residual potential due to repeated use is lower than that of the invention described in Patent Document 1.

Hereinafter, preferred embodiments of the present invention will be described.
In this embodiment, an image carrier for an image forming apparatus is provided by using the compound represented by the general formula (I) as a charge transport material. That is, an image carrier for an image forming apparatus in which a photosensitive layer is formed on a conductive support, and the photosensitive layer contains the compound represented by the general formula (I).
The conductive support in this embodiment is a conductive material having a volume resistivity measured based on JIS K 7194 “Resistivity Test Method by Conductive Plastic Four-Probe Method” of less than 10 ⁷ Ω · cm. It refers to a support formed of a conductive material or having a conductive layer formed of the conductive material on a substrate surface.

  The photosensitive layer in the image carrier for the image forming apparatus is a single layer type photosensitive layer containing the charge generating material and the charge transporting material in the same layer, or a layer containing the charge generating material and a layer containing the charge transporting material are adjacent to each other. Thus, any of the function-separated photosensitive layers provided separately may contain the compound represented by the above general formula (I) as a charge transport material.

  As the charge generation material, a known charge generation material such as oxytitanium phthalocyanine, chlorogallium phthalocyanine, or hydroxygallium phthalocyanine can be used. The image carrier for an image forming apparatus may be provided with a protective layer on the outermost surface (position farthest from the conductive support). In this case, the protective layer has a charge transport property. It preferably comprises a crosslinkable silicone resin.

(Image carrier for image forming apparatus)
The image carrier for an image forming apparatus according to the exemplary embodiment is an image carrier for an image forming apparatus in which a photosensitive layer containing a compound represented by the following general formula (I) is formed on a support.
Here, the compound represented by formula (I) will be described.

  In general formula (I), each Ar independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted monovalent aromatic group, or a substituted or unsubstituted 1 containing an aromatic heterocyclic ring. Represents a valent aromatic group, and n represents an integer of 1 to 3.

  Specific examples of the group representing Ar in the general formula (I) include the following groups.

  Examples of the alkyl group represented by Ar in the general formula (I) include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms). Examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The alkyl group may be linear or branched.

The monovalent aromatic group represented by Ar in the general formula (I) is not particularly limited in the number of aromatic rings, but specifically, for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aromatic ring number. Examples thereof include a monovalent polynuclear aromatic hydrocarbon group having 2 or more and 20 or less, or a monovalent condensed aromatic hydrocarbon group having 2 or more and 20 or less substituted or unsubstituted aromatic rings.

  Here, the “polynuclear aromatic hydrocarbon” specifically means a polycyclic aromatic as defined below. That is, the “polynuclear aromatic hydrocarbon” represents a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present and the rings are bonded by a carbon-carbon bond. Specific examples include biphenyl, terphenyl, and stilbene.

  The “condensed aromatic hydrocarbon” specifically means a polycyclic aromatic as defined below. That is, the “condensed aromatic hydrocarbon” is a carbonization in which two or more aromatic rings composed of carbon and hydrogen exist, and these aromatic rings share a pair of adjacent bonded carbon atoms. Represents hydrogen. Specific examples include naphthalene, anthracene, phenanthrene, pyrene, perylene, and fluorene.

  The substituted or unsubstituted monovalent aromatic group containing an aromatic heterocycle represented by Ar in the general formula (I) represents a monovalent aromatic group containing at least one aromatic heterocycle, and is aromatic. There are no particular restrictions on the number of rings and heterocycles. Here, the “aromatic heterocycle” represents an aromatic ring containing an element other than carbon and hydrogen. Nr = 5 and / or 6 is preferably used as the number of atoms (Nr) constituting the ring skeleton. Further, the type and number of atoms (heterogeneous atoms) other than carbon atoms constituting the ring skeleton are not limited, but for example, a sulfur atom, a nitrogen atom, or an oxygen atom is preferably used, and two or more kinds in the ring skeleton are used. And / or two or more heteroatoms may be included. In particular, as the heterocyclic ring having a 5-membered ring structure, thiophene, pyrrole, furan, or a heterocyclic ring in which the 3- and 4-position carbons thereof are further substituted with nitrogen is preferably used. Preferable examples include pyridine ring.

  The “monovalent aromatic group containing an aromatic heterocyclic ring” represents a linking group containing at least one kind of the aromatic heterocyclic ring in an atomic group forming a skeleton. These may be either all composed of a conjugated system or partly composed of a conjugated system, but those composed entirely of a conjugated system are preferred from the viewpoint of charge transportability. Specific examples include a phenylthiophene ring, a phenylpyrrole ring, or a phenylpyridine ring.

  Examples of the substituent that can be substituted with the group represented by Ar in formula (I) include a hydrogen atom, an alkyl group, an alkoxy group, a phenoxy group, an aryl group, an aralkyl group, a substituted amino group, and a halogen atom. . As said alkyl group, a C1-C10 thing is preferable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a hexyl group etc. are mentioned. As said alkoxy group, a C1-C10 thing is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group etc. are mentioned. As said aryl group, a C6-C20 thing is preferable, for example, a phenyl group or a toluyl group etc. are mentioned. As said aralkyl group, a C7-C20 thing is preferable, for example, a benzyl group or a phenethyl group etc. are mentioned. Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, and an aralkyl group.

  Further, n in the general formula (I) represents an integer of 1 to 3, but preferably represents an integer of 1 to 2.

Here, from the viewpoint that the fluctuation of the residual potential due to repeated use is low, the compound represented by the general formula (I) is preferably
Ar is each independently an alkyl group, a phenyl group, or an aryl group such as a thiophene ring, and n is a compound that represents an integer of 1 to 2.
More preferably,
In the compound, Ar independently represents an alkyl group, a phenyl group, or a thiophene ring, and n represents 2.

  Among these, the compound represented by the following general formula (II) is particularly preferable as the compound represented by the general formula (I) from the viewpoint that the fluctuation of the residual potential due to repeated use is low.

  In general formula (II), R represents a hydrogen atom, an alkyl group, or an alkoxy group each independently, and n represents an integer of 1 or more and 3 or less.

Examples of the alkyl group represented by R in the general formula (II) include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms). Examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The alkyl group may be linear or branched.
Examples of the alkoxy group represented by R in the general formula (II) include an alkoxy group having 1 to 10 carbon atoms (preferably 3 to 8 and more preferably 3 to 6). For example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, etc. are mentioned.

  Further, n in the general formula (II) represents an integer of 1 to 3, but preferably represents an integer of 1 to 2.

  Hereinafter, specific examples of the compound represented by the general formula (I) will be exemplified, but the present invention is not limited thereto.

Hereinafter, the manufacturing method of the phenothiazine compound shown by general formula (I) of this embodiment is demonstrated.
The phenothiazine compound represented by the general formula (I) of the present embodiment can be obtained using, for example, cross-coupling biaryl synthesis. In the cross-coupling biaryl synthesis, for example, the Suzuki reaction, the Kharasch reaction, the Negishi reaction, the Stille reaction, the Grignard reaction, or the Ullmann reaction is used.

  Although the phenothiazine compound of this embodiment is synthesize | combined as follows, for example, the synthesis | combining method is not limited to this. Specifically, the phenothiazine compound of the present embodiment is, for example, a compound represented by the general formula (III) and a compound represented by the general formula (IV) in a solvent, for example, a metal or metal It can be obtained by reacting in the presence of at least one of a catalyst and a base.

Here, in general formula (III) and general formula (IV), X and G are a halogen atom, B (OH) ₂ , or the structure shown below independently, respectively.

  n represents an integer of 1 to 3.

Examples of the metal used in the above reaction include Pd, Cu, Ti, Sn, Ni, or Pt.
As the metal catalyst, metal complexes _{(e.g., Pd (P (C 6 H} 5) 3) 4, Pd (OCOCH 3) 2, Pd 2 (dba) 3, Pd (P (C 6 H 5) 3) ₂ Cl ₂ , Pd (dppf) ₂ Cl ₂ , or Pd / C, Ni (C ₅ H ₇ O ₂ ) ₂ ) or the like (where dba represents dibenzylideneacetone and dppf represents bis (diphenylphosphino) ferrocene. )) And the like.
Examples of the base include an inorganic base (for example, Na ₂ Co ₃ , K ₂ Co ₃ , Cs ₂ CO ₃ , or Ba (OH) ₂ ), an organic base (for example, N (C ₂ H ₅ ) ₃ , NH ((CH ₃ ) ₂ CH) ₂ , NH (C ₂ H ₅ ) ₂ , NH (CH ₃ ) ₂ , N (CH ₃ ) ₃ , DBU (1,8-diazabicyclo [5.4.0] undecene-7), DMAP (N, N-dimethyl-4-aminopyridine) or pyridine).
The solvent may be any solvent that does not significantly inhibit the reaction. For example, an aromatic hydrocarbon solvent (such as benzene, toluene, xylene, or mesitylene), an ether solvent (such as diethyl ether, tetrahydrofuran, or dioxane). ), Acetonitrile, dimethylformamide, dimethyl sulfoxide, methanol, ethanol, isopropyl alcohol, or water. Further, as the _{solvent, P (C 6 H 5)} 3, P (o-CH 3 C 6 H 4) 3, P (C (CH 3) 3) 3, or _{P (C 2} H _{5) 3,} etc. It may be used.

Here, the amount of the metal and the metal catalyst used in the reaction is not particularly limited, and for example, 0.001 mol in terms of a molar ratio with respect to the compound represented by the general formula (III). % To 10 mol%, more preferably 0.01 mol% to 5.0 mol%.
The amount of the base used is, for example, in the range of 0.5 mol% or more and 4.0 mol% or less, more preferably 1.0 mol, relative to the compound represented by the general formula (III). % Or more and 2.5 mol% or less.

  Moreover, although the said reaction is implemented under inert gas atmosphere, such as nitrogen and argon, for example, under normal pressure, you may implement it on pressurization conditions. The above reaction is carried out, for example, at a reaction temperature in the range of 20 ° C. to 300 ° C., more preferably in the range of 50 ° C. to 180 ° C. Here, although reaction time changes with reaction conditions, what is necessary is just to select from the range of several minutes or more and 20 hours or less.

  Then, after the above reaction, the reaction solution is poured into water, stirred well, and when the reaction product is a solid (crystal), a crude product is obtained by filtration by suction filtration. On the other hand, when the reaction product is an oily product, a crude product is obtained by extraction with an appropriate solvent such as ethyl acetate or toluene. Then, column purification (column purification using silica gel, alumina, activated clay, activated carbon, etc.) of the obtained composition organisms, or treatment such as adding these adsorbents to the solution to adsorb unnecessary components To purify. When the reaction product is a crystal, it is further purified by recrystallization from an appropriate solvent (for example, hexane, methanol, acetone, ethanol, ethyl acetate, or toluene). In this way, the desired phenothiazine compound represented by the general formula (I) is obtained.

  The photosensitive layer of the image carrier for the image forming apparatus of this embodiment is excellent in compatibility with the binder by using the phenothiazine compound represented by the general formula (I), and the obtained coating film has uneven film thickness. There is no. Further, the image carrier for an image forming apparatus of the present embodiment has a photosensitive layer containing the phenothiazine compound represented by the general formula (I), so that residual potential fluctuation due to repeated use is low, and excellent environmental sustainability. Demonstrate. Furthermore, since the image forming apparatus and the process cartridge according to the present embodiment use the image carrier for the image forming apparatus according to the present embodiment, good image quality can be obtained over a long period of time, and the environmental load is reduced and the cost is greatly reduced. It also becomes.

The image carrier for an image forming apparatus according to the exemplary embodiment is an image carrier for an image forming apparatus having a photosensitive layer on a conductive support, and the compound represented by the general formula (I) is added to the photosensitive layer. It is characterized by containing.
1 to 3 are schematic cross-sectional views showing first to third embodiments of the image carrier for an image forming apparatus according to this embodiment, respectively.
In either case, the image carrier 1 for an image forming apparatus is cut along the stacking direction of the conductive support 2 and the photosensitive layer 3.

  The image carrier 1 for an image forming apparatus according to the first and second embodiments shown in FIGS. 1 and 2 includes a function-separated type photosensitive layer in which a charge generation material and a charge transport material are contained in different layers. It is. That is, in the photosensitive layer 3, a layer containing a charge generation material (charge generation layer 5) and a layer containing a charge transport material (charge transport layer 6) are formed separately and laminated so that they are adjacent to each other. ing.

  On the other hand, the image carrier 1 for an image forming apparatus according to the third embodiment shown in FIG. 3 includes a single-layer type photosensitive layer in which the charge generation material and the charge transport material are contained in the same layer. That is, a charge generation / transport layer 8 containing a charge generation material and a charge transport material is formed in the photosensitive layer 3.

  More specifically, in the image carrier 1 for an image forming apparatus according to the first embodiment, an undercoat layer 4, a charge generation layer 5, and a charge transport layer 6 are laminated in this order on a conductive support 2. In the image carrier 1 for an image forming apparatus according to the second embodiment, the undercoat layer 4, the charge generation layer 5, the charge transport layer 6, and the protective layer 7 are formed on the conductive support 2. Are laminated in this order to form the photosensitive layer 3. In the image carrier 1 for an image forming apparatus according to the third embodiment, the undercoat layer 4 and the charge generation / transport layer 8 are laminated in this order on the conductive support 2 to form the photosensitive layer 3. ing.

  In addition, although illustration is abbreviate | omitted, as a deformation | transformation aspect of 2nd Embodiment, the aspect which reversed the lamination | stacking order of the charge generation layer 5 and the charge transport layer 6 in 2nd Embodiment, or a deformation | transformation aspect of 3rd Embodiment Another example is a mode in which the protective layer 7 made of the components used in the first and second embodiments is formed on the charge generation / transport layer 8 of the third embodiment.

  As the conductive support 2, aluminum is used in a drum shape, a sheet shape, a plate shape, or the like, but is not limited thereto. The conductive support 2 may be subjected to anodic oxidation treatment, boehmite treatment, honing treatment or the like.

  As shown in FIGS. 1 to 3, an undercoat layer 4 is provided in a region sandwiched between the conductive support 2 and the photosensitive layer 3 or a region sandwiched between the conductive support 2 and the charge generation / transport layer 8. As the undercoat layer 4, an organic zirconium compound such as a zirconium chelate compound, a zirconium alkoxide compound, or a zirconium coupling agent; an organic titanium compound such as a titanium chelate compound, a titanium alkoxide compound, or a titanate coupling agent; an aluminum chelate compound, or In addition to organoaluminum compounds such as aluminum coupling agents; 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 compound or aluminum zirconium alkoxide compound Organometallic compounds such is used. In particular, an organic zirconium compound, an organic titanyl compound, or an organic aluminum compound is preferably used.

  Also, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyl Triethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, or β-3,4-epoxycyclohexyl A silane coupling agent such as trimethoxysilane is further contained.

Furthermore, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenol resin, vinyl chloride- A known binder resin such as vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, or polyacrylic acid may be further contained. These mixing ratios are set as necessary.
Further, an electron transporting pigment can be mixed / dispersed in the undercoat layer.

  Examples of the electron transporting pigment include organic pigments such as perylene pigments, bisbenzimidazole perylene pigments, polycyclic quinone pigments, indigo pigments, and quinacridone pigments described in JP-A-47-30330. Further, organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as cyano group, nitro group, nitroso group, or halogen atom, and inorganic pigments such as zinc oxide or titanium oxide. Among these pigments, a perylene pigment, a bisbenzimidazole perylene pigment, a polycyclic quinone pigment, zinc oxide, or titanium oxide is preferable.

  In addition, the surface of these pigments may be surface-treated with the above coupling agent or binder. The content of the electron transporting pigment is 95% by weight or less, preferably 90% by weight or less, based on the total amount of the undercoat layer.

  As a method for mixing / dispersing the electron transporting pigment in 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, as long as the organic solvent dissolves an organometallic compound or resin and does not cause gelation or aggregation when an electron transporting pigment is mixed / dispersed. Anything is used. For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene Or usual organic solvents, such as toluene, are used individually or in mixture of 2 or more types.

The thickness of the undercoat layer is preferably from 0.1 μm to 30 μm, and more preferably from 0.2 μm to 25 μm.
The coating method used when providing the undercoat layer is a normal method such as blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, or curtain coating method. Is used.

  An undercoat layer is obtained by drying a coating film formed by applying an undercoat layer-forming composition containing the above-mentioned components. Usually, drying is carried out at a temperature at which a solvent can be evaporated to form a film. In particular, a base material that has been subjected to an acidic solution treatment or a boehmite treatment is preferably formed with an undercoat layer because the defect concealing power of the base material tends to be insufficient.

  The charge generation material contained in the charge generation layer 5 is an azo pigment such as bisazo or trisazo; a fused aromatic pigment such as dibromoanthanthrone; a perylene pigment, a pyrrolopyrrole pigment, or a phthalocyanine pigment. Although metal and metal-free phthalocyanine pigments are particularly preferred. Among these, 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 Dichlorotin phthalocyanine disclosed in JP-A-5-140473 or titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 is particularly preferable.

The charge generation layer is formed by mixing a charge generation material and a binder resin. Such a binder resin is selected from a wide range of insulating resins, and includes poly-N-vinylcarbazole, polyvinyl anthracene. , Polyvinylpyrene, or an organic photoconductive polymer such as polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin Insulating resin such as, but not limited to, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, or polyvinyl pyrrolidone resin. These binder resins are used alone or in combination of two or more.
The insulating resin in the present invention is an insulating resin having a volume resistivity measured based on JIS K 7194 “Resistivity testing method of conductive plastic by four-probe method” of 10 ¹² Ω · cm or more. Point to.

The blending ratio (weight ratio) of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10, more preferably 8: 3 to 3: 8.
In addition, as a method for dispersing them, a normal method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method is used. At this time, the condition that the crystal form of the charge generation material is not changed by the dispersion is required. . Incidentally, it has been confirmed that the crystal form does not change before dispersion for any of the dispersion methods used in this embodiment.

Further, at the time of dispersion, it is effective to make the particles of the charge generating material have a particle size of 0.5 μm or less, preferably 0.3 μm or less, 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, tetrahydrofuran Ordinary organic solvents such as methylene chloride, chloroform, chlorobenzene, or toluene are used alone or in admixture of two or more.

  The thickness of the charge generation layer is preferably from 0.1 μm to 5 μm, more preferably from 0.2 μm to 2.0 μm. In addition, as a coating method used when the charge generation layer 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, or a curtain coating method is used. Is used.

As the charge transport layer 6, a layer formed by a known technique can be used except that it contains the compound represented by the general formula (I). The charge transport layer 6 is formed containing a charge transport material and a binder resin, or is formed containing a polymer charge transport material.
As the charge transport material, the compound represented by the general formula (I) is used. In addition to the compound represented by the general formula (I), quinone compounds such as p-benzoquinone, chloranil, bromanyl and anthraquinone; tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, Electron transport compounds such as xanthone compounds, benzophenone compounds, cyanovinyl compounds, ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds One or more other charge transport materials such as a compound and a hole transporting compound such as a hydrazone compound are mixed and used, but are not limited thereto.

In the total amount of the charge transport layer, the content of the compound represented by the general formula (I) is 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, and still more preferably 20%. It is not less than 50% by mass.
When a compound other than the compound represented by the general formula (I) is used as a charge transport material, the content of the compound represented by the general formula (I) is 1% by mass or more in the total amount of the charge transport material. It is preferable to be 5% by mass or more.

  As the compound to be mixed with the compound represented by the general formula (I), a compound represented by the following general formula (V) or general formula (VI) is preferable.

In general formula (V), R ² represents a hydrogen atom or a methyl group. n represents 1 or 2. Ar ² and Ar ³ each independently represent a substituted or unsubstituted aryl group. The substituent of the substituted aryl group is a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon number having 1 to 5 carbon atoms. Examples thereof include a substituted amino group substituted with an alkoxy group or an alkyl group having 1 to 3 carbon atoms.

In general formula (VI), R ⁷ and R ⁸ each independently represent 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 ³ , R ⁴ , R ⁵ and R ⁶ 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 A substituted amino group substituted with a group or a substituted or unsubstituted aryl group is shown. p and q each independently represent an integer of 0 or more and 2 or less.

  The binder resin used for the charge transport layer is 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-vinyl Carbazole, polysilane, or a polymer charge transport material such as a polyester-based polymer charge transport material disclosed in JP-A-8-176293 or JP-A-8-208820 is used. These binder resins are used alone or in combination of two or more. The blending ratio (weight ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1:10, more preferably 8: 3 to 3: 8.

  A polymer charge transport material is also used as the charge transport material. As the polymer charge transporting material, known materials having charge transporting properties such as poly-N-vinylcarbazole or polysilane are used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 are particularly preferable. The polymer charge transporting material alone is used as a charge transporting layer, but may be mixed with the binder resin to form a film.

  The polymer charge transport material is preferably a polymer compound represented by the following general formula (VII-1) or the following general formula (VII-2).

In General Formula (VII-1) and General Formula (VII-2), A ¹ is independently selected from at least a structure represented by General Formula (VIII-1) and General Formula (VIII-2) below. 1 type, R ⁹ is independently a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, a substituted or unsubstituted monovalent aromatic ring having 2 to 10 aromatic rings. A condensed aromatic hydrocarbon group, a monovalent linear hydrocarbon group having 1 to 6 carbon atoms, a monovalent branched hydrocarbon group having 2 to 10 carbon atoms, or a hydroxy group. Each Y ¹ independently represents a divalent alcohol residue, each Z ¹ independently represents a divalent carboxylic acid residue, each m independently represents an integer of 1 to 5, and g Each independently represents an integer of 5 or more and 5000 or less. B and B ′ are each independently a group represented by —O— (Y ¹ —O) _m —H or O— (Y ¹ —O) _m —CO—Z ¹ —CO—OR ¹⁰ ( Y ¹ , Z ¹ and m are as defined above, and R ¹⁰ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.

  In general formula (VIII-1) and general formula (VIII-2), Ar is each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic having 2 to 10 aromatic rings. A hydrocarbon group, a monovalent condensed aromatic hydrocarbon group having 2 or more and 10 or less substituted or unsubstituted aromatic rings or a substituted or unsubstituted monovalent aromatic heterocyclic group, and X is substituted or unsubstituted A divalent polynuclear aromatic hydrocarbon group having 2 to 10 substituted or unsubstituted aromatic rings, a divalent condensed aromatic hydrocarbon group having 2 to 10 substituted or unsubstituted aromatic rings, Or a substituted or unsubstituted divalent aromatic heterocyclic group, j independently represents 0 or 1, and T independently represents a divalent linear hydrocarbon having 1 to 6 carbon atoms. Group or divalent having 2 to 10 carbon atoms It shows a branch chain hydrocarbon group.

The thickness of the charge transport layer is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 30 μm or less.
As a coating method, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used.

  Solvents used when providing the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene, or chlorobenzene; ketones such as acetone or 2-butanone; methylene chloride, chloroform, or ethylene chloride. Halogenated aliphatic hydrocarbons: normal organic solvents such as tetrahydrofuran or cyclic ethers such as ethyl ether or a mixture of two or more of them are used.

Moreover, you may add additives, such as antioxidant, a light stabilizer, and a heat stabilizer, in a photosensitive layer.
Examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone or their derivatives, organic sulfur compounds, or organic phosphorus compounds.
Examples of light stabilizers include derivatives such as benzophenone, benzotriazole, dithiocarbamate, or tetramethylpiperidine.

Moreover, you may contain an at least 1 sort (s) of electron-accepting substance. Examples of the electron acceptor used include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m -Dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, or phthalic acid. Of these, fluorenone-based, quinone-based, or benzene derivatives having an electron-withdrawing substituent such as Cl, CN, NO ₂ are particularly preferable.

  The image carrier for an image forming apparatus of the present embodiment may be provided with a protective layer (surface layer), but the protective layer is preferably a high-strength protective layer (high-strength surface layer). As this high-strength protective layer, conductive particles are dispersed in a binder resin, lubricating particles such as fluorine resin and acrylic resin are dispersed in a normal charge transport layer material, hard coat such as silicone and acrylic An agent or the like is used. The high-strength protective layer preferably has a charge transporting property and contains a siloxane-based resin having a crosslinked structure, and among these, a layer having a structure represented by the following general formula (IX) is particularly preferable.

G-D-F (IX)
In general formula (IX), G represents an inorganic glassy network subgroup, D represents a flexible organic subunit, and F represents a charge transporting subunit. As F, a structure having photocarrier transport properties includes a triarylamine compound, a benzidine compound, an arylalkane compound, an aryl-substituted ethylene compound, a stilbene compound, an anthracene compound, a hydrazone compound, a quinone compound, Examples include fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, and ethylene compounds.

G in the general formula (IX) is preferably a reactive Si group, which causes a cross-linking reaction with each other to form an inorganic glassy network that is a three-dimensional Si—O—Si bond.
D in the general formula (IX) is for binding F for imparting charge transporting properties directly to a three-dimensional inorganic glassy network.

In the compound represented by the general formula (IX), the group represented by D and directly bonded to the inorganic glassy network is a silanol group generated when the compound represented by the general formula (IX) is hydrolyzed. A group to be bonded is meant, and a group represented by -Si (R ₁₁ ) (3-a) Qa, an epoxy group, an isocyanate group, a carboxy group, a hydroxy group, or a halogen atom is preferable. Among these, a compound having a group represented by —Si (R ₁₁ ) (3-a) Qa, an epoxy group, or an isocyanate group is preferable. R ₁₁ is a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, and Q is a hydrolyzable group. a is an integer of 0 to 3.
Those having two or more of these groups in the molecule are preferable because the crosslinked structure of the cured film becomes three-dimensional.

The protective layer may be used by mixing other coupling agents and fluorine compounds. As this compound, various silane coupling agents and commercially available silicone hard coat agents are used.
As silane coupling agents, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, Alternatively, dimethyldimethoxysilane or the like is used.
Examples of commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), AY42-440, AY42-441, or AY49-208 (manufactured by Toray Dow Corning). Etc.) are used.

  The protective layer also includes (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyl Triethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, or 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane The fluorine-containing compound may be added.

The amount of the silane coupling agent is set as necessary, but the amount of the fluorine-containing compound is desirably 0.25 parts by weight or less with respect to 1 part by weight of the compound not containing fluorine. Further, it is more preferable to use a compound having two or more substituted silicon groups having a hydrolyzable group represented by -Si (R ₁₁ ) (3-a) Qa.

  These coating solutions are prepared without a solvent or, if necessary, alcohols such as methanol, ethanol, propanol, or butanol; ketones such as acetone or methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether, or dioxane. Are used, and those having a boiling point of 100 ° C. or lower are preferred. These are mixed and used as necessary. The amount of the solvent is set as necessary, but it is 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 1 part by weight of the compound represented by the general formula (IX). The

  Although the reaction temperature and time vary depending on the type of raw material, it is usually 0 to 100 ° C., preferably 10 to 70 ° C., particularly preferably 15 to 50 ° C. The reaction time is not particularly limited, but the reaction time is preferably in the range of 10 minutes to 100 hours.

  Examples of the curing catalyst include a protic acid such as hydrochloric acid, acetic acid, phosphoric acid, or sulfuric acid, a base such as ammonia or triethylamine, an organic tin compound such as dibutyltin diacetate, dibutyltin dioctoate, or stannous oxalate, tetra- Organotitanium compounds such as n-butyl titanate or tetraisopropyl titanate, organoaluminum compounds such as aluminum tributoxide or aluminum triacetylacetonate, iron salts, manganese salts, cobalt salts, zinc salts or zirconium salts of organic carboxylic acids However, metal compounds are preferred, metal acetylacetonate or acetylacetate is preferred, and aluminum triacetylacetonate is particularly preferred.

The amount of the curing catalyst used is set as necessary, but is preferably 0.1% by weight or more and 20% by weight or less, and preferably 0.3% by weight or more and 10% by weight or less with respect to the total amount of materials containing hydrolyzable silicon substituents. More preferably, it is less than wt%.
The curing temperature is set as required, but is set to 60 ° C. or higher, more preferably 80 ° C. or higher in order to obtain a desired strength. The curing time is set as required, but is preferably 10 minutes to 5 hours.
It is also effective to maintain a high humidity state after the curing reaction. Further, depending on the application, surface treatment is performed using hexamethyldisilazane, trimethylchlorosilane, or the like to make it hydrophobic.

It is preferable to add an antioxidant to the protective layer of the image carrier for the image forming apparatus.
Antioxidants are preferably hindered phenols or hindered amines, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, or benzimidazole antioxidants. You may use well-known antioxidants, such as an agent. The addition amount of the antioxidant is preferably 20% by weight or less and more preferably 10% by weight or less in the total amount of the protective layer.

  Examples of the hindered phenol antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, N, N′-hexamethylenebis (3,5-di -T-butyl-4-hydroxyhydrocinnamide, 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o-cresol, 2, 6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4 , 4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,5-di-tert-amylhydroquinone, 2-tert-butyl-6- (3-butyl-2-hydroxy-5-methyl) Benzyl) -4-methylphenyl acrylate, or 4,4'-butylidenebis (3-methyl -6-t-butylphenol), and the like.

Further, a resin that dissolves in alcohol may be added to the protective layer of the image carrier for the image forming apparatus. Examples of resins soluble in alcohol solvents include polyvinyl acetal resins such as polyvinyl butyral resin, polyvinyl formal resin, or partially acetalized polyvinyl acetal resin in which a part of butyral is modified with formal, acetoacetal, or the like (for example, Sekisui Chemical Co., Ltd. S-Rec B, K, etc.), polyamide resin, cellulose resin, or phenol resin. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics. The weight average molecular weight of the resin is preferably 2000 or more and 100,000 or less, and more preferably 5,000 or more and 50,000 or less.
The addition amount of the resin is preferably 1% to 40%, more preferably 1% to 30%, and particularly preferably 5% to 20%.

  Furthermore, various particles may be added to the protective layer. They may be used alone or in combination. An example of the particles is silicon-containing particles. The silicon-containing particles are particles containing silicon as a constituent element, and specifically include colloidal silica or silicone particles. The colloidal silica used as the silicon-containing particles is from an acid or alkaline aqueous dispersion having an average particle diameter of 1 nm to 100 nm, preferably 10 nm to 30 nm, or dispersed in an organic solvent such as alcohol, ketone or ester. Use one that is selected and generally commercially available. The solid content of colloidal silica in the outermost surface layer is not particularly limited, but it is 0.1% by weight or more in the total solid content of the outermost surface layer in terms of film forming properties, electrical characteristics, and strength. % By weight or less, preferably 0.1% by weight or more and 30% by weight or less.

  Silicone particles used as silicon-containing particles are spherical and have an average particle diameter of 1 nm to 500 nm, preferably 10 nm to 100 nm, selected from silicone resin particles, silicone rubber particles, or silicone surface-treated silica particles, and are generally commercially available. Use what you have. The content of the silicone particles in the outermost surface layer in the image carrier for an image forming apparatus is preferably 0.1% by weight or more and 30% by weight or less, and more preferably 0.5% by weight or more and 10% by weight in the total solid content of the outermost surface layer. % Or less is more preferable.

Other particles include fluorine-based particles such as ethylene tetrafluoride, trifluoride ethylene, propylene hexafluoride, vinyl fluoride, or vinylidene fluoride, and “8th Polymer Material Forum Lecture Proceedings, p89”. Particles containing a copolymer obtained by copolymerizing the fluororesin and a monomer having a hydroxyl group, ZnO-Al ₂ O ₃ , SnO ₂ -Sb ₂ O ₃ , In ₂ O ₃ -SnO ₂ , ZnO-TiO ₂ , Examples thereof include semiconductive metal oxides such as ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, or MgO.
Here, semi-conductive means that the volume resistivity measured based on JIS K 7194 “Resistivity Test Method by Conductive Plastic Four-Probe Method” is 10 ⁷ Ω · cm or more and 10 ¹¹ Ω · cm or less. means.

  In addition, an oil such as silicone oil can be added to the protective layer. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, or phenylmethylsiloxane; amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, Reactive silicone oils such as mercapto-modified polysiloxane or phenol-modified polysiloxane; cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, or dodecamethylcyclohexasiloxane; 1 , 3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7- Cyclic methylphenylcyclosiloxanes such as traphenylcyclotetrasiloxane or 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylcyclopentasiloxane; hexaphenylcyclotrisiloxane Cyclic phenylcyclosiloxanes; fluorine-containing cyclosiloxanes such as 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane; hydrosilyls such as methylhydrosiloxane mixtures, pentamethylcyclopentasiloxane, or phenylhydrocyclosiloxanes Group-containing cyclosiloxanes; and cyclic siloxanes such as vinyl group-containing cyclosiloxanes such as pentavinylpentamethylcyclopentasiloxane.

In the case of a single layer type photosensitive layer, the single layer type photosensitive layer contains the charge generation material, the charge transport material (including the compound represented by the general formula (I) of the present embodiment), and a binder resin. Can be formed. The charge transport material may contain a polymer charge transport material. As the binder resin, those listed as binder resins used in the charge generation layer and the charge transport layer are used. The content of the charge generating material in the single-layer type photosensitive layer is from 10% by weight to 85% by weight, preferably from 20% by weight to 50% by weight. The content of the charge transport material in the single-layer type photosensitive layer is preferably 5% by weight or more and 50% by weight or less.
The above-mentioned thing is used for the solvent and application | coating method used for application | coating. The film thickness of the single layer type photosensitive layer is preferably 5 μm or more and 50 μm or less, and more preferably 10 μm or more and 40 μm or less.

  The outermost layer disposed at the position farthest from the conductive support of the image carrier for the image forming apparatus is coated with an aqueous dispersion of a modified resin containing a fluororesin as an essential component, or is immersed. obtain.

  An aqueous dispersion of a modified resin containing a fluororesin as an essential component applied to the outermost layer of the image carrier for an image forming apparatus will be described below. Examples of fluororesins include tetrafluoroethylene homopolymers or copolymers of tetrafluoroethylene and olefins, fluorine-containing olefins, perfluoroolefins, or fluoroalkyl vinyl ethers; vinylidene fluoride homopolymers or vinylidene fluoride and olefins. Copolymers of fluorine olefins, perfluoroolefins, fluoroalkyl vinyl ethers, etc .; homopolymers of chlorotrifluoroethylene or copolymers of chlorotrifluoroethylene and olefins, fluorine-containing olefins, perfluoroolefins, fluoroalkyl vinyl ethers, etc. In particular, a homopolymer or copolymer of tetrafluoroethylene is preferable, and a homopolymer of tetrafluoroethylene and various copolymers can be used. In an amount ratio of 95: it is preferable to use a mixture with 5 to 10:90.

  A modified resin containing a fluororesin as an essential component is used as an aqueous dispersion, and this aqueous dispersion further contains wax and / or silicone. By containing wax and / or silicone, it is preferable to promote penetration of the fluorine-based resin into the blade.

Here, examples of the wax include paraffin wax, microcrystalline wax, and perotratam. Examples of the silicone include silicone oil, silicone grease, oil compound, and silicone varnish.
For aqueous dispersions of modified resins containing fluorine resin as an essential component, fluorine-based or other nonionic, cationic, anionic or amphoteric surfactants, pH adjusters, solvents, polyhydric alcohols, flexible An agent, a viscosity modifier, a light stabilizer, an antioxidant, or the like is mixed. The penetration layer is formed by immersing the blade member in an aqueous dispersion of a modified resin containing a fluorine-based resin as an essential component, but can also be performed under reduced pressure. The pressure at this time is 0.9 atm or less, preferably 0.8 atm or less, more preferably 0.7 atm or less.

  It is also effective to heat the aqueous dispersion to 40 ° C. or higher, preferably 50 ° C. or higher. Further, it is effective to treat at 0.1 atm or higher, preferably 0.2 atm or higher, more preferably 0.3 atm or higher, and it is also effective to combine decompression, pressurization and heat treatment. is there. Moreover, after making it adhere to a blade member by spraying or the apply | coating method, a osmosis | permeation layer is formed by heating to 40 degreeC or more, Preferably it is 50 degreeC or more. Further, after attaching an aqueous dispersion of a modified resin containing a fluorine-based resin as an essential component, wiping or washing is performed before or after heat drying.

(Image forming device)
The image forming apparatus according to the present embodiment includes the above-described image carrier for the image forming apparatus according to the present embodiment, a charging device that charges the image carrier for the image forming apparatus, and the charged image carrier for the image forming apparatus. An exposure device that forms an electrostatic latent image by exposing the toner, a developing device that develops the electrostatic latent image to form a toner image, and a transfer device that transfers the toner image to a transfer target. It is characterized by.
FIG. 4 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the image forming apparatus of the present embodiment.
An image forming apparatus 200 shown in FIG. 4 is connected to the image holding apparatus for image forming apparatus 207 of the present embodiment, a charging apparatus 208 for charging the image holding apparatus for image forming apparatus 207 by a contact charging method, and the charging apparatus 208. The image forming apparatus image carrier 207 charged by the power source 209 and the charging apparatus 208 is exposed to form an electrostatic latent image, and the electrostatic latent image formed by the exposure apparatus 210 is made of toner. A developing device 211 that develops a toner image, a transfer device 212 that transfers the toner image formed by the developing device 211 to the transfer target 500, a cleaning device 213, a static eliminator 214, and a fixing device 215. Prepare.

The charging device 208 shown in FIG. 4 applies a voltage to the image holding member by bringing a contact-type charging member (for example, a charging roll) into contact with the surface of the image holding member 207 for the image forming apparatus. It is to be charged.
As the contact-type charging member, a roller-shaped member in which an elastic layer, a resistance layer, a protective layer and the like are provided on the outer peripheral surface of the core material is preferably used. The shape of the contact-type charging member may be any of the above-described roller shape, brush shape, blade shape, pin electrode shape, and the like, and is selected according to the specifications and form of the image forming apparatus.

As the core material of the roller-shaped contact-type charging member, a conductive material such as iron, copper, brass, stainless steel, aluminum, or nickel is used. In addition, a resin molded product in which conductive particles are dispersed is used. As the material of the elastic layer, a conductive or semiconductive material, for example, a rubber material in which conductive particles or semiconductive particles are dispersed is used. As the material of the resistance layer and the protective layer, conductive particles or semiconductive particles are dispersed in a binder resin, and the resistance is controlled.
When charging the image carrier using these contact-type charging members, a voltage is applied to the contact-type charging member. The applied voltage may be either a DC voltage or a DC voltage superimposed with an AC voltage. .
Instead of the contact-type charging member in FIG. 4, a non-contact type corona charging device such as corotron or scorotron is also used. These are selected according to the specifications and form of the image forming apparatus.

  As the exposure apparatus 210, an optical system apparatus or the like that exposes a light source such as a semiconductor laser, an LED (light emitting diode), a liquid crystal shutter, or the like on the surface of the image carrier for the image forming apparatus in a desired image manner.

  As the developing device 211, a conventionally known developing device using a regular or reversal developer such as a one-component system or a two-component system is used. The shape of the toner used in the developing device 211 is not particularly limited, but a spherical toner is preferable.

  Examples of the transfer device 212 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. Can be mentioned.

  The cleaning device 213 is for removing residual toner adhering to the surface of the image holding member for the image forming apparatus after the transfer process, and the image holding member for the image forming device thus cleaned has the above-mentioned image formation. Used repeatedly in the process. As the cleaning device, a cleaning blade, brush cleaning, roll cleaning, or the like is used. Of these, it is preferable to use a cleaning blade. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber.

Although the above embodiment has one image forming unit, an image forming apparatus according to another embodiment is a tandem type image forming apparatus having a plurality of image forming units.
For example, when there are four image forming units, each developing device of the four image forming units uses, for example, four color component toners of yellow, magenta, cyan, and blank. The tandem image forming apparatus includes a belt that is common to the four image forming units and conveys a recording material, a conveyance device that conveys the belt, a toner supply device that supplies a toner image to each developing device, and a color toner. A fixing device for fixing the image to the recording material is preferably provided.

  Further, the image forming apparatus of the present embodiment preferably has a mechanism for supplying only the toner alone when the image carrier is used for 200000 cycles or more, further 250,000 cycles, or 300000 cycles or more.

(Process cartridge)
The process cartridge according to the present embodiment includes at least the image carrier for an image forming apparatus according to the above-described embodiment, and a charging device that charges the image carrier for the image forming apparatus. An exposure device that exposes an image carrier to form an electrostatic latent image, a developing device that develops the electrostatic latent image to form a toner image, a transfer device that transfers the toner image to a transfer target, and the image And at least one selected from a cleaning device for cleaning the image carrier for the forming apparatus.

FIG. 5 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of a process cartridge including an image carrier for an image forming apparatus according to this embodiment.
The process cartridge 300 includes an image holder 207 for an image forming apparatus, a charging device 208, a developing device 211, a cleaning device (cleaning means) 213, an opening 218 for exposure, and an opening 217 for discharge exposure. They are combined and integrated using mounting rails 216.
The process cartridge 300 is used for an image forming apparatus main body including a transfer device 212 that transfers a toner image formed by the developing device 211 to the transfer target 500, a fixing device 215, and other components not shown. The image forming apparatus is configured together with the image forming apparatus main body.
Although the present embodiment has been described above, the present embodiment can be variously modified and changed within the scope of the gist.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

<Synthesis of phenothiazine compound represented by general formula (I)>
(Synthesis Example 1-Exemplary Compound 9-)
According to the following scheme, phenothiazine (16.1 g), 1-bromo-4-iodobenzene (22.6 g), copper sulfate pentahydrate (2.0 g), potassium carbonate (18 g), o-dichlorobenzene (100 ml) Was placed in a 200 ml two-necked flask and heated at 180 ° C. for 6 hours under a nitrogen atmosphere. After completion of the reaction, toluene was added and filtered. The solvent of the filtrate was distilled off with a rotary evaporator to obtain a crude product. This was purified by column chromatography (chloroform: hexane = 2: 5) and recrystallized from ethanol + hexane to obtain 6.4 g of 10- (4-bromophenyl) -10H-phenothiazine.

  Next, according to the following scheme, aluminum chloride (5.0 g) and dichloromethane (30 ml) were added to a 200 ml flask and stirred. Hexanoic acid chloride (4.6 g) dissolved in dichloromethane (12 ml) was added dropwise and dissolved in dichloromethane (30 ml). The obtained 10- (4-bromophenyl) -10H-phenothiazine (6.0 g) was added dropwise and stirred at room temperature (25 ° C.) for one day. After completion of the reaction, 5% by mass aqueous sodium hydrogen carbonate solution was added, chloroform was further added, washed with pure water, and dried over sodium sulfate. This was purified by column chromatography (ethyl acetate: hexane = 1: 9) and recrystallized from hexane + ethyl acetate to obtain 5.8 g of a phenothiazine acyl compound.

  Next, according to the following scheme, a phenothiazine acyl compound (5.8 g) was placed in a 300 ml flask and dissolved in trifluoroacetic acid (45 ml). Triethylsilane (5.4 g) was further added, and the mixture was stirred at room temperature (25 ° C.) for 5 hours. After completion of the reaction, 10% by mass aqueous sodium hydroxide solution was added to make it basic, ethyl acetate was added, and the mixed solution was washed with pure water and dried over sodium sulfate. This was purified by column chromatography (hexane) to obtain 4.5 g of 10- (4-bromophenyl) -3,7-dihexyl-10H-phenothiazine.

  Next, according to the following scheme, tetra (triphenylphosphine) palladium (0.3 g) was dissolved in toluene (5 ml) in a 300 ml flask under a nitrogen atmosphere. Subsequently, 10- (4-bromophenyl) -3,7-dihexyl-10H-phenothiazine (4.5 g), toluene (10 ml), 1M aqueous sodium hydrogen carbonate solution (10 ml), ethanol (5 ml), 2-chlorothiophene boron The acid (1.99 g) was added in that order and refluxed for 11 hours. After completion of the reaction, the reaction solution was filtered, washed with pure water, and dried over sodium sulfate. This was purified by column chromatography (chloroform: hexane = 1: 9) and 3.6 g of 10- (4- (5-chlorothiophen-2-yl) phenyl) -3,7-dihexyl-10H-phenothiazine. Got.

  Further, according to the following scheme, nickel chloride (0.84 g) and triphenylphosphine (6.7 g) were placed in a 100 ml flask under a nitrogen atmosphere and dissolved in anhydrous DMF (dimethylformamide: 20 ml). Then, it heated to 50 degreeC and added zinc (0.4g). After confirming that the solution turned red, the solution was further heated at 50 ° C. for 1 hour. Thereafter, 10- (4- (5-chlorothiophen-2-yl) phenyl) -3,7-dihexyl-10H-phenothiazine (3.6 g) dissolved in DMF (15 ml) was added, and further 3 Heated for hours. After completion of the reaction, the reaction solution was put into pure water and stirred. Filtered, washed with 5% by mass EDTA aqueous solution (ethylenediaminetetraacetic acid aqueous solution) and pure water, and dried to obtain a crude product. The crude product was recrystallized from ethyl acetate + hexane to obtain 1.6 g of [Exemplary Compound 9].

(Synthesis Example 2-Exemplary Compound 10-)
The same procedure as in Synthetic Example 1 was performed except that n-octanoyl chloride (5.6 g) was used instead of hexanoic acid chloride (4.6 g) in Synthesis Example 1, and 2.0 g of [Exemplary Compound 10] was obtained. It was.

(Synthesis Example 3-Exemplary Compound 23-)

  According to the following scheme, in a 200 ml two-necked flask, phenothiazine (10.0 g), 2-chloro-5- (4-iodophenyl) thiophene (14.5 g), copper sulfate pentahydrate (1.3 g), potassium carbonate (10 g) and o-dichlorobenzene (50 ml) were added and heated at 180 ° C. for 13 hours under a nitrogen atmosphere. After completion of the reaction, toluene was added and filtered, and this was recrystallized from column chromatography (chloroform: hexane = 1: 4) and ethanol and chloroform to give 10- (4- (5-chlorothiophen-2-yl) phenyl. ) 7.6 g of -10H-phenothiazine was obtained.

  Next, according to the following scheme, 10- (4- (5-chlorothiophen-2-yl) phenyl) -10H-phenothiazine (7.6 g) was dissolved in chloroform (100 ml) in a 300 ml flask. N-bromosuccinimide (6.9 g) was added and stirred at room temperature (25 ° C.) for 2 hours. After completion of the reaction, it was washed with pure water and dried with sodium sulfate. This was recrystallized from column chromatography (chloroform: hexane = 1: 5) and hexane + chloroform, and 3,7-dibromo-10- (4- (5-chlorothiophen-2-yl) phenyl) -10H- 5.1 g of phenothiazine was obtained.

  Next, tetra (triphenylphosphine) palladium (0.6 g) was dissolved in toluene (5 ml) in a 200 ml flask according to the following scheme. Subsequently, 3,7-dibromo-10- (4- (5-chlorothiophen-2-yl) phenyl) -10H-phenothiazine (5.0 g), toluene (50 ml), 1M aqueous sodium hydrogen carbonate solution (50 ml), ethanol ( 10 ml) and 2-hexylthiopheneboronic acid (5.6 g) in this order and refluxed for 16 hours. After completion of the reaction, the reaction solution was filtered with suction, washed with pure water and dried over calcium chloride. This was recrystallized from ethanol + chloroform and 10- (4- (5-chlorothiophen-2-yl) phenyl-3,7-bis (5-hexylthiophen-2-yl) -10H-phenothiazine 4.6 g. Got.

  Subsequently, according to the following scheme, nickel chloride (0.8 g) and triphenylphosphine (6.7 g) were placed in a 200 ml flask, dissolved in anhydrous DMF (50 ml), heated to 50 ° C. under a nitrogen atmosphere, and then zinc (0.4 g) was added. After the reaction solution turned red, it was heated at 50 ° C. for 1 hour. Thereafter, 10- (4- (5-chlorothiophen-2-yl) phenyl-3,7-bis (5-hexylthiophen-2-yl) -10H-phenothiazine (4.6 g) was added, and further at 50 ° C. After the reaction was completed, pure water was added and stirred, followed by suction filtration, washing with 5% EDTA aqueous solution and pure water, and drying to obtain a crude product, which was ethyl acetate + hexane. And 2.7 g of [Exemplary Compound 23] was obtained.

(Synthesis Example 4-Exemplary Compound 15-)
In Synthesis Example 3, the same procedure as in Synthesis Example 3 was performed except that 2-thiopheneboronic acid (8.8 g) was used instead of 2-hexylthiopheneboronic acid (5.6 g), and [Exemplary Compound 15] 3 0.1 g was obtained.

Moreover, the obtained compound is infrared absorption measurement (KBr tablet method, Horiba, Ltd., FT-730, resolution 4 cm ⁻¹ )), NMR measurement ( ¹ H-NMR, solvent: CDCl ₃ , manufactured by Varian Co., Ltd., UNITY-300, 300 MHz).
As an example, the infrared absorption spectrum of [Exemplary Compound 9] is shown in FIG. 6, the ¹ H-NMR spectrum is shown in FIG. 7, the infrared absorption spectrum of [Exemplary Compound 23] is shown in FIG. 8, and the ¹ H-NMR spectrum ( ¹ H— NMR, solvent: CDCl ₃ ) is shown in FIG.

Example 1
A solution comprising 10 parts by weight of a zirconium compound (Orgatechs ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 1 part by weight of a silane compound (A1110, manufactured by Nihon Unicar), 40 parts by weight of i-propanol and 20 parts by weight of butanol on an aluminum substrate. The film was applied by a dip coating method and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.6 μm. On top of this, chlorogallium phthalocyanine crystals with strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in the X-ray diffraction spectrum. 1 part by weight is mixed with 1 part by weight of polyvinyl butyral resin (S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by weight of n-butyl acetate, and dispersed with a glass shaker and a paint shaker for 1 hour. The obtained coating solution was applied onto the undercoat layer by a dip coating method and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer.
Next, 2 parts by weight of Exemplified Compound 9 obtained above and 3 parts by weight of a bisphenol (Z) polymer compound (viscosity average molecular weight: 40,000) having the following structure are heated and dissolved in 35 parts by weight of chlorobenzene. , Returned to room temperature (25 ° C.). This coating solution was applied onto the charge generation layer by dip coating, and heated at 110 ° C. for 60 minutes to form a charge transport layer having a thickness of 20 μm.

(Example 2 to Example 4)
An image carrier for an image forming apparatus was produced by the method described in Example 1, except that Example Compound 10, Example Compound 23, and Example Compound 15 were used instead of Example Compound 9 used in Example 1. .

(Example 5)
Instead of the chlorogallium phthalocyanine crystal used in Example 1, 7.5 °, 9.9 °, 12.5 °, 16.3 ° of the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum, An image carrier for an image forming apparatus was produced by the method described in Example 1, except that a hydroxygallium phthalocyanine crystal having strong diffraction peaks at 18.6 °, 25.1 °, and 28.3 ° was used.

(Comparative Example 1)
An image carrier for an image forming apparatus was produced by the method described in Example 1 except that the compound (X) having the following structure was used instead of the exemplified compound 9 used in Example 1.

(Comparative Example 2)
An image carrier for an image forming apparatus was produced by the method described in Example 1 except that the compound (XI) having the following structure was used instead of the exemplified compound 9 used in Example 1.

Using the respective image forming apparatus image carriers obtained in Examples 1 to 5 and Comparative Examples 1 to 2, the electrophotographic characteristics of the electrophotographic copying paper test apparatus (electrostatic analyzer EPA- 8100, manufactured by Kawaguchi Denki Co., Ltd.), charged at −6 KV corona discharge in an environment of normal temperature and normal humidity (20 ° C., 40% RH), and charged with a monochromator using a monochromator. Irradiation was performed with a monochromatic light of 800 nm, adjusted to 1 μW / cm ² on the surface of the photoreceptor. Then, the surface potential VO (volt) and the half-exposure amount E1 / 2 (erg / cm ² ) were measured, and then 10 lux white light was irradiated for 1 second, and the residual potential VRP (volt) was measured. Further, V0, E1 / 2, and VRP after 1000 times of the above charging and exposure were measured, and ΔV0, ΔE1 / 2, and ΔVRP were evaluated for their fluctuation amounts (stability and durability).

Next, an image forming apparatus was produced using the image carrier for the image forming apparatus obtained in the above examples and comparative examples. As elements other than the image carrier for the image forming apparatus, those mounted on a printer Documenter C6550I manufactured by Fuji Xerox were used.
Each image forming apparatus was subjected to an image forming test (image density 10%, cyan 100%) for 10,000 sheets in an environment of high temperature and high humidity (28 ° C., 75% RH). In this test condition, the process of each cartridge is performed as usual, but toners of cartridges other than cyan are not used (supplied). After the test, toner cleaning properties (charger contamination and image quality deterioration due to poor cleaning) and image quality (process black 1 dot line oblique 45 degree fine line reproducibility) were evaluated. The obtained results are shown in Table 1.

Toner cleaning property evaluation method
○: Good △: Partially (about 10% or less of the total) streak-like image quality defect ×: Extensive streak-like image quality defect was determined based on the criteria.

The image quality was judged using a magnifying glass and evaluated based on the following evaluation criteria.
A: Good B: Partially defective (no problem in practical use)
C: Defects (thin lines cannot be reproduced)

  From the above results, it can be seen that the image carrier for the image forming apparatus obtained in this example has a lower residual potential variation due to repeated use than in the comparative example. It can also be seen that the image obtained by the image forming apparatus having the image carrier for the image forming apparatus has good image quality.

1 is a schematic cross-sectional view of an image carrier for an image forming apparatus according to a first embodiment. FIG. 6 is a schematic cross-sectional view of an image carrier for an image forming apparatus according to a second embodiment. FIG. 10 is a schematic cross-sectional view of an image holding body for an image forming apparatus according to a third embodiment. 1 is a schematic configuration diagram of an image forming apparatus according to an embodiment. It is a schematic block diagram of the process cartridge which concerns on embodiment. 3 is a graph showing an infrared absorption spectrum of the compound obtained in Synthesis Example 1. 3 is a graph showing an NMR spectrum of the compound obtained in Synthesis Example 1. 6 is a graph showing an infrared absorption spectrum of the compound obtained in Synthesis Example 3. 6 is a graph showing an NMR spectrum of the compound obtained in Synthesis Example 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Image carrier for image forming apparatuses 2 Conductive support 3 Photosensitive layer 4 Subbing layer 5 Charge generation layer 6 Charge transport layer 7 Protective layer 8 Charge generation / transport layer 200 Image forming apparatus 207 Image carrier for image forming apparatus 208 Charging device 209 Power source 210 Exposure device 211 Development device 212 Transfer device 213 Cleaning device 214 Static eliminator 215 Fixing device 216 Mounting rail 217 Opening portion 218 for static elimination exposure Opening portion 300 for exposure Process cartridge 500 Transfer object

Claims (3)

An image carrier for an image forming apparatus, comprising: a support; and a photosensitive layer containing a compound represented by the following general formula (I) on the support.

[In the general formula (I), each Ar is independently a substituted or unsubstituted hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted monovalent aromatic group, or an aromatic heterocyclic ring. Represents a monovalent aromatic group, and n represents an integer of 1 to 3. ]   2. An image carrier for an image forming apparatus according to claim 1, charging means for charging the image carrier for the image forming apparatus, and exposure for exposing the charged image carrier for the image forming apparatus to form an electrostatic latent image. At least selected from: developing means for developing the electrostatic latent image to form a toner image; transfer means for transferring the toner image to a transfer target; and cleaning means for cleaning the image carrier for the image forming apparatus. And a process cartridge having at least one.   2. An image carrier for an image forming apparatus according to claim 1, charging means for charging the image carrier for the image forming apparatus, and exposing the charged image carrier for the image forming apparatus to form an electrostatic latent image. An image forming apparatus comprising: an exposing unit that develops; a developing unit that develops the electrostatic latent image to form a toner image; and a transfer unit that transfers the toner image to a transfer target.

Images