JP2006154801A - Electrophotographic photoreceptor, electrophotographic photoreceptor material and method for manufacturing the same, electrophotographic photoreceptor cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent electrophotographic photoreceptor that has high sensitivity and excellent long-term stability and is easily manufactured and relatively inexpensive. <P>SOLUTION: A triarylamine compound is used as a charge transporting substance, the compound synthesized from an amine compound and aryl halide as source materials by using a catalyst prepared by mixing tricycloalkylphosphine and a palladium compound in a 5/1 to 15/1 ratio. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrophotographic photosensitive member, a material for an electrophotographic photosensitive member, a manufacturing method thereof, an electrophotographic photosensitive member cartridge, and an image forming apparatus. More specifically, an electrophotographic photoreceptor using a triarylamine compound as a charge transport material, an electrophotographic photoreceptor material comprising the triarylamine compound, a method for producing the same, and an electrophotographic photoreceptor using the electrophotographic photoreceptor. The present invention relates to a cartridge and an image forming apparatus.

  In recent years, so-called function-separated type photoreceptors have been proposed in which the functions of charge carrier generation and transport are assigned to different compounds, and layers containing these compounds are individually provided and laminated. Since the electrophotographic photosensitive member having this laminated structure is effective for high sensitivity, surface strength, ozone resistance, etc., development of an organic electrophotographic photosensitive member of this type has become the mainstream, and practical use is It is done.

  Generally, as a charge carrier transport medium used in an electrophotographic photoreceptor, there are a case where a polymer charge transport material is used and a case where a low molecular weight photoconductive compound is dispersed and dissolved in a binder polymer. Many organic compounds have been proposed as these charge transport materials, but in particular, compounds having a triarylamine structure are easier to design and have a higher hole mobility. Since many of them have excellent characteristics, many compounds suitable for charge transport materials have been proposed since then.

  However, even when these triarylamine compounds are used as charge transport materials, the sensitivity characteristics of the photoconductor are not always sufficient, such as potential fluctuations during repeated use, image defects under low and high humidity, etc. There are points to be improved.

  Furthermore, the characteristics of the electrophotographic photosensitive member are influenced not only by the structure of the charge transport material but also by the manufacturing method thereof. In particular, it has been found that the influence of the manufacturing method of the charge transport material appears strongly with respect to the change in the residual potential and the image characteristics. Such effects cannot be explained only by the purity and impurities of the charge transport material, and there is a strong demand for a method for producing an arylamine that is effective in electrical characteristics.

  Generally, an amine compound used for a charge transport material is synthesized by a condensation reaction between a corresponding aryl halide and an amine compound. As an example, a method of synthesizing a corresponding iodobenzene and an amine compound using a copper catalyst (Ullmann reaction) is known. However, in the reaction using these copper catalysts, a large amount of copper catalyst is used, a high reaction temperature is required, and the reaction time is long. Coloring impurities and decomposition products that adversely affect electrophotographic characteristics are by-produced. Therefore, it is difficult to purify arylamines from the reaction system, and there is a problem that high cost is required for purification.

  In contrast, a synthesis method has recently been reported in which amines are synthesized using an aryl halide and an amine compound as raw materials and an organic phosphine compound and a palladium compound as a catalyst in the presence of a base (Non-patent Document 1). -3 etc.) Since this reaction proceeds under relatively mild conditions, it is considered that the amount of impurities generated is significantly reduced compared to the Ullmann reaction.

  As a synthesis method of a triarylamine compound to which this reaction is applied, Patent Document 1 and Patent Document 2 disclose a synthesis method of a triarylamine compound using a trialkylphosphine and a palladium compound as a catalyst. According to these documents, tri-tert-butylphosphine has the highest catalytic activity among various trialkylphosphines. By using this, aryl bromide which is advantageous in terms of cost is used as a raw material. There is a description that it is possible to obtain merits such as being able to be performed, the reaction temperature being relatively low, the reaction time being shortened, and the yield being very good.

  Patent Document 3 discloses a method for synthesizing a triarylamine compound using a trialkyl / arylphosphine compound and a palladium compound as catalysts.

  Further, Patent Document 4 discloses a method for synthesizing a triarylamine compound from an aryl iodide and an amine compound using a 4/1 complex-forming substance of tricyclohexylphosphine and a palladium acetate compound as a catalyst. .

Japanese Patent No. 3161360 Japanese Patent Laid-Open No. 10-310561 JP 2001-356507 A JP 2003-226673 A Tetrahedron. Lett., Vol. 36, No. 21, 3609 (1995) J. Am. Chem. Soc., Vol.120, 9722 (1998) J. Org. Chem., Vol. 61, 1133 (1996)

  However, in the methods described in Patent Document 1 and Patent Document 2, tri-tert-butylphosphine used as a catalyst is very expensive, and the manufacturing cost is high, and the method is very unstable in the air and is difficult to handle. There are problems such as difficulty.

    In the method described in Patent Document 3, impurities resulting from the catalyst remain in the product charge transporting material (triarylamine compound) although a trace amount remains, which adversely affects the electrical characteristics of the electrophotographic photosensitive member. There is a problem of giving. In some cases, the catalytic activity is insufficient and the coupling reaction may not be successful.

  In the method described in Patent Document 4, aryl iodide having high reaction activity is used as a raw material. However, since aryl iodide is relatively expensive and has a large molecular weight, when used as a raw material, the amount of use (weight) increases, and the production cost increases, which is economically disadvantageous. Furthermore, when a 4/1 complex-forming substance of tricyclohexylphosphine and a palladium acetate compound described in the same document is used as a catalyst component, a halide other than aryl iodide (inexpensive aryl bromide or aryl chloride) As a raw material, sufficient catalytic activity cannot be obtained, so unresolved issues such as a decrease in productivity due to an extended reaction time and a deterioration in the electrical characteristics of the electrophotographic photosensitive member due to a decrease in the purity of the product. It is left. In particular, when the starting amine compound is a primary amine, if the molar ratio of phosphine / palladium is not 5/1 or more, the yield of the charge transport material and There is also a problem that satisfactory results cannot be obtained for any of the purities.

  The present invention was devised in view of the above problems, and its purpose is an electrophotographic photosensitive member using a triarylamine compound as a charge transport material, which has high sensitivity, excellent durability stability, and production. To provide an excellent electrophotographic photosensitive member that is easy and relatively inexpensive, to provide such an electrophotographic photosensitive member, and to provide an excellent material for an electrophotographic photosensitive member and a method for producing the same, and Another object of the present invention is to provide an electrophotographic photosensitive member cartridge and an image forming apparatus using the electrophotographic photosensitive member.

  As a result of intensive studies to solve the above problems, the present inventors have found that the storage stability, safety, and safety of the catalyst ligands such as tri-tert-butylphosphine described in Patent Document 1 and Patent Document 2 are improved. It has been found that sufficient catalytic activity is exhibited by using a tricycloalkylphosphine compound, which is superior in cost, in combination with a palladium compound as a catalyst ligand when synthesizing a triarylamine compound. Furthermore, by using the above catalyst ligand, an inexpensive aryl chloride or aryl bromide can be used as a raw material, and when the obtained triarylamine compound is used for an electrophotographic photoreceptor as a charge transport material. The present invention was completed by finding that it exhibited excellent characteristics such as potential stability during durability and environmental stability.

  That is, the gist of the present invention is an electrophotographic photosensitive member in which at least a photosensitive layer containing a charge generation material and a charge transport material is provided on a conductive support, wherein the charge transport material is an amine compound and an aryl compound. An electrophotographic photoreceptor characterized in that it is a triarylamine compound synthesized using a halide as a raw material and a catalyst in which a tricycloalkylphosphine and a palladium compound are mixed at a ratio of 5/1 to 15/1. (Claim 1).

  Here, the triarylamine compound is preferably synthesized in the presence of a base (Claim 2), and is preferably synthesized under nitrogen flow (Claim 3).

（一般式（１）及び一般式（２）中、Ａ〜Ｉで表わされる環は、それぞれ独立して、置換基を有しても良いベンゼン環を表わす。） The triarylamine compound is preferably a compound represented by the following general formula (1) or the following general formula (2) (claim 4).

(In General Formula (1) and General Formula (2), the rings represented by A to I each independently represent an optionally substituted benzene ring.)

  Another object of the present invention is a material used for a photosensitive layer of an electrophotographic photosensitive member, which is composed of at least a triarylamine compound, and is made from an amine compound and an aryl halide as raw materials, and a tricycloalkylphosphine compound and a palladium compound. In the material for an electrophotographic photosensitive member, characterized in that it is synthesized using as a catalyst.

  A method for producing a material used for a photosensitive layer of an electrophotographic photoreceptor comprising at least a triarylamine compound, wherein an amine compound and an aryl halide are used as raw materials, and a tricycloalkylphosphine compound and a palladium compound are used as a catalyst. The present invention resides in a method for producing a material for an electrophotographic photosensitive member, comprising a step.

  Another object of the present invention is to provide the above-described electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image, and The electrophotographic photosensitive member cartridge includes at least one developing unit that develops the electrostatic latent image formed on the electrophotographic photosensitive member.

  Another object of the present invention is to provide the above-described electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, and an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image. And an image forming apparatus comprising a developing unit that develops the electrostatic latent image formed on the electrophotographic photosensitive member.

  The electrophotographic photoreceptor of the present invention has excellent characteristics such as high sensitivity, excellent durability stability, easy production, and relatively low cost. Further, according to the material for an electrophotographic photosensitive member of the present invention, such an excellent electrophotographic photosensitive member can be realized. Moreover, according to the method for producing a material for an electrophotographic photosensitive member of the present invention, the above-described material for an electrophotographic photosensitive member can be efficiently produced.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following descriptions, and can be implemented with appropriate modifications without departing from the gist of the present invention.

  The electrophotographic photosensitive member of the present invention is obtained by providing a photosensitive layer containing at least a charge generation material and a charge transport material on a conductive support, and the charge transport material is synthesized by a specific synthesis method. It is characterized by using a triarylamine compound.

  The charge transport material used in the electrophotographic photoreceptor of the present invention (hereinafter abbreviated as “charge transport material of the present invention” as appropriate) will be described first, and then the other details of the electrophotographic photoreceptor of the present invention will be described. Next, an image forming apparatus using the electrophotographic photosensitive member of the present invention will be described.

[1. Charge transport material)
The charge transport material of the present invention is a material composed of a triarylamine compound, which uses an amine compound and an aryl halide as raw materials, and a specific catalyst (a ratio of 5/1 to 15/1 of a tricycloalkylphosphine compound and a palladium compound). And the catalyst mixed in the above.

  Hereinafter, after first describing the tricycloalkylphosphine compound and the palladium compound used as the catalyst, the synthesis procedure of the triarylamine compound using this catalyst will be described in detail.

(Tricycloalkylphosphine compound)
A tricycloalkylphosphine compound is a compound having a structure in which three cycloalkyl groups are bonded to a phosphorus atom.

  The kind of individual cycloalkyl group is not particularly limited. The number of rings may be single or plural, and in the case of plural rings, they may be condensed with each other, but it is preferably a single ring. The number of carbon atoms in each ring is usually 3 or more, preferably 5 or more, and usually 8 or less, preferably 7 or less. The total number of carbon atoms in the cycloalkyl group is usually 9 or more, preferably 15 or more, and usually 24 or less, preferably 21 or less. Preferable specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc. Among them, a cyclohexyl group is preferable because of easy production.

  Each cycloalkyl group may further have a substituent. When it has a substituent, the type is not particularly limited as long as it does not violate the gist of the present invention. Examples include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, and butyl groups, and aryl groups having 6 to 12 carbon atoms such as phenyl and naphthyl groups. Of these, an alkyl group is preferable, and a methyl group is particularly preferable among the alkyl groups. However, each cycloalkyl group is preferably unsubstituted or, when having a substituent, preferably a methyl group, and most preferably unsubstituted.

When the three cycloalkyl groups have a substituent, they may all be the same including the substituent, or any two or three may be different from each other. However, from the viewpoint of ease of synthesis, all are preferably the same.
Also, any two or all three of these cycloalkyl groups may be linked to each other via any linking group.

  Specific examples of the tricycloalkylphosphine compound used in the present invention are shown below, but are not limited thereto.

  Among the above-exemplified tricycloalkylphosphine compounds, in view of the stability of the catalyst, tricyclohexylphosphine, tris (2-methylcyclohexyl) phosphine, and tricyclopentylphosphine are preferable. Among these, from the viewpoint of production cost, tricyclohexylphosphine is preferable. Is particularly preferred.

  In addition, any one of the tricycloalkylphosphine compounds may be used alone, or two or more thereof may be used in any combination and ratio.

  The tricycloalkylphosphine compound is superior in terms of storage stability and safety compared to tri-tert-butylphosphine described in Patent Document 1 and Patent Document 2. That is, tri-tert-butylphosphine and the like may emit smoke when contacted with air, or may ignite in some cases, whereas tricycloalkylphosphine compounds are exposed to air at room temperature for a short time. In addition, there is no risk of smoke or fire, and it can be handled relatively easily without losing its catalytic activity.

(Palladium compound)
Although it does not specifically limit as a palladium compound, For example, Tetravalent palladium compounds, such as sodium hexachloro palladium (IV) acid tetrahydrate and hexachloro palladium (IV) potassium tetrahydrate; Palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraminepalladium ( II), divalent palladium compounds such as dichloro (cycloocta-1,5-diene) palladium (II); tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex (0) Tetrakis (triphenylphosphine) Palladium compounds such as indium (0) and the like. Of these, palladium (II) acetate and palladium (II) chloride are preferable, and palladium (II) acetate is particularly preferable in view of catalytic activity. In addition, a palladium compound may be used individually by 1 type, and may use 2 or more types by arbitrary combinations and a ratio.

(Triarylamine compound)
The triarylamine compound synthesized using the above-described catalyst (tricycloalkylphosphine compound and palladium compound) is not particularly limited as long as it can be used as a charge transport material for an electrophotographic photoreceptor. However, it is preferable to have a triphenylamine structure from the viewpoint that the effects of the present invention can be remarkably obtained when synthesized using the above-mentioned catalyst, and among them, the following general formula (1) or the following general formula A compound represented by (2) is particularly preferred.

  In general formula (1) and general formula (2), the rings represented by A to I each independently represent a benzene ring which may have a substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, a vinyl group, and a butadienyl group. These substituents may be further substituted with an organic group such as an alkyl group, an alkoxy group, or an aryl group. The number of carbon atoms of the substituent is a value including those when further substituted with other organic groups, and is usually 2 or more, preferably 4 or more, and usually 30 or less, preferably 15 or less. It is. The number of substituents that each benzene ring has is usually from 0 to 4, and preferably from 0 to 2. In the case of having a plurality of substituents, these may be bonded to each other via a linking group or directly to form a ring structure.

  In particular, the triarylamine compound is preferably a compound represented by the following general formula (3), the following general formula (4), or the following general formula (5).

  In the above general formula (3), general formula (4), and general formula (5), R1 to R13 are each independently a hydrogen atom or an alkyl group or alkoxy which may have a substituent. Represents a group or an aryl group. In particular, an alkyl group and an aryl group are preferable, and an alkyl group is preferable from the viewpoint of the obtained effect. Of the alkyl groups, a methyl group is preferred.

  Y represents a hydrogen atom, an alkyl group, or an alkoxy group. Among these, a hydrogen atom or an alkyl group is preferable.

  l represents an integer of 1 to 3. 2 or 3 is preferable from the viewpoint of electrical characteristics, and 2 is particularly preferable from the viewpoint of solubility.

  m, n, o and p each independently represent an integer of 0 to 5. Among these, 1 or 2 is preferable. x represents 0 or 1; Of these, 0 is preferred.

  Specific examples of the above-described triarylamine compounds are shown below, but the triarylamine compounds that can be used as the charge transport material of the present invention are not limited to these examples.

  Among the above-exemplified triarylamine compounds, compounds in which the effects of the present invention are particularly prominent include compounds having a tetraphenylbenzidine structure such as (CT-1) and (CT-5), and (CT-8). And compounds having a triphenylamine structure such as (CT-9).

(Aryl halides and amine compounds)
In this invention, an aryl halide and an amine compound are used as a raw material for synthesize | combining the above-mentioned triarylamine compound. The type of the aryl halide and the amine compound is not particularly limited as long as it is a combination corresponding to the structure of the desired triarylamine compound. Specifically, examples of the aryl halide include aryl chloride, aryl bromide, and aryl iodide depending on the type of halide. Among these, from the viewpoint of production cost, a bromo compound that is relatively inexpensive and excellent in reaction activity is more preferable. Depending on the difference in the number of halides, aryl monohalides, aryl dihalides, etc. may be mentioned, and any of these may be used. Examples of the amine compound include arylamine and diarylamine depending on the number of aryl groups, and any of these may be used. Among these, a combination of aryl monohalide and diarylamine, a combination of aryl dihalide and diarylamine, a combination of aryl monohalide and arylamine, and the like are preferable. In addition, an aryl halide and an amine compound may each be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

(Ratio of raw materials and catalyst)
The ratio of the aryl halide and amine compound, which are raw materials, is selected so as to be an appropriate equivalent ratio depending on the combination of the aryl halide and amine compound used and the type of the target triarylamine compound. If the ratio of the raw materials does not satisfy an appropriate equivalent ratio, excessive raw materials remain without being involved in the reaction, which is not preferable in terms of cost and reaction efficiency, and may cause unintended side reactions. .

  The ratio of the tricycloalkylphosphine compound and the palladium compound as the catalyst component is a value of the molar ratio of tricycloalkylphosphine compound / palladium compound, usually 5/1 or more, preferably 6/1 or more, and usually 15 / The range is 1 or less, preferably 10/1 or less. If the proportion of the tricycloalkylphosphine compound is too low, sufficient catalytic activity may not be obtained when a halide other than aryl iodide (inexpensive aryl bromide or aryl chloride) is used as a raw material. In particular, when the amine compound as a raw material is a primary amine, the yield of the charge transporting material and In terms of purity, satisfactory results cannot be obtained. On the other hand, if the proportion of the tricycloalkylphosphine compound is too large (the phosphine / palladium molar ratio is 15/1 or more), an effect commensurate with the amount added cannot be obtained, and conversely, the phosphorus component remains in the charge transport material. Therefore, it is not preferable to adversely affect the electrical characteristics. When a plurality of types of tricycloalkylphosphine compounds and / or a plurality of types of palladium compounds are used in combination, the total amount of the plurality of types of tricycloalkylphosphine compounds and / or a plurality of types of palladium compounds is within the above-mentioned range. Try to meet.

  The addition amount of the catalyst ligand in terms of the palladium compound is usually 0.005 mol% or more, preferably 0.02 mol% or more, and usually 1 mol% or less, based on 1 mol of the halogen atom on the aryl halide compound ring. Preferably it is the range of 0.1 mol% or less. If the ratio of the catalyst component is too small, it is not preferable because sufficient catalytic activity cannot be obtained. Conversely, if the ratio of the catalyst component is too large, an effect corresponding to the amount added cannot be obtained, which is economically disadvantageous. It is not preferable for the reason.

(Reaction solvent)
The synthesis reaction of a triarylamine compound is usually carried out in the presence of a solvent. The reaction solvent is not particularly limited as long as it is a general inert organic solvent other than a halogen solvent, but in terms of solubility in raw materials (aryl halide and amine compound), toluene, Aromatic hydrocarbon solvents such as xylene, trimethylbenzene and tetralin, and ether solvents such as monoglyme are preferred, with xylene being particularly preferred.

  When the reaction solvent is used, the amount used is not particularly limited, but is usually 100% by weight or more, preferably 200% by weight or more, and usually 800% by weight in terms of the weight ratio to the total raw materials (aryl halide and amine compound). % Or less, preferably 600% by weight or less. If the proportion of the reaction solvent is too small, it is not preferable because the purity of the product may be lowered. Conversely, if the proportion of the reaction solvent is too large, it is not preferable because the synthesis efficiency deteriorates.

(Synthetic reaction)
The procedure for the synthesis reaction of the triarylamine compound is not particularly limited, but usually the aryl halide as the raw material is brought into contact with the amine compound in the reaction vessel in the presence of the tricycloalkylphosphine compound and the palladium compound as the catalyst components. And react. The order in which the individual catalysts and raw materials are added is not particularly limited, but usually, a raw material aryl halide and an amine compound are mixed in the presence of a solvent to prepare a reaction system solution, and this reaction system solution is mixed with catalyst components. A tricycloalkylphosphine compound and a palladium compound are added to initiate the reaction. Each of the tricycloalkylphosphine compound and the palladium compound, which are individual catalyst components, may be added alone to the reaction system solution, but these catalyst components are mixed in the presence of a solvent in advance to form a complex. May be added to the reaction system solution.

  In addition, it is preferable to add a base to the reaction system solution. When the synthesis reaction of the triarylamine compound is carried out in the presence of a base, there is an advantage that hydrogen halide produced as a by-product can be efficiently removed. The base used may be selected from inorganic bases and / or organic bases, and is not particularly limited, but includes sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, Alkali metal alkoxides such as sodium-tert-butoxide and potassium-tert-butoxide are preferred, and sodium-tert-butoxide is more preferred. In addition, inorganic bases such as tripotassium phosphate and cesium carbonate are also effective. The amount of the base used is not particularly limited, but is usually in the range of 100 mol% or more, preferably 120 mol% or more, and usually 600 mol% or less, preferably 500 mol% or less, in terms of the molar ratio with respect to the starting arylamine compound. If the ratio of the base is too small, it is not preferable because the reaction hardly proceeds.

  Also, at the time of the synthesis reaction, it is also effective to forcibly discharge alcohol generated in the system early out of the system from the viewpoint of increasing the catalytic activity of the cycloalkylphosphine compound and promoting the reaction efficiently. Nitrogen flow is effective for discharging. When the synthesis reaction is performed under a nitrogen flow (nitrogen flow), the nitrogen flow rate is usually 0.0001% or more, preferably 0.001% or more, and usually 5% per minute with respect to the volume of the reaction vessel. % Or less, preferably 3% or less. Nitrogen to be used is preferably of high purity, but nitrogen produced from liquid nitrogen may be used for inexpensive production.

  The temperature during the reaction is not particularly limited, but is usually in the range of 70 ° C or higher, preferably 100 ° C or higher, and usually 170 ° C or lower, preferably 150 ° C or lower. If the temperature at the time of reaction is too low, it is not preferable because the reaction rate becomes slow. Conversely, if the temperature at the time of reaction is too high, it is also not preferable because the target triarylamine compound is easily colored.

The pressure during the reaction is not particularly limited, but is usually in the range of 1 × 10 ⁴ Pa or more, preferably 5 × 10 ⁴ Pa or more, and usually 1 × 10 ⁷ Pa or less, preferably 1 × 10 ⁶ Pa or less. If the pressure during the reaction is too low, it is not preferable because the required reaction temperature cannot be achieved and the reaction does not proceed easily. Conversely, if the pressure during the reaction is too high, investment related to the safety of the production equipment increases. Again, it is not preferable because it may be.

  The reaction time is not particularly limited, but may be performed until the reaction reaches the end point (that is, until almost all the raw materials are reacted and the remaining raw materials are substantially eliminated). Whether or not the reaction has reached the end point can be confirmed by a technique such as gas chromatography or high performance liquid chromatography. The time until the reaction reaches the end point varies depending on the types and amounts of raw materials and catalyst components used, the reaction temperature, the reaction pressure, etc., but cannot be generally stated, but the reaction is usually at the end point for 2 hours or more, preferably Is in the range of 3 hours or more, usually 10 hours or less, preferably 6 hours or less.

After completion of the reaction, the reaction system solution is post-treated as necessary. For example, when a base is added to the reaction system solution, it is preferable to extract the base component by solvent fractionation using purified water to neutralize the reaction system solution.
A crude product is obtained by removing the solvent from the reaction system solution after the reaction (and after the post-treatment). The method for removing the solvent is not particularly limited, and the solvent may be evaporated while stirring the reaction system solution as necessary under normal temperature or heating conditions, and normal pressure or reduced pressure conditions.
The intended triarylamine compound can be obtained by purifying the obtained crude product by a technique such as filtration or flash column chromatography.

(Other)
In the present invention, the yield and purity of the triarylamine compound obtained by the above synthesis reaction are not particularly limited, but the yield is usually 70% or more, preferably 80% or more, and the purity is usually 98. % Or more, preferably 99% or more. The yield can be calculated from the weight ratio of the raw material to the obtained product, and the purity can be calculated from the peak area value obtained by analyzing the obtained product by high performance liquid chromatography or the like.

  The triarylamine compound obtained by the synthesis method described above exhibits excellent properties such as potential stability during durability and environmental stability when incorporated in the photosensitive layer of an electrophotographic photoreceptor as a charge transport material. . In addition, the tricycloalkylphosphine compound used as a catalyst component during the synthesis reaction has storage stability, safety, and cost compared to conventional catalysts such as tri-tert-butylphosphine described in Patent Document 1 and Patent Document 2. Excellent in terms. Furthermore, by using the above catalyst ligand, inexpensive aryl chloride or aryl bromide has been used as a raw material, and the yield and purity of the obtained triarylamine compound are high. Therefore, by using this triarylamine compound as a charge transport material, it is possible to obtain an excellent electrophotographic photoreceptor having high sensitivity, excellent durability stability, easy production and relatively low cost.

[2. Electrophotographic photoreceptor]
The electrophotographic photoreceptor of the present invention has a photosensitive layer on a conductive support and contains the charge transport material of the present invention described above in the photosensitive layer.

(Conductive support)
There are no particular restrictions on the electrically conductive support, but for example, metal materials such as aluminum, aluminum alloy, stainless steel, copper and nickel, and conductive powders such as metal, carbon and tin oxide are added to provide conductivity. Mainly used are resin, glass, paper, or the like obtained by depositing or coating a conductive material such as aluminum, nickel, or ITO (indium oxide tin oxide alloy) on the surface. Moreover, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. As the form, for example, a drum shape, a sheet shape, a belt shape or the like is used. Further, a conductive material having an appropriate resistance value may be used on a conductive support made of a metal material in order to control conductivity and surface properties or to cover defects.

  Further, when a metal material such as an aluminum alloy is used as the conductive support, it may be used after anodizing. In addition, when anodizing is performed, it is desirable to perform sealing by a known method.

  The surface of the support may be smooth, or may be roughened by using a special cutting method or performing a polishing treatment. Further, it may be roughened by mixing particles having an appropriate particle diameter with the material constituting the support. In order to reduce the cost, it is possible to use the drawing tube as it is without performing the cutting process.

  Specifically, when an aluminum drum is used, the material used is, for example, an extruded / pulled tube of aluminum alloy such as 3000 series, 5000 series, 6000 series, etc., or those obtained by cutting them, as defined by JIS. As the surface roughness, the value of the maximum surface roughness Rmax is preferably 2.5 μm or less.

(Underlayer)
An undercoat layer may be provided between the conductive support and the photosensitive layer described later for improving adhesion and blocking properties. As the undercoat layer, a resin, a resin in which particles such as a metal oxide are dispersed, or the like is used.

  The types of metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, and titanium. Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium acid and barium titanate. One kind of these particles may be used alone, or a plurality of kinds of particles may be mixed and used. Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be treated with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicone. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. Moreover, the thing of a several crystal state may be contained. There are no particular restrictions on the particle size of the metal oxide particles, and various types can be used. Among them, the average primary particle size is usually 1 nm from the standpoint of the characteristics of the resin as the raw material for the undercoat layer and the stability of the liquid. Above, preferably 10 nm or more, and usually 100 nm or less, preferably 50 nm or less is desirable.

  The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. Examples of the binder resin used for the undercoat layer include phenoxy, epoxy, polyvinyl pyrrolidone, polyvinyl alcohol, casein, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, and polyamide. These may be used alone or in combination of two or more in any combination and ratio. Moreover, you may use with the hardening | curing form with the hardening | curing agent. Among these, alcohol-soluble copolymerized polyamide, modified polyamide, and the like are preferable because they exhibit good dispersibility and coatability.

  The mixing ratio of the metal oxide particles to the binder resin in the undercoat layer is not particularly limited, but it is preferably used in the range of usually 10% by weight or more and 500% by weight or less in terms of dispersion stability and coatability. .

  In addition to these binder resins and binder resins, the undercoat layer may contain an arbitrary substance such as a known antioxidant as long as it does not depart from its purpose.

  The thickness of the undercoat layer is not particularly limited and can be arbitrarily selected. However, from the viewpoint of improving the photoreceptor characteristics and coatability, it is usually 0.1 μm or more, preferably 0.2 μm or more, and usually 20 μm. Hereinafter, the range of 5 μm or less is desirable.

(Photosensitive layer)
The photosensitive layer is a layer containing the above-described arylamine compound of the present invention as a charge transport material, and is formed on the above-mentioned conductive support (on the undercoat layer when an undercoat layer is provided). The type of the photosensitive layer includes a single layer type in which the charge generation material and the charge transport material are present in the same layer and dispersed in the binder resin, and a charge generation layer and a charge in which the charge generation material is dispersed in the binder resin. The layered type includes two layers of a charge transport layer in which a transport material is dispersed in a binder resin. In general, it is known that the charge transport material exhibits the same performance as a charge transfer function regardless of whether it is a single layer type or a multilayer type.

  In addition, as the laminated photosensitive layer, a charge generation layer and a charge transport layer are laminated in this order from the conductive support side, and a charge transport layer and a charge generation layer are laminated in this order. There are reverse laminated type photosensitive layers, and any of them can be adopted, but a forward laminated type photosensitive layer capable of exhibiting the most balanced photoconductivity is preferable.

(Charge generation layer)
In the case of a multilayer photosensitive layer, the charge generation layer is prepared by dispersing a charge generation material in a solution in which a binder resin is dissolved in an organic solvent to prepare a coating solution, which is applied onto a conductive support, and generating a charge. It is formed by binding substances with various binder resins.

  Examples of the charge generating material include selenium and its alloys, cadmium sulfide, and other inorganic photoconductive materials, and organic photoconductive materials such as organic pigments. Organic photoconductive materials are preferred, especially organic Pigments are preferred. Specific examples of organic pigments include phthalocyanine pigments, azo pigments, dithioketopyrrolopyrrole pigments, squalene (squarylium) pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, and benzimidazole pigments. It is done.

  Among the organic pigments exemplified above, a phthalocyanine pigment or an azo pigment is particularly preferable as the charge generation material. The phthalocyanine pigment provides a highly sensitive photoconductor for a relatively long wavelength laser beam having a wavelength of 600 nm to 900 nm, and the azo pigment is a white light and a relatively short wavelength laser having a wavelength of 300 to 500 nm. Each is excellent in that it has sufficient sensitivity to light.

  When a phthalocyanine compound is used as the charge generation material, specifically, a metal such as metal-free phthalocyanine, copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, or an oxide, halide, hydroxide thereof And various crystal forms of coordinated phthalocyanines such as alkoxides. In particular, titanyl phthalocyanines (also known as oxytitanium) such as X-type, τ-type metal-free phthalocyanine, A-type (also known as β-type), B-type (also known as α-type), and D-type (also known as Y-type), which are highly sensitive crystal types Phthalocyanine), vanadyl phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine such as type II, hydroxygallium phthalocyanine such as type V, μ-oxo-gallium phthalocyanine dimer such as type G and I, μ-oxo such as type II -Aluminum phthalocyanine dimer is preferred.

  Among the phthalocyanines, oxytitanium phthalocyanine having a main diffraction peak at a Bragg angle (2θ ± 0.2 °) of X-ray diffraction spectrum with respect to CuKa characteristic X-ray of 27.3 ° is 9.3 °, 13. Titanyl phthalocyanine (oxytitanium phthalocyanine) showing main diffraction peaks at 2 °, 26.2 ° and 27.1 °, 9.2 °, 14.1 °, 15.3 °, 19.7 °, 27.1 ° Dihydroxy silicon phthalocyanine having main diffraction peaks at 8.5 °, 12.2 °, 13.8 °, 16.9 °, 22.4 °, 28.4 ° and 30.1 ° Dichlorotin phthalocyanine, hydroxy potassium phthalose showing main diffraction peaks at 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° Nin, and, 7.4 °, 16.6 °, chlorogallium phthalocyanine preferably exhibits a diffraction peak at 25.5 ° and 28.3 °. Among these, titanyl phthalocyanine (oxytitanium phthalocyanine) showing a main diffraction peak at 27.3 ° is particularly preferable, and in this case, titanyl phthalocyanine showing main diffraction peaks at 9.5 °, 24.1 ° and 27.3 °. (Oxytitanium phthalocyanine) is particularly preferred.

  As the phthalocyanine compound, one kind of compound may be used alone, or plural kinds of compounds may be used in a mixed or mixed crystal state. As the mixed state in the phthalocyanine compound or crystal state here, the respective constituent elements may be mixed and used later, or a mixed state is generated in the production / treatment process of phthalocyanine compound such as synthesis, pigmentation, crystallization, etc. It can be stuffed. As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known. In order to generate a mixed crystal state, as described in JP-A-10-48859, two types of crystals are mixed, mechanically ground and made amorphous, and then converted into a specific crystal state by solvent treatment. The method of doing is mentioned.

  On the other hand, when an azo pigment is used as the charge generation material, various known bisazo pigments and trisazo pigments are preferably used. When an azo pigment is used as the charge generation material, various known bisazo pigments and trisazo pigments are preferably used. Examples of preferred azo pigments are shown below.

  The organic pigments exemplified above may be used alone or as a mixture of two or more pigments. In this case, it is preferable to use a combination of two or more kinds of charge generating materials having spectral sensitivity characteristics in different spectral regions of the visible region and the near red region, and among them, it is preferable to use a disazo pigment or a trisazo pigment and a phthalocyanine pigment in combination. More preferred.

  The charge generation layer may be formed on a vapor deposition film or the like by using the above-described charge generation material alone, but is usually used in a form in which the charge generation material is bound with a binder resin. In particular, when an organic pigment is used as the charge generation material, it is preferable to use the organic pigment in a form in which fine particles of the organic pigment are bound with a binder resin. The type of the binder resin is not particularly limited. For example, polyester resin, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin , Cellulose ester, cellulose ether and the like.

  The usage ratio of the charge generation material to the binder resin is such that the charge generation material is usually 30 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the binder resin.

  In the charge generation layer, in addition to the charge generation material and binder resin described above, a leveling agent, an antioxidant, a sensitizer, and the like for improving the coating property, if necessary, unless otherwise contrary to the purpose. These various components may be included.

  The film thickness of the charge generation layer is usually 0.1 μm or more, preferably 0.15 μm or more, and usually 1 μm or less, preferably 0.6 μm or less.

(Charge transport layer)
The charge transport layer of the multilayer photoconductor contains a charge transport material and usually contains a binder resin and other components used as necessary. Specifically, such a charge transport layer is prepared by, for example, preparing a coating solution by dissolving or dispersing a charge transport material or the like and a binder resin in a solvent. In addition, in the case of a reverse lamination type photosensitive layer, it can be obtained by coating and drying on a conductive support (on the undercoat layer when an undercoat layer is provided).

  As the charge transport material, the above-described charge transport material of the present invention is used. Any one of the charge transport materials of the present invention may be used alone, or two or more may be used in any combination and ratio.

  Furthermore, in addition to one or two or more kinds of the charge transport materials of the present invention, one or more known other charge transport materials may be used in combination. When other charge transport materials are used in combination, the kind thereof is not particularly limited. For example, carbazole derivatives, hydrazone compounds, aromatic amine derivatives, stilbene derivatives, butadiene derivatives and those in which a plurality of these derivatives are bonded are preferable. More specifically, compounds described in JP-A-2-230255, JP-A-63-225660, JP-A-58-198043, JP-B-58-32372, and JP-B-7-21646 Are preferably used. The combination and ratio of the charge transport material of the present invention and other charge transport materials are not particularly limited. However, from the viewpoint of obtaining the above-described effects of the charge transport material of the present invention, it is preferable to use only the charge transport material of the present invention as the charge transport material, and the ratio is as small as possible even when other charge transport materials are used in combination. It is preferable.

  The binder resin is used for securing the film strength. The type of the binder resin is not particularly limited. For example, polymers and copolymers of vinyl compounds such as butadiene, styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinyl alcohol, ethyl vinyl ether, polyvinyl butyral, polyvinyl Formal, partially modified polyvinyl acetal, polycarbonate, polyester, polyarylate, polyamide, polyurethane, cellulose ether, phenoxy resin, silicon resin, epoxy resin, poly-N-vinylcarbazole resin and the like can be mentioned. Of these, polycarbonate and polyarylate are particularly preferred. These can also be used after being crosslinked with heat, light or the like using an appropriate curing agent or the like. Moreover, these binder resins may be used alone or in combination of two or more in any combination and ratio.

  The ratio of the binder resin and the charge transport material is such that the charge transport material is used in a ratio of 20 parts by weight or more with respect to 100 parts by weight of the binder resin. Among these, 30 parts by weight or more is preferable from the viewpoint of residual potential reduction, and 40 parts by weight or more is more preferable from the viewpoint of stability and charge mobility when repeatedly used. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, the charge transport material is usually used at a ratio of 150 parts by weight or less. Among these, 110 parts by weight or less is preferable from the viewpoint of compatibility between the charge transport material and the binder resin, 80 parts by weight or less is more preferable from the viewpoint of printing durability, and 70 parts by weight or less is most preferable from the viewpoint of scratch resistance.

  In the charge transport layer, in addition to the above-described charge transport material and binder resin, antioxidants such as hindered phenols and hindered amines, ultraviolet absorbers, sensitizers, leveling agents, electron withdrawing materials, etc. Various additives may be included.

  The thickness of the charge transport layer is not particularly limited, but is usually 5 μm or more, preferably 10 μm or more, and usually 50 μm or less, preferably 45 μm or less, from the viewpoint of long life, image stability, and high resolution. Is in the range of 30 μm or less.

(Single layer type photosensitive layer)
In addition to the charge generation material and the charge transport material, the photosensitive layer of the single-layer photoconductor is formed using a binder resin in order to ensure film strength, in the same manner as the charge transport layer of the multilayer photoconductor. Specifically, a charge generation material, a charge transport material, and various binder resins are dissolved or dispersed in a solvent to prepare a coating solution, and on a conductive support (or an undercoat layer when an undercoat layer is provided). It can be obtained by coating and drying.

  The types of the charge transport material and the binder resin and the use ratios thereof are the same as those described for the charge transport layer of the multilayer photoreceptor. A charge generating material is further dispersed in a charge transport medium comprising these charge transport materials and a binder resin.

  As the charge generation material, the same materials as those described for the charge generation layer of the multilayer photoreceptor can be used. However, in the case of a photosensitive layer of a single-layer type photoreceptor, it is necessary to sufficiently reduce the particle size of the charge generating material. Specifically, the range is usually 1 μm or less, preferably 0.5 μm or less.

  If the amount of the charge generating material dispersed in the single-layer type photosensitive layer is too small, sufficient sensitivity cannot be obtained, but if it is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. It is usually used in the range of 0.5% by weight or more, preferably 1% by weight or more, and usually 50% by weight or less, preferably 20% by weight or less based on the whole layer type photosensitive layer.

  In addition, the usage ratio of the binder resin and the charge generating material in the single-layer type photosensitive layer is such that the charge generating material is usually 0.1 parts by weight or more, preferably 1 part by weight or more, based on 100 parts by weight of the binder resin. It is 30 parts by weight or less, preferably 10 parts by weight or less.

  The film thickness of the single-layer type photosensitive layer is usually 5 μm or more, preferably 10 μm or more, and usually 100 μm or less, preferably 50 μm or less.

(Other)
For the purpose of improving film forming properties, flexibility, coating properties, contamination resistance, gas resistance, light resistance, etc., in both the photosensitive layer and the layers constituting the photosensitive layer, both of the multilayer type photosensitive member and the single layer type photosensitive member. Additives such as well-known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds, leveling agents, and visible light shielding agents may be included.

  In addition, in both the multilayer type photoreceptor and the single layer type photoreceptor, the photosensitive layer formed by the above-mentioned procedure may be the uppermost layer, that is, the surface layer, but another layer is provided on the photosensitive layer, and this is used as the surface layer. Also good. For example, a protective layer may be provided for the purpose of preventing the photosensitive layer from being worn out or preventing or reducing the deterioration of the photosensitive layer due to discharge products generated from a charger or the like.

  Further, for the purpose of reducing the frictional resistance and wear on the surface of the photoreceptor, a resin such as a fluorine-based resin or a silicone resin, or particles made of these resins or particles of an inorganic compound may be contained in the surface layer. Alternatively, a layer containing these resins and particles may be newly formed as a surface layer.

(Layer formation method)
Each layer constituting these photoreceptors is formed by immersing, coating, spraying, nozzle coating, bar coating, roll coating, blade coating, etc., on a support, a coating solution obtained by dissolving or dispersing a substance to be contained in a solvent. Are formed by sequential application by the known method.

  There are no particular restrictions on the solvent or dispersion medium used for the preparation of the coating solution, but specific examples include alcohols such as methanol, ethanol, propanol and 2-methoxyethanol, tetrahydrofuran, 1,4-dioxane, dimethoxyethane and the like. Ethers, esters such as methyl formate and ethyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, dichloromethane, chloroform, 1,2-dichloroethane, 1,1, Chlorinated hydrocarbons such as 2-trichloroethane, 1,1,1-trichloroethane, tetrachloroethane, 1,2-dichloropropane, trichloroethylene, n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenedi Min, nitrogen-containing compounds such as triethylenediamine, acetonitrile, N- methylpyrrolidone, N, N- dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide and the like. Moreover, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and kinds.

  The amount of the solvent or dispersion medium used is not particularly limited, but considering the purpose of each layer and the properties of the selected solvent / dispersion medium, it is appropriate so that the physical properties such as solid content concentration and viscosity of the coating liquid are within a desired range. It is preferable to adjust.

  For example, in the case of a photosensitive layer of a single layer type photoreceptor and a charge transport layer of a laminated type photoreceptor, the solid content concentration of the coating liquid or dispersion is usually 5% by weight or more, preferably 10% by weight or more. The range is usually 40% by weight or less, preferably 35% by weight or less. Furthermore, the viscosity of the coating solution or dispersion is usually in the range of 10 cps or more, preferably 50 cps or more, and usually 500 cps or less, preferably 400 cps or less.

  In the case of a charge generating layer of a multilayer photoreceptor, the solid content concentration of the coating solution or dispersion is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 15% by weight or less, preferably Is in the range of 10% by weight or less. Furthermore, the viscosity of the coating solution or dispersion is usually in the range of 0.01 cps or more, preferably 0.1 cps or more, and usually 20 cps or less, preferably 10 cps or less.

  Examples of the coating method include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, an air knife coating method, and a curtain coating method. Other known coating methods can also be used.

  The coating liquid is preferably dried by touching at room temperature, usually in the temperature range of 30 ° C. or higher and 200 ° C. or lower, for 1 minute to 2 hours, statically or under ventilation. The heating temperature may be constant or the heating may be performed while changing the temperature during drying.

[3. Image forming apparatus]
Next, an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.

  As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, and a developing device 4, and further, a transfer device 5, a cleaning device 6 and a fixing device as necessary. A device 7 is provided.

  The electrophotographic photoreceptor 1 is not particularly limited as long as it is the above-described electrophotographic photoreceptor of the present invention, but in FIG. 1, as an example, a drum in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. The photoconductor is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are disposed along the outer peripheral surface of the electrophotographic photosensitive member 1.

  The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2, but other corona charging devices such as corotron and scorotron, and contact-type charging devices such as charging brushes are often used.

  In many cases, the electrophotographic photosensitive member 1 and the charging device 2 are designed to be removable from the main body of the image forming apparatus as a cartridge including both of them (hereinafter, appropriately referred to as a photosensitive cartridge). For example, when the electrophotographic photoreceptor 1 or the charging device 2 deteriorates, the photoreceptor cartridge can be removed from the image forming apparatus main body, and another new photosensitive cartridge can be mounted on the image forming apparatus main body. ing. Also, the toner described later is often stored in the toner cartridge and designed to be removable from the main body of the image forming apparatus. When the toner in the used toner cartridge runs out, this toner cartridge is removed. It can be removed from the main body of the image forming apparatus and another new toner cartridge can be mounted. Further, a cartridge equipped with all of the electrophotographic photosensitive member 1, the charging device 2, and the toner may be used.

  The type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary. For example, the exposure may be performed using monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light with a short wavelength of 380 nm to 500 nm. .

  The type of the developing device 4 is not particularly limited, and an arbitrary device such as a dry development method such as cascade development, one-component conductive toner development, two-component magnetic brush development, or a wet development method can be used. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. The replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

  The supply roller 43 is formed from a conductive sponge or the like. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating such a metal roll with a silicone resin, a urethane resin, a fluorine resin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary.

  The developing roller 44 is disposed between the electrophotographic photoreceptor 1 and the supply roller 43 and is in contact with the electrophotographic photoreceptor 1 and the supply roller 43, respectively. The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown). The supply roller 43 carries the stored toner T and supplies it to the developing roller 44. The developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the electrophotographic photosensitive member 1.

  The regulating member 45 is formed of a resin blade such as a silicone resin or a urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such a metal blade with a resin. The regulating member 45 contacts the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

  The agitator 42 is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes.

  The type of the toner T is arbitrary, and in addition to the powdery toner, a polymerized toner using a suspension polymerization method, an emulsion polymerization method, or the like can be used. In particular, when a polymerized toner is used, a toner having a small particle diameter of about 4 to 8 μm is preferable, and the toner particles are used in various shapes ranging from a nearly spherical shape to a shape outside the spherical shape on the potato. be able to. The polymerized toner is excellent in charging uniformity and transferability and is suitably used for high image quality.

  The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like that are disposed to face the electrophotographic photoreceptor 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to a recording paper (paper, medium) P. Is.

  There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 is for scraping off residual toner adhering to the photoreceptor 1 with a cleaning member and collecting the residual toner.

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. Each of the upper and lower fixing members 71 and 72 includes a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, and a fixing sheet. A member can be used. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

  When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.

  The type of the fixing device is not particularly limited, and a fixing device of any type such as heat roller fixing, flash fixing, oven fixing, pressure fixing, etc. can be provided including those used here.

  In the electrophotographic apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the photoreceptor 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.

  Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. The developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.

  The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and the negative polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1.

  When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning device 6.

  After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.

  In addition to the above-described configuration, the image forming apparatus may have a configuration capable of performing, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.

  The image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.

  Hereinafter, the present invention will be described in more detail with reference to production examples, examples and comparative examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless departing from the gist thereof. In the present specification, “parts” means “parts by weight” unless otherwise specified.

<Production of charge transport material (triarylamine compound)>
(Production Example 1: Production of Exemplified Compound CT-5)
At room temperature, 40.60 g (0.1 mol) of 4,4′-diiodobiphenyl and 40.45 g of p, p′-ditolylamine were added to a 500 ml four-necked flask equipped with a stirrer, a thermometer, and a precision distillation apparatus. (0.205 mol), 22.10 g (0.23 mol) of sodium tert-butoxide, and 200 ml of sufficiently deoxygenated xylene were sequentially added, and the system was replaced with nitrogen, followed by stirring for about 10 minutes. On the other hand, 5.6 mg of palladium acetate was added to 5 ml of deoxygenated xylene, and further 234 mg of a 15% toluene solution of tricyclohexylphosphine was added, followed by sonication for about 2 to 3 minutes to complex the catalyst. . Thereafter, while adding a nitrogen flow, the obtained catalyst solution was quickly added to the reactor, heated to 140 ° C., and kept at that temperature to continue heating and refluxing to carry out the reaction. During the reaction, the reaction system solution is monitored by high performance liquid chromatography (column: Inert Sil ODS-3V manufactured by GL Sciences Inc., solvent: acetonitrile) at regular intervals, and the reaction system solution The reaction was continued until no 4,4′-dibromobiphenyl was detected (about 2 hours). After completion of the reaction, the mixture was cooled to 70 ° C., and 50 ml of water and 250 ml of xylene were added to separate the layers. The obtained organic layer was washed with 70 ° C. demineralized water until the pH became neutral, then 10 g of magnesium sulfate was added to remove water, and magnesium sulfate was filtered and removed to take out the organic layer. It was. The obtained organic phase (solution) was concentrated under reduced pressure until it was half the amount of xylene solvent. After stirring at room temperature for about 30 minutes and confirming the precipitation of crystals, 200 ml of methanol was slowly poured to completely crystallize the crude product. The precipitated crystals were separated by filtration, passed through flash column chromatography (silica gel 300 g, developing solvent: toluene / hexane = 1/2), and further purified by reprecipitation with methanol. After vacuum drying, the exemplified compound CT-5 was obtained as white fine crystals (yield 50.05 g, yield 92%, purity 99.5%). The product was confirmed to be the target exemplified compound by ¹ H-NMR analysis. The purity was calculated from the simple area ratio value on the high performance liquid chromatography chart.

(Production Example 2: Production of Exemplified Compound CT-5)
Using 31.20 g (0.1 mol) of 4,4′-dibromobiphenyl as a raw material, a complex formed of 11.24 mg of palladium acetate and 562 mg of a 15% toluene solution of tricyclohexylphosphine was used as a catalyst, and the reaction time was Except for 3 hours, Exemplified Compound CT-5 was obtained as white crystals by the same production method as in Production Example 1 described above (yield 50.66 g, yield 93%, purity 99.4%).

(Production Example 3: Production of Exemplified Compound CT-8)
Using 44.70 g (0.205 mol) of p-iodotoluene and 40.45 g (0.2 mol) of p, p′-ditolylamine as raw materials, consisting of 11.51 mg of palladium acetate and 479 mg of a 15% toluene solution of tricyclohexylphosphine. Except that the complex formed product was used as a catalyst and the reaction time was 2 hours, Exemplified Compound CT-8 was converted into white crystals by the same production method as in Production Example 1 (Production of Exemplified Compound CT-5) described above. Obtained (yield 51.15 g, yield 89%, purity 99.4%).

(Production Example 4: Production of Exemplified Compound CT-8)
Using 35.06 g (0.205 mol) of p-bromotoluene and 40.45 g (0.2 mol) of p, p'-ditolylamine as raw materials, 23.01 mg of palladium acetate and 1.15 g of 15% toluene solution of tricyclohexylphosphine Exemplified Compound CT-8 was produced in the same manner as in Production Example 1 (Production of Exemplified Compound CT-5) except that the complex formed product was used as a catalyst and the reaction time was 3 hours. Obtained as crystals (yield 50.58 g, yield 88%, purity 99.7%).

(Production Example 5: Production of Exemplified Compound CT-8)
Using 27.85 g (0.22 mol) of p-chlorotoluene and 40.45 g (0.2 mol) of p, p′-ditolylamine as raw materials, 44.45 mg of palladium acetate and 2.59 g of a 15% toluene solution of tricyclohexylphosphine Exemplified Compound CT-8 was produced in the same manner as in Production Example 1 (Production of Exemplified Compound CT-5) except that the complex formed product was used as a catalyst and the reaction time was 7 hours. Obtained as crystals (yield 47.14 g, yield 82%, purity 99.6%).

(Production Example 6: Production of exemplary compound CT-8)
Using p-iodotoluene 47.97 g (0.22 mol) and p-toluidine 10.72 g (0.10 mol) as raw materials, a complex formed of 12.35 mg palladium acetate and 823 mg of a 15% toluene solution of tricyclohexylphosphine. Was used as a catalyst, and Exemplified Compound CT-8 was obtained as white crystals by the same production method as Production Example 1 (Production of Exemplified Compound CT-5) except that the reaction time was 2 hours ( Yield 25.00 g, yield 87%, purity 99.3%).

(Production Example 7: Production of Exemplified Compound CT-8)
Using 37.63 g (0.22 mol) of p-bromotoluene and 10.72 g (0.10 mol) of p-toluidine as raw materials, a complex consisting of 24.70 mg of palladium acetate and 1.85 g of a 15% toluene solution of tricyclohexylphosphine. Exemplified compound CT-8 was obtained as white crystals by the same production method as in Production Example 1 (Production of Exemplified Compound CT-5) except that the formed product was used as a catalyst and the reaction time was 3 hours. (Yield 25.01 g, Yield 87%, Purity 99.4%).

(Production Example 8: Production of Exemplified Compound CT-8)
Using 27.85 g (0.22 mol) of p-chlorotoluene and 10.72 g (0.10 mol) of p-toluidine as raw materials, a complex consisting of 44.45 mg of palladium acetate and 3.70 g of a 15% toluene solution of tricyclohexylphosphine. Exemplified compound CT-8 was obtained as white crystals by the same production method as in Production Example 1 (Production of Exemplified Compound CT-5) except that the formed product was used as a catalyst and the reaction time was 6 hours. (Yield 23.27 g, Yield 81%, Purity 99.3%).

(Production Example 9: Production of Exemplified Compound CT-9)
Using 73.65 g (0.205 mol) of a compound having the following structural formula and 40.45 g (0.2 mol) of p, p′-ditolylamine as raw materials, 23.01 mg of palladium acetate and a 15% toluene solution of tricyclohexylphosphine 1 Exemplified compound CT-9 was produced in the same manner as in Production Example 1 (Production of Exemplified Compound CT-5) except that a complex formed of .15 g was used as a catalyst and the reaction time was 4 hours. Was obtained as pale yellow crystals (yield 88.46 g, yield 93%, purity 99.2%).

The results of the above examples are summarized in Table 1.

(Comparative Production Examples 1 to 4)
According to the same raw materials, charge amounts and purification procedures as in the above Production Examples 1 and 2, except that a complex product having a tricyclohexylphosphine / palladium acetate molar ratio of 16/1 and 17/1 was used as a catalyst component. Then, the charge transport material CT-5 was synthesized and purified. The yield and purity were as shown in Table 2 below. The purity of the product was calculated from the simple area value of the peak obtained by analyzing the product by high performance liquid chromatography.

  As described above, when a complex-forming product having a tricyclohexylphosphine / palladium acetate molar ratio of 15/1 or more is used as a catalyst component, the purity of the charge transport material falls to 99% or less. Therefore, it is reasonable that the molar ratio of phosphine / palladium is 15/1 or less.

(Comparative Production Examples 5 to 13)
Instead of the tricyclohexylphosphine used in each of the above Production Examples 1 to 9, the same raw material as in each of the above Production Examples 1 to 9 except that a phosphine compound having the following structure described in Patent Document 3 was used, The charge transport material was synthesized and purified according to the amount charged and the purification procedure. The yield and purity were as shown in Table 3 below. The purity of the product was calculated from the simple area value of the peak obtained by analyzing the product by high performance liquid chromatography.

(Comparative Production Example 14)
The charge transport material was synthesized in the same manner as in Production Example 5 except that triphenylphosphine, which is a phosphine compound described in Patent Document 3, was used instead of the tricyclohexylphosphine of the present application used in Production Example 5. Attempts were made, but the reaction was very difficult to proceed. After reacting for a day, the reaction mixture could not be separated and a charge transport material could not be prepared.

(Comparative Production Example 15)
The charge transport material was synthesized in the same manner as in Production Example 6 except that triphenylphosphine, which is a phosphine compound described in Patent Document 3, was used in place of the tricyclohexylphosphine of the present application used in Production Example 6. Although it tried to go, even if it reacted for 2 days, reaction did not advance at all and a charge transport material could not be created.

(Comparative Production Examples 16 to 24)
Charge transport was carried out by the same raw materials and purification procedures as in Production Examples 1 to 9, except that a complex-forming product (described in Patent Document 4) composed of tricyclohexylphosphine and palladium acetate having a molar ratio of 4/1 was used as a reaction catalyst. The material was synthesized and purified. The yield and purity were as shown in Table 4 below. The reaction time means the elapsed time until the change of the reaction system is not recognized after the reaction is traced by high performance liquid chromatography every 30 minutes after the start of the reaction. The chromatographic analysis was performed, and the peak was calculated from the simple area value.

  When Examples 1 to 9 and Comparative Examples 16 to 24 using the same charge transport material were compared and compared, respectively, as a reaction catalyst, a complex formed of tricyclohexylphosphine and palladium acetate having a molar ratio of 4/1 (patent In the case of using the aryl iodide having the highest reaction activity, the reaction time is extended from the production method described in the present invention, and the yield and purity of the product are also May be inferior to the production method described. Furthermore, when a halide other than aryl iodide is used as a raw material, sufficient catalytic activity cannot be obtained, so that the reaction time is prolonged and the yield and purity of the product are clearly reduced. In particular, when the starting amine compound is a primary amine, it can be seen that a 4/1 molar complex of tricyclohexylphosphine and palladium acetate is very difficult to apply as a reaction catalyst. Therefore, the production method of the present invention is very useful for producing a high yield and high purity charge transport material.

<Production of electrophotographic photoreceptor>
(Examples 1 to 9: electrophotographic photoreceptors A1 to A9)
Using a conductive support in which an aluminum vapor-deposited layer (thickness 70 nm) is formed on the surface of a biaxially stretched polyethylene terephthalate resin film (thickness 75 μm), the following undercoat layer dispersion is formed on the aluminum vapor-deposited layer of the conductive support The liquid was applied by a bar coater so that the film thickness after drying was 1.25 μm and dried to form an undercoat layer.

  The undercoat layer dispersion was produced as follows. That is, a rutile type titanium oxide having an average primary particle size of 40 nm (“TTO55N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by weight of methyldimethoxysilane (“TSL8117” manufactured by Toshiba Silicone Co., Ltd.) with respect to the titanium oxide were flowed at high speed. In a mixed solvent of methanol / 1-propanol in a mixed solvent of methanol / 1-propanol, which was put into a high-pressure mixing kneader (“SMG300” manufactured by Kawata Co., Ltd.) and mixed at a high rotational speed of 34.5 m / sec Then, a dispersion slurry of hydrophobized titanium oxide was obtained by dispersing with a ball mill. The dispersion slurry, a mixed solvent of methanol / 1-propanol / toluene, and ε-caprolactam [compound represented by the following formula (A)] / bis (4-amino-3-methylcyclohexyl) methane [the following formula (B Compound represented by the following formula (C)] / decamethylene dicarboxylic acid [compound represented by the following formula (D)] / octadecamethylene dicarboxylic acid [in the following formula (E) The compositional molar ratio of the compound represented] is 75% / 9.5% / 3% / 9.5% / 3% of the copolymerized polyamide pellets with heating and stirring and mixing to dissolve the polyamide pellets. After that, by carrying out ultrasonic dispersion treatment, the weight ratio of methanol / 1-propanol / toluene is 7/1/2, and hydrophobically treated titanium oxide. The copolymerized polyamide in a weight ratio of 3/1, and a solid concentration of 18.0% of the undercoat layer dispersion.

  Separately, A-type oxytitanium phthalocyanine (showing diffraction peaks at 9.3 °, 10.6 °, and 26.3 ° at Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum for CuKa characteristic X-ray) 10 Part by weight was added to 150 parts by weight of 4-methoxy-4-methyl-2-pentanone, and pulverized and dispersed in a sand grind mill for 1 hour. Thereafter, 100 parts by weight of a 5 wt% 1,2-dimethoxyethane solution of polyvinyl butyral (“Denkabutyral # 6000C” manufactured by Denki Kagaku Kogyo Co., Ltd.) as a binder resin, and phenoxy resin (“PKHH” manufactured by Union Carbide) A coating solution for a charge generation layer was prepared by adding 100 parts by weight of a 5 wt% 1,2-dimethoxyethane solution. The charge generation layer coating solution was applied onto the undercoat layer of the conductive support with a bar coater so that the film thickness after drying was 0.4 μm, and dried to form a charge generation layer. .

  Separately, 50 parts by weight of each exemplary compound obtained in Production Examples 1 to 4 as a charge transport material, 100 parts by weight of a binder resin, and 0.03 parts by weight of silicone oil as a leveling agent were added to tetrahydrofuran / toluene ( (Weight ratio 8/2) A charge transport layer coating solution was prepared by dissolving in 640 parts by weight of a mixed solvent. The binder resin includes 51 mol% of repeating units having 2,2-bis (4-hydroxy-3-methylphenyl) propane as an aromatic diol component as shown below, and 1,1-bis ( A polycarbonate resin (viscosity average molecular weight 30000) having a terminal structure derived from p-tert-butylphenol, comprising 49 mol% of repeating units having 4-hydroxyphenyl) -1-phenylethane as an aromatic diol component.

  The charge transport layer coating solution is applied onto the charge generation layer with a film applicator so that the film thickness after drying is 20 μm, and is dried to form a charge transport layer. Photoconductors A1 to A9 were produced. The obtained electrophotographic photoreceptors A1 to A9 correspond to those containing the charge transport materials according to Production Examples 1 to 9, respectively.

(Comparative Examples 1-4: electrophotographic photoreceptors P1-P4)
According to the same procedure as in Example 1, except that the charge transport material CT-5 produced using a complex product having a tricyclohexylphosphine / palladium molar ratio of 16/1 and 17/1 as a catalyst component was used. Electrophotographic photoreceptors P1 to P4 as Examples 1 to 4 were obtained.

(Comparative Examples 5 to 13: electrophotographic photoreceptors P5 to P13)
Electrophotography as Comparative Examples 5 to 13 according to the same procedure as Examples 1 to 9, except that the charge transport materials of Comparative Production Examples 5 to 13 produced using the phosphine compound described in Patent Document 3 were used. Photoconductors P5 to P13 were obtained.

(Comparative Examples 14 to 22: electrophotographic photoreceptors P14 to P22)
Example 1 except that the charge transport materials of Comparative Production Examples 16 to 24, which were produced by using a complex formed of palladium acetate and tricyclohexylphosphine described in Patent Document 4 and having a molar ratio of 1/4 as a catalyst, were used. The electrophotographic photoreceptors P14 to P22 as Comparative Examples 14 to 22 were obtained in accordance with the same procedure as that for.

<Evaluation of electrical characteristics of electrophotographic photoreceptor>
The electrophotographic characteristics of the obtained electrophotographic photoreceptors A1 to A9 and P1 to P22 were measured by the static method as follows using a photoreceptor evaluation apparatus (Cynthia 55, manufactured by Gentec Corporation).

First, the electrophotographic photosensitive member is discharged with a scorotron charger in a dark place so that the surface potential is about −700 V, and the electrophotographic photosensitive member is charged at a constant speed (125 mm / sec) and charged. The voltage was measured to determine the initial voltage (hereinafter sometimes referred to as “V ₀ ”). Thereafter, a decrease in potential when left for 2.5 seconds was measured (hereinafter sometimes referred to as “DD”). Next, irradiation with 780 nm monochromatic light with an intensity of 1.0 μW / cm ² was performed, and the half-exposure energy (μJ / cm ² ) required until the photoreceptor surface potential changed from −550 V to −275 V was obtained (hereinafter “ E _1/2 "). Further, the residual potential 10 seconds after irradiation was determined.
Tables 5 and 6 show the evaluation results of the electrophotographic photoreceptors A1 to A9 and P1 to P22.

  When the examples using the same charge transport material and the comparative examples are compared with each other (Examples 1 and 2 and Comparative Examples 1 to 4), a complex having a molar ratio of tricyclohexylphosphine / palladium acetate of 15/1 or more is obtained. When the formed product was used as a catalyst component, the electrical properties of the charge transport material deteriorated. Therefore, in order to pursue better electrical characteristics, the phosphine / palladium molar ratio needs to be 15/1 or less.

  Further, when Examples 1 to 9 and Comparative Examples 5 to 13 are respectively compared and compared, an electrophotographic photosensitive member P5 of a comparative example using a charge transport material synthesized using a phosphine compound described in Patent Document 3 as a catalyst. -P13 did not show good electrical properties despite the high purity of the charge transport material, whereas in Examples 1-9 using the charge transport material synthesized using the catalyst system of the present application. Each of the electrophotographic photoreceptors A1 to A9 was able to sufficiently exhibit the charge transport ability and exhibited good electrical characteristics.

  Further, when Examples 1 to 9 and Comparative Examples 14 to 22 are compared with each other and compared, synthesis is performed using a complex formed of palladium acetate and tricyclohexylphosphine described in Patent Document 4 with a molar ratio of 1/4. In the electrophotographic photoreceptors P14 to P22 of Comparative Examples using the prepared charge transport materials (Comparative Production Examples 14 to 22), the purity of the charge transport materials was insufficient, so that measurement was impossible or deterioration of electrical characteristics was observed. It was.

<Image formation test and photoreceptor stability / durability test>
(Example 10)
A coating solution for a charge generation layer and a charge transport layer prepared in the same manner as the electrophotographic photoreceptor A1 is dip-coated on an aluminum tube having a diameter of 3 cm and a length of 25.4 cm, which has been anodized and sealed. Were sequentially coated and dried to produce an electrophotographic photosensitive drum having a film thickness of 0.3 μm and a charge transport layer of 20 μm. When this electrophotographic photosensitive drum was mounted on a laser printer and a laser jet 4 (LJ4) modified machine manufactured by Hewlett Packard, an image test was performed, and a good image free from image defects and noise was obtained. Subsequently, 10,000 sheets were continuously printed, but no image deterioration such as ghosting, fogging, and black spots was observed, and the printing was stable.

(Comparative Example 23)
Instead of using the material (CT-5) produced in Production Example 1, an electrophotographic photosensitive member was produced according to the same procedure as in Example 10 except that the material produced in Comparative Production Example 5 was used, and image formation was performed. Tests and photoreceptor stability / durability tests were conducted. The image density was low from the beginning, and fog was observed in repetition.

  From the above results, it was confirmed that the electrophotographic photosensitive member as an example of the present invention has excellent electrophotographic characteristics and excellent repetitive characteristics.

  The electrophotographic photoreceptor of the present invention has the advantages of high sensitivity, excellent durability stability, easy production and relatively low cost. Therefore, it can be suitably used in various fields in which the electrophotographic photosensitive member is used, for example, in the fields of copying machines, printers, printing machines, and the like.

1 is a schematic diagram illustrating a main configuration of an embodiment of an image forming apparatus of the present invention.

Explanation of symbols

1 Photoconductor (Electrophotographic photoconductor)
2 Charging device (charging roller; charging unit)
3 Exposure equipment (exposure section)
4 Development device (development unit)
5 Transfer device 6 Cleaning device (cleaning part)
7 Fixing Device 41 Developing Tank 42 Agitator 43 Supply Roller 44 Developing Roller 45 Regulating Member 71 Upper Fixing Member (Fixing Roller)
72 Lower fixing member (fixing roller)
73 Heating device T Toner P Recording paper (paper, medium)

Claims (8)

An electrophotographic photosensitive member comprising at least a photosensitive layer containing a charge generation material and a charge transport material on a conductive support,
The charge transport material is a triarylamine compound synthesized using a catalyst in which an amine compound and an aryl halide are used as raw materials and a tricycloalkylphosphine and a palladium compound are mixed at a ratio of 5/1 to 15/1. An electrophotographic photoreceptor characterized by the above. 2. The electrophotographic photoreceptor according to claim 1, wherein the triarylamine compound is synthesized in the presence of a base. The electrophotographic photosensitive member according to claim 1, wherein the triarylamine compound is synthesized under a nitrogen flow. The electrophotographic photoreceptor according to claim 1, wherein the triarylamine compound is a compound represented by the following general formula (1) or the following general formula (2).

(In General Formula (1) and General Formula (2), the rings represented by A to I each independently represent an optionally substituted benzene ring.) A material used for a photosensitive layer of an electrophotographic photoreceptor, comprising at least a triarylamine compound,
A material for an electrophotographic photoreceptor, which is synthesized using an amine compound and an aryl halide as raw materials and a tricycloalkylphosphine compound and a palladium compound as catalysts. A method for producing a material used for a photosensitive layer of an electrophotographic photoreceptor, comprising at least a triarylamine compound,
A method for producing a material for an electrophotographic photoreceptor, comprising a step of synthesizing an amine compound and an aryl halide as raw materials and using a tricycloalkylphosphine compound and a palladium compound as a catalyst. The electrophotographic photosensitive member according to any one of claims 1 to 4,
A charging unit for charging the electrophotographic photosensitive member, an exposure unit for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, and developing the electrostatic latent image formed on the electrophotographic photosensitive member An electrophotographic photosensitive member cartridge comprising at least one of the developing units. 5. The electrophotographic photosensitive member according to claim 1, a charging unit that charges the electrophotographic photosensitive member, and an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image. And an image forming apparatus comprising: a developing unit that develops the electrostatic latent image formed on the electrophotographic photosensitive member.

Images