JPH1039527A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophoographic photoreceptor having stable electrical characteristics over a long period of time, giving an image having clear image quantity and excellent in durability by using an amine compd., having a specified stricture as an electric charge transferring material. SOLUTION: This electrophotohgraphic photoreceptor contains at least an amine compd. represented by formula I in the photosensitive layer. In the formulas I, each of R1 -R3 is H, alkyl, alkoxy, substd. amino, halogen or aryl, R4 is alkyl, aryl or aralykyl, X is one of groups represented by formulae II-IV, (k) is 1 when X is a group represented by the formula II or III, (k) is 0 when X is a group represented by the formula IV, R5 is H, 1-4C alkyl or 1-4C alkoxy and R6 is H, 1-4C alkyl, 1-4C alkoxy, phenyl, aralkyl or halogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member using a specific amine compound as a charge transport material.

[0002]

2. Description of the Related Art Organic photoreceptors are now mainstream because they have advantages in safety and cost as compared with conventional inorganic photoreceptors such as selenium, zinc oxide and cadmium sulfide. Most of the organic photoreceptor has a layered structure, which is advantageous in terms of sensitivity, durability and the like, and uses a charge transport layer having excellent mechanical strength as the outermost surface. Furthermore, the charge transport layer is excellent in injecting charges from the charge generation layer and has high charge mobility, for example, a triarylamine (JP-A-58-123542) and a hydrazone derivative (JP-A-57-123572). 101844), oxadiazole derivatives (Japanese Patent Publication No. 34-5466), pyrazoline derivatives (Japanese Patent Publication No. 52-4188), stilbene derivatives (Japanese Patent Application Laid-Open No. 58-180443), and triphenylmethane derivatives ( Kosho 45-55
No. 5) or a 1,3-butadiene derivative (Japanese Unexamined Patent Publication No.
It is formed by dispersing a low-molecular charge-transporting material such as JP-A-2-287257) in an insulating resin such as a polycarbonate resin and an acrylic resin.

[0003]

However, when the charge transporting agent is made compatible with a resin such as a polycarbonate resin or an acrylic resin to form a charge transporting layer, the charge transporting layer is required to have a sufficient charge transporting property. 40 to 5 transport agents
It is used after being molecularly dispersed in the range of 0% by weight. For this reason, the mechanical strength inherent in the resin is significantly reduced, and it is difficult to obtain a strong film. Further, these charge transporting agents have a problem that the compatibility with the resin is not sufficient, and crystallization or the like is likely to occur during long-term use.

As a method for solving these problems, for example, Japanese Patent Application Laid-Open No. 63-113465 and Japanese Patent Application Laid-Open No.
No. 0550 proposes to introduce an alkylene carboxylate group which is easily compatible with the resin into the charge transporting agent. However, the charge transporting agent having an alkylene carboxylate group is excellent in compatibility with the resin, so that the above-mentioned problems can be solved. On the other hand, the alkylene carboxylate group has a freedom of movement. Is high, the charge transport agent having the same is difficult to crystallize and is difficult to industrially produce, and because it is difficult to obtain a high-purity product, such as chromatography There is a problem that a purification means is required. Further, since the alkylene carboxylate group has an electron-withdrawing property, there is also a problem that the mobility is apt to decrease.

[0005] The present invention has been made in view of the above-mentioned circumstances in the prior art. That is, an object of the present invention is to use an amine compound having a specific structure having excellent solubility, mobility and charge injecting properties as a charge transporting material, thereby stabilizing electrical characteristics for a long time and obtaining a clear image. And to provide an electrophotographic photoreceptor having excellent durability.

[0006]

The present inventors have studied in detail the structure of a charge transporting material having an alkylene carboxylate group, and as a result, the electric characteristics of the charge transporting material largely depend on the structure and the substitution position of the alkylene group. It turned out to be. That is, when the alkylene group in the alkylene carboxylic acid ester group is a methylene group having 1 carbon atom, since the ester group of the electron-withdrawing substituent is located near the arylamine skeleton responsible for the charge transport function, As a result of a bias in the electron distribution, which causes a decrease in mobility and an increase in the dependence of mobility on the electrolytic strength, even when satisfactory electrical characteristics are obtained in the initial stage, the charge tends to accumulate as the electrophotographic method is repeated. I understood that.

[0007] On the other hand, it has been revealed that when the alkylene group has 3 or more carbon atoms, the molecular flexibility is increased, and as a result, a crystalline charge transport material is hardly obtained. The fact that the charge transporting material cannot be obtained as crystals is not a major problem when the material is used for an electrophotographic photoreceptor,
When the charge transporting material is used for an electrophotographic photoreceptor, its purity has a significant effect on the electrical characteristics, so that a material of high purity is required and purification is required. In general, distillation, chromatography, recrystallization, and the like are industrially performed as a method for purifying an organic compound. However, in a charge transporting material having an alkylene carboxylic acid ester group, purification by distillation is substantially performed due to a large molecular weight. Impossible. Chromatography can be applied to the purification of most organic compounds as long as it is stable with respect to the adsorbent. However, since a large amount of solvent is used and the treatment requires a long time, it causes a significant cost increase. . Therefore, as an industrial purification method of the charge transport material having an alkylene carboxylate group, recrystallization is the only method,
In the case of a charge transport material having an alkylene group having 3 or more carbon atoms, industrialization is very difficult.

The inventors of the present invention have conducted intensive studies based on the above facts. As a result, by selecting an ethylene group as an alkylene group in a specific amine compound having an alkylene carboxylate group directly bonded to an aromatic ring. The problem of the electrical characteristics observed in the methylene group is greatly improved, and crystallization is facilitated by introducing the ethylene group in the 4-position. It has been found that a charge transport material having high purity and practical use can be obtained by recrystallization. Furthermore, among the specific triphenylamine derivatives, the basic skeleton of triphenylamine or tri-p-tolylamine easily causes a photooxidation reaction in the air to produce a carbazole derivative, which causes electrical degradation. By introducing a group in which an aromatic ring is substituted or condensed, the fluorescence emission efficiency is increased, the photooxidation reaction is easily deactivated from the excited state to the ground state, and the photooxidation reaction is significantly reduced. And found that a stable compound was obtained, and completed the present invention.

That is, an electrophotographic photoreceptor of the present invention comprises an electrophotographic photoreceptor having a photosensitive layer provided on a conductive substrate, wherein at least an amine compound represented by the following general formula (I) is contained in the photosensitive layer. It is characterized by containing.

[0010]

Embedded image (Wherein, R _{1 to} R ₃ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom,
A substituted or unsubstituted aryl group; R ₄ represents an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group; and X is selected from the following groups (1) to (3) Represents a group. k represents a group (1) or a group (2)
Is 1 in the case of, and 0 in the case of the group (3). )

Embedded image (Wherein, R ₅ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Shows an alkoxy group having 1 to 4 carbon atoms. R ₆ is a hydrogen atom,
It represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a halogen atom. In the present invention, among the amine compounds represented by the above general formula (I) to be contained in the photosensitive layer provided on the conductive substrate, those having a melting point of 50 ° C. or more are preferably used.

[0011]

Embodiments of the present invention will be described below in detail. First, a method for producing the amine compound represented by the general formula (I) used in the present invention will be described. In the present invention, the amine compound represented by the general formula (I) is obtained by performing a copper-catalyzed coupling reaction between a compound represented by the following general formula (II) and a compound represented by the following general formula (III). The compound represented by the following general formula (IV) is obtained by hydrolysis, and then the compound represented by the following general formula (IV) and the compound represented by the following general formula (V) are subjected to a coupling reaction with a copper catalyst. Can be obtained.

Embedded image (Wherein, R _{1 to} R ₃ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom,
It represents a substituted or unsubstituted aryl group, and R ₄ represents an alkyl group. G represents a bromine atom or an iodine atom, and X has the same meaning as described above. )

In the coupling reaction between the compound represented by the general formula (II) and the compound represented by the general formula (III), the compound represented by the general formula (III) includes aniline, o-toluidine, m- Toluidine, p-toluidine, 2,3-xylidine, 2,4-xylidine, 2,5
-Xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, 2,4,6-trimethylaniline, o-biphenylamine, m-biphenylamine,
An acetyl form such as p-biphenylamine is used. In this coupling reaction, the compound represented by the general formula (II) is used in 0.5 to 1.5 equivalents, preferably 0.7 to 1.2 equivalents, relative to 1 equivalent of these acetylated forms. . As the copper catalyst, copper powder, cuprous oxide, copper sulfate, etc. can be used,
0.1 part by weight of the compound represented by the general formula (II)
001 to 3 parts by weight, preferably 0.01 to 2 parts by weight. As the base, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like can be used. Based on 1 equivalent of the compound represented by the general formula (II),
It is used in 0.5 to 3 equivalents, preferably 0.7 to 2 equivalents.

In the above coupling reaction, it is not necessary to use a solvent. However, preferable solvents for use include high-boiling water-insoluble hydrocarbon solvents such as n-tridecane and tetralin. It is used in an amount of 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight, based on 1 part by weight of the compound represented by the general formula (II). In addition, this reaction is carried out under an atmosphere of an inert gas such as nitrogen in a range of 100 to 300.
° C, preferably 150 to 270 ° C, more preferably 1 to
It is preferable to carry out the reaction in a temperature range of 80 to 250 ° C. while stirring sufficiently and efficiently, and to carry out the reaction while removing water generated during the reaction. After completion of the reaction, if necessary, after cooling, methanol, ethanol, n-octanol, ethylene glycol, propylene glycol,
Hydrolysis is performed using a solvent such as glycerin and a base such as sodium hydroxide and potassium hydroxide. The amount of the solvent used in this case is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 1 part by weight of the compound represented by the general formula (II). 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, per part by weight of the compound represented by
Used by weight.

In the hydrolysis reaction, after performing the above-mentioned coupling reaction, a solvent and a base are added directly into the reaction vessel, and the mixture is heated at a temperature ranging from 50 ° C. to the boiling point of the solvent under an atmosphere of an inert gas such as nitrogen. And stirring with sufficient efficiency. In this case, as the solvent, a carboxylate is generated and solidified by the coupling reaction, and therefore, a solvent having a high boiling point of 150 ° C. or higher, which can raise the reaction temperature, is used, and water is used in the post-treatment. It is particularly preferable to add water-soluble ethylene glycol, propylene glycol, glycerin and the like in order to release the compound represented by the general formula (IV) by neutralizing with hydrochloric acid or the like after the injection. After completion of the hydrolysis reaction,
The reaction product is poured into water and further neutralized with hydrochloric acid or the like to release the compound represented by the general formula (IV), and then sufficiently washed, and if necessary, dissolved in an appropriate solvent. , Silica gel, alumina, activated clay, activated carbon, etc., or perform a process such as adding these adsorbents to the solution to adsorb unnecessary components, and further apply a suitable solvent such as ethanol, ethyl acetate, toluene, etc. Similar purification may be performed after recrystallization and purification from a suitable solvent, or after esterification to a methyl ester or an ethyl ester.

Next, the compound represented by the general formula (IV) and the compound represented by the general formula (V) obtained above are subjected to a copper-catalyzed coupling reaction and then esterified or After esterifying the compound represented by the formula (IV) to a methyl ester or an ethyl ester, the compound represented by the general formula (V) is subjected to a copper-catalyzed coupling reaction to give a compound represented by the general formula (I). Amine compound can be obtained.

Specific examples of the amine compound represented by the general formula (I) used as the charge transporting material in the present invention are shown in Tables 1, 2 and 3, but those used in the present invention are not limited to these. is not.

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

In the coupling reaction between the compound represented by the general formula (IV) and the compound represented by the general formula (V), the compound represented by the general formula (V) may be a halogen 2
When a substituent is used, 1.5 to 5 equivalents, preferably 1.7 to 5 equivalents to 1 equivalent of the compound represented by the general formula (V) is used.
Four equivalents of the compound represented by the general formula (IV) are used.
As the copper catalyst, copper powder, cuprous oxide, copper sulfate and the like can be used, and based on 1 part by weight of the compound represented by the general formula (V),
It is used in an amount of 0.001 to 3 parts by weight, preferably 0.01 to 2 parts by weight. As the base, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like can be used, and 1 to 1 equivalent of the compound represented by the general formula (V) is used.
It is used in 6 equivalents, preferably 1.4 to 4 equivalents. The solvent is used as needed, but is preferably n
-A high-boiling water-insoluble hydrocarbon solvent such as tridecane or tetralin;
0.1 to 3 parts by weight, preferably 0.2 to 3 parts by weight,
2 parts by weight are used. This reaction is carried out in an atmosphere of an inert gas such as nitrogen at 100 to 300 ° C., preferably 150 to 300 ° C.
It is preferable that the reaction is carried out at 270 ° C., more preferably 180 to 250 ° C., with sufficient and efficient stirring, and the reaction is carried out while removing water generated during the reaction. After completion of the reaction, the reaction product is dissolved in a solvent such as toluene, isopar, n-tridecane, etc., and if necessary, unnecessary substances are removed by washing or filtration, and further, silica gel, alumina, activated clay, activated carbon, etc. Or purifying the solution by adding these adsorbents to the solution, adsorbing unnecessary components, and recrystallizing from an appropriate solvent such as ethanol, ethyl acetate or toluene.

In the case where a halogen-substituted compound represented by the general formula (V) used in the coupling reaction is used, the compound represented by the general formula (IV) is
About 1 equivalent of the compound represented by formula (V), a copper catalyst, a base, and, if necessary, a solvent are used. As the copper catalyst, copper powder, cuprous oxide, copper sulfate and the like can be used, and based on 1 part by weight of the compound represented by the general formula (V),
It is used in an amount of 0.001 to 3 parts by weight, preferably 0.01 to 2 parts by weight. As the base, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like can be used, and the amount of the base is 0.1 to 1 equivalent of the compound represented by the general formula (V).
It is used in 5 to 3 equivalents, preferably 0.7 to 2 equivalents.
As the solvent, it is preferable to use a high boiling non-water-soluble hydrocarbon solvent such as n-tridecane and tetralin,
0.1 part by weight of the compound represented by the general formula (V)
To 3 parts by weight, preferably 0.2 to 2 parts by weight.
This reaction, subsequent treatment and purification are carried out in the same manner as in the case where the compound represented by the general formula (V) is a disubstituted halogen.

When the compound represented by the general formula (V) is a halogen-substituted compound (GX), to obtain an amine compound for a charge transporting material used in the present invention, stability, mobility, cost, etc. From the viewpoint, it is preferable to use a compound represented by the following group (3) as X.

[0022]

Embedded image (Wherein, R ₆ has the same meaning as described above.) When the compound represented by the general formula (V) is a disubstituted halogen (G-X-G), X represents the following group ( 1)
Alternatively, it is preferred to use group (2).

Embedded image (Wherein, R ₅ has the same meaning as described above.)

Next, the electrophotographic photosensitive member of the present invention will be described. The layer constitution of the electrophotographic photoreceptor in the invention is not limited at all, and the photosensitive layer may have a laminated structure or a single layer structure. Also,
When the photosensitive layer has a laminated structure, the charge transport layer may be laminated on the charge generation layer, or, on the contrary, the charge generation layer may be laminated on the charge transport layer. If desired, a surface protective layer may be provided on the outermost surface of the photoreceptor, or an undercoat layer may be provided between the conductive support and the photosensitive layer.

As a material for forming the electrophotographic photosensitive member, a conductive support includes metals such as aluminum, nickel, chromium, and stainless steel, or aluminum, titanium,
Nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, plastic film provided with a thin film such as ITO, or applying a conductivity imparting agent,
Impregnated paper, plastic film, or the like is used. These conductive supports are used in an appropriate shape such as a drum shape, a sheet shape, and a plate shape, but are not limited thereto. If necessary, the surface of the conductive support may be subjected to various treatments within a range that does not affect the image quality. For example, surface oxidation treatment, chemical treatment, coloring treatment, or the like, or irregular reflection treatment such as graining can be performed.

If necessary, an undercoat layer may be provided between the conductive support and the photosensitive layer. This undercoat layer prevents charge injection from the conductive support into the photosensitive layer during charging of the photosensitive layer having a laminated structure,
It acts as an adhesive layer for integrally adhering and holding the photosensitive layer and the conductive support, or, in some cases, an action of preventing reflected light from the conductive support. As the binder resin used for the undercoat layer, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin,
Vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, vinylidene chloride resin, polyvinyl acetal resin,
Vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose,
Use of known materials such as casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound, titanyl chelate compound, titanyl alkoxide compound, organic titanyl compound, and silane coupling material. Can be. Undercoat layer thickness is 0.01-10μ
m, preferably 0.05 to 2 μm. Further, as an application method used for forming the undercoat layer, a blade coating method, a Meyer bar coating method,
Conventional methods such as spray coating, dip coating, bead coating, air knife coating, curtain coating and the like can be mentioned.

Next, a photosensitive layer is provided on the undercoat layer. Hereinafter, the case where the photosensitive layer is a laminated type and the charge transport layer is provided on the conductive support will be described in order. The charge transporting material of the charge transporting layer in the present invention may be an amine compound represented by the general formula (I) alone or 2
More than one species may be used in combination, and further, a benzidine compound, a triarylamine compound, a hydrazone compound,
It may be used by mixing with a conventionally known charge transporting material such as a stilbene compound. Examples of the binder resin for the charge transport layer include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, and vinylidene chloride-acrylic. Nitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinyl Carbazole, polysilane,
Known resins such as a charge transporting polyester and a charge transporting polycarbonate can be used, but are not limited thereto.

Among these binder resins, the following formula (PC-
When a polycarbonate resin having a repeating structural unit represented by 1) to (PC-5) or a polycarbonate resin obtained by copolymerizing the same is used, the compatibility is good and a uniform film can be formed. Exhibit particularly excellent properties. In addition, these binder resins, alone,
Alternatively, two or more kinds can be used as a mixture.

[0028]

Embedded image

The mixing ratio (weight ratio) of the charge transport material to the binder resin is preferably from 10: 1 to 1: 5. The thickness of the charge transport layer is suitably from 10 to 50 μm, preferably from 15 to 40 μm. Further, as a coating method used for forming the charge transport layer, usual methods such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method are used. Used.

Next, a charge generation layer is provided on the charge transport layer. As the charge generation material of the charge generation layer, known charge generation materials such as azo pigments, perylene pigments, squarylium pigments, anthrone pigments, phthalocyanine pigments, and the like can be used. It is preferable to use various phthalocyanine crystals such as phthalocyanine. The binder resin used for the charge generation layer can be selected from a wide range of insulating resins. Further, it can be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin And insulating resins such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin and polyvinyl pyrrolidone resin, but are not limited thereto. These binder resins may be used alone or in combination of two or more. The thickness of the charge generation layer is 0.01 to 2 μm,
Preferably, 0.02 to 1 μm is appropriate. Further, as a coating method used for forming the charge generation layer, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like. Can be used.

The mixing ratio (weight ratio) of the charge generating material to the binder resin is preferably in the range of 10: 1 to 1:10. Also,
As a dispersion method of the charge generation material, a ball mill dispersion method,
Conventional methods such as an attritor dispersion method and a sand mill dispersion method can be used. Further, the particle size used in this dispersion is 0.5 μm or less, preferably 0.3 μm or less.
It is effective to reduce the particle size to not more than μm, more preferably not more than 0.15 μm. These dispersing solvents include methanol, ethanol, n-propanol and n-propanol.
-Butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate,
Ordinary organic solvents such as dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene are used alone or in combination of two or more. Each layer of the above-described electrophotographic photoreceptor may be formed by drying at 50 to 200 ° C., preferably 70 to 150 ° C. each time the coating solution of each layer is applied, or all layers may be formed. After applying the coating liquid in order, 50 to 200
C., preferably at 70 to 150.degree.

[0032]

The present invention will be specifically described below with reference to examples. Synthesis Example 1 10.1 g of N, N'-diphenylbenzidine, 20.0 g of ethyl 4-iodohydrocinnamate, potassium carbonate
9 g, copper sulfate pentahydrate 1.0 g, n-tridecane 20 m
1 in a 100 ml flask and placed under a nitrogen stream at 230 ° C.
For 1.5 hours. After the reaction, cool to room temperature,
The residue was dissolved in 50 ml of toluene, the insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene. As a result, 18.7 g of an oily compound (2) was obtained. IR of compound (2) obtained
The spectrum is shown in FIG.

Synthesis Example 2 6.7 g of p-acetotoluidide, 10.0 g of 4-iodohydrocinnamic acid, 5.7 g of potassium carbonate, 1.0 g of copper sulfate pentahydrate, and 20 ml of n-tridecane were placed in a 200 ml flask. The mixture was heated and reacted at 230 ° C. for 3.5 hours in an air stream. After the reaction, 33 ml of ethylene glycol and 6.6 g of potassium hydroxide were added thereto, and the mixture was heated and refluxed under a nitrogen stream for 2 hours, cooled to room temperature, poured into 50 ml of water, and neutralized with hydrochloric acid to precipitate crystals. Was. Filter this,
After washing thoroughly with water, it was transferred to a 500 ml flask. 100 ml of toluene was added thereto, and the mixture was heated and refluxed to remove water by azeotropic distillation. Thereafter, 50 ml of methanol and 1 ml of concentrated sulfuric acid were further added, and the mixture was heated and refluxed for 1 hour under a nitrogen stream. After the reaction, the mixture was poured into 200 ml of distilled water, extracted with toluene, and the organic layer was sufficiently washed with a dilute aqueous sodium carbonate solution and distilled water. Furthermore, 10 g of activated clay is added to the organic layer.
, And the mixture was heated under reflux for 1 hour. The activated clay was filtered off, and the filtrate was concentrated to give N- (4-methylphenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine. 6.7 g were obtained. 6.0 g of the obtained N- (4-methylphenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine, 4.3 g of 4,4'-diiodo-3,3'-dimethylbiphenyl, carbonic acid 1.6 g of potassium, 0.5 g of copper sulfate pentahydrate, and 10 ml of n-tridecane were placed in a 100 ml flask, and heated and reacted at 230 ° C. for 5 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 20 ml of toluene, and the insoluble material was filtered.
The filtrate was purified with activated clay using toluene. This was recrystallized from acetone to give compound (4) 5.
6 g were obtained as a white powder. The resulting compound (4)
Its melting point is 183-184 ° C., and its IR spectrum is shown in FIG.

Synthesis Example 3 29.3 g of 3,4-dimethylacetanilide, 40.0 g of 4-iodohydrocinnamic acid, 22.3 g of potassium carbonate,
1.0 g of copper sulfate pentahydrate and 200 ml of n-tridecane were placed in a 2000 ml flask, and reacted by heating at 230 ° C. for 5 hours under a nitrogen stream. After this reaction, 100 ml of ethylene glycol and 26.0 g of potassium hydroxide were added,
After heating and refluxing for 2 hours under a nitrogen stream, the mixture was cooled to room temperature,
This was poured into 1 liter of water and neutralized with hydrochloric acid to precipitate crystals. After filtering this and washing thoroughly with water,
Transferred to 1 flask. After adding 200 ml of toluene and heating under reflux to remove water by azeotropic distillation, 100 ml of methanol and 3 ml of concentrated sulfuric acid were added, and the mixture was added under nitrogen stream.
Heated to reflux for an hour. After the reaction, pour into 2 liters of distilled water,
This was extracted with toluene. The organic layer was sufficiently washed with a dilute aqueous solution of sodium carbonate and distilled water, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from methanol to give N- (3,4-dimethylamine). 33.2 g of phenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine were obtained. The obtained N- (3,4-dimethylphenyl) -N- [4- (2-
Methoxycarbonylethyl) phenyl] amine 4.5
g, 3.0 g of 4,4'-diiodo-3,3'-dimethylbiphenyl, 2.7 g of potassium carbonate, 0.5 g of copper sulfate pentahydrate and 5 ml of n-tridecane were placed in a 500 ml flask, and placed under a nitrogen stream. The reaction was carried out at 230 ° C. for 5 hours.
After the reaction, the mixture was cooled to room temperature, dissolved in 20 ml of toluene, the insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene.
This was recrystallized from a mixed solvent of ethyl acetate and ethanol to obtain 3.8 g of compound (6) as a pale yellow powder. The obtained compound (6) has a melting point of 162 to 163 ° C., and its IR spectrum is shown in FIG.

Synthesis Example 4 30.0 g of 3,5-dimethylacetanilide, 42.0 g of 4-iodohydrocinnamic acid, 23.2 g of potassium carbonate,
1.0 g of copper sulfate pentahydrate and 50 ml of n-tridecane
The mixture was placed in a 00 ml flask and reacted under heating at 230 ° C. for 2 hours under a nitrogen stream. After this reaction, ethylene glycol 1
After adding 00 ml and 25.0 g of potassium hydroxide and heating and refluxing under a nitrogen stream for 2 hours, the mixture was cooled to room temperature, poured into 500 ml of water, and neutralized with hydrochloric acid to precipitate crystals. This was filtered, washed sufficiently with water, and then transferred to a 500 ml flask. After adding 200 ml of toluene and heating under reflux to remove water by azeotropic distillation, 100 ml of methanol was added.
1 and concentrated sulfuric acid (2 ml) were added, and the mixture was heated and refluxed for 2 hours under a nitrogen stream. After the reaction, the mixture was poured into 300 ml of distilled water and extracted with toluene. The organic layer was sufficiently washed with a dilute aqueous sodium carbonate solution and distilled water, then dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and N- (3,5) was recrystallized from toluene / hexane. 35.5 g of -dimethylphenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine were obtained. The obtained N- (3,
5-dimethylphenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine 15.0 g,
4'-diiodo-3,3'-dimethylbiphenyl
0 g, potassium carbonate 8.0 g, copper sulfate pentahydrate 0.5
g and 20 ml of n-tridecane were placed in a 500 ml flask, and heated and reacted at 230 ° C. for 3 hours under a nitrogen stream. After the reaction, the reaction mixture was cooled to room temperature, dissolved in 100 ml of toluene, filtered to remove insolubles, and the filtrate was purified by silica gel column chromatography using toluene. This is recrystallized from a mixed solvent of ethyl acetate and ethanol,
16.0 g of compound (7) was obtained as a pale yellow powder. The obtained compound (7) has a melting point of 177 to 179 ° C., and its IR spectrum is shown in FIG.

Synthesis Example 5 25.0 g of p-acetoanisidide, 33.8 g of 4-iodohydrocinnamic acid, 19.2 g of potassium carbonate, 1.0 g of copper sulfate pentahydrate, and 15 ml of n-tridecane were placed in a 200 ml flask. The mixture was heated and reacted at 230 ° C. for 5 hours in an air stream. After the reaction, 100 ml of ethylene glycol and 22.0 g of potassium hydroxide were added, and the mixture was heated and refluxed for 2 hours under a nitrogen stream, cooled to room temperature, poured into 200 ml of water, and neutralized with hydrochloric acid to precipitate crystals. This was filtered, washed sufficiently with water, and then transferred to a 500 ml flask. 200 ml of toluene was added thereto, and the mixture was heated under reflux to remove water by azeotropic distillation, then 100 ml of methanol and 3 ml of concentrated sulfuric acid.
Was added and the mixture was heated and refluxed under a nitrogen stream for 2 hours. After the reaction, the reaction solution was poured into 2 liters of distilled water and extracted with toluene. The organic layer was sufficiently washed with a dilute aqueous solution of sodium carbonate and distilled water, then dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
19.5 g of (4-methoxyphenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine were obtained. The obtained N- (4-methoxyphenyl) -N- [4
-(2-methoxycarbonylethyl) phenyl] amine 5.0 g, 4,4'-diiodo-3,3'-dimethylbiphenyl 3.4 g, potassium carbonate 2.9 g, copper sulfate pentahydrate 0.5 g, n -5 ml of tridecane was placed in a 100 ml flask and heated and reacted at 230 ° C for 15 hours under a nitrogen stream. After the reaction, the reaction mixture was cooled to room temperature, dissolved in 20 ml of toluene, the insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene to obtain 5.3 g of compound (9) as a pale yellow oil. Was. FIG. 5 shows the IR spectrum of the obtained compound (9).

Synthesis Example 6 N- (3,4-dimethylphenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine 5.0 g, obtained in the same manner as in Synthesis Example 3, 4,4 ″ -Diiodine-
3.8 g of 1,1 ': 4', 1 "-terphenyl, 2.9 g of potassium carbonate, 1.0 g of copper sulfate pentahydrate, and 10 ml of n-tridecane were placed in a 200 ml flask and heated at 230 ° C. under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 20 ml of toluene, filtered to remove insolubles, and the filtrate was purified by silica gel column chromatography using toluene and recrystallized from acetone. As a result, 3.7 g of compound (15) was obtained as a pale yellow powder, and the obtained compound (15) had a melting point of 146 to 147 ° C., and its IR spectrum is shown in FIG.

Synthesis Example 7 5.0 g of N- (3,4-dimethylphenyl) -N- [4- (2-methoxycarbonylethyl) phenyl] amine obtained in the same manner as in Synthesis Example 3, 4-iodobiphenyl 4.8 g, potassium carbonate 2.8 g, copper sulfate pentahydrate 0.
5 g and 5 ml of n-tridecane were placed in a 100 ml flask, and reacted under heating at 230 ° C. for 5 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 20 ml of toluene, and insolubles were filtered. The filtrate was purified by silica gel column chromatography using toluene, and this was recrystallized from a mixed solvent of ethyl acetate and ethanol.
4.5 g of compound (27) was obtained as a pale yellow powder. The obtained compound (27) had a melting point of 148.5 to 150.
° C and its IR spectrum is shown in FIG.

Synthesis Example 8 (Production of compound-A) 5.3 g of N, N'-diphenylbenzidine, 10.0 g of ethyl 4-iodophenylacetate, 5.6 potassium carbonate
g, copper sulfate pentahydrate 0.5 g, n-tridecane 10 ml
Was placed in a 100 ml flask, and heated and reacted at 230 ° C. for 1 hour under a nitrogen stream. After the reaction, the reaction mixture was cooled to room temperature, dissolved in 20 ml of toluene, filtered to remove insolubles, and the filtrate was purified by silica gel column chromatography using toluene. Thereby, oily N, N'-diphenyl-N, N'-bis (4-ethoxycarbonylmethylphenyl)-[1,1'-biphenyl] -4,4'-
6.2 g of diamine (compound-A) was obtained. FIG. 8 shows the IR spectrum of the obtained compound-A.

Synthesis Example 9 (Production of Compound-B) 10.8 g of N, N'-diphenylbenzidine, 23.0 g of ethyl 3-iodocinnamate, 11.6 g of potassium carbonate,
1.0 g of copper sulfate pentahydrate and 20 ml of n-tridecane
Put in a 00 ml flask and place at 230 ° C under nitrogen flow for 1 hour.
The reaction was carried out by heating for hours. After the reaction, the reaction mixture was cooled to room temperature, dissolved in 50 ml of toluene, filtered to remove insolubles, and the filtrate was purified by silica gel column chromatography using toluene. Thereby, oily N, N'-diphenyl-N, N'-bis [3- (2-ethoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,
19.6 g of 4'-diamine (Compound-B) was obtained. FIG. 9 shows the IR spectrum of the obtained Compound-B.

Synthesis Example 10 (Production of Compound-C) 16.3 g of 3,4-dimethylacetanilide, 24.8 g of 4-iodophenylacetic acid, 15.5 g of potassium carbonate,
Copper powder 10.0g, n-tridecane 10ml 200ml
And heated and reacted at 200 ° C. for 24 hours under a nitrogen stream. After the reaction, 60 ml of ethylene glycol and 10.0 g of potassium hydroxide were added, and the mixture was heated under reflux for 2 hours under a nitrogen stream, cooled to room temperature, poured into 1 liter of water, and neutralized with hydrochloric acid to precipitate crystals. I let it. This was filtered, and the filtrate was sufficiently washed with water and then transferred to a 500 ml flask. Add 200 ml of toluene and heat to reflux,
After water was removed by azeotropic distillation, 100 ml of methanol and 3 ml of concentrated sulfuric acid were added, and the mixture was refluxed for 2 hours under a nitrogen stream.
After the reaction, the mixture was poured into 2 liters of distilled water, extracted with toluene, and the organic layer was sufficiently washed with a dilute aqueous sodium carbonate solution and distilled water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure and recrystallized from methanol to give N- (3,4-dimethylphenyl).
-N- [4- (methoxycarbonylmethyl) phenyl]
21.3 g of the amine were obtained. 9.0 g of the obtained N- (3,4-dimethylphenyl) -N- [4- (methoxycarbonylmethyl) phenyl] amine, 4,4'-diiodo-
6.2 g of 3,3'-dimethylbiphenyl, 5.5 g of potassium carbonate, 1.0 g of copper sulfate pentahydrate, n-tridecane 1
0 ml into a 200 ml flask, and place it under a nitrogen stream.
The reaction was carried out at 0 ° C. for 5 hours. After the reaction, cool to room temperature,
It was dissolved in 40 ml of toluene, the insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene. Recrystallized from a mixed solvent of ethyl acetate and ethanol to give 3,3'-dimethyl-N, N '
-Bis (3,4-dimethylphenyl) -N, N'-bis (4-methoxycarbonylmethylphenyl)-[1,
1'-biphenyl] -4,4'-diamine (compound-
C) 7.1 g was obtained as a pale yellow powder. The melting point of compound-C obtained was 179 to 181 ° C., and its IR
The spectrum is shown in FIG.

Synthesis Example 11 (Production of Compound-D) 15.6 g of 3,4-dimethylacetanilide, 4- (4
-Iodophenyl) -n-butyric acid (19.0 g), potassium carbonate (15.8 g), copper sulfate pentahydrate (1.0 g), and n-tridecane (10 ml) were placed in a 300 ml flask, and heated and reacted at 210 ° C. for 4 hours under a nitrogen stream. Was. After the reaction, 100 ml of ethylene glycol and 16.1 g of potassium hydroxide were added, and the mixture was heated and refluxed for 2 hours under a nitrogen stream, cooled to room temperature, poured into 1 liter of water, and neutralized with hydrochloric acid to precipitate crystals. . After filtering this and washing thoroughly with water,
Transferred to 1 flask. 200 ml of toluene was added thereto, and the mixture was refluxed under heating. After water was removed by azeotropic distillation, 100 ml of methanol and 3 ml of concentrated sulfuric acid were added, and the mixture was refluxed under a nitrogen stream for 2 hours. After the reaction, the mixture was poured into 1 liter of distilled water and extracted with toluene. The organic layer is sufficiently washed with a dilute aqueous sodium carbonate solution and distilled water, dried over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure, and the residue is recrystallized from methanol to give N- (3,4-dimethylphenyl). -N- [4- (3-methoxycarbonylpropyl)
13.4 g of [phenyl] amine were obtained. The obtained N-
6.7 g of (3,4-dimethylphenyl) -N- [4- (3-methoxycarbonylpropyl) phenyl] amine,
3.9 g of 4,4'-diiodo-3,3'-dimethylbiphenyl, 3.8 g of potassium carbonate, 0.1 g of copper sulfate pentahydrate.
5 g and 10 ml of n-tridecane were placed in a 50 ml flask, and heated and reacted at 230 ° C. for 10 hours in a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 20 ml of toluene,
The insoluble material was filtered, and the filtrate was purified by silica gel column chromatography using toluene to obtain oily 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, 6.5 g of N'-bis [4- (3-methoxycarbonylpropyl) phenyl]-[1,1'-biphenyl] -4,4'-diamine (Compound-D) was obtained. FIG. 11 shows the IR spectrum of the obtained Compound-D.

Example 1 A zirconium compound (trade name: ORGATICS Z) was placed on a honing-treated 30 mmφ aluminum cylindrical substrate.
C540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), a solution composed of 100 parts of a silane compound (trade name: A1110, manufactured by Japan Junker Co., Ltd.), 400 parts of iso-propanol and 200 parts of butanol was applied by a dip coating method. After heating and drying for a minute, an undercoat layer having a thickness of 0.5 μm was formed. Next, in the powder X-ray diffraction spectrum, the Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °,
10 parts of a chlorogallium phthalocyanine pigment having strong diffraction peaks at 25.5 ° and 28.3 ° were combined with 10 parts of a polyvinyl butyral resin (trade name: Esrec BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 500 parts of n-butyl acetate. After mixing and dispersing by treating with a glass bead for 1 hour using a paint shaker, the obtained coating solution was applied onto the undercoat layer by using a dip coating method, and dried by heating at 100 ° C. for 10 minutes. Next, 2.5 parts of the compound (2) obtained in Synthesis Example 1 and a polycarbonate resin (PC
(Z)) A coating liquid obtained by dissolving 2.5 parts of a charge transport material in 38 parts of monochlorobenzene is applied on an aluminum cylindrical substrate on which a charge generation layer is formed by a dip coating method, The resultant was dried by heating at 120 ° C. for 1 hour to form a charge transporting layer having a thickness of 15 μm, thereby producing an electrophotographic photoconductor. In order to evaluate the electrophotographic characteristics of the thus obtained electrophotographic photosensitive member, a laser beam printer (XP-
11, Fuji Xerox Co., Ltd.)
Print test in an environment of 40 ° C and 40% RH).
The image quality of each of the first, 2,000-th, and 5,000-th images was evaluated. Table 4 shows the results.

Examples 2 to 10 Compound (2) used in Example 1 as a charge transporting material
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1, except that the compounds shown in Table 4 were used in place of the above. Table 4 shows the results. Comparative Examples 1-4 Compound (2) used in Example 1 as a charge transport material
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the compounds shown in Table 4 were used in place of the above.
Table 4 shows the results.

[0045]

[Table 4]

[0046]

According to the electrophotographic photoreceptor of the present invention, since an amine compound having a specific structure obtained by the above-mentioned manufacturing method is used as a charge transporting material, a photosensitive layer can be easily formed and a high quality image can be obtained. As well as being obtained, they have excellent electrical characteristics that are stable over a long period of time and have a long life.

[Brief description of the drawings]

1 is an IR spectrum of the amine compound obtained in Synthesis Example 1. FIG.

FIG. 2 is an IR spectrum of the amine compound obtained in Synthesis Example 2.

FIG. 3 is an IR spectrum of the amine compound obtained in Synthesis Example 3.

FIG. 4 is an IR spectrum of the amine compound obtained in Synthesis Example 4.

FIG. 5 is an IR spectrum of the amine compound obtained in Synthesis Example 5.

FIG. 6 is an IR spectrum of the amine compound obtained in Synthesis Example 6.

FIG. 7 is an IR spectrum of the amine compound obtained in Synthesis Example 7.

FIG. 8 is an IR spectrum of the amine compound obtained in Synthesis Example 8.

9 is an IR spectrum of the amine compound obtained in Synthesis Example 9. FIG.

FIG. 10 IR of the amine compound obtained in Synthesis Example 10.
It is a spectrum diagram.

FIG. 11 IR of the amine compound obtained in Synthesis Example 11.
It is a spectrum diagram.

Claims (2)

[Claims] 1. An electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer provided thereon, wherein the photosensitive layer contains at least an amine compound represented by the following general formula (I). Photoconductor. Embedded image (Wherein, R _{1 to} R ₃ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom,
A substituted or unsubstituted aryl group; R ₄ represents an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group; and X is selected from the following groups (1) to (3) Represents a group. k represents a group (1) or a group (2)
Is 1 in the case of, and 0 in the case of the group (3). ) (Wherein, R ₅ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Shows an alkoxy group having 1 to 4 carbon atoms. R ₆ is a hydrogen atom,
It represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a halogen atom. ) 2. The electrophotographic photosensitive member according to claim 1, wherein among the amine compounds represented by the general formula (I), those having a melting point of 50 ° C. or higher are used.