JP2006023562A - Method for manufacturing electrophotographic photoreceptor, electrophotographic photoreceptor, process cartridge and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an electrophotographic photoreceptor by which electrophotographic properties of an electrophotographic photoreceptor using a triarylamine compound or a derivative thereof as a charge transport material is improved furthermore, and also to provide an electrophotographic photoreceptor manufactured by the manufacturing method, and a process cartridge and an electrophotographic apparatus with the electrophotographic photoreceptor. <P>SOLUTION: When a charge transport material is synthesized, a metal-containing compound and an amino substituted phosphorus compound having a phosphorus atom to which at least one amino group bonds are used as a catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing an electrophotographic photosensitive member, an electrophotographic photosensitive member, a process cartridge having an electrophotographic photosensitive member, and an electrophotographic apparatus.

  As one type of charge transport materials used in electrophotographic photoreceptors, triarylamine compounds and derivatives thereof that are easy to design molecules and have high hole mobility are known. As a method for synthesizing a triarylamine compound used as the charge transport material, a method using a copper catalyst, that is, a method using a so-called Ullmann reaction is known.

  However, the Ullmann reaction uses a large amount of copper catalyst, requires a high reaction temperature, and has a disadvantage that the yield of the triarylamine compound is low due to a long reaction time and the electrophotographic characteristics. There is a disadvantage that coloring impurities and decomposition products which adversely affect the color are produced as a by-product.

As a technique for improving this defect, Japanese Patent Application Laid-Open No. 2001-356507 (Patent Document 1) discloses a triarylamine compound synthesized using a catalyst composed of a phosphorus compound having a specific structure and a palladium compound. Techniques used as charge transport materials are disclosed. According to this technique, a triarylamine compound can be synthesized with high yield and high purity, and the electrophotographic characteristics of an electrophotographic photoreceptor using the triarylamine compound as a charge transport material can be improved.
JP 2001-356507 A

  The technique disclosed in Japanese Patent Application Laid-Open No. 2001-356507 is excellent in terms of the yield and purity of the triarylamine compound and the electrophotographic characteristics of the electrophotographic photoreceptor, but there is still room for improvement. .

  An object of the present invention is to provide a method for producing an electrophotographic photosensitive member that can further improve the electrophotographic characteristics of the electrophotographic photosensitive member using a triarylamine compound or a derivative thereof as a charge transport material.

  Another object of the present invention is to provide an electrophotographic photosensitive member produced by the production method, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

The present invention is a method for producing an electrophotographic photosensitive member having a layer containing a charge transport material on a support,
A charge transport material synthesis step for synthesizing the charge transport material by an amination reaction of a halogenated aromatic compound or a halogenated heterocyclic compound with an amine compound in the presence of a base, and a charge synthesized by the charge transport material synthesis step A coating liquid preparation step for preparing a coating liquid for a layer containing the charge transport material using a transport material, and a layer containing the charge transport material using the coating liquid prepared by the coating liquid preparation step A method of producing an electrophotographic photosensitive member having a layer forming step,
In the charge transport material synthesizing step, a method for producing an electrophotographic photosensitive member is characterized in that a metal-containing compound and an amino-substituted phosphorus compound having a phosphorus atom bonded to at least one amino group are used as a catalyst.

  The present invention also provides an electrophotographic photosensitive member manufactured by the above-described manufacturing method, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  According to the present invention, it is possible to provide a method for producing an electrophotographic photosensitive member that can further improve the electrophotographic characteristics of an electrophotographic photosensitive member using a triarylamine compound or a derivative thereof as a charge transport material, and An electrophotographic photosensitive member manufactured by the manufacturing method, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member can be provided.

  Hereinafter, the present invention will be described in detail.

In the following description, “Me” means a methyl group (—CH ₃ ), “Et” means an ethyl group (—CH ₂ CH ₃ ), and “n-Pr” means a normal propyl group (—CH _2). means CH ₂ CH _3), "i-Pr" represents an isopropyl group (-CH _{(CH 3) 2)} means, "n-Bu" is n-butyl group _{(-CH 2 CH 2 CH 2 CH} 3) “I-Bu” means an isobutyl group (—CH ₂ CH (CH ₃ ) ₂ ), and “t-Bu” means a tertiary butyl group (—C (CH ₃ ) ₃ ). “Oac” means acetonato, “acac” means acetriacetonate, and “dba” means 1,5-diphenyl-1,4-pentadiene-3-nat.

  Although the details of the reason why the above-described effect can be obtained by the present invention are unclear, the present inventors presume as follows.

  That is, when a charge transport material (triarylamine compound or derivative thereof) is synthesized by amination reaction of a halogenated aromatic compound or a halogenated heterocyclic compound with an amine compound in the presence of a base, a metal-containing compound is used as a catalyst. And amino-substituted phosphorus compounds increase the catalytic activity and increase the reaction efficiency, resulting in high-purity and high-yield charge transport materials (triarylamine compounds or derivatives thereof), thereby providing superior electrophotography It is assumed that an electrophotographic photoreceptor having characteristics can be provided.

  The amino-substituted phosphorus compound used as a catalyst in the charge transport material synthesis step of the method for producing an electrophotographic photoreceptor of the present invention is such that a lone pair on a nitrogen atom constituting an amino group donates an electron to the phosphorus atom. Thus, it is considered that the charge density in the phosphorus atom is increased and the reactivity is improved.

  The phosphorus compound described in JP-A-2001-356507 (Patent Document 1) is a phosphorus compound having at least one aryl group, and is thus substituted with an aryl group, so that the stability of the phosphorus compound is increased. The decomposition product derived from the phosphorus compound is less likely to be generated, and the charge transport material produced by the production method using this phosphorus compound is highly purified, and the characteristics of the electrophotographic photoreceptor are improved.

  However, since the electron donating property to the phosphorus atom of the aryl group is inferior to the electron donating property to the phosphorus atom of the amino group, there is a tendency that a difference in the reaction rate of the triarylamine synthesis reaction occurs (a difference in reaction efficiency occurs). is there. Along with this, there is a difference in the amount of by-products, especially tar-like substances produced, and the amino-substituted phosphorus compounds used in the present invention hardly form tar-like products, and the triarylamine compound is highly purified in the next purification stage. It becomes. This is considered to be the reason why the electrophotographic characteristics of the electrophotographic photosensitive member are further improved by the present invention.

  The amino-substituted phosphorus compound is preferably a compound having a structure represented by any one of the following formulas (1) to (4).

(In Formula (1), R < ¹¹ > -R < ¹³ > shows a C1-C4 alkyl group each independently.)

(In formula (2), R ^{21 to} R ²³ each independently represents an alkyl group having 1 to 4 carbon atoms, and R ²⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(In formula (3), R ^{31 to} R ³⁴ each independently represents an alkyl group having 1 to 4 carbon atoms.)

(In formula (4), R ^{41 to} R ⁴⁵ each independently represents an alkyl group having 1 to 4 carbon atoms.)
Examples of the alkyl group having 1 to 4 carbon atoms of R ^{11 to} R ¹³ , R ^{21 to} R ²⁴ , R ^{31 to} R ³⁴ , and R ^{41 to} R ^{45 in} the above formulas (1) to (4) include a methyl group, Examples thereof include an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group.

R ^{11 to} R ¹³ in the formula (1) are preferably each independently an isopropyl group or an isobutyl group.

R ^{21 to} R ²³ in the above formula (2) are preferably each independently an isopropyl group or an isobutyl group.

R ²⁴ in the above formula (2) is preferably a hydrogen atom, a methyl group, an ethyl group, a normal propyl group, a normal butyl group or a tertiary butyl group, and in particular, a hydrogen atom, a methyl group or a tertiary butyl group. More preferably, it is a group.

R ³¹ and R ³² in the above formula (3) are preferably each independently an isopropyl group or an isobutyl group.

In the above formula (3), at least one of R ³³ and R ³⁴ is preferably a tertiary butyl group.

In the above formula (4), R ⁴¹ , R ⁴² , R ⁴⁴ and R ⁴⁵ are preferably each independently an isopropyl group or an isobutyl group.

R ⁴³ in the above formula (4) is preferably a tertiary butyl group.

  Hereinafter, preferred examples of the compound having the structure represented by the formula (1) will be shown.

  Among these, (1-3), (1-4), (1-5), (1-6) and (1-7) are preferable, and (1-5) and (1-6) are particularly preferable. More preferred.

  Hereinafter, suitable examples of the compound having the structure represented by the above formula (2) will be shown.

  Among these, (2-3), (2-4), (2-5), and (2-6) are preferable, and (2-5) and (2-6) are more preferable.

  Hereinafter, suitable examples of the compound having the structure represented by the above formula (3) will be shown.

  Among these, (3-6), (3-9), (3-11), and (3-12) are preferable, and (3-11) and (3-12) are more preferable.

  Hereinafter, suitable examples of the compound having the structure represented by the above formula (4) will be shown.

  Among these, (4-5), (4-6), (4-7), and (4-8) are preferable, and (4-6) and (4-7) are more preferable.

The metal of the metal-containing compound used as a catalyst in the charge transport material synthesis step of the method for producing an electrophotographic photoreceptor of the present invention is preferably palladium. Examples of the compound containing palladium include Pd (Oac) ₂ , Pd (acac) ₂ , (CH ₃ CN) ₂ Pd (NO ₂ ) Cl, (C ₁₀ H ₈ N ₂ ) ₂ PdCl ₂ , Pd ₂ ( Preferred examples include dba) ₃ , PdCl _{2 and the} like.

  The amount of the amino-substituted phosphorus compound used as a catalyst in the charge transport material synthesis step of the method for producing an electrophotographic photoreceptor of the present invention is 50 to 50 based on the amount of the metal-containing compound used as a catalyst in the step. It is preferably 1000% by mass, and more preferably 80 to 500% by mass.

  In addition, the amount of the metal-containing compound used as a catalyst in the charge transport material synthesis step of the method for producing an electrophotographic photoreceptor of the present invention depends on the charge transport material raw material (amine compound and halogenated aromatic compound or halogenated complex). The amount is preferably 0.0001 to 20 mol%, more preferably 0.002 to 10 mol%, based on the ring compound).

  When the amino-substituted phosphorus compound and the metal-containing compound used as a catalyst in the charge transport material synthesis step of the method for producing an electrophotographic photoreceptor of the present invention act as a catalyst, the amino-substituted phosphorus compound is converted into the metal-containing compound. It becomes a coordinated state. The state in which the amino-substituted phosphorus compound is coordinated to the metal-containing compound may be formed in advance outside the charge transport material synthesis reaction system, or the amino-substituted phosphorus compound and the metal-containing compound may be included in the reaction system. To form a coordinated state in the reaction system.

  In addition, the charge transport material synthesis step of the method for producing an electrophotographic photoreceptor of the present invention is performed in the presence of a base, and this base is preferably a strong base, specifically, an alkali metal alkoxide, Alkaline earth metal alkoxide, potassium carbonate, and tripotassium phosphate are preferred.

  Examples of the alkali metal alkoxide include lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium-isopropoxide, sodium-isopropoxide, potassium-isopropoxide, Examples thereof include lithium-tertiary butoxide, sodium-tertiary butoxide, and potassium-tertiary butoxide.

  Examples of the alkaline earth metal alkoxide include magnesium di (methoxide), magnesium di (ethoxide), magnesium di (isopropoxide), magnesium di (potassium-tertiary butoxide), and the like.

  Among these bases, alkali metal alkoxides are preferable, and sodium-tertiary butoxide and potassium-tertiary butoxide are particularly preferable from the viewpoint of improving the yield of the charge transport material.

  Solvents used in the charge transport material synthesis step of the method for producing an electrophotographic photosensitive member of the present invention include aromatic hydrocarbons such as benzene, toluene and xylene, and rings such as monoglyme, diglyme, tetrahydrofuran and 1,4-dioxane. And a formula or acyclic ether compound. Among these, xylene and 1,4-dioxane are preferable.

  The charge transport material synthesis step of the method for producing an electrophotographic photosensitive member of the present invention can be performed under normal pressure or in air, but may be performed under pressure. The reaction temperature is preferably 50 to 200 ° C., and more preferably 150 ° C. or less from the viewpoint of reaction selectivity. In addition, the reaction time depends on the type of raw material, catalyst, base, solvent, etc. used, the amount used and the reaction temperature, but from the viewpoint of reaction selectivity, the reaction time is preferably shorter. It is preferably 2 minutes to 120 hours.

  The halogenated aromatic compound or halogenated heterocyclic compound, which is a raw material of the charge transport material used in the electrophotographic photoreceptor of the present invention, may be any material as long as it has a structure corresponding to the structure of the charge transport material. Depending on the structure, one or more suitable substituents can be introduced. Examples of the substituent include alkyl groups such as methyl group, ethyl group, and propyl group, alkoxy groups such as methoxy group and ethoxy group, fluorinated alkyl groups such as trifluoromethyl group and pentafluoroethyl group, dimethylamino group, and the like. Group, an alkylamino group such as diethylamino group and diphenylamino group, a dialkylamino group, an arylamino group, and a diarylamino group. The aromatic compound is a cyclic hydrocarbon having aromaticity and a derivative thereof, and examples thereof include aromatic hydrocarbons such as a benzene derivative, a biphenyl derivative, a terphenyl derivative, a naphthalene derivative, and an anthracene derivative. . Examples of the heterocyclic compound include heterocyclic hydrocarbons such as furan, pyrrole, thiophene, and pyridine.

  Examples of the halogenated aromatic compound and the halogenated heterocyclic compound include chloroaromatic compounds such as chlorobenzene, 1-chloro-4-methylbenzene, 1-chloro-2,4-dimethylbenzene, 1-chloronaphthalene, Bromobenzene, 1-bromo-4-methylbenzene, 1-bromo-2,4-dimethylbenzene, 1-bromo-3,4-dimethylbenzene, 4-bromobiphenyl, 2-bromo-9,9-dimethylfluorene, Brominated aromatic compounds such as 1-bromonaphthalene, 4-bromoterphenyl, 6-bromobenzofuran, 6-bromobenzothiophene, 2,8-dibromodibenzothiophene, iodobenzene, 1-iodo-4-methylbenzene, 1-iodo-2,4-dimethylbenzene, 1-iodo-3,4-dimethylbenzene, 1- Examples thereof include iodoaromatic compounds such as dobiphenyl, 2-iodo-9,9-dimethylfluorene, and 1-iodonaphthalene. From the viewpoint of reaction efficiency and electrophotographic characteristics of the produced charge transport material, brominated aroma Group compounds are preferred.

  The amine compound which is another raw material of the charge transport material used in the electrophotographic photoreceptor of the present invention has a structure corresponding to the structure of the charge transport material or the structure of the intermediate during the synthesis of the charge transport material. Any amine compound (secondary amine, primary amine, etc.) may be used.

  The charge transport material used in the electrophotographic photosensitive member of the present invention is synthesized by amination reaction of a compound synthesized in the charge transport material synthesis step, that is, a halogenated aromatic compound or a halogenated heterocyclic compound with an amine compound. And a compound having a skeleton in which three aromatic rings are bonded to a nitrogen atom (a triarylamine compound or a derivative thereof).

  Hereinafter, preferred examples of the charge transport material will be shown.

  In the above formulas (5-14) to (5-17), E and E ′ each independently represent a monovalent end group, and n represents the number of structures in parentheses or the average degree of polymerization.

  Next, the configuration of the electrophotographic photosensitive member of the present invention will be described.

  The electrophotographic photoreceptor is generally an electrophotographic photoreceptor having a photosensitive layer on a support.

  The photosensitive layer is separated into a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material even if it is a single layer type photosensitive layer containing the charge transporting material and the charge generating material in the same layer. A laminated type (functional separation type) photosensitive layer may be used, but a laminated type photosensitive layer is preferred from the viewpoint of electrophotographic characteristics. The laminated photosensitive layer has a normal layer type photosensitive layer laminated in the order of the charge generation layer and the charge transport layer from the support side, and a reverse layer type photosensitive layer laminated in the order of the charge transport layer and the charge generation layer from the support side. However, a normal photosensitive layer is preferred from the viewpoint of electrophotographic characteristics. Further, the charge generation layer may have a laminated structure, and the charge transport layer may have a laminated structure.

  In the present invention, the “layer containing a charge transport material” means that when the photosensitive layer is a single layer type photosensitive layer, the single layer type photosensitive layer is a “layer containing a charge transport material”. In the case where is a laminated photosensitive layer, the charge transport layer is a “layer containing a charge transport material” among the photosensitive layers. Further, when the electrophotographic photoreceptor has two or more “layers containing a charge transport material”, at least one of them may be a “layer containing a charge transport material” as defined in the present invention.

  The support only needs to have conductivity (conductive support). For example, a support made of metal (made of alloy) such as aluminum, aluminum alloy, copper, chromium, nickel, zinc, and stainless steel is used. be able to. Moreover, the said metal support body and plastic support body which have a layer in which aluminum, an aluminum alloy, an indium oxide tin oxide alloy etc. were formed into a film by vacuum deposition can also be used. In addition, a support in which conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles are impregnated into plastic or paper together with an appropriate binder resin, or a plastic support having a conductive binder resin, etc. Can also be used. In addition, examples of the shape of the support include a cylindrical shape and a belt shape, and a cylindrical shape is preferable.

  The surface of the support may be subjected to cutting treatment, roughening treatment, alumite treatment, etc. for the purpose of preventing interference fringes due to scattering of laser light or the like.

  Between the support and the photosensitive layer (charge generation layer, charge transport layer) or an intermediate layer described later, there is a conductive layer for the purpose of preventing interference fringes due to scattering of laser light or the like and covering the scratches on the support. It may be provided.

  The conductive layer can be formed by dispersing conductive particles such as carbon black, metal particles, and metal oxide particles in a binder resin.

  The thickness of the conductive layer is preferably 5 to 40 μm, and more preferably 10 to 30 μm.

  Further, an intermediate layer having a barrier function or an adhesive function may be provided between the support or the conductive layer and the photosensitive layer (charge generation layer, charge transport layer). The intermediate layer is formed for the purpose of improving the adhesion of the photosensitive layer, improving the coating property, improving the charge injection property from the support, and protecting the photosensitive layer from electrical breakdown.

  The intermediate layer is acrylic resin, allyl resin, alkyd resin, ethyl cellulose resin, ethylene-acrylic acid copolymer, epoxy resin, casein resin, silicone resin, gelatin resin, nylon, phenol resin, butyral resin, polyacrylate resin, polyacetal resin, polyamide Imide resin, polyamide resin, polyallyl ether resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyvinyl alcohol resin, polybutadiene resin, polypropylene resin, urea resin, etc. It can be formed using a material such as aluminum.

  The thickness of the intermediate layer is preferably 0.05 to 5 μm, and more preferably 0.3 to 1 μm.

  Examples of the charge generating material used in the electrophotographic photosensitive member of the present invention include azo pigments such as monoazo, disazo, and trisazo, phthalocyanine pigments such as metal phthalocyanine and nonmetal phthalocyanine, indigo pigments such as indigo and thioindigo, Perylene pigments such as perylene acid anhydride and perylene imide, polycyclic quinone pigments such as anthraquinone and pyrenequinone, squarylium dyes, pyrylium salts and thiapyrylium salts, triphenylmethane dyes, selenium, selenium-tellurium, amorphous Examples thereof include inorganic substances such as silicon, quinacridone pigments, azulenium salt pigments, cyanine dyes, xanthene dyes, quinoneimine dyes, styryl dyes, cadmium sulfide, and zinc oxide. These charge generation materials may be used alone or in combination of two or more.

  When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin used for the charge generation layer include acrylic resin, allyl resin, alkyd resin, epoxy resin, diallyl phthalate resin, silicone resin, styrene-butadiene copolymer, nylon, Phenol resin, butyral resin, benzal resin, polyacrylate resin, polyacetal resin, polyamideimide resin, polyamide resin, polyallyl ether resin, polyarylate resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, Polysulfone resin, polyvinyl acetal resin, polybutadiene resin, polypropylene resin, methacrylic resin, urea resin, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, etc. It is. In particular, a butyral resin is preferable. These can be used singly or in combination of two or more as a mixture or copolymer.

  The charge generation layer can be formed by applying and drying a charge generation layer coating solution obtained by dispersing a charge generation material together with a binder resin and a solvent. Examples of the dispersion method include a method using a homogenizer, an ultrasonic disperser, a ball mill, a sand mill, a roll mill, a vibration mill, an attritor, a liquid collision type high-speed disperser, and the like. The ratio between the charge generating material and the binder resin is preferably in the range of 1: 0.3 to 1: 4 (mass ratio).

  The solvent used in the coating solution for the charge generation layer is selected from the solubility and dispersion stability of the binder resin and charge generation material used, and the organic solvents include alcohols, sulfoxides, ketones, ethers, esters, aliphatic halogens. Hydrocarbons and aromatic compounds.

  The thickness of the charge generation layer is preferably 5 μm or less, and more preferably 0.1 to 2 μm.

  In addition, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers, and the like can be added to the charge generation layer as necessary.

  At least one of the charge transport materials used in the electrophotographic photoreceptor of the present invention is a charge transport material synthesized by the charge transport material synthesis step. In addition, you may use together the charge transport material synthesize | combined by the other method in the range which does not impair the effect of this invention. Examples of charge transport materials that can be used in combination include triarylamine compounds, hydrazone compounds, styryl compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, and triarylmethane compounds synthesized by other methods. .

  When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin used for the charge transport layer include acrylic resin, acrylonitrile resin, allyl resin, alkyd resin, epoxy resin, silicone resin, nylon, phenol resin, phenoxy resin, Butyral resin, polyacrylamide resin, polyacetal resin, polyamideimide resin, polyamide resin, polyallyl ether resin, polyarylate resin, polyimide resin, polyurethane resin, polyester resin, polyethylene resin, polycarbonate resin, polystyrene resin, polystyrene resin, polysulfone resin, Examples include polyvinyl butyral resin, polyphenylene oxide resin, polybutadiene resin, polypropylene resin, methacrylic resin, urea resin, vinyl chloride resin, and vinyl acetate resin. . These can be used singly or in combination of two or more as a mixture or copolymer. In particular, polyarylate resin, polycarbonate resin and the like are preferable. The viscosity average molecular weight (Mv) of the polycarbonate resin is preferably 20000 to 80000. The weight average molecular weight (Mw) of the polyarylate resin is preferably 50,000 to 200,000, and more preferably 80000 to 150,000.

  The charge transport layer can be formed by applying and drying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent. The ratio of the charge transport material and the binder resin is preferably in the range of 1:10 to 12:10 (mass ratio), and from the viewpoint of charge transport ability and layer strength, 2:10 to 10:10 (mass ratio). The range of is more preferable.

  Solvents used in the charge transport layer coating solution include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as toluene and xylene, ethers such as 1,4-dioxane and tetrahydrofuran, and chlorobenzene. , Hydrocarbons substituted with halogen atoms such as chloroform and carbon tetrachloride are used.

  The thickness of the charge transport layer is preferably 5 to 40 μm, and more preferably 10 to 25 μm.

  In addition, an antioxidant, an ultraviolet absorber, a plasticizer, and the like can be added to the charge transport layer as necessary.

  When the photosensitive layer is a single-layer type photosensitive layer, the single-layer type photosensitive layer is a coating for a single-layer type photosensitive layer obtained by dispersing the charge generation material and the charge transport material together with the binder resin and the solvent. It can be formed by applying a liquid and drying.

  Further, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. The protective layer can be formed by applying and drying a protective layer coating solution obtained by dissolving the various binder resins described above in a solvent.

  The binder resin used for the protective layer is preferably a high molecular weight thermoplastic resin such as a high molecular weight polycarbonate resin or a high molecular weight polyarylate resin, or a curable resin such as a phenol resin, an acrylic resin or an epoxy resin.

  The thickness of the protective layer is preferably 0.5 to 10 μm, and particularly preferably 1 to 5 μm.

  When applying the coating liquid for each of the above layers, for example, a coating method such as a dip coating method (dip coating method), a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method, a blade coating method, or the like should be used. Can do.

  If necessary, a material for imparting lubricity to the surface of the electrophotographic photosensitive member may be added to the surface layer of the electrophotographic photosensitive member. Examples of such materials include fluorine atom-containing resin particles such as tetrafluoroethylene resin particles, silica particles, and alumina particles.

  When the protective layer is provided, the protective layer is the surface layer of the electrophotographic photosensitive member, and when the protective layer is not provided, the photosensitive layer is the surface layer of the electrophotographic photosensitive member. Further, when the photosensitive layer is a surface layer of an electrophotographic photosensitive member, when the photosensitive layer is a single layer type photosensitive layer, the single layer type photosensitive layer is a surface layer of the electrophotographic photosensitive member, and the photosensitive layer is In the case of the normal type photosensitive layer, the charge transport layer is the surface layer of the electrophotographic photosensitive member, and in the case of the reverse layer type photosensitive layer, the charge generating layer is the surface layer of the electrophotographic photosensitive member.

  FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 1, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is rotationally driven in a direction of an arrow about a shaft 2 at a predetermined peripheral speed.

  The surface of the electrophotographic photosensitive member 1 that is rotationally driven is uniformly charged to a predetermined positive or negative potential by a charging unit (primary charging unit: charging roller or the like) 3, and then subjected to slit exposure, laser beam scanning exposure, or the like. Exposure light (image exposure light) 4 output from exposure means (not shown) is received. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the surface of the electrophotographic photosensitive member 1.

  The electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is developed with toner contained in the developer of the developing means 5 to become a toner image. Next, the toner image formed and supported on the surface of the electrophotographic photoreceptor 1 is transferred from a transfer material supply means (not shown) to the electrophotographic photoreceptor 1 and the transfer means by a transfer bias from a transfer means (transfer roller or the like) 6. 6 (contact portion) is sequentially transferred onto a transfer material (paper or the like) P taken out and fed in synchronization with the rotation of the electrophotographic photosensitive member 1.

  The transfer material P that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member 1 and introduced into the fixing means 8 to receive the image fixing, and is printed out as an image formed product (print, copy). Is done.

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by a cleaning means (cleaning blade or the like) 7 to remove the developer (toner) remaining after transfer, and further from a pre-exposure means (not shown). After being subjected to charge removal processing by pre-exposure light (not shown), it is repeatedly used for image formation. As shown in FIG. 1, when the charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.

  Among the above-described components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6 and the cleaning unit 7, a plurality of components are housed in a container and integrally combined as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. In FIG. 1, an electrophotographic photosensitive member 1, a charging unit 3, a developing unit 5 and a cleaning unit 7 are integrally supported to form a cartridge, and an electrophotographic apparatus is provided using a guide unit 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is detachable from the main body.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these. In the examples, “part” means “part by mass”.

(Charge transport material synthesis process example 1)
Synthesis of a charge transport material having the structure represented by the above formula (5-3) A bis (3,4-dimethylphenyl) amine as an amine compound was added to a 200 ml three-necked flask equipped with a Dimro-type condenser, thermometer and stirrer. 11.3 g (0.05 mol), 11.7 g (0.05 mol) of 1-bromo-4-phenylbenzene as a halogenated aromatic compound, 5.60 g (0.07 mol) of sodium tertiary butoxide as a base, amino substitution 0.432 g (0.002 mol) of an amino-substituted phosphorus compound having the structure represented by the above formula (1-1) as a phosphorus compound, 0.112 g (0.0005 mol) of Pd (Oac) ₂ as a metal-containing compound, and xylene as a solvent Add 90ml, heat to 130 ° C in an oil bath, stir for 1 hour to react, then room temperature In and allowed to cool.

  Next, the reaction solution was neutralized with hydrochloric acid, toluene was added, the organic layer was treated with alumina and dried over calcium chloride, and then the organic solvent was distilled off.

  The obtained crude product was purified by a silica gel column using 10 times the amount of silica gel as the composition amount and a mixed solvent of toluene / hexane = 1/1 as a developing solvent, and the above formula (5-3) 17.1 g of a charge transport material having the structure shown was obtained (yield: 91.2% by mass). The results are shown in Table 1.

(Charge transport material synthesis process examples 2 to 12)
A charge transport material was synthesized in the same manner as in the charge transport material synthesis step example 1 except that the amino-substituted phosphorus compound and the metal-containing compound were changed as shown in Table 1 in the charge transport material synthesis step example 1. The results are shown in Table 1.

(Charge transport material synthesis process examples C1 to C3)
The charge transport material is the same as the charge transport material synthesis step example 1 except that the phosphorus compound is changed to an amino-substituted phosphorus compound having a structure represented by the following formulas (6-1), (6-2), and (6-3). A charge transport material was synthesized in the same manner as in Synthesis Example 1. The results are shown in Table 1.

(Charge transport material synthesis process example C4)
A charge transport material having a structure represented by the above formula (5-3) was synthesized by a synthesis method using the Ullmann reaction.

In a 200 ml three-necked flask, 11.3 g (0.05 mol) of bis (3,4-dimethylphenyl) amine as an amine compound, 14.0 g (0.05 mol) of 1-iodo-4-phenylbenzene as a halogenated aromatic compound, Add 9.53 g (0.15 mol) of copper powder, 13.8 g (0.1 mol) of potassium carbonate, 100 ml of o-dichlorobenzene as a solvent, heat to 200 ° C. in an oil bath, and stir for 6 hours to react. And then allowed to cool to room temperature.
Next, after filtering the solid in the reaction solution, toluene was added, the organic layer was treated with alumina and dried over calcium chloride, and then the organic solvent was distilled off.

  The obtained crude product was purified by a silica gel column using 10 times the amount of silica gel with respect to the composition amount and using a mixed solvent of toluene: hexane = 1: 1 as a developing solvent, and represented by the above formula (5-3). A charge transport material having the structure shown was obtained in 12.3 g (yield: 65.3% by mass). The results are shown in Table 1.

(Charge transport material synthesis step example 13)
Synthesis of charge transport material having the structure represented by the above formula (5-13) Bis (2,4-dimethylphenyl) as a halogenated aromatic compound was added to a 500 ml three-necked reaction vessel equipped with a cooling tube and a mechanical stirrer. 36.4 g (0.05 mol) of [4- (4-{(2,4-dimethylphenyl) [4- (4-bromophenyl) phenyl] amino} phenyl) phenyl] amine as the amine compound (2,4- Dimethylphenyl) {8-[(2,4dimethylphenyl) amino] dibenzo [b] benzo [b] thiophen-2-yl} amine 10.6 g (0.025 mol), Pd (Oac) ₂ 0 as the metal-containing compound 2. 57 g (0.0025 mol), an amino-substituted phosphorus compound having a structure represented by the above formula (1-1) as an amino-substituted phosphorus compound g (0.01 mol), sodium as base - tertiary butoxide 6.7 g (0.07 mol), was placed xylene 200 ml, a nitrogen gas atmosphere, heated in an oil bath and refluxed for 4 hours. After completion of the reaction, it was allowed to cool to room temperature.

  Next, extraction with toluene / water and washing with aqueous hydrochloric acid were performed, and then the organic layer was evaporated under reduced pressure.

  The obtained crude product was purified by a silica gel column using 10 times the amount of silica gel as the composition amount and a mixed solvent of toluene / hexane = 1/1 as a developing solvent, and the above formula (5-13) 38.8 g of a charge transport material having the structure shown was obtained (yield 90.4% by mass). The results are shown in Table 2.

(Charge transport material synthesis process examples 14 to 24, C5 to C7)
A charge transport material was synthesized in the same manner as in the charge transport material synthesis step example 13 except that the amino-substituted phosphorus compound and the metal-containing compound were changed as shown in Table 2 in the charge transport material synthesis step example 13. The results are shown in Table 2.

(Charge Transport Material Synthesis Process Example 25)
Synthesis of a charge transport material having the structure represented by the above formula (5-14) 12.1 g of 3,4-dimethylphenylamine as an amine compound in a 500 ml three-necked flask equipped with a Dimro-type condenser, thermometer and stirrer (0.10 mol), 31.2 g (0.10 mol) of 1,4-dibromobiphenyl as a halogenated aromatic compound, 27.3 g (0.30 mol) of sodium-tertiary butoxide as a base, and the above formula as an amino-substituted phosphorus compound (32) Amino-substituted phosphorus compound having a structure represented by (1-1) 4.32 g (0.02 mol), Pd (Oac) ₂ 1.12 g (0.005 mol) as a metal-containing compound, 200 ml of xylene as a solvent, and oil After heating to 130 ° C in a bath and stirring for 1 hour to react, 3,4-dimethylbutane Mobenzen 0.93 g (0.0050 mol) was added and stirred for 30 minutes. Then, it stood to cool to room temperature.

  Next, the reaction solution was neutralized with hydrochloric acid, toluene was added, the organic layer was treated with alumina and dried over calcium chloride, and then the organic solvent was distilled off.

  The obtained crude product was purified by a silica gel column using 10 times the amount of silica gel with respect to the composition amount and using a mixed solvent of toluene / hexane = 1/1 as a developing solvent, and the above formula (5-14) 23.8 g of a charge transport material having the structure shown was obtained (yield: 87.3% by mass). The charge transport material having the structure represented by the above formula (5-14) obtained in this example has an average polymerization degree n of 6, E of 2,4-dimethylphenyl group, and E ′ of 2,4-dimethylphenyl. The polymer had a weight average molecular weight (Mw) of 1700 and a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 1.52. In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are the values by a gel permission average molecular weight measurement. The results are shown in Table 3.

(Charge transport material synthesis process examples 26 to 36, C8 to C10)
In the charge transport material synthesis step example 25, a charge transport material was synthesized in the same manner as the charge transport material synthesis step example 25 except that the amino-substituted phosphorus compound and the metal-containing compound were changed as shown in Table 3. The results are shown in Table 3. In addition, E and E ′ of those synthesized in the charge transport material synthesis process examples 26 to 36 and C8 to C10 are the same as those synthesized in the charge transport material synthesis process example 25.

Example 1
An aluminum cylinder having a diameter of 30 mm and a length of 357 mm was used as a support (cylindrical support).

Next, 10 parts of SnO ₂ coated barium sulfate (conductive particles), 2 parts of titanium oxide (for resistance adjustment), 6 parts of phenol resin, 0.001 part of silicone oil (leveling agent), and 4 parts of methanol / methoxy A mixed solvent of 16 parts of propanol was dispersed in a sand mill apparatus using glass beads having a diameter of 1 mm for 2 hours to prepare a coating solution for a conductive layer.

  This conductive layer coating solution was applied by dip coating on a support and thermally cured at 140 ° C. for 30 minutes to form a conductive layer having a thickness of 15 μm.

  Next, 3 parts of N-methoxymethylated nylon and 3 parts of copolymer nylon were dissolved in a mixed solvent of 65 parts of methanol / 30 parts of n-butanol to prepare an intermediate layer coating solution.

  This intermediate layer coating solution was dip coated on the conductive layer and dried at 100 ° C. for 10 minutes to form an intermediate layer having a thickness of 0.5 μm.

  Next, strong peaks at 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction 4 parts of a crystalline form of hydroxygallium phthalocyanine crystal having 2 parts, 2 parts of polyvinyl butyral (trade name: S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 60 parts of cyclohexanone are mixed with a sand mill using glass beads having a diameter of 1 mm. After time dispersion, 100 parts of ethyl acetate was added to prepare a charge generation layer coating solution.

  This charge generation layer coating solution was dip coated on the intermediate layer and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm.

  Next, 10 parts of the charge transport material having the structure represented by the above formula (5-3) synthesized in the charge transport material synthesis step example 1, and polycarbonate resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) ) 10 parts was dissolved in 80 parts of monochlorobenzene to prepare a coating solution for charge transport layer.

  This charge transport layer coating solution was dip coated on the charge generation layer and dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 25 μm.

  In this way, an electrophotographic photoreceptor having a surface layer as a charge transport layer was produced.

The produced electrophotographic photosensitive member is modified so that the exposure amount from the exposure means is 0.4 μJ / cm ^{2 on} the surface of the electrophotographic photosensitive member of the Canon Co., Ltd., copy machine GP215 (contact charging method). 30000 images in a mode in which A4 size plain paper is continuously printed in a room temperature and low humidity environment (23 ° C., 10% RH). Output was done.

  The initial dark part potential (VD), light part potential (VL), and residual potential (VSL) were measured.

Further, the dark part potential (VD ₃₀₀₀₀ ), the bright part potential (VL ₃₀₀₀₀ ) and the residual potential (VSL ₃₀₀₀₀ ) after the output of 30,000 sheets were measured, and the dark part potential fluctuation (ΔVD = | VD) when the electrophotographic photosensitive member was repeatedly used. ₃₀₀₀₀ −VD |), bright part potential fluctuation (ΔVL = | VL ₃₀₀₀₀ −VL |) and residual potential fluctuation (ΔVSL = | VSL ₃₀₀₀₀ −VSL |) were evaluated.

  The surface potential of the electrophotographic photosensitive member is measured at the position of the developing device by exchanging the jig and the developing device fixed so that the potential measuring probe is positioned 180 mm from the end of the electrophotographic photosensitive member. It was. The evaluation results are shown in Table 4.

(Examples 2 to 12, Comparative Examples 1 to 4)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the charge transport material was changed to the charge transport material synthesized in the charge transport material synthesis process example shown in Table 4 in Example 1. The evaluation results are shown in Table 4.

(Examples 13-24, Comparative Examples 5-7)
In Example 1, an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the charge transport material was changed to the charge transport material synthesized in the charge transport material synthesis step example shown in Table 5, respectively. However, the charge transport material was 5 parts, and the polycarbonate resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics) was 10 parts. The evaluation results are shown in Table 5.

(Examples 25-36, Comparative Examples 8-10)
In Example 1, an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the charge transport material was changed to the charge transport material synthesized in the charge transport material synthesis step example shown in Table 6, respectively. However, the charge transport material was 4 parts, and the polycarbonate resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics) was 10 parts. The evaluation results are shown in Table 6.

1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Cleaning means 8 Fixing means 9 Process cartridge 10 Guide means P Transfer material

Claims (14)

A method for producing an electrophotographic photosensitive member having a layer containing a charge transport material on a support,
A charge transport material synthesis step for synthesizing the charge transport material by an amination reaction of a halogenated aromatic compound or a halogenated heterocyclic compound with an amine compound in the presence of a base, and a charge synthesized by the charge transport material synthesis step A coating liquid preparation step for preparing a coating liquid for a layer containing the charge transport material using a transport material, and a layer containing the charge transport material using the coating liquid prepared by the coating liquid preparation step A method of producing an electrophotographic photosensitive member having a layer forming step,
In the charge transport material synthesis step, a metal-containing compound and an amino-substituted phosphorus compound having a phosphorus atom bonded to at least one amino group are used as a catalyst. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the amino-substituted phosphorus compound having a phosphorus atom to which at least one amino group is bonded is a compound having a structure represented by the following formula (1).

(In Formula (1), R < ¹¹ > -R < ¹³ > shows a C1-C4 alkyl group each independently.) The method for producing an electrophotographic photoreceptor according to claim 1, wherein the amino-substituted phosphorus compound having a phosphorus atom to which at least one amino group is bonded is a compound having a structure represented by the following formula (2).

(In formula (2), R ^{21 to} R ²³ each independently represents an alkyl group having 1 to 4 carbon atoms, and R ²⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 2. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the amino-substituted phosphorus compound having a phosphorus atom to which at least one amino group is bonded is a compound having a structure represented by the following formula (3).

(In formula (3), R ^{31 to} R ³⁴ each independently represents an alkyl group having 1 to 4 carbon atoms.) The method for producing an electrophotographic photosensitive member according to claim 4, wherein at least one of R ³³ and R ^{34 in} the formula (3) is a tertiary butyl group. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the amino-substituted phosphorus compound having a phosphorus atom to which at least one amino group is bonded is a compound having a structure represented by the following formula (4).

(In formula (4), R ^{41 to} R ⁴⁵ each independently represents an alkyl group having 1 to 4 carbon atoms.) The process for producing an electrophotographic photosensitive member according to claim 6, wherein R ⁴³ in the formula (4) is a tertiary butyl group.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the metal of the metal-containing compound used as a catalyst in the charge transport material synthesis step is palladium. The metal-containing compound used as a catalyst in the charge transport material synthesis step is Pd (Oac) ₂ , Pd (acac) ₂ , (CH ₃ CN) ₂ Pd (NO ₂ ) Cl, (C ₁₀ H ₈ N ₂ ) _2. The method for producing an electrophotographic photosensitive member according to claim 8, which is at least one metal-containing compound selected from the group consisting of PdCl ₂ , Pd ₂ (dba) ₃ and PdCl ₂ .   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the base used in the charge transport material synthesis step is an alkali metal alkoxide.   The method for producing an electrophotographic photosensitive member according to claim 1, wherein the halogenated aromatic compound used in the charge transport material synthesis step is a brominated aromatic compound.   An electrophotographic photoreceptor produced by the production method according to claim 1.   The electrophotographic photosensitive member according to claim 12 and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means are integrally supported and detachable from the main body of the electrophotographic apparatus. A process cartridge characterized by that. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 12, a charging unit, an exposure unit, a developing unit, and a transfer unit.

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