JP2006084711A - Additive for electrophotographic photoreceptor, electrophotographic photoreceptor, image forming apparatus and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive for an electrophotographic photoreceptor for improving electrical properties of the electrophotographic photoreceptor and an electrophotographic photoreceptor using the additive, and to provide an image forming apparatus and a process cartridge using the electrophotographic photoreceptor. <P>SOLUTION: The additive for an electrophotographic photoreceptor has structure represented by formula (I) wherein F denotes an n-valent organic group having hole transport property; T denotes a divalent group; Y denotes O or S; R<SP>1</SP>-R<SP>3</SP>each independently denote H or a monovalent organic group; R<SP>4</SP>denotes a monovalent organic group; m denotes 0 or 1; and n denotes an integer of 1-4, provided that R<SP>3</SP>and R<SP>4</SP>may bond to each other to form a heterocycle having Y as a hetero atom. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  A so-called xerographic image forming apparatus includes an electrophotographic photosensitive member (hereinafter sometimes referred to as “photosensitive member”), a charging device, an exposure device, a developing device, and a transfer device, and forms an image by an electrophotographic process using them. Do.

  2. Description of the Related Art In recent years, xerographic image forming apparatuses have been further improved in speed and life due to technological progress of each member and system. Accordingly, demands for high-speed compatibility and high reliability of each subsystem are higher than ever. In particular, photoreceptors used for image writing are more demanded for high-speed compatibility and high reliability, and further improvements in electrophotographic characteristics are required.

In order to improve the electrophotographic characteristics of the electrophotographic photosensitive member, for example, Patent Documents 1 and 2 propose that the photosensitive layer contains a charge transport material having a specific structure having a hydroxyl group.
JP 2002-82469 A JP 2003-186234 A

  However, in the specific charge transport materials described in Patent Documents 1 and 2, a part of the hydroxyl group is likely to be an oxide such as carboxylic acid or formyl in a coating solution for producing a photoreceptor. Further, when a hydroxyl group remains in the manufactured photoreceptor, the hydroxyl group tends to be an oxide due to charging stress associated with the electrophotographic process. Thus, it is considered that the oxide generated from the hydroxyl group acts as a carrier trap that hinders charge transport in the photoreceptor, and deteriorates the electrical characteristics of the photoreceptor. For this reason, the electrophotographic photosensitive member containing the charge transport material having a specific structure described in Patent Documents 1 and 2 has insufficient electrical characteristics and has not yet achieved high image quality.

  The present invention has been made in view of such circumstances, and an additive for an electrophotographic photoreceptor capable of sufficiently improving the electrical characteristics of the electrophotographic photoreceptor, an electrophotographic photoreceptor using the same, and An object is to provide an image forming apparatus and a process cartridge using the electrophotographic photosensitive member.

［式（Ｉ）中、Ｆは正孔輸送性を有するｎ価の有機基を、Ｔは２価の基を、Ｙは酸素原子又は硫黄原子を、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ独立に水素原子又は１価の有機基を、Ｒ^４は１価の有機基を、ｍは０又は１を、ｎは１〜４の整数を、それぞれ示す。但し、Ｒ^３とＲ^４は互いに結合してＹをヘテロ原子とする複素環を形成してもよい。］ In order to solve the above-mentioned problems, the present invention provides an additive for an electrophotographic photosensitive member having a structure represented by the following general formula (I).

[In Formula (I), F is an n-valent organic group having a hole transporting property, T is a divalent group, Y is an oxygen atom or a sulfur atom, and R ¹ , R ² and R ³ are independent of each other. Represents a hydrogen atom or a monovalent organic group, R ⁴ represents a monovalent organic group, m represents 0 or 1, and n represents an integer of 1 to 4, respectively. However, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a heteroatom. ]

In the additive for an electrophotographic photoreceptor of the present invention, an n-valent organic group F having a hole transport property and a site represented by the following formula (Ia) are represented by-(T) _m -O-. It has a structure linked through a site. Here, in the formula ^(I-a), Y, R ^1, R 2, ^{R 3} and ^{R 4} are as defined ^Y in formula (I), and R ^1, R 2, ^{R 3} and ^{R 4.}

In the additive for an electrophotographic photoreceptor of the present invention, the site represented by the formula (Ia) is considered to function as a protective group. The site represented by-(T) _m -O- in the above formula (I) is protected by the site represented by the above formula (Ia) in the coating solution, and the coating solution for producing the photoreceptor. It is thought that it can exist stably without changing to oxides such as carboxylic acid and formyl. Further, when the coating liquid is applied and reacted, the site represented by the formula (Ia) is easily removed from the structure represented by the formula (I), and the structure represented by the formula (I) is − (T) It is considered that the oxygen atom at the site represented by _m- O- forms a bond with other constituent materials of the photosensitive layer and is uniformly dispersed in the photosensitive layer. Therefore, the electrophotographic photoreceptor additive of the present invention can sufficiently improve the electrical characteristics of the photoreceptor without generating carrier traps that hinder charge transport in the photoreceptor.

  In addition, since the additive for an electrophotographic photosensitive member of the present invention can exist stably without chemically changing in the coating solution, precipitates and gelation hardly occur in the coating solution, and the pot life is excellent. Therefore, the additive for an electrophotographic photosensitive member of the present invention can increase the productivity of the photosensitive member and can realize cost reduction of the photosensitive member.

The site represented by-(T) _m -O- in the structure represented by the above formula (I) is highly reactive when the divalent group T is an alkylene group (particularly a methylene group). By setting it as the structure shown by the said Formula (I), stability in a coating liquid is improved and the effect mentioned above is fully acquired.

［式（ＩＩ）中、Ａｒ^１、Ａｒ^２、Ａｒ^３及びＡｒ^４はそれぞれ独立に置換又は未置換のアリール基を、Ａｒ^５は置換若しくは未置換のアリール基又はアリーレン基を、ｋは０又は１を、それぞれ示す。但し、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ａｒ^４及びＡｒ^５のうち１〜４個は上記一般式（Ｉ）で示される構造における２価の基Ｔと結合するための結合手を有する。］ The electrophotographic photoreceptor additive of the present invention preferably has a structure in which the n-valent organic group F having hole transportability is represented by the following general formula (II). With such a structure, sufficient charge transportability can be obtained.

[In the formula (II), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group, Ar ⁵ is a substituted or unsubstituted aryl group or arylene group, and k is 0 or 1 is shown respectively. However, ^{1 to 4 of} Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ have a bond for binding to the divalent group T in the structure represented by the general formula (I). ]

  The present invention includes a conductive support and a photosensitive layer formed on the conductive support, and the photosensitive layer contains the additive for an electrophotographic photoreceptor of the present invention or a reaction product thereof. An electrophotographic photosensitive member is provided. The present invention further comprises a conductive support and a photosensitive layer formed on the conductive support, wherein the photosensitive layer is formed using the additive for an electrophotographic photoreceptor of the present invention. An electrophotographic photosensitive member is provided. Since the electrophotographic photosensitive member of the present invention is formed using the above-described additive for an electrophotographic photosensitive member of the present invention, it has excellent electrical characteristics and can realize high image quality.

  The electrophotographic photosensitive member of the present invention is preferably contained in a layer in which the additive for an electrophotographic photosensitive member or a reaction product thereof is disposed at a position farthest from the conductive support of the photosensitive layer. Thereby, the electrical characteristics of the photosensitive layer can be sufficiently improved.

  In the electrophotographic photoreceptor of the present invention, it is preferable that the layer of the photosensitive layer disposed at the furthest position from the conductive support further contains a resin having a crosslinked structure, and the resin having the crosslinked structure. Is more preferably at least one of phenol resin, melamine resin, benzoguanamine resin, siloxane resin and urethane resin.

  When a resin having a cross-linked structure is used as a constituent material of the layer disposed farthest from the conductive support of the photosensitive layer, the mechanical strength of the surface of the photosensitive layer is increased and wear is less likely to occur. For this reason, when oxides are generated in the photosensitive layer due to charging stress or the like, what has been removed by the abrasion of the surface of the photosensitive layer in the past is not removed, which causes the electrical characteristics of the photoreceptor to deteriorate. . In the electrophotographic photoreceptor of the present invention, by using the additive for an electrophotographic photoreceptor of the present invention together with a resin having a crosslinked structure, the formation of oxides on the photoreceptor is suppressed, and the electrical characteristics of the photoreceptor are at a high level. Can be maintained. In addition, when a phenol resin is used as the resin having a crosslinked structure, the additive for an electrophotographic photosensitive member of the present invention and the phenol resin sufficiently react with each other. The characteristics can be sufficiently enhanced.

  The image forming apparatus of the present invention also forms an electrostatic latent image by exposing the electrophotographic photosensitive member of the present invention, a charging device for charging the electrophotographic photosensitive member, and the charged electrophotographic photosensitive member. The image forming apparatus includes an exposure device, 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 medium.

  The process cartridge of the present invention includes an electrophotographic photosensitive member of the present invention, a charging device for charging the electrophotographic photosensitive member, and an exposure device for forming an electrostatic latent image by exposing the charged electrophotographic photosensitive member. And at least one selected from a cleaning device for cleaning the electrophotographic photosensitive member.

  Since the image forming apparatus and the process cartridge according to the present invention include the electrophotographic photosensitive member according to the present invention, good image quality can be obtained over a long period of time.

  According to the present invention, an additive for an electrophotographic photoreceptor capable of sufficiently improving the electrical characteristics of the electrophotographic photoreceptor, an electrophotographic photoreceptor excellent in electrical characteristics and capable of realizing high image quality, and good for a long period of time. It is possible to provide an image forming apparatus and a process cartridge capable of obtaining a high image quality.

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

(Additives for electrophotographic photoreceptors)
The additive for electrophotographic photoreceptors of the present invention has a structure represented by the following general formula (I).

Here, in the above formula (I), F is an n-valent organic group having a hole transport property, T is a divalent group, Y is an oxygen atom or a sulfur atom, R ¹ , R ² and R ^3. Each independently represents a hydrogen atom or a monovalent organic group, R ⁴ represents a monovalent organic group, m represents 0 or 1, and n represents an integer of 1 to 4, respectively. However, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a heteroatom.

  The divalent group T is preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, more preferably an alkylene group, and more preferably a methylene group. The divalent group T may have a carbonyl group.

R ¹ , R ² , R ³ and R ⁴ are more preferably monovalent hydrocarbon groups and more preferably alkyl groups as monovalent organic groups. The preferred carbon number of the monovalent organic group is 1-18. In addition, when R < ³ > and R < ⁴ > couple | bond together and form the heterocyclic ring which uses Y as a hetero atom, heterocyclic rings other than an aromatic are preferable.

Moreover, it is preferable that the site | part shown by the following formula (Ia) among the structures shown by the said Formula (I) is carbon number 20 or less, and it is more preferable that it is carbon number 15 or less. Here, in the formula ^(I-a), Y, R ^1, R 2, ^{R 3} and ^{R 4} are as defined ^Y in formula (I), and R ^1, R 2, ^{R 3} and ^{R 4.}

  The n-valent organic group F having a hole transporting property is a compound derived from a hole transporting compound. Examples of the hole transporting compound include triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, and the like.

  The n-valent organic group F having hole transportability preferably has a structure represented by the following general formula (II).

In the above formula (II), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group, Ar ⁵ is a substituted or unsubstituted aryl group or arylene group, k Represents 0 or 1, respectively. However, ^{1 to 4 of} Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ have a bond for binding to the divalent group T in the structure represented by the general formula (I).

Specific examples of the substituted or unsubstituted aryl group represented by Ar ^{1 to} Ar ⁴ in the structure represented by the general formula (II) include aryl represented by the following formulas (II-1) to (II-7): Groups are preferred.

  Ar in the aryl group represented by the above formula (II-7) is preferably an arylene group represented by the following formula (II-8) or (II-9).

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

Here, in the above formula (II-1) ~ (II -17), R 6 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an unsubstituted phenyl group, an alkyl group or a carbon number of 1 to 4 carbon atoms A phenyl group substituted with an alkoxy group having 1 to 4 or an aralkyl group having 7 to 10 carbon atoms, R ^{7 to} R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. An alkoxy group, an unsubstituted phenyl group, a phenyl group substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, m and s Each independently represents 0 or 1, q and r each independently represent an integer of 1 to 10, and t each independently represents an integer of 1 to 3.

  In the formulas (II-1) to (II-7), X represents a site other than F in the structure represented by the formula (I).

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

  Specific examples of the additive for an electrophotographic photoreceptor of the present invention described above include the following compounds (I-1) to (I-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. The additive for an electrophotographic photoreceptor of the present invention includes, for example, a hole transporting compound corresponding to F in the structure represented by the above formula (I) and F in the structure represented by the above formula (I). It can be obtained by reacting a compound corresponding to other site with a predetermined catalyst. Such a synthesis method is described in detail in, for example, Experimental Chemistry Course 4th edition, Volume 20 (Maruzen), Encyclopedia of Reagents for Organic Synthesis, Vol 3 (Jhon Wiley & Sons).

(Electrophotographic photoreceptor)
Next, the electrophotographic photoreceptor of the present invention will be described. The electrophotographic photoreceptor of the present invention includes a conductive support and a photosensitive layer formed on the conductive support. Such a photosensitive layer is formed using the electrophotographic photoreceptor additive of the present invention and contains the electrophotographic photoreceptor additive of the present invention or a reaction product thereof. Note that the additive for an electrophotographic photoreceptor of the present invention may be present separately in the photosensitive layer in a site represented by the above formula (Ia) and other sites. That is, in the present invention, the reaction product of the additive for an electrophotographic photoreceptor is a compound having a site represented by the above formula (Ia) in the structure represented by the above general formula (I), or the above general formula. The compound having a site other than the site represented by the above formula (Ia) in the structure represented by (I) refers to a compound derived from the electrophotographic photoreceptor additive of the present invention. More specifically, a compound in which the site represented by the above formula (Ia) in the structure represented by the above general formula (I) or the other site is bonded to another constituent material of the photosensitive layer is exemplified. In the following description, in some cases, the additive for an electrophotographic photoreceptor of the present invention or a reaction product thereof is simply referred to as the additive for an electrophotographic photoreceptor of the present invention.

  The photosensitive layer provided in the electrophotographic photosensitive member of the present invention includes a single-layer type photosensitive layer containing a charge generation material and a charge transport material in the same layer, or a layer containing a charge generation material (charge generation layer). Any of the function-separated photosensitive layers provided separately with a layer containing a charge transport material (charge transport layer) may be used. In the case of the function-separated type photosensitive layer, any of the stacking order of the charge generation layer and the charge transport layer may be the upper layer. In the case of a function-separated photosensitive layer, it is possible to achieve functional separation because it is possible to perform functional separation in which each layer only has to satisfy each function.

  FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the electrophotographic photosensitive member of the present invention. As shown in FIG. 1, the electrophotographic photosensitive member 1 includes a conductive support 2 and a photosensitive layer 3. The photosensitive layer 3 has a structure in which 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 electrophotographic photoreceptor 1 shown in FIG. 1, the charge transport layer 6 contains the additive for an electrophotographic photoreceptor of the present invention.

  2 to 5 are schematic sectional views showing other preferred embodiments of the electrophotographic photosensitive member of the present invention. The electrophotographic photosensitive member shown in FIGS. 2 to 3 includes the photosensitive layer 3 in which the functions are separated into the charge generation layer 5 and the charge transport layer 6 as in the electrophotographic photosensitive member shown in FIG. 4 to 5 show that the charge generation material and the charge transport material are contained in the same layer (single-layer type photosensitive layer 8).

  The electrophotographic photoreceptor 1 shown in FIG. 2 has a structure in which an undercoat layer 4, a charge generation layer 5, a charge transport layer 6 and a protective layer 7 are sequentially laminated on a conductive support 2. The electrophotographic photoreceptor 1 shown in FIG. 3 has a structure in which an undercoat layer 4, a charge transport layer 6, a charge generation layer 5, and a protective layer 7 are sequentially laminated on a conductive support 2. In the electrophotographic photoreceptor 1 shown in FIGS. 2 and 3, the protective layer 7 contains the additive for an electrophotographic photoreceptor of the present invention. The electrophotographic photoreceptor 1 shown in FIG. 4 has a structure in which an undercoat layer 4 and a single-layer type photosensitive layer 8 are sequentially laminated on a conductive support 2. Contains the additive for electrophotographic photoreceptors of the present invention. The electrophotographic photoreceptor 1 shown in FIG. 5 has a structure in which an undercoat layer 4, a single-layer type photosensitive layer 8, and a protective layer 7 are sequentially laminated on a conductive support 2. Contains the additive for electrophotographic photoreceptors of the present invention. In the electrophotographic photoreceptor 1, the undercoat layer 4 is not necessarily provided.

  Hereinafter, each element will be described based on the electrophotographic photosensitive member 1 shown in FIG.

  Examples of the conductive support 2 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. Further, as the conductive support 2, paper, plastic film, belt or 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 can be used.

  The surface of the conductive support 2 is preferably roughened to a centerline 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 on the surface of the conductive support 2 is less than 0.04 μm, the effect of preventing interference tends to be insufficient because it is close to a mirror surface. On the other hand, if Ra exceeds 0.5 μm, the image quality tends to be insufficient even if a film is formed. When non-interfering light is used as a light source, it is not particularly necessary to roughen the interference fringes, and it is possible to prevent the occurrence of defects due to irregularities on the surface of the conductive support 2, which is suitable for longer life.

  As a roughening method, wet polishing is performed by suspending an abrasive in water and spraying the conductive support 2, or the conductive support 2 is pressed against a rotating grindstone and continuously subjected to grinding. Centerless grinding, anodizing treatment or the like is preferable.

  As a roughening method, without roughening the surface of the conductive support 2, a conductive or semiconductive powder is dispersed in the resin, and a layer is formed on the surface of the support. A method of roughening with fine particles dispersed therein is also preferably used.

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

  The thickness of the anodized film is preferably 0.3 to 15 μm. If it is less than 0.3 μm, the barrier property against injection tends to be poor and the effect tends to be insufficient. On the other hand, when it exceeds 15 μm, there is a tendency that the residual potential increases due to repeated use.

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

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

  The undercoat layer 4 is formed on the conductive support 2. The undercoat layer 4 includes an organometallic compound and / or 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 because of low residual potential and good electrophotographic characteristics.

  As the binder resin, 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, Examples include known vinyl chloride-vinyl acetate copolymers, epoxy resins, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, polyacrylic acid, and the like. When these are used in combination of two or more, the mixing ratio 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, A silane coupling agent such as β-3,4-epoxycyclohexyltrimethoxysilane may be contained.

  In the undercoat layer 4, an electron transporting pigment can also be mixed / dispersed from the viewpoints of lowering the residual potential and environmental stability. 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, polycyclic quinone pigments, zinc oxide or titanium oxide are preferably used because of their high electron mobility.

  In addition, the surface of these pigments may be surface-treated with the above coupling agent or binder resin for the purpose of controlling dispersibility and charge transporting property.

  If the amount of the electron transporting pigment is too large, the strength of the undercoat layer 4 is reduced and causes coating film defects. Therefore, the amount is preferably 95% by mass or less, more preferably 90% by mass based on the total solid content of the undercoat layer 4. % Used.

  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 formed using an undercoat layer forming coating solution containing the above-described constituent materials. The organic solvent used in the coating solution for forming the undercoat layer is one that dissolves an organometallic compound or a binder resin and does not cause gelation or aggregation when an electron transporting pigment is mixed and / or dispersed. If it is.

  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. , Chloroform, chlorobenzene, toluene and the like. These can be used individually by 1 type or in mixture of 2 or more types.

  As a method for mixing and / or dispersing each constituent material, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, a vibrating ball mill, a colloid mill, a paint shaker ultrasonic wave, or the like is applied. Mixing and / or dispersion is performed in an organic solvent.

  As a coating method for forming the undercoat layer 4, 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. be able to.

  The drying is usually performed at a temperature at which the solvent can be evaporated and a film can be formed. In particular, the conductive support 2 subjected to the acidic solution treatment and the boehmite treatment is preferably formed with the undercoat layer 4 because the defect concealing power of the substrate tends to be insufficient.

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

  The charge generation layer 5 includes a charge generation material and, if necessary, a binder resin.

  Known 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. Can be used. As the charge generation material, metal and metal-free phthalocyanine pigments, trigonal selenium, dibromoanthanthrone and the like are particularly preferable when a light source having an exposure wavelength of 380 to 500 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 and titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 are particularly preferred.

  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.

  The binder resin is preferably 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, Insulating resins such as acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, and polyvinyl pyrrolidone resin can be mentioned, but are not limited thereto. These binder resins can be used individually by 1 type or in mixture of 2 or more types.

  The charge generation layer 5 is formed by vapor deposition of a charge generation material or a coating solution for forming a charge generation layer containing a charge generation material and a binder resin. When the charge generation layer 5 is formed using a charge generation layer forming coating solution, the blending ratio (mass ratio) of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10.

  As a method for dispersing each of the constituent materials in the charge generation layer forming coating solution, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method, or the like can be used. At this time, a condition that the crystal form of the pigment is not changed by the dispersion is required. Further, at the time of 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 further preferably 0.15 μm or less.

  Solvents used for dispersion 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.

  When forming the charge generation layer 5 using the coating solution for forming the charge generation layer, the coating methods are blade coating method, wire bar coating method, spray coating method, dip coating method, bead coating method, air knife coating. Ordinary methods such as a method and a curtain coating method can be used.

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

  The charge transport layer 6 includes a charge transport material and a binder resin, or 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, but are not limited to, hole transporting compounds. These charge transport materials can be used singly or in combination of two or more.

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

Here, in the above formula (III-1), R ¹⁴ is a hydrogen atom or a methyl group, k is 1 or 2, Ar ⁶ and Ar ⁷ are each independently a substituted or unsubstituted aryl group, —C ₆ H ₄ —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), or —C ₆ H ₄ —CH═CH—CH═C (Ar) ₂ is represented, and the substituent is a halogen atom, carbon number 1 The substituted amino group substituted by the alkyl group of -5, a C1-C5 alkoxy group, or a C1-C3 alkyl group is shown. R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group.

Here, in the above formula (III-2), R ¹⁵ and R ¹⁵ ′ 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 ¹⁶ , R ¹⁶ ′, R ¹⁷ and R ¹⁷ ′ 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 or unsubstituted aryl group, —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), or —CH═CH—CH═C (Ar) ₂ , wherein R ¹⁸ , R ^19, and R ²⁰ 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. m and n each independently represents an integer of 0 to 2.

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

  Examples of the binder resin used for the charge transport layer 6 include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, and 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, and the like. These binder resins can be used individually by 1 type or in mixture of 2 or more types. The blending ratio (mass ratio) of the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  As the polymer charge transport material, known materials having charge transport properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, the 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.

  Although the polymer charge transport material alone can be used as a constituent material of the charge transport layer 6, it may be mixed with the binder resin to form a film.

  The charge transport layer 6 is formed using a charge transport layer forming coating solution containing the above-described constituent materials.

  Examples of the solvent for 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 halogenated fats such as methylene chloride, chloroform and ethylene chloride. Examples thereof include ordinary organic solvents such as aromatic 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.

  As a coating method of the coating solution for forming the charge transport layer, 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 should be used. Can do.

  The film thickness of the charge transport layer 6 is preferably 5 to 50 μm, more preferably 10 to 30 μm.

  In the photosensitive layer 3, additives such as an antioxidant, a light stabilizer, and a heat stabilizer are added 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. Can be added.

  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 photosensitive layer 3 can 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 7 is configured to contain the additive for an electrophotographic photosensitive member of the present invention and a binder resin.

  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. Among these, thermosetting resins such as phenol resin, thermosetting acrylic resin, thermosetting silicone resin, epoxy resin, melamine resin, urethane resin, polyimide resin, and polybenzimidazole resin are preferable. Among these, in particular, phenol resin, melamine resin, benzoguanamine resin, siloxane resin, and urethane resin are preferably used, and at the same time in the step of drying the solvent after applying a coating liquid containing these resins or their precursors as a main component. Heat treatment is performed to cure and form an insoluble cured film.

  Examples of the phenol resin include monomers of monomethylolphenols, dimethylolphenols or trimethylolphenols, mixtures thereof, oligomers thereof, or mixtures of these monomers and oligomers. Such phenol resins include resorcin, bisphenol, substituted phenols containing one hydroxyl group such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, and substituted phenols containing two hydroxyl groups such as catechol, resorcinol, hydroquinone, etc. It is obtained by reacting a compound having a phenol structure such as bisphenols such as bisphenol A and bisphenol Z and biphenols with formaldehyde, paraformaldehyde and the like in the presence of an acid catalyst or an alkali catalyst. As a phenol resin, what is generally marketed as a phenol resin can be used. Moreover, as a phenol resin, a resol type phenol resin is preferable. In the present specification, a relatively large molecule having about 2 to 20 repeating molecular structural units is referred to as an oligomer, and a molecule smaller than that is referred to as a monomer.

As the acid catalyst, sulfuric acid, paratoluenesulfonic acid, phosphoric acid and the like are used. Further, as the alkali catalyst, hydroxides or amine catalysts of alkali metals and alkaline earth metals such as NaOH, KOH, Ca (OH) ₂ and Ba (OH) ₂ are used.

  Examples of the amine catalyst include, but are not limited to, ammonia, hexamethylenetetramine, trimethylamine, triethylamine, and triethanolamine. When a basic catalyst is used, the carrier is remarkably trapped by the remaining catalyst, and the electrophotographic characteristics tend to be deteriorated. Therefore, it is preferable to inactivate or remove by neutralizing with an acid or contacting with an adsorbent such as silica gel or an ion exchange resin.

  As the melamine resin and the benzoguanamine resin, various types such as a methylol type in which the methylol group is intact, a full ether type in which all the methylol groups are alkyl etherified, a fluino type, a mixed type of methylol and imino group can be used. Among these, the ether type is preferable from the viewpoint of the stability of the coating solution.

  As the urethane resin, polyfunctional isocyanate, isocyanurate, or blocked isocyanate obtained by blocking these with alcohol or ketone can be used. Among these, from the viewpoint of the stability of the coating solution, blocked isocyanate or isocyanurate is preferable, and these are preferable because they are overheat-crosslinked with the electrophotographic photoreceptor additive of the present invention.

  As the silicone resin, a resin derived from a compound represented by the following general formula (IV-1) or (IV-2) can be used.

  These binder resins can be used alone or as a mixture of two or more thereof, and the blending ratio (mass ratio) of the additive for electrophotographic photoreceptor of the present invention and the binder resin is 10: 1 to 1: 5. preferable.

  Further, conductive particles may be added to the protective layer 7 in order to reduce the residual potential. Examples of the conductive particles include metals, metal oxides, and carbon black. Among these, metals or metal oxides are more preferable. Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, or those obtained by depositing these metals on the surface of plastic particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. It is done. These can be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion. From the viewpoint of the transparency of the protective layer 7, the average particle diameter of the conductive particles is preferably 0.3 μm or less, and particularly preferably 0.1 μm or less.

In addition, a compound represented by the following general formula (IV-1) can also be added to the protective layer 7 in order to control various physical properties such as strength and film resistance of the protective layer 7.
Si (R ³⁰ ) _(4-c) Q _c (IV-1)
In the above formula (IV-1), R ³⁰ 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 (IV-1) include the following silane coupling agents. Examples of silane coupling agents include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl L) Triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H , 1H, 2H, 2H-perfluorodecyltriethoxysilane, trifunctional alkoxysilanes such as 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (c = 3); dimethyldimethoxysilane, diphenyldimethoxysilane, methyl And bifunctional alkoxysilanes such as phenyldimethoxysilane (c = 2); monofunctional alkoxysilanes such as trimethylmethoxysilane (c = 1), and the like. Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and monofunctional and bifunctional alkoxysilanes are preferable for improving the flexibility and film formability.

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

In order to increase the strength of the protective layer 7, it is also preferable to use a compound having two or more silicon atoms as shown in the general formula (IV-2).
B- (Si (R ³¹ ) _(3-d) Q _d ) ₂ (IV-2)
In the above formula (IV-2), B represents a divalent organic group, R ³¹ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and a represents 1 to 3. Indicates an integer. More specific examples of the compound represented by the general formula (IV-2) include the following compounds (IV-2-1) to (IV-2-16).

  Further, the protective layer 7 has a cyclic compound having a repeating structural unit represented by the following general formula (IV-3) in order to extend pot life, control film characteristics, reduce torque, and improve the uniformity of the coating film surface, Alternatively, a derivative from the compound can be contained.

上記式（ＩＶ−３）中、Ａ^１及びＡ^２は、それぞれ独立に一価の有機基を示す。

In the above formula (IV-3), A ¹ and A ² each independently represent a monovalent organic group.

  Commercially available cyclic siloxane can be mentioned as a cyclic compound which has a repeating structural unit shown by general formula (IV-3). 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 control the antifouling substance adhesion, lubricity, hardness and the like on the surface of the electrophotographic photosensitive member. They can be used alone or in combination of two or more.

  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 an 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. What was chosen from what was disperse | distributed and generally marketed can be used. The solid content of colloidal silica in the protective layer 7 is not particularly limited, but preferably 0.1 to 0.1 based on the total solid content of the protective layer 7 in terms of film formability, electrical characteristics, and strength. It is used in the range of 50% by mass, more preferably in the range of 0.1-30% by mass.

  The silicone fine particles used as the silicon atom-containing fine particles are spherical and preferably have an average particle size 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, it is possible to improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and to maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles in the protective layer 7 is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.5 to 10% by mass based on the total solid content of the protective layer 7. .

Other fine particles include fluorine-based fine particles such as ethylene tetrafluoride, trifluoride ethylene, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Material Forum Lecture Proceedings p89. Fine particles made of a resin obtained by copolymerizing 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. For the same purpose, an oil such as silicone oil can be added.

  Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Examples include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes. These may be added in advance to the protective layer-forming coating solution, or may be impregnated under reduced pressure or increased pressure after producing the photoreceptor.

  In addition, additives such as plasticizers, surface modifiers, antioxidants, and photodegradation inhibitors can also be used. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons. An antioxidant having a hindered phenol, hindered amine, thioether, or phosphite partial structure can be added to the protective layer 7, which is effective in improving the potential stability and image quality when the environment changes.

  Examples of the antioxidant include the following compounds. For example, hindered phenols include “Sumilizer BHT-R”, “Sumilizer MDP-S”, “Sumilizer 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 "," 114 " ”,“ 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. Examples of hindered amines include “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”. ”,“ Mark LA68 ”,“ Mark LA63 ”,“ Smilizer TPS ”,“ Smilizer TP-D ”for thioethers,“ Mark 2112 ”,“ Mark PEP 8 ”,“ Mark PEP ”for phosphites -24G "," Mark PEP.36 "," Mark 329K "," Mark HP.10 ", and hindered phenols and hindered amine antioxidants are particularly preferable. 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.

Further, in order to remove the catalyst during synthesis from a resin having a crosslinked structure such as a phenol resin, a melamine resin, or a benzoguanamine resin, the resin is dissolved in an appropriate solvent such as methanol, ethanol, toluene, ethyl acetate, and washed with water. It is preferable to perform treatment such as reprecipitation using a poor solvent, or to perform treatment using, for example, the materials exemplified below. Such materials include Amberlite 15, Amberlite 200C, Amberlist 15E (above, manufactured by Rohm and Haas), Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co., Ltd.), Levacit SPC-108, Levacit SPC-118 (manufactured by Bayer), Diaion RCP-150H (Mitsubishi Kasei), Sumikaion KC-470, Duolite C26-C, Duolite C-433 Cation exchange resins such as Duolite-464 (manufactured by Sumitomo Chemical Co., Ltd.) and Nafion-H (manufactured by DuPont); Amberlite IRA-400, Amberlite IRA-45 (above, Rohm and Haas) Anion exchange resin such as Zr (O ₃ PCH ₂ CH ₂ SO) ₃ H) ₂ , Th (O ₃ PCH ₂ CH ₂ COOH) An inorganic solid in which a group containing a protonic acid group such as ₂ is bonded to the surface; containing a protonic acid group such as a polyorganosiloxane having a sulfonic acid group Polyorganosiloxanes; 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, silica - magnesia, silica - zirconia, composite-based metal oxides such as zeolites; acid clay, activated clay, montmorillonite, clay mineral such as kaolinite; LiSO _4, metal sulfates, such as MgSO _4; phosphate zirconia , metal phosphates such as lanthanum phosphate; LiNO , Mn (NO ₃₎ metal nitrate such as _2; inorganic group containing an amino group such as solid obtained by reacting aminopropyltriethoxysilane on silica gel is bonded to a surface solid; amino-modified silicone resin And polyorganosiloxanes containing amino groups such as

  In addition, polyglycidyl methacrylate, glycidyl bisphenols, epoxy-containing compounds such as phenol epoxy resins, terephthalic acid, maleic acid, pyromellitic acid, biphenyltetracarboxylic acid are used to adjust film properties such as hardness, adhesion, and flexibility. Acids or the like or anhydrides thereof may be added. The addition amount is preferably 0.05 to 1 part by mass, and more preferably 0.1 to 0.7 part by mass with respect to 1 part by mass of the additive for electrophotographic photosensitive member of the present invention.

  Further, in the protective layer 7, 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 An insulating resin such as a resin, a polyacrylamide resin, a polyvinyl pyridine resin, a cellulose resin, a urethane resin, an epoxy resin, casein, a polyvinyl alcohol resin, or a polyvinyl pyrrolidone resin can be mixed in a desired ratio. Thereby, the adhesiveness with the electric charge transport layer 6, the coating film defect by heat shrink or repellency, etc. can also be suppressed.

  The protective layer 7 is formed using a coating liquid for forming a protective layer containing the above-described constituent materials. That is, the protective layer 7 is formed by applying a coating liquid for forming a protective layer on the charge transport layer 6 and curing it.

  In the coating solution for forming the protective layer, a solvent such as alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran; ethers such as diethyl ether and dioxane is used as necessary. . In addition to these, various solvents can be used, but in order to apply the dip coating method generally used in the production of electrophotographic photoreceptors, alcohol-based or ketone-based solvents, or mixed solvents thereof Is preferable. The boiling point is preferably 50 to 150 ° C. and can be arbitrarily mixed and used. The amount of the solvent can be set arbitrarily, but if it is too small, it is likely to precipitate, so 0.5 to 30 parts by mass is preferable with respect to a total of 1 part by mass of the solid content contained in the coating liquid for forming the protective layer. Part by mass is more preferable.

  Furthermore, when crosslinking, a curing catalyst may be used in the protective layer forming coating solution. Curing catalysts include bissulfonyldiazomethanes such as bis (isopropylsulfonyl) diazomethane, bissulfonylmethanes such as methylsulfonyl p-toluenesulfonylmethane, sulfonylcarbonyldiazomethanes such as cyclohexylsulfonylcyclohexylcarbonyldiazomethane, 2-methyl Sulfonylcarbonyl alkanes such as 2- (4-methylphenylsulfonyl) propiophenone, nitrobenzyl sulfonates such as 2-nitrobenzyl p-toluenesulfonate, alkyl and aryl sulfonates such as pyrogallol trismethanesulfonate ( g) Benzoin sulfonates such as benzoin tosylate, N- such as N- (trifluoromethylsulfonyloxy) phthalimide. Sulfonyloxyimides, pyridones such as (4-fluorobenzenesulfonyloxy) -3,4,6-trimethyl-2-pyridone, 2,2,2-trifluoro-1-trifluoromethyl-1- ( Photoacid generators such as sulfonic acid esters such as 3-vinylphenyl) -ethyl-4-chlorobenzenesulfonate, onium salts such as triphenylsulfonium methanesulfonate, diphenyliodonium trifluoromethanesulfonate, protonic acids or Lewis acids. Preferred examples include compounds neutralized with Lewis bases, mixtures of Lewis acids and trialkyl phosphates, sulfonate esters, phosphate esters, onium compounds, and carboxylic anhydride compounds.

Compounds obtained by neutralizing a protonic acid or Lewis acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphoric acid esters, boric acid mono- and diesters, and the like. Various amines such as monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, or trialkylphosphine, triarylphosphine, trialkylphosphite, triaryl Compounds neutralized with phosphite, as well as NureCure 2500X, 4167, X-47-110, 3525, 5225 commercially available as acid-base blocking catalysts (trade name, King Ndasutori Co., Ltd.), and the like. Examples of the compound obtained by neutralizing a Lewis acid with a Lewis base include compounds obtained by neutralizing a Lewis acid such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the above Lewis base.

  Examples of the onium compound include triphenylsulfonium methanesulfonate, diphenyliodonium trifluoromethanesulfonate, and the like.

  Examples of the carboxylic anhydride compound include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, lauric anhydride, oleic anhydride, stearic anhydride, n-caproic anhydride, n-caprylic anhydride, and n-capric anhydride. , Palmitic anhydride, myristic anhydride, trichloroacetic anhydride, dichloroacetic anhydride, monochloroacetic anhydride, trifluoroacetic anhydride, heptafluorobutyric anhydride, and the like.

  Specific examples of Lewis acids include, for example, boron trifluoride, aluminum trichloride, ferrous chloride, ferric chloride, ferrous chloride, ferric chloride, zinc chloride, zinc bromide, stannous chloride. , Metal halides such as stannic chloride, stannous bromide, stannic bromide, organometallic compounds such as trialkylboron, trialkylaluminum, dialkylaluminum halide, monoalkylaluminum halide, tetraalkyltin , Diisopropoxyethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, tris (acetylacetonato) aluminum, diisopropoxy bis (ethyl acetoacetate) titanium, diisopropoxy bis (acetylacetonato) titanium, tetrakis (N-propylacetoacetate Zirconium, tetrakis (acetylacetonato) zirconium, tetrakis (ethylacetoacetate) zirconium, dibutyl bis (acetylacetonato) tin, tris (acetylacetonato) iron, tris (acetylacetonato) rhodium, bis (acetyl) Acetonato) zinc, tris (acetylacetonato) cobalt and other metal chelate compounds, dibutyltin dilaurate, dioctyltin ester malate, magnesium naphthenate, calcium naphthenate, manganese naphthenate, iron naphthenate, cobalt naphthenate, copper naphthenate , Zinc naphthenate, zirconium naphthenate, lead naphthenate, calcium octylate, manganese octylate, iron octylate, cobalt octylate, zinc octylate, zirconium octylate, Tin chill acid, lead octylate, zinc laurate, magnesium stearate, aluminum stearate, calcium stearate, cobalt stearate, zinc stearate, and metal soaps such as stearate lead. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Although the usage-amount of these catalysts is not restrict | limited, 0.1-20 mass parts is preferable with respect to the total 100 mass parts of solid content contained in the coating liquid for protective layer formation, and 0.3-10 mass parts is preferable. Particularly preferred.

  When the coating liquid for forming the protective layer is applied onto the charge transport layer 6, the coating methods are blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating. Ordinary methods such as a method can be used. And after application | coating, the protective layer 7 forms by drying a coating film.

  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.

  When the protective layer 7 is formed using a resin having a crosslinked structure, the curing temperature is preferably 100 to 170 ° C., more preferably 100 to 160 ° C. when crosslinking is performed. The curing time is preferably 30 minutes to 2 hours, more preferably 30 minutes to 1 hour, and the heating temperature may be changed to another stage.

  The atmosphere in which the crosslinking reaction is performed can be prevented in a gas atmosphere inert to so-called oxidation such as nitrogen, helium, and argon, thereby preventing deterioration of electrical characteristics. When the crosslinking reaction is performed in an inert gas atmosphere, the curing temperature can be set higher than in an air atmosphere, and the curing temperature is preferably 100 to 180 ° C, more preferably 110 to 160 ° C. The curing time is preferably 30 minutes to 2 hours, more preferably 30 minutes to 1 hour.

  The thickness of the protective layer 7 is preferably 0.5 to 15 μm, more preferably 1 to 10 μm, and further preferably 1 to 5 μm.

Oxygen permeability at 25 ° C. of the protective layer 7 is preferably not more than ^{4 × 10 12 fm / s ·} Pa, more preferably not more than ^{3.5 × 10 12 fm / s ·} Pa, 3 × 10 More preferably, it is ¹² fm / s · Pa or less.

  Here, the oxygen permeation coefficient is a scale representing the ease of oxygen gas permeation of the layer, but it can also be regarded as a substitute characteristic of the physical gap ratio of the layer if the view is changed. In addition, although the absolute value of the transmittance changes if the type of gas changes, there is almost no reversal of the magnitude relationship between the layers serving as specimens. Therefore, the oxygen permeation coefficient may be interpreted as a measure expressing the general ease of gas permeation.

  That is, when the oxygen permeation coefficient at 25 ° C. of the protective layer 7 satisfies the above conditions, the gas hardly penetrates into the protective layer 7. Therefore, the permeation of the discharge product generated by the image forming process is suppressed, the deterioration of the compound contained in the protective layer 7 is suppressed, the electrical characteristics can be maintained at a high level, and the image quality is improved and the life is extended. It is valid.

  In this embodiment, the layer containing the additive for an electrophotographic photoreceptor of the present invention is the protective layer 7, but the layer containing the additive for an electrophotographic photoreceptor of the present invention is shown in FIG. 1, for example. In the electrophotographic photosensitive member, the charge transport layer 6 may be used.

  In the case of constituting a single layer type photosensitive layer, the single layer type photosensitive layer is formed containing a charge generating material and a binder resin. The charge generation material is the same as that used for the charge generation layer in the function separation type photosensitive layer, and the binder resin is a binder resin used for the charge generation layer and the charge transport layer in the function separation type photosensitive layer. Similar ones can be used. The content of the charge generating material in the single-layer type photosensitive layer is preferably 10 to 85% by mass, more preferably 20 to 50% by mass, based on the total solid content in the single-layer type photosensitive layer. A charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer for the purpose of improving photoelectric characteristics. The addition amount is preferably 5 to 50% by mass based on the total solid content in the single-layer type photosensitive layer. Moreover, the solvent and coating method used for coating can be the same as those for the above layers. The thickness of the single-layer type photosensitive layer is preferably about 5 to 50 μm, more preferably 10 to 40 μm. In the electrophotographic photosensitive member 1 shown in FIG. 4, the single-layer type photosensitive layer 8 contains the additive for an electrophotographic photosensitive member of the present invention in the same manner as the protective layer 7 of the electrophotographic photosensitive member 1 shown in FIG. The constituent material is selected and configured so as to be a layer to be contained.

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

  FIG. 6 is a schematic diagram showing a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 100 shown in FIG. 6 includes a process cartridge 20 including an electrophotographic photosensitive member 1, an exposure device 30, a transfer device 40, and an intermediate transfer member 50 in an image forming apparatus main body (not shown). . In the image forming apparatus 100, the exposure device 30 is disposed at a position where the electrophotographic photosensitive member 1 can be exposed from the opening of the process cartridge 20. The intermediate transfer member 50 is disposed such that a part of the intermediate transfer member 50 can come into contact with the electrophotographic photosensitive member 1.

  The process cartridge 20 is obtained by integrating a charging device 21, a developing device 25, a cleaning device 27, and a fibrous member (toothbrush shape) 29 together with an electrophotographic photosensitive member 1 by a mounting rail in a case. The case is provided with an opening for exposure.

  Here, the charging device 21 charges the electrophotographic photosensitive member 1 by a contact method. The developing device 25 develops the electrostatic latent image on the electrophotographic photosensitive member 1 to form a toner image.

Hereinafter, the toner used for the developing device 25 will be described. The toner preferably has an average shape factor (ML ² / A) of 100 to 150, and more preferably 100 to 140. Further, the toner preferably has a volume average particle diameter of 2 to 12 μm, more preferably 3 to 12 μm, and further preferably 3 to 9 μm. By using a toner satisfying such an average shape factor and volume average particle diameter, developability and transferability are improved, and a high-quality image called so-called photographic image quality can be obtained.

  The toner is not particularly limited by the production method as long as it satisfies the above average shape factor and volume average particle diameter. For example, the toner may include a binder resin, a colorant, a release agent, and the like. A kneading and pulverizing method in which a charge control agent is added, kneading, pulverizing, and classifying; a method in which the shape of particles obtained by the kneading and pulverizing method is changed by mechanical impact force or thermal energy; Emulsion polymerization of the body, and the resulting dispersion is mixed with a dispersion of a colorant, a release agent and, if necessary, a charge control agent, and then agglomerated and heat-fused to obtain toner particles. Suspension polymerization method in which a polymerizable monomer for obtaining a binder resin, a colorant, a release agent, and a charge control agent, if necessary, are suspended in an aqueous solvent and polymerized; A water-based solution of a resin, a colorant, a release agent, and a solution such as a charge control agent as necessary. Toner is used which is suspended in and produced by a dissolution suspension method in which granulated.

  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 give a core-shell structure can be used. As a toner production method, a suspension polymerization method, an emulsion polymerization aggregation method, and a dissolution suspension method in which an aqueous solvent is used are preferable from the viewpoint of shape control and particle size distribution control, and an emulsion polymerization aggregation method is particularly preferable.

  The toner base particles are composed of a binder resin, a colorant, and a release agent, and include silica and a charge control agent as necessary.

  Binder resins used for toner base particles include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Α-methylene aliphatics such as vinyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers and copolymers of monocarboxylic acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone Polyester resins by copolymerization of dicarboxylic acids and diols.

  Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. A polymer, polyethylene, polypropylene, a polyester resin, etc. can be mentioned. In addition, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can also be mentioned.

  In addition, as colorants, 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, malachite green oxalate, 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.

  As the charge control agent, known ones can be used, and azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups 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.

  The toner used in the developing device 25 can be manufactured by mixing the toner base particles and the external additive with a Henschel mixer or a V blender. In addition, when the toner base particles are produced by a wet method, external addition can also be performed by a wet method.

  Lubricating particles may be added to the toner used in the developing device 25. Lubricating particles include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids and fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene and polybutene, silicones having a softening point upon heating, oleic amides Aliphatic amides such as erucic acid amide, ricinoleic acid amide, stearic acid amide, etc., plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animals such as beeswax Minerals such as system waxes, montan waxes, ozokerites, ceresins, paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, etc., petroleum waxes, and modified products thereof can be used. These can be used individually by 1 type or in combination of 2 or more types. However, the average particle size is preferably in the range of 0.1 to 10 μm, and the particles having the above chemical structure may be pulverized to make the particle sizes uniform. The amount added to the toner is preferably in the range of 0.05 to 2.0 mass%, more preferably 0.1 to 1.5 mass%.

  To the toner used in the developing device 25, inorganic fine particles, organic fine particles, composite fine particles obtained by attaching inorganic fine particles to the organic fine particles, and the like can be added for the purpose of removing deposits and deteriorated matters on the surface of the electrophotographic photoreceptor. .

  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.

  In addition, the inorganic fine particles are mixed with titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, γ- (2- Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxy Silane 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. In addition, those hydrophobized with higher fatty acid metal salts such as silicone oil, aluminum stearate, zinc stearate and calcium stearate are also preferably used.

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

  The particle diameter is preferably a number average particle diameter of 5 nm to 1000 nm, more preferably 5 nm to 800 nm, and still more preferably 5 nm to 700 nm. If the average particle size is less than the lower limit, the polishing ability tends to be lacking. On the other hand, if the average particle size exceeds the upper limit, the surface of the electrophotographic photoreceptor tends to be damaged. Moreover, it is preferable that the sum of the addition amount of the particle | grains mentioned above and lubricity particle | grains is 0.6 mass% or more.

  Other inorganic oxides added to the toner are small-diameter inorganic oxides with a primary particle size of 40 nm or less for powder flowability, 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 for precise charge control. Further, the surface treatment of the small-diameter inorganic fine particles increases the dispersibility and increases the powder flowability. Furthermore, it is also preferable to add carbonates such as calcium carbonate and magnesium carbonate and inorganic minerals such as hydrotalcite in order to remove the discharge purified product.

  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 surface coated with resin coating are used. The mixing ratio with the carrier can be set as appropriate.

  The cleaning device 27 includes a fibrous member (roll shape) 27a and a cleaning blade 27b.

Although the cleaning device 27 is provided with the fibrous member 27a and the cleaning blade 27b, the cleaning device 27 may be provided with either one. The fibrous member 27a may have a toothbrush shape in addition to the roll shape. Further, the fibrous member 27a may be fixed to the cleaning device main body, may be supported so as to be rotatable, and may be supported so as to be capable of oscillating in the photosensitive member axial direction. As the fibrous member 27a, polyester, nylon, acrylic, etc., cloth-like ones made of ultrafine fibers such as Toraysee (made by Toray Industries), resin fibers such as nylon, acrylic, polyolefin, polyester, etc. are used as a substrate or carpet. The brush-like thing etc. which were flocked to can be mentioned. Further, as the fibrous member 27a, a conductive powder or an ionic conductive agent is added to the above-described material to impart conductivity, or a conductive layer is formed inside or outside of each fiber. Can also be used. When conductivity is imparted, the resistance value is preferably 10 ² to 10 ⁹ Ω as a single fiber. The fiber thickness of the fibrous member 27a is preferably 30 d (denier) or less, more preferably 20 d or less, and the fiber density is preferably 20,000 fibers / inch ² or more, more preferably 30,000 fibers / inch. inch ² or more. The fibrous member 29 can be the same as the fibrous member 27a.

  The cleaning device 27 is required to remove deposits (for example, discharge products) on the surface of the photoreceptor with a cleaning blade and a cleaning brush. In order to achieve this purpose over a long period of time and stabilize the function of the cleaning member, the cleaning member may be supplied with a lubricating substance (lubricating component) such as metal soap, higher alcohol, wax, silicone oil or the like. preferable.

  For example, when a roll-shaped member is used as the fibrous member 27a, it is preferable to supply a lubricating component to the surface of the electrophotographic photosensitive member by bringing it into contact with a lubricating substance such as metal soap or wax. A normal rubber blade is used as the cleaning blade 27b. As described above, when a rubber blade is used as the cleaning blade 27b, supplying a lubricating component to the surface of the electrophotographic photosensitive member is particularly effective in suppressing chipping and wear of the blade.

  The process cartridge 20 described above is detachable from the image forming apparatus main body, and constitutes the image forming apparatus together with the image forming apparatus main body.

  The exposure device 30 may be any device that exposes the charged electrophotographic photosensitive member 1 to form an electrostatic latent image. Further, it is preferable to use a multi-beam surface emitting laser as the light source of the exposure apparatus 30.

  The transfer device 40 may be any device that transfers the toner image on the electrophotographic photosensitive member 1 to a transfer medium (intermediate transfer member 50). For example, a roll-shaped one that is usually used is used.

  As the intermediate transfer member 50, a belt-like member (intermediate transfer belt) made of polyimide, polyamideimide, polycarbonate, polyarylate, polyester, rubber or the like having semiconductivity is used. Further, as the form of the intermediate transfer member 50, a drum-like member can be used in addition to the belt-like member.

  When using the electrophotographic photoreceptor of the present invention, paper dust, talc, etc. are generated from the print paper, which easily adheres to the electrophotographic photoreceptor, and the electrophotographic photoreceptor of the present invention is resistant. It is difficult to remove paper dust, talc and the like because of its high wear resistance. Therefore, it is preferable to use the intermediate transfer member 50 in order to prevent adhesion of paper dust and talc and obtain a stable image.

  The transfer medium referred to in the present invention is not particularly limited as long as it is a medium to which a toner image formed on the electrophotographic photoreceptor 1 is transferred. For example, when transferring directly from the electrophotographic photosensitive member 1 to paper or the like, paper or the like is a transfer medium, and when the intermediate transfer member 50 is used, the intermediate transfer member is a transfer medium.

  FIG. 7 is a schematic view showing another embodiment of the image forming apparatus of the present invention. In the image forming apparatus 110 shown in FIG. 7, the electrophotographic photosensitive member 1 is fixed to the main body of the image forming apparatus, and the charging device 22, the developing device 25, and the cleaning device 27 are each formed into a cartridge. It is provided independently as a cleaning cartridge. Note that the charging device 22 includes a charging device for charging by a corona discharge method.

  In the image forming apparatus 110, the electrophotographic photosensitive member 1 and other apparatuses are separated, and the charging device 22, the developing device 25, and the cleaning device 27 are fixed to the image forming apparatus main body by screws, caulking, adhesion, or welding. It is possible to detach it by the operation by pulling out and pushing in without being done.

  In the electrophotographic photoreceptor of the present invention, when a resin having a crosslinked structure is used as a constituent material of the protective layer, the surface of the photoreceptor is excellent in wear resistance, so that it may not be necessary to make a cartridge. . Therefore, the charging device 22, the developing device 25, or the cleaning device 27 can be detached and attached by an operation by pulling out and pushing in without being fixed to the main body by screws, caulking, adhesion, or welding. The member cost per hit can be reduced. Further, two or more of these devices can be detachable as an integrated cartridge, thereby further reducing the member cost per print.

  The image forming apparatus 110 has the same configuration as that of the image forming apparatus 100 except that the charging device 22, the developing device 25, and the cleaning device 27 are each formed as a cartridge.

  FIG. 8 is a schematic diagram showing another embodiment of the image forming apparatus of the present invention. The image forming apparatus 120 is a tandem full-color image forming apparatus equipped with four process cartridges 20. In the image forming apparatus 120, four process cartridges 20 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member can be used for one color. The image forming apparatus 120 has the same configuration as that of the image forming apparatus 100 except that it is a tandem system.

  In the tandem-type image forming apparatus 120, the amount of wear of each electrophotographic photosensitive member varies depending on the use ratio of each color, and thus the electrical characteristics of each electrophotographic photosensitive member tend to vary. Along with this, the toner development characteristics gradually change from the initial state, and the hue of the print image changes, so that a stable image cannot be obtained. In particular, in order to reduce the size of the image forming apparatus, a small-diameter electrophotographic photosensitive member tends to be used, and this tendency becomes remarkable when one having a diameter of 30 mmΦ or less is used. Here, when the configuration of the electrophotographic photosensitive member of the present invention is adopted as the electrophotographic photosensitive member, the surface wear is sufficiently suppressed even when the diameter is 30 mmΦ or less. Therefore, the electrophotographic photosensitive member of the present invention is particularly effective for a tandem type image forming apparatus.

  FIG. 9 is a schematic view showing another embodiment of the image forming apparatus of the present invention. The image forming apparatus 130 shown in FIG. 9 is a so-called four-cycle image forming apparatus that forms toner images of a plurality of colors with one electrophotographic photosensitive member. The image forming apparatus 130 includes a photosensitive drum 1 that is rotated by a driving device (not shown) at a predetermined rotational speed in the direction of arrow A in the figure, and above the photosensitive drum 1 is a photosensitive member. A charging device 22 for charging the outer peripheral surface of the drum 1 is provided.

  Further, an exposure device 30 having a surface emitting laser array as an exposure light source is disposed above the charging device 22. The exposure device 30 modulates a plurality of laser beams emitted from a light source in accordance with an image to be formed and deflects the laser beams in the main scanning direction so that the axis of the photosensitive drum 1 is on the outer peripheral surface of the photosensitive drum 1. Scan in parallel. Thereby, an electrostatic latent image is formed on the outer peripheral surface of the charged photosensitive drum 1.

  A developing device 25 is disposed on the side of the photosensitive drum 1. The developing device 25 includes a roller-shaped container that is rotatably arranged. Four containers are formed inside the container, and developing units 25Y, 25M, 25C, and 25K are provided in each container. The developing devices 25Y, 25M, 25C, and 25K each include a developing roller 26, and store Y, M, C, and K color toners therein.

  The full-color image is formed by the image forming apparatus 130 while the photosensitive drum 1 is rotated four times. That is, during four rotations of the photosensitive drum 1, the charging device 22 charges the outer peripheral surface of the photosensitive drum 1, and the exposure device 20 includes Y, M, C, K image data representing a color image to be formed. Scanning the outer peripheral surface of the photosensitive drum 1 with the laser beam modulated according to any one is repeated while switching the image data used for modulation of the laser beam each time the photosensitive drum 1 rotates. Further, the developing device 25 operates the developing device corresponding to the outer peripheral surface in a state where any of the developing rollers 26 of the developing devices 25Y, 25M, 25C, and 25K corresponds to the outer peripheral surface of the photosensitive drum 1. The photosensitive drum 1 is the one that develops the electrostatic latent image formed on the outer peripheral surface of the photosensitive drum 1 to a specific color and forms a toner image of the specific color on the outer peripheral surface of the photosensitive drum 1. Each time it rotates, the process is repeated while rotating the container so that the developing unit used for developing the electrostatic latent image is switched. Thus, every time the photosensitive drum 1 rotates, Y, M, C, and K toner images are formed on the outer peripheral surface of the photosensitive drum 1.

  An endless intermediate transfer belt 50 is disposed substantially below the photosensitive drum 1. The intermediate transfer belt 50 is wound around rollers 51, 53, and 55, and is disposed so that the outer peripheral surface is in contact with the outer peripheral surface of the photosensitive drum 1. The rollers 51, 53, and 55 are rotated by a driving force of a motor (not shown) and rotate the intermediate transfer belt 50 in the direction of arrow B in FIG.

  A transfer device (transfer device) 40 is disposed on the opposite side of the photosensitive drum 1 across the intermediate transfer belt 50, and the toner image formed on the outer peripheral surface of the photosensitive drum 1 is intermediate transferred by the transfer device 40. The image is transferred onto the image forming surface of the belt 50. The intermediate transfer belt 50 is also rotated in accordance with the rotation of the photosensitive drum 1, and a full-color toner image is formed on the intermediate transfer belt 50 when the photosensitive drum 1 is rotated four times.

  A lubricant supply device 29 and a cleaning device 27 are disposed on the outer peripheral surface of the photosensitive drum 1 on the opposite side of the developing device 25 with the photosensitive drum 1 interposed therebetween. When the toner image formed on the outer peripheral surface of the photoconductive drum 12 is transferred to the intermediate transfer belt 50, the lubricant is supplied to the outer peripheral surface of the photoconductive drum 1 by the lubricant supply device 29. The area carrying the transferred toner image is cleaned by the cleaning device 27.

  A tray 60 is disposed below the intermediate transfer belt 50, and a large number of sheets P as recording materials are accommodated in the tray 60 in a stacked state. A take-out roller 61 is disposed obliquely above and to the left of the tray 60, and a roller pair 63 and a roller 65 are arranged in this order on the downstream side in the take-out direction of the paper P by the take-out roller 61. The uppermost recording sheet in the stacked state is taken out from the tray 60 by the take-out roller 61 rotating, and is conveyed by the roller pair 63 and the roller 65.

  A transfer device 42 is disposed on the opposite side of the roller 55 with the intermediate transfer belt 50 interposed therebetween. The paper P conveyed by the roller pair 63 and the roller 65 is sent between the intermediate transfer belt 50 and the transfer device 42, and the toner image formed on the image forming surface of the intermediate transfer belt 50 is transferred by the transfer device 42. . A fixing device 44 having a pair of fixing rollers is arranged on the downstream side of the transfer device 42 in the conveyance direction of the paper P. The paper P on which the toner image is transferred is transferred by the fixing device 44. After being fused and fixed, the sheet is discharged out of the image forming apparatus 130 and placed on a discharge tray (not shown).

  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 at all. In the following examples, “part” means part by mass.

  In this example, first, a photoreceptor a having a charge generation layer and a charge transport layer formed on a conductive support, and an undercoat layer, a charge generation layer and a charge transport layer were formed on the conductive support. Photoreceptor b was produced. Next, the additive for an electrophotographic photoreceptor of the present invention was synthesized, and a protective layer was formed on the photoreceptor a or b using the additive to obtain the photoreceptor of this example. Then, an image forming apparatus was manufactured using the obtained photoreceptor, and an image forming test was performed.

(Photoreceptor a)
First, a 30 mmφ cylindrical aluminum base material was prepared. This 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 base material subjected to the centerless polishing treatment, degreasing treatment, etching treatment with 2 wt% sodium hydroxide solution for 1 minute, neutralization treatment, and pure water washing were performed in this order. Next, an anodized film (current density: 1.0 A / dm ² ) was formed on the surface of the aluminum substrate using a 10 wt% sulfuric acid solution. After washing with water, sealing treatment was performed by dipping in a 1 wt% nickel acetate solution at 80 ° C. for 20 minutes. Further, pure water washing and drying treatment were performed. In this way, an aluminum substrate having a 7 μm anodic oxide film formed on the surface was obtained.

  1 part of chlorogallium phthalocyanine with strong diffraction peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum, polyvinyl Mix 1 part of butyral (Esreck BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate, and disperse with glass beads for 1 hour with a paint shaker to obtain a coating solution for forming a charge generation layer. It was. This coating solution was dip coated on the obtained aluminum substrate and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  2.5 parts of a benzidine compound represented by the following formula (V-1), 3 parts of a polymer compound (viscosity average molecular weight 39,000) having a structural unit represented by the following formula (V-2), and 20 parts of chlorobenzene Partially mixed and dissolved to obtain a coating solution for forming a charge transport layer.

  This 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. In this way, the photoreceptor in which the charge generation layer and the charge transport layer were formed on the aluminum base material on which the anodized film was formed was designated as “photoreceptor a”.

(Photoreceptor b)
First, a 84 mmφ cylindrical aluminum base material subjected to a honing treatment was prepared. Next, 100 parts of a zirconium compound (trade name: Olgatrix ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts of a silane compound (trade name: A1100, manufactured by Nihon Unicar Co., Ltd.), 400 parts of isopropanol, and 200 parts of butanol are mixed. Thus, a coating solution for forming the undercoat layer was obtained. This coating solution was dip-coated on an aluminum substrate and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer of 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 ° and Mix 1 part of hydroxygallium phthalocyanine with a strong diffraction peak at 28.3 °, 1 part of polyvinyl butyral (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts of n-butyl acetate, and paint with glass beads. Dispersion was carried out with a shaker for 1 hour to obtain a coating solution for forming a charge generation layer. This 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 of a charge transport material represented by the following formula (V-3), 3 parts of a polymer compound having a structural unit represented by the above formula (V-4) (viscosity average molecular weight 50,000), and 20 parts of chlorobenzene was mixed to obtain a coating solution for forming a charge transport layer.

  The obtained coating solution for forming a charge transport layer 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. In this way, the photoconductor in which the undercoat layer, the charge generation layer, and the charge transport layer were formed on the honing-treated aluminum base material was referred to as “photoconductor b”.

  Next, the additive for an electrophotographic photoreceptor of the present invention was synthesized. As an additive for an electrophotographic photoreceptor of the present invention, first, the compound (I-9) is synthesized, and then the compounds (I-1), (I-3), ( I-13) and (I-32) were synthesized.

(Synthesis Example: Compound (I-9))
In a 1 L-flask, 100 parts of 4,4′-bishydroxymethyltriphenylamine, 500 parts of ethyl vinyl ether and 5 parts of 2-ethylhexyl phosphate were placed and stirred at room temperature for 2 hours. After the reaction, the mixture was neutralized with a dilute aqueous sodium carbonate solution and washed with water. Thereafter, the organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was dissolved in toluene and purified by silica gel chromatography to obtain 110 parts of the above compound (I-9) as a colorless oil. The infrared absorption spectrum of the obtained compound is shown in FIG. The infrared absorption spectrum was measured using an infrared spectrophotometer FT-730 (manufactured by Horiba Seisakusho).

Example 1
5.5 parts of the compound (I-3), 7 parts of a resol type phenol resin (PL-2211, manufactured by Gunei Chemical Co., Ltd.) and 0.03 part of methylphenylpolysiloxane were prepared. This was dissolved in 15 parts of isopropanol and 5 parts of methyl ethyl ketone to obtain a coating solution for forming a protective layer. This coating solution was applied onto the photoreceptor a by a dip coating method and dried at 130 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. The obtained photoreceptor is referred to as “PR-1”. Further, when the protective layer-forming coating solution was sealed and stored at room temperature (20 °), precipitation and viscosity increase did not occur even after 1 month, and no problem in producing the photoconductor occurred.

(Example 2)
A protective layer was formed in the same manner as in Example 1 except that the drying conditions in Example 1 were changed to 150 ° C. for 1 hour in a nitrogen atmosphere. The obtained photoreceptor is referred to as “PR-2”.

(Example 3)
A protective layer was formed in the same manner as in Example 1 except that 0.2 part of NACURE 2500X (Enomoto Chemical) was added to the protective layer-forming coating solution of Example 1. The obtained photoreceptor is referred to as “PR-3”.

(Comparative Example 1)
A protective layer was formed in the same manner as in Example 1 except that a compound represented by the following formula (V-5) was used as the charge transport material instead of the compound (I-3). The obtained photoreceptor is referred to as “RPR-1”. Further, when the coating solution for forming the protective layer was stored tightly at room temperature (20 ° C.), precipitation occurred in 2 days, making it impossible to produce a photoreceptor.

(Comparative Example 2)
A protective layer was formed in the same manner as in Comparative Example 1 except that the drying conditions were 150 ° C. for 1 hour under a nitrogen atmosphere. The obtained photoreceptor is referred to as “RPR-2”.

Example 4
A protective layer was formed in the same manner as in Example 3 except that the compound (I-3) was replaced with the compound (I-1). The obtained photoreceptor is referred to as “PR-4”.

(Example 5)
A protective layer was formed in the same manner as in Example 3 except that the compound (I-3) was replaced with the compound (I-9). The obtained photoreceptor is referred to as “PR-5”.

(Example 6)
6 parts of the above compound (I-13), 7 parts of resol type phenol resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.), 0.5 part of butyral resin, 0.5 part of bisglycidyl bisphenol A, biphenyltetracarboxylic 0.5 parts of acid, 0.03 parts of methylphenylpolysiloxane, and 0.2 parts of Sanol LS2626 were prepared. This was dissolved in 20 parts of isopropanol to obtain a coating solution for forming a protective layer. This coating solution was applied onto the photoreceptor a by a dip coating method and dried at 130 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. The obtained photoreceptor is referred to as “PR-6”.

(Example 7)
0.2 parts of fluorine atom-containing fine particles (Lublon L-2, manufactured by Daikin Industries) and 0.01 part of GF-300 (manufactured by Toagosei Co., Ltd.) are added to the protective layer-forming coating solution of Example 1, and As media, 50 parts of 1 mmφ glass beads were added and dispersed for 1 hour in a paint shaker. This dispersion was used as a coating solution for forming a protective layer, and a protective layer was formed in the same manner as in Example 1. The obtained photoreceptor is referred to as “PR-7”.

(Example 8)
A protective layer was formed in the same manner as in Example 6 except that the resol type phenolic resin was replaced with a methylated melamine resin (Nicalac MW-30: Sanwa Chemical). The obtained photoreceptor is referred to as “PR-8”.

Example 9
A protective layer was formed in the same manner as in Example 6 except that the resol type phenol resin was replaced with a benzoguanamine resin (Nicalak BL-60: Sanwa Chemical). The obtained photoreceptor is referred to as “PR-9”.

(Example 10)
A protective layer was formed in the same manner as in Example 3 except that the compound (I-3) was replaced with the compound (I-32). The obtained photoreceptor is referred to as “PR-10”.

(Example 11)
6 parts of the above compound (I-32), 7 parts of blocked isocyanate resin (JA-925, manufactured by Jujo Chemical Co., Ltd.), 0.5 part of butyral resin, 0.05 part of dibutyltin dilaurate, and 0.02 of sanol LS2626. Two copies were prepared. This was dissolved in 20 parts of isopropanol to obtain a coating solution for forming a protective layer. This coating solution was applied onto the photoreceptor a by a dip coating method and dried at 130 ° C. for 40 minutes to form a protective layer having a thickness of 3 μm. The obtained photoreceptor is referred to as “PR-11”.

(Examples 12 to 22)
A protective layer was formed in the same manner as in Examples 1 to 11 except that the photoreceptor b was used instead of the photoreceptor a. The obtained photoreceptor is designated “PR-12-22”.

(Comparative Examples 3-4)
A protective layer was formed in the same manner as in Comparative Examples 1 and 2 except that the photoreceptor b was used instead of the photoreceptor a. The obtained photoreceptor was designated as “RPR-3 to 4”.

Hereinafter, the developer used in this embodiment will be described. The various physical property values of the developer were measured by the following methods. 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. The volume average particle diameter D50v was obtained as D50v, which is the 50% particle diameter calculated from the large particle side of the particle size distribution according to the particle volume. In addition, the average shape factor (ML ² / A) of the toner and the composite particles means a value calculated by the following formula. In the case of a true sphere, ML ² / A = 100.
ML ² / A = (maximum length) ² × π × 100 / (projection area × 4).
In order to obtain the average shape factor, specifically, a toner image is taken from an optical microscope into an image analyzer (LUZEX III, manufactured by Nireco), an equivalent circle diameter is measured, and an individual length is calculated from the maximum length and the projected area. The value of ML ² / A in the above formula was determined for the particles.

(Developer 1)
(Toner mother particles)
(Adjustment of resin fine particle dispersion)
Styrene 370 g, n-butyl acrylate 30 g, acrylic acid 8 g, dodecanethiol 24 g, and carbon tetrabromide 4 g were mixed and dissolved. Add 6 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 10 g of anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in 550 g of ion-exchanged water. Thus, emulsion polymerization was carried out, and 50 g of ion-exchanged water in which 4 g of ammonium persulfate was dissolved was added while slowly mixing for 10 minutes. After carrying out nitrogen substitution, the inside of the flask was stirred with an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin fine particle dispersion in which resin particles having an average particle diameter of 150 nm, Tg = 58 ° C., and mass average molecular weight Mw = 11500 was obtained. The solid content concentration of this dispersion was 40% by mass.

(Adjustment of colorant dispersion (1))
Carbon black (Mogal L, manufactured by Cabot) -60g,
Nonionic surfactant (Nonipol 400, Sanyo Chemical Co., Ltd.)-6g and ion-exchanged water-240g were prepared.
The above components were mixed, dissolved, and stirred for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA). Thereafter, the colorant dispersant (1) in which colorant (carbon black) particles having an average particle diameter of 250 nm were dispersed was prepared by dispersing with an optimizer.

(Adjustment of colorant dispersion (2))
Cyan pigment B15: 3-60 g,
Nonionic surfactant (Nonipol 400, Sanyo Chemical Co., Ltd.)-5g and ion-exchanged water-240g were prepared.
The above components were mixed, dissolved, and stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, a colorant dispersant (2) in which colorant (Cyan pigment) particles having an average particle diameter of 250 nm were dispersed was prepared by dispersing with an optimizer.

(Adjustment of colorant dispersion (3))
Magenta pigment R122-60g,
Nonionic surfactant (Nonipol 400, Sanyo Chemical Co., Ltd.)-5g and ion-exchanged water-240g were prepared.
The above components were mixed, dissolved, and stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, a colorant dispersant (3) in which colorant (Magenta pigment) particles having an average particle diameter of 250 nm were dispersed was prepared by dispersing with an optimizer.

(Adjustment of colored dispersion (4))
Yellow pigment Y180-90 g,
Nonionic surfactant (Nonipol 400, Sanyo Chemical Co., Ltd.)-5g and ion-exchanged water-240g were prepared.
The above components were mixed, dissolved, and stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, a colorant dispersant (4) in which colorant (Yellow pigment) particles having an average particle diameter of 250 nm were dispersed was prepared by dispersing with an optimizer.

(Release agent dispersion)
Paraffin wax (HNP0190, Nippon Seiwa Co., Ltd., melting point 85 ° C.)-100 g,
Cationic surfactant (Sanisol B50, manufactured by Kao Corporation) -5 g and ion-exchanged water-240 g were prepared.
The above components were dispersed in a round stainless steel flask for 10 minutes using a homogenizer (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.

(Adjustment of toner mother particles K1)
Resin fine particle dispersion -234 parts,
Colorant dispersion (1) -30 parts,
Release agent dispersion-40 parts,
Polyaluminum hydroxide (Asada Chemical Co., Ltd., Paho2S) -0.5 part and ion-exchanged water-600 parts were prepared.
The above components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then heated to 40 ° C. while stirring the flask in a heating oil bath. . After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a volume average particle diameter D50v of 4.5 μm were generated. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and the volume average particle diameter D50v was 5.3 μm. Thereafter, 26 parts of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The dispersion containing the aggregated particles was added with 1N sodium hydroxide to adjust the pH of the system to 7.0, and then the stainless steel flask was sealed and heated to 80 ° C. while continuing stirring using a magnetic seal. And held for 4 hours. After cooling, the toner base particles were separated by filtration, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K1. The volume average particle diameter D50v of the toner base particles K1 is 5.9 μm, and the average shape factor ML ² / A is 132.

(Adjustment of toner base particle C1)
Toner base particles C1 were obtained in the same manner as toner base particles K1, except that the colorant dispersion (2) was used instead of the colorant dispersion (1). The toner base particle C1 has a volume average particle diameter D50v of 5.8 μm and an average shape factor ML ² / A of 131.

(Adjustment of toner mother particles M1)
Toner base particles M1 were obtained in the same manner as toner base particles K1, except that the colorant dispersion (3) was used instead of the colorant dispersion (1). The volume average particle diameter D50v of the toner base particles M1 is 5.5 μm, and the average shape factor ML ² / A is 135.

(Adjustment of toner mother particle Y1)
Toner base particles Y1 were obtained in the same manner as toner base particles K1, except that the colorant dispersion liquid (4) was used instead of the colorant dispersion liquid (1). The volume average particle diameter D50v of the toner base particles Y1 is 5.9 μm, and the average shape factor ML ² / A is 130.

(Manufacture of carriers)
Ferrite particles (volume average particle size: 50 μm) -100 parts,
Toluene-14 parts,
Styrene / methacrylate copolymer (component ratio: 90 / 10-2 parts) and carbon black (R330, manufactured by Cabot Corporation) -0.2 parts were prepared.
First, the above components excluding ferrite particles were stirred with a stirrer for 10 minutes to prepare a dispersed coating solution. Next, the coating liquid and ferrite particles were put in a vacuum degassing type kneader, stirred at 60 ° C. for 30 minutes, further depressurized while being heated, degassed, and dried to obtain a carrier. This carrier had a volume resistivity value of 10 ¹¹ Ωcm when an electric field of 1000 V / cm was applied.

  100 parts of each of the toner base particles K1, C1, M1, and Y1 were prepared. In addition, 1 part of rutile type titanium oxide (volume average particle diameter 20 nm, n-decyltrimethoxysilane treatment), silica (volume average particle diameter 40 nm, silicone oil treatment, gas phase oxidation method) 2.0 parts, cerium oxide (volume) Jet mill of 1 part of average particle size 0.7 μm), higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700), zinc stearate and calcium carbonate (volume average average particle size 0.1 μm) at a mass ratio of 5: 1: 1 Then, 0.3 parts of a volume average particle diameter of 8.0 μm was added, and blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s × 15 minutes. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain toner 1. Further, 100 parts of the carrier and 5 parts of the obtained toner were stirred with a V-blender at 40 rpm × 20 minutes, and sieved with a sieve having an opening of 212 μm to obtain developer 1.

(Developer 2)
(Adjustment of toner mother particles K2)
Resin fine particle dispersion -234 parts,
Colorant dispersion (1) -30 parts,
Release agent dispersion-40 parts,
Polyaluminum hydroxide (Asada Chemical Co., Ltd., Paho2S) -0.5 part and ion-exchanged water-600 parts were prepared.
The above components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then heated to 40 ° C. while stirring the flask in a heating oil bath. . After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a volume average particle diameter D50v of 4.5 μm were generated. Further, the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, and the volume average particle diameter D50v was 5.3 μm. Thereafter, 26 parts of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The dispersion containing the aggregated particles is added with 1N sodium hydroxide to adjust the pH of the system to 5.0, and then the stainless steel flask is sealed and heated to 95 ° C. while stirring with a magnetic seal. And held for 4 hours. After cooling, the toner base particles were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K2. The volume average particle diameter D50v of the toner base particles K2 is 5.8 μm, and the average shape factor ML ² / A is 109.

(Adjustment of toner base particle C2)
Toner base particles C2 were obtained in the same manner as toner base particles K2, except that the colorant dispersion liquid (2) was used instead of the colorant dispersion liquid (1). The toner base particle C2 has a volume average particle diameter D50v of 5.7 μm and an average shape factor ML ² / A of 110.

(Adjustment of toner mother particles M2)
Toner base particles M2 were obtained in the same manner as toner base particles K2, except that the colorant dispersion liquid (3) was used instead of the colorant dispersion liquid (1). The volume average particle diameter D50v of the toner base particles M2 is 5.6 μm, and the average shape factor ML ² / A is 114.

(Adjustment of toner mother particle Y2)
Toner base particles Y2 were obtained in the same manner as above except that the colorant dispersion (4) was used instead of the colorant dispersion (1). The volume average particle diameter D50v of the toner base particles Y2 is 5.8 μm, and the average shape factor ML ² / A is 108.

  K2, C2, M2, and Y2 were used as toner base particles, aluminum oxide (volume average particle size 0.1 μm) was used instead of 1 part of cerium oxide (volume average particle size 0.7 μm), and magnesium carbonate ( A developer 2 was obtained in exactly the same manner as the toner 1 and the developer 1 except that the volume average particle diameter was 0.1 μm.

(Developer 3)
(Adjustment of toner mother particles K3)
100 parts of polyester resin,
Carbon black-4 parts and carnauba wax-5 parts were prepared.
The above mixture is kneaded with an extruder, pulverized with a jet mill, and then classified with an air classifier to obtain toner base particles K3 having a volume average particle diameter D50v of 5.9 μm and an average shape factor (ML ² / A) of 145. It was. The polyester resin was a linear polyester obtained from terephthalic acid-bisphenol A ethylene oxide adduct-cyclohexanedimethanol, and had Tg: 62 ° C., Mn 12000, Mw: 32000.

(Adjustment of toner mother particle C3)
The volume average particle diameter D50v is 5.6 μm and the average shape factor (ML ² / A) 141 is the same as K3 except that a cyan colorant (CI Pigment Blue 15: 3) is used instead of carbon black. Toner mother particles C3 were obtained.

(Adjustment of toner mother particles M3)
A toner base particle M3 having a volume average particle diameter D50v of 5.9 μm and an average shape factor (ML ² / A) of 149 was obtained in the same manner as K3 except that magenta colorant (R122) was used instead of carbon black.

(Adjustment of toner mother particle Y3)
A toner base particle Y3 having a volume average particle diameter D50v of 5.8 μm and an average shape factor (ML ² / A) of 144 was obtained in the same manner as K3 except that a yellow colorant (Y180) was used instead of carbon black.

  Developer 3 was obtained in exactly the same manner as toner 2 and developer 2, except that K3, C3, M3, and Y3 were used as toner base particles.

(Examples 23 to 33 and Comparative Examples 5 to 9)
The tandem type image forming apparatus shown in FIG. 8 (manufactured by Fuji Xerox Co., Ltd., DocuCenter Color 400CP) is formed by combining the photoreceptors PR-1 to 11 and RPR-1 to 2 and developers 1 to 3 as shown in Table 17. Manufactured.

  Table 17 also shows the oxygen transmission coefficient at 25 ° C. of each photoconductor. For the oxygen permeability coefficient, a protective layer-forming coating solution was applied on an aluminum plate to the same thickness as the photoreceptor, and dried under the same conditions as the drying conditions for producing the photoreceptor. And it dried and peel | exfoliated the film | membrane, and measured the oxygen-permeation coefficient in 25 degreeC with the gas-permeation coefficient measuring apparatus (the Toyo Seiki company make, MC-3).

(Examples 34 to 44 and Comparative Examples 10 to 13)
The photoconductors PR-12 to 22 and RPR-3 to 4 and developers 1 to 3 are combined as shown in Table 19, and a four-cycle image forming apparatus shown in FIG. 9 (manufactured by Fuji Xerox Co., Ltd., DocuCenter Color 500). ) Was manufactured. In this image forming apparatus, the exposure apparatus is modified to a multi-beam surface emitting laser having an oscillation wavelength of 780 nm. Table 19 also shows the oxygen transmission coefficient at 25 ° C. of each photoconductor.

(Examples 45 to 46)
The photoconductor PR-12 and the developers 1 and 3 were combined as shown in Table 19 to produce a 4-cycle image forming apparatus (Fuji Xerox Co., Ltd., DocuCenter Color 500) shown in FIG. In this image forming apparatus, a member in which Toraysee is pasted on the sponge with a width of 3 mm at the rear part of the blade cleaning apparatus is pressed against the electrophotographic photosensitive member with a pressing pressure of 1 g / mm. The exposure apparatus was modified to a multi-beam surface emitting laser with an oscillation wavelength of 780 nm.

(Image formation test)
An image formation test was performed using the image forming apparatuses of Examples 23 to 46 and Comparative Examples 5 to 13. In the image formation test, an image formation test of 10,000 sheets is performed in an environment of low temperature and low humidity (10 ° C., 20% RH), and then 10,000 in an environment of high temperature and high humidity (28 ° C., 75% RH). A sheet image formation test was performed. Then, the following criteria were evaluated with respect to the surface potential of the photoconductor, the deposit on the photoconductor, the cleaning property, the wear rate of the photoconductor, and the image quality. The obtained results are shown in Tables 18 and 20, respectively.

The surface potential of the photoreceptor is evaluated by charging it to −700 V at normal temperature and normal humidity (20 ° C., 50% RH), exposing to 5 mJ / m ² flash at 780 nm, and then monitoring the surface potential (VL) after 50 msec. I went there.
Deposits on the photoreceptor were judged visually, and evaluated based on the following criteria: ○: no adhesion, Δ: partial (about 30% or less of the total), and x: adhesion.
The cleaning property was determined visually, and evaluated based on the criteria of ○: good, Δ: partial (about 10% or less of the whole) image defects such as streaks, and x: extensive image defect.
The wear rate of the photoconductor was calculated by measuring the wear amount of the photoconductor and calculating the wear rate per 1000 revolutions.
The image quality was evaluated by visually judging the print image quality after printing a total of 20,000 sheets, based on the criteria of ○: good, x: streak-like defects, and occurrence of low image density on the entire surface.

  As can be seen from the results shown in the table above, it was confirmed that the photoconductors of the examples were excellent in electrical characteristics and that no surface adhesion remained even after long-term use, and an image forming apparatus using the photoconductors of the examples It was confirmed that can achieve high image quality and long life.

1 is a schematic cross-sectional view showing a preferred embodiment of an electrophotographic photoreceptor of the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member of the present invention. 1 is a schematic diagram showing a preferred embodiment of an image forming apparatus of the present invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is an infrared absorption spectrum of a compound (I-9).

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photosensitive member, 2 ... Conductive support body, 3 ... Photosensitive layer, 4 ... Undercoat layer, 5 ... Charge generation layer, 6 ... Charge transport layer, 7 ... Protective layer, 8 ... Single layer type photosensitive layer, 20 Process cartridge, 100, 110, 120, 130 Image forming apparatus.

Claims (9)

An additive for an electrophotographic photoreceptor, which has a structure represented by the following general formula (I).

[In Formula (I), F is an n-valent organic group having a hole transporting property, T is a divalent group, Y is an oxygen atom or a sulfur atom, and R ¹ , R ² and R ³ are independent of each other. Represents a hydrogen atom or a monovalent organic group, R ⁴ represents a monovalent organic group, m represents 0 or 1, and n represents an integer of 1 to 4, respectively. However, R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a heteroatom. ] 2. The additive for an electrophotographic photoreceptor according to claim 1, wherein the n-valent organic group F having a hole transporting property has a structure represented by the following general formula (II).

[In the formula (II), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group, Ar ⁵ is a substituted or unsubstituted aryl group or arylene group, and k is 0 or 1 is shown respectively. However, ^{1 to 4 of} Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ have a bond for binding to the divalent group T in the structure represented by the general formula (I). ] Comprising a conductive support and a photosensitive layer formed on the conductive support;
An electrophotographic photosensitive member, wherein the photosensitive layer contains the additive for an electrophotographic photosensitive member according to claim 1 or 2 or a reaction product thereof.   4. The electrophotographic photosensitive member according to claim 3, wherein the additive for an electrophotographic photosensitive member or a reaction product thereof is contained in a layer disposed at a position farthest from the conductive support of the photosensitive layer. .   5. The electrophotographic photosensitive member according to claim 4, wherein the layer disposed at a position farthest from the conductive support of the photosensitive layer further contains a resin having a crosslinked structure.   6. The electrophotographic photosensitive member according to claim 5, wherein the resin having a crosslinked structure is at least one of a phenol resin, a melamine resin, a benzoguanamine resin, a siloxane resin, and a urethane resin. Comprising a conductive support and a photosensitive layer formed on the conductive support;
An electrophotographic photosensitive member, wherein the photosensitive layer is formed using the additive for an electrophotographic photosensitive member according to claim 1. The electrophotographic photoreceptor according to any one of claims 3 to 7,
A charging device for charging the electrophotographic photoreceptor;
An exposure apparatus that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image;
A developing device for developing the electrostatic latent image to form a toner image;
A transfer device for transferring the toner image to a transfer medium;
An image forming apparatus comprising: The electrophotographic photoreceptor according to any one of claims 3 to 7,
At least one selected from a charging device for charging the electrophotographic photosensitive member, an exposure device for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, and a cleaning device for cleaning the electrophotographic photosensitive member. When,
A process cartridge comprising:

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