JPH1073936A - Electrophotographic photoreceptor, bisamine compound, intermediate, and manufacture of bisamine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoreceptor which has excellent stability to temperature and humidity and high charging characteristic, and is hardly reduced in sensitivity even by the repeated use by containing a specified bisamine compound in a carrier moving material. SOLUTION: This electrophotographic photoreceptor contains a bisamine compound represented by the formula in a carrier moving material. In the formula, Ar1 , Ar2 represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, or a heterocyclic substituted alkyl group. Z represents O, S, or Se atom. R1 , R2 each represent an alkyl group having 1-3 carbon atoms which may have a substituent, an alkoxy group having 1-3 carbon atoms, a dialkylamino group having 1-3 carbon atoms, a halogen atom or hydrogen atom. m represents an integer of 1-4, and n represents an integer of 1-3. When n and m are 2 or more, R1 and R2 may be the same or different, or mutually form a ring.

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 in which a specific bisamine compound is contained in a photosensitive layer formed on a conductive support, and a bisamine compound, an intermediate, And a method for producing these intermediates and bisamine compounds.

[0002]

2. Description of the Related Art In general, there are various systems in an electrophotographic process, and a direct system and a latent image transfer system are known as typical examples. In the electrophotographic photoreceptor used in these electrophotographic processes, basic properties required as a photoconductive layer material constituting the photoconductive layer include: 1) high chargeability by corona discharge in a dark place. thing.

[0003] 2) The attenuation due to the obtained corona discharge is small in a dark place.

[0004] 3) The light is quickly dissipated by light irradiation.

[0005] 4) Less residue after light irradiation.

5) The increase in residual potential and the decrease in initial potential due to repeated use are small.

6) The change in electrophotographic characteristics due to temperature and humidity is small.

And the like.

As such materials, inorganic photoconductive materials such as zinc oxide (JP-B-57-19780), cadmium sulfide (JP-B-58-46018), and amorphous selenium alloy have been used. Although it has been used, various problems have been pointed out in recent years. That is, in the case of a zinc oxide-based material, the sensitizer causes charge deterioration due to corona discharge and photobleaching due to exposure, so that a stable image cannot be provided over a long period of time. In a cadmium sulfide-based material, stable sensitivity cannot be obtained under humid conditions. The selenium-based material has thermal stability, deterioration of characteristics due to crystallization, difficulty in production, and the like.

Therefore, from a future perspective, electrophotography composed of an organic material rather than an inorganic material, which has a problem of production due to depletion of resources, a concern of pollution due to toxicity, and a problem of environment. Research on photoconductors has been actively conducted, and as a result, electrophotographic photoconductors using various organic compounds have been studied. In particular, research and development in recent years have tended to actively introduce the concept of a function-separated type photoreceptor, and in particular, a carrier generation layer and a hole-transport carrier-transport layer on a conductive layer. Are sequentially stacked, and the moving surface is negatively charged. And in this way, by separating the functions,
Materials having individual functions of carrier generation and carrier transfer can be independently developed. As a result, a large number of carrier generating materials having various molecular structures and carrier transfer materials have been developed.

The electrophotographic photoreceptor using these organic compounds is manufactured by coating a photosensitive layer on a conductive support. Known manufacturing methods include a baker applicator and a bar coater in the case of a sheet, and a spraying method, a vertical ring method, and a dip coating method in the case of a drum. The dip coating method is adopted.

Here, paying attention to the carrier transfer material,
When typical ones among them are classified based on their structural characteristics, they are classified into hysorazone type (JP-A-54-59143),
Stilbene-styryl series (Japanese Patent Application Laid-Open No. 58-180433)
Publication), triarylamines (JP-B-58-323)
No. 72), phenothiazines, triazoles, quinoxalines, oxadiazoles, oxazoles,
Pyrazolin, triphenylmethane, dihydronicotinamide compounds, indoline compounds, semicarbazone compounds and the like have been developed.

[0013]

However, despite the fact that many organic compounds have been developed as carrier transfer materials, 1) the compatibility with the binder is low.

2) Crystals are easily deposited.

3) When used repeatedly, sensitivity changes.

4) Poor chargeability and repetition characteristics.

5) Poor residual potential characteristics.

No organic compound satisfies all of the problems described above, and the basic properties required for the above-mentioned photoreceptor,
Further, at present, those satisfying mechanical strength, high durability and the like have not yet been sufficiently obtained.

An object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity and high durability, a bisamine compound, an intermediate, and a method for producing these intermediates and a bisamine compound. In particular, according to the present invention, it is possible to provide a photoreceptor which is excellent in stability against temperature and humidity, has high charging characteristics, and hardly causes a decrease in sensitivity even when used repeatedly.

[0020]

Means for Solving the Problems The present inventors have studied the photoconductive substance having high sensitivity and high durability for the above purpose, and as a result, the bisamine compound represented by the following general formula (1) is effective. And reached the present invention.

In the electrophotosensitive material of the present invention, the carrier transfer material may be represented by the following general formula (1):

[0022]

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[In the formula, Ar1 and Ar2 represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent,
Represents an aralkyl group which may have a substituent, or a heterocyclic-substituted alkyl group, and Z is an O, S, or Se atom. R1 and R2 each represent an optionally substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom, or a hydrogen atom. , M is an integer of 1 to 4, and n is an integer of 1 to 3. Where n and m are 2
In the above, R1 and R2 may be the same or different, and may form a ring with each other. ] It is characterized by including the bisamine compound of the above.

The bisamine compound represented by the general formula (1) is preferably the following structural formula (2)

[0025]

Embedded image

Wherein Ar1, Ar2, R1, R2,
m and n have the same meanings as in the above formula (1)].

The bisamine compound represented by the general formula (1) is more preferably the following structural formula (3)

[0028]

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[In the formula, R3 and R4 each represent an optionally substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, or Represents a hydrogen atom, and l and k are integers of 1 to 3. R1, R2, m and n have the same meanings as in the above formula (1)].

The electrophotographic photoreceptor is characterized in that the photosensitive layer comprises a layer containing the above-mentioned carrier transfer substance and carrier generation substance. Alternatively, the photosensitive layer comprises a laminate of a carrier generation layer containing the carrier generation substance and a carrier transfer layer containing the carrier transfer substance.

The bisamine compound of the present invention has the following general formula (4):

[0032]

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[Wherein, Ar1, Ar2, Z, R1, R
2, m and n have the same meanings as in the above general formula (1). ] The compound shown by these is characterized by the above-mentioned.

Here, the general formula (5) is

[0035]

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[Wherein, X represents a Cl, Br, I atom;
Z, R1, R2, m and n have the same meanings as in the above general formula (1). ]
The halogenated benzofuran, benzothiophene, or benzoselenophene derivative represented by is useful as a synthetic intermediate of an asymmetric bisamine compound.

The general formula (6) is

[0038]

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[Wherein Ar1, Z, R1, R2, m, n
Has the same meaning as in the above general formula (1). The bisamine compound having a secondary amino group represented by the formula [1] is useful as a synthetic intermediate for bisamine and bisenamine compounds.

Further, the method for producing a halogenated derivative represented by the general formula (5) according to the present invention comprises the following general formula (7):

[0041]

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[Wherein, Z, R1, R2, m and n have the same meanings as in the above formula (1). ] Is converted into a halide by a Sandmeyer reaction.

Further, the method for producing a bisamine compound having a secondary amino group represented by the general formula (6) according to the present invention comprises:
The halogenated derivative represented by the general formula (5) is coupled with an aniline derivative by an Ullmann reaction.

The method for producing a bisamine compound represented by the general formula (4) according to the present invention comprises a bisamine compound having a secondary amino group represented by the general formula (6) or an amine compound represented by the general formula (7) And an aryl halide are coupled by an Ullmann reaction.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS General formula (1) according to the present invention

[0046]

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In the bisamine compound of Ar1, A
r2 represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, or a heterocyclic-substituted alkyl group; S,
Or it is a Se atom. R1 and R2 each represent an alkyl group having 1 to 3 carbon atoms which may have a substituent;
Represents an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom, or a hydrogen atom, m is an integer of 1 to 4, and n is an integer of 1 to 3. However, when n and m are 2 or more, R1 and R2 may be the same or different, and may form a ring with each other.

Specific examples of the bisamine compound of the present invention represented by the general formula (1) include those having the structures shown in Tables 1 to 5, whereby the bisamine compound of the present invention can be obtained. It is not limited.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

Incidentally, among the exemplified compounds in Tables 1 to 5, N
o. 1 to 43, the structural formula (2)

[0055]

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[Wherein Ar1, Ar2, R1, R2,
m and n have the same meanings as in the above general formula (1)], because the synthesis cost of the electrophotographic photoreceptor is low. In addition, among the exemplified compounds in Tables 1 to 5, 1 to 10, 24, 27 to 29, 32 to 3
4, 37, 39, 40, the structural formula (3)

[0057]

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[In the formula, R3 and R4 each represent an optionally substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, or Represents a hydrogen atom, and l and k are integers of 1 to 3. R1, R2, m and n have the same meanings as in the above general formula (1)], because the electrophotographic photosensitive member has good electrophotographic properties.

The bisamine compound represented by the general formula (1) can be synthesized by various methods, but is usually easily synthesized by the following synthesis process. That is, the general formula (7)

[0060]

Embedded image

[Wherein, Z, R1, R2, m and n have the same meanings as in the above formula (1). ] (1.0)
Mol) and the halogen derivative corresponding to A1 and A2 (5.
(0 mol), copper, potassium carbonate and 18-crown-6, and the mixture is allowed to react under reflux for 12 to 24 hours using an o-dichlorobenzene solvent.

In particular, the general formula (5)

[0063]

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[Wherein, X represents a Cl, Br, I atom;
Z, R1, R2, m and n have the same meanings as in the above general formula (1). ]
Are useful as intermediates when synthesizing a bisamine compound having an asymmetric structure. For example, the halogenated derivative [eg, 2- (4-I
(odophenyl) -5-iodobenzofur
ane] and N- (Tolyl) aniline are subjected to an Ullmann reaction, whereby Exemplified Compound 15 in Table 1 can be easily synthesized. Furthermore, the general formula (6)

[0065]

Embedded image

[Wherein, Ar1, Z, R1, R2, m, n
Has the same meaning as in the above general formula (1). The bisamine compound having a secondary amino group represented by the formula [1] is useful not only as an intermediate when synthesizing a bisamine compound having an asymmetric structure but also as an intermediate for synthesizing an enamine-type compound.

In the method for producing the halogenated derivative represented by the above general formula (5), by utilizing the side-Meyer reaction, a hazardous reagent such as a halogen molecule is not used, the reaction is carried out under mild conditions, There is an advantage that the position can be regulated and halogen can be introduced. Further, the method for producing a bisamine compound having a secondary amino group represented by the general formula (6) has an advantage that it can be synthesized under mild conditions without using an autoclave or the like.

The electrophotographic photoreceptor according to the present invention can be obtained by containing one or more of the above-mentioned amine compounds. In some cases, the following styryl compounds {eg, β-phenyl- [4- (benzylamino)] stilbene, β-
Phenyl- [4- (N-ethyl-N-phenylamino)] stilbene, 1,1-bis (4-diethylaminophenyl) -4,4-diphenylbutadiene or the following hydrazone compound {for example, 4- (di- Benzylamino) benzaldehyde-N, N-diphenylhydrazone, 4- (ethylphenylamino) benzaldehyde-
N, N-diphenylhydrazone, 4-di (p-tolylamino) benzaldehyde-N, N-diphenylhydrazone, 3,3- (4′-diethylaminophenyl) -acrolein-N, N-diphenylhydrazone, or A triphenylamine compound {for example, 4-methoxy-4 ′-(4-methoxystyryl) triphenylamine, 4-methoxy-4′-styryltriphenylamine} and the like can also be contained. Various methods can be considered for using these amine compounds as the electrophotographic photoreceptor. For example, a photoreceptor comprising an amine compound and a sensitizing dye, optionally added with a chemical sensitizer or an electron-withdrawing compound, dissolved or dispersed in a binder resin, and provided on a conductive support. Alternatively, in the form of a laminated structure composed of a carrier generating layer and a carrier moving layer having a high carrier generation efficiency, a sensitizing dye or an azo pigment, a pigment represented by a phthalocyanine pigment is mainly provided on a conductive support. A laminated photoreceptor comprising the amine compound of the present invention dissolved or dispersed in a binder by adding an antioxidant compound or an electron-withdrawing compound, if necessary, onto the carrier generation layer thus obtained, and providing the resulting compound as a carrier transfer layer. And so on, but it is possible to apply in any case.

In preparing a photoreceptor using the compound of the present invention, a polymer film-forming binder is applied on a support such as a metal drum, a metal plate, a conductively processed paper, or a plastic film. To make a film. In this case, in order to further increase the sensitivity, it is desirable to add a sensitizer and a substance imparting plasticity to the polymerizable film-forming binder as described later to form a uniform photoreceptor film.
These polymerizable film forming binders include various substances depending on the field of use. That is, in the field of photoconductors for copiers or printers, polystyrene resins, polyvinyl acetal resins, polysulfone resins, polycarbonate resins, polyphenylene oxide resins,
Polyester resin, alkyd resin, polyarylate resin and the like are desirable. These may be used alone or in combination of two or more. Above all, resins such as polystyrene, polycarbonate, polyarylate, and polyphenylene oxide have a volume resistivity of 1013Ω or more,
Excellent film properties, potential characteristics, etc.

The amount of these binders to be added to the bisamine compound of the present invention is 0.2 to 20 times by weight, preferably 0.5 to 5 times, and less than 0.2. In such a case, a disadvantage occurs in that the bisamine compound is precipitated from the surface of the photoreceptor, and when the ratio is 20 times or more, the sensitivity is remarkably reduced.

For use in printing plates, an alkaline binder is particularly required. The alkaline binder is an acidic group soluble in water or an alcoholic alkaline solvent (including a mixed system), for example, an acid anhydride group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group,
Alternatively, it is a polymer substance having a sulfonimide group. Usually, these alkaline binder resins preferably have a high acid value of 100 or more. A binder resin having a large acid value easily dissolves in an alkaline solvent or easily swells. These binder resins include, for example, styrene:
Maleic anhydride copolymer, vinyl acetate: maleic anhydride copolymer, vinyl acetate: crotonic acid copolymer, methacrylic acid: methacrylic acid ester copolymer, phenolic resin, methacrylic acid: styrene: methacrylic acid ester copolymer And so on. The proportion of these resins to the photoconductive organic substance may be substantially the same as in the case of a photoconductor for a copying machine.

Next, sensitizing dyes added to the photosensitive layer include methyl violet, crystal violet,
Triphenylmethane dyes such as night blue and Victoria blue, erythrosine, rhodamine B, rhodamine 3R, acridine orange, acridine dyes such as frappeosin, thiazine dyes such as methylene blue and methylene green, and capri blue ,
Examples thereof include oxazine dyes represented by Meldora Blue, etc., other cyanine dyes, styryl dyes, pyrylium salt dyes, and thiopyrylium salt dyes.

Examples of photoconductive pigments that generate carriers with extremely high efficiency by light absorption in the photosensitive layer include phthalocyanine pigments such as various metal phthalocyanines, metal-free phthalocyanines, halogenated metal-free phthalocyanines, peryleneimide, perylene Examples include perylene acid pigments such as acid anhydrides, azo pigments such as bisazo pigments and trisazo pigments, quinacridone pigments, and anthraquinone pigments. In particular, those using a metal-free phthalocyanine pigment, a titanyl phthalocyanine pigment, a fluorene, a bisazo pigment containing a fluorenone ring, a bisazo pigment composed of an aromatic amine, and a trisazo pigment as a carrier-generating pigment have excellent sensitivity. Give a photoreceptor.

Further, the above-mentioned dyes may be used as the carrier-generating substance. These dyes may be used alone, but they often generate carriers with higher efficiency by coexisting with a pigment.

In addition to the above-mentioned spectral sensitizers, it is necessary to add various chemical substances for the purpose of preventing an increase in residual potential, a decrease in charge potential, a decrease in sensitivity, etc. upon repeated use. It becomes. These added substances include 1-chloroanthraquinone, benzoquinone, 2,3
-Dichloronaphthoquinone, naphthoquinone, 4,4'-dinitrobenzophenone, 4,4'-dichlorobenzophenone, 4-nitrobenzophenone, 4-nitrobenzalmalonedinitrile, α-cyano-β- (p-cyanophenyl) acrylic acid Ethyl, 9-anthracenylmethylmalondinitrile, 1-cyano-1- (p-nitrophenyl) -2- (p-chlorophenyl) ethylene, 2,7
-Electron-withdrawing compounds such as dinitrofluorenone. In addition, an antioxidant, an anti-curl agent, a leveling agent, and the like can be added as necessary to the photoreceptor.

The bisamine compound of the present invention is dissolved or dispersed in an appropriate solvent together with the above-mentioned various additives depending on the form of the photoreceptor, and the coating solution is coated on the above-mentioned conductive support. Dry to produce a photoreceptor. As the coating solvent, aromatic hydrocarbons such as benzene, toluene, xylene and monochlorobenzene, halogenated hydrocarbons such as dichloromethane and dichloroethane, solvents such as dioxane, dimethoxymethyl ether and dimethylformamide, alone or in combination of two or more Alternatively, if necessary, a solvent such as alcohols, acetonitrile, methyl ethyl ketone or the like can be further added and used.

The electrophotographic photoreceptor of the present invention uses the bisamine compound represented by the above general formula (1) as a carrier transfer material, and various modes can be considered in the embodiment. Hereinafter, the structure of the photoreceptor is schematically shown in FIGS. 1 to 6.

FIG. 1 shows a photosensitive layer 4 on a conductive support 1.
As a function-separated type photoconductor, a carrier generation layer 5 in which a carrier generation material 2 is dispersed in a binder as a main component and a carrier migration layer 6 in which the carrier migration material 3 is dispersed in a binder as a main component are used. The carrier transfer layer 6 is formed on the surface of the carrier generation layer 5, and shows the structure of a photoreceptor using the bisamine compound of the present invention as the carrier transfer substance 3 in the carrier transfer layer 6.

FIG. 2 shows a function-separated type photoreceptor comprising the same lamination of a carrier generation layer 5 and a carrier transfer layer 6 as in FIG. 1. However, contrary to FIG.
A carrier generation layer 5 is formed on the surface of the photoconductor, and the structure of a photoreceptor using the bisamine compound of the present invention as the carrier transporting substance 3 in the carrier transporting layer 6 is shown.

FIG. 3 shows the photosensitive layer 4 on the conductive support 1.
1 shows a configuration of a photoconductor composed of a single layer in which a carrier generating substance 2 and a carrier transporting substance 3 are dispersed in a binder.

FIG. 4 shows a structure in which a surface protective layer 7 is further provided on the surface of the photoreceptor of FIG. 3, and the photoreceptor comprises a single layer.

FIG. 5 shows a structure in which an intermediate layer 8 is provided between the conductive support 1 and the same photosensitive layer 4 as that shown in FIG. is there.

FIG. 6 shows a structure in which an intermediate layer 8 is provided between the conductive support 1 and the same photosensitive layer 4 'as in FIG. 3, and shows a single-layer photosensitive member. .

The surface protective layer 7 provided on the surface of the photosensitive layer 4 is intended to improve durability against mechanical stress and to receive and hold corona discharge in a dark place. Yes, composed of a chemically stable substance, has the ability to transmit light that the generating layer is sensitive to, transmits light at the time of exposure to reach the generating layer, and receives the injection of generated light to neutralize the surface It is necessary that the generated substance be as transparent as possible in the wavelength region of the maximum absorption of light of the generated substance. As a material having such properties, an acrylic resin, a polyaryl resin, a polycarbonate resin, an organic insulating film forming material such as a urethane resin, or a single or dispersed low-resistance compound such as tin oxide or indium oxide, Acrylic-modified silicone resin, epoxy-modified silicone resin, alkyd-modified silicone resin, polyester-modified silicone resin, urethane-modified silicone resin, or silicone resin as a hard coat agent is used alone or as a modified silicone resin for the purpose of improving durability. A suitable material is a mixture of a metal alkoxy compound, which contains titanium, indium oxide, and zirconium oxide as a main component and can form a film. Further, an organic plasma polymerized film can also be used, and if necessary, oxygen, nitrogen, halogen, atoms of Groups I and V of the periodic table can be included, and further, metals such as inorganic materials and metal oxides can be used. Can also be formed by a technique such as vapor deposition or sputtering.

The intermediate layer 8 provided between the conductive support 1 and the photosensitive layer 4 provides a protective function and an adhesive function, improves coating properties, and further improves the injection from the base to the photosensitive layer. Such materials include casein,
Suitable are polyvinyl butyral, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon 610; copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin aluminum oxide and the like.

Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples.

Synthesis Example (Exemplified Compound: No. 3) 5.0 g of 2- (4-aminophenyl) -5-aminobenzo [b] furan was placed in a 300 ml three-necked flask.
Equiv.), 24.3 g (5.0 equiv.) Of 3-iodotoluene, 49.3 g (16.0 equiv.) Of potassium carbonate, 11.3 g (8.0 equiv.) Of copper powder, 18-crown-6
2.4 g (0.4 equivalent), o-dichlorobenzene 100
Add 2 ml under vigorous stirring under an argon atmosphere.
Reflux for 2 hours. Thin-layer chromatography (TL)
C. ), The completion of the reaction was confirmed, the solid content was removed by filtration, and the solvent o-dichlorobenzene was distilled off under reduced pressure. The obtained crude product was recrystallized from an ethyl acetate / ethanol system to obtain 11.4 g (87%) of a desired product.

The obtained compound was analyzed by 1H-NMR spectrum, ordinary 13C-NMR spectrum, DEPT-13
5 according to the 13C-NMR spectrum and IR spectrum. 3 was confirmed.

FIG. 7 shows the 1 H-NMR spectrum, FIG. 8 shows a normal 13 C-NMR spectrum, and FIG. 9 shows DEPT-13.
13 shows a 13C-NMR spectrum, and FIG. 10 shows an IR spectrum.

Examples 1 to 5 An aluminum-evaporated polyester film (thickness: 80 μm) was used as a support.

[0091]

Embedded image

The bisazo pigment represented by the formula (1) was added to a 1% THF solution of a phenoxy resin (manufactured by Union Carbide: PKHH) in the same amount as the resin in a weight ratio. 5mm
Was dispersed for about 2 hours together with the glass beads, and applied and dried by a doctor blade method. The film thickness after drying was 0.2 μm.

On this pigment layer (carrier generation layer), the exemplary compound No. 1, No. 3, No. 16, N
o. 36 or No. 45 g and a solution (15%) of 1.2 g of a polyarylate resin (U-100, manufactured by Unitika) in methylene chloride was applied by a squeezing doctor, and a resin-bisamine compound solid solution phase having a dry film thickness of 25 μm ( Carrier moving layer).

The electrophotographic characteristics of the laminated electrophotographic photosensitive member prepared as described above were evaluated using an electrostatic recording paper tester (SP-428, manufactured by Kawaguchi Electric). The measurement conditions were as follows: applied voltage: -6 kV, static: No. 3, from -700 V to -1 by white light irradiation (irradiation light: 5 lux)
Exposure amount E ₁₀₀ required to attenuate to 00V (looks
Second) and the initial potential V ₀ (−volt) were measured, and the values are shown in Table 6. Further, using the same apparatus, the exposure amount E ₁₀₀ (lux seconds) and the exposure amount after performing the same operation 10,000 times with one cycle of charge-discharge (static light: irradiation of 40 lux white light for 1 second) and Measure the initial potential V ₀ (−volt),
We examined the changes in the E ₁₀₀ and V _0.

[0095]

[Table 6]

Table 6 shows that the bisamine compound of the present invention also has good sensitivity repetition characteristics.

Example 6 An x-type metal-free phthalocyanine (Fast Genble-8, manufactured by Dainippon Ink) on an aluminum-evaporated polyester film
120) 0.4 g was added to 30 ml of an ethyl acetate solution in which 0.3 g of a vinyl chloride: vinyl acetate copolymer resin (manufactured by Sekisui Chemical Co., Ltd .: Eslex M) was dissolved, and dispersed in a paint conditioner for about 20 minutes. The carrier generation layer was formed so that the film was coated by a blade method and dried to have a thickness of 0.4 μm.

On this carrier generating layer, the exemplary compound No. A polyarylate layer containing 50% by weight of the bisamine compound No. 5 was laminated to form a two-layer photoreceptor.

The energy (E ₅₀ ) required for halving the potential and the initial potential (−V ₀ ) of this photosensitive member using 780 nm light
Were obtained, V ₀ = 780 (volts) and E ₅₀ =
The photosensitive member had a very high sensitivity of 2.8 (erg / cm ² ) and a high chargeability.

Further, a laser printer (WD-580P) manufactured by Sharp Corporation was remodeled, the photoreceptor was attached to the drum section, and a continuous blank copy (Non Copy Agin) was performed.
After performing g) 10,000 times, the degree of the decrease in the initial potential and the sensitivity was also examined. As a result, V ₀ = 765 (V), E ₅₀ = 2.8 (ergs / cm ²⁾ and the variation of the most value compared with the first round was not observed.

Examples 7 to 10 Anodized aluminum substrate surface (alumite layer: 7 μm)
m) on the support thus prepared. 3, N
o. 10, No. 38 or No. 1 g of 45, the following structural formula

[0102]

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1.1 g of a polyarylate resin represented by the following formula:
A solution prepared by dissolving 0.15 g of N, N-3,5-xylyl-3,4,9,10-perylenetetracarboximide and 0.05 g of an ultraviolet absorber in methylene chloride (an imide compound is partially dispersed) is applied by an applicator. Apply,
A single-layer photoreceptor having a dry film thickness of 20 μm was obtained.

The electrophotographic characteristics of the photoreceptor prepared as described above were evaluated using an electrostatic recording paper tester. The measurement conditions were as follows: applied voltage: -5.5 kV, static: No. 3 was performed. The exposure amount E ₁₀₀ (lux · second) required for attenuating from +700 V to +100 V by white light irradiation was measured, and the value is shown in Table 7. In addition, Perform a blank copy test of 10,000 times, the degree of reduction in sensitivity (E ₁₀₀₎ are also shown in Table 7.

[0105]

[Table 7]

The photoreceptor using the bisamine compound of the present invention was found to have excellent sensitivity and repetition characteristics even in positive charging.

[0107]

As described above, according to the present invention, the photoreceptor contains a bisamine compound, so that an organic electrophotographic photoreceptor having high sensitivity and high durability can be provided. It has the advantages of organic photoreceptors that are non-toxic, have no problem with resources, have good transparency, are lightweight, have excellent film-forming properties, have both positive and negative chargeability, and are easy to manufacture. A useful electrophotographic photoreceptor having excellent characteristics that photosensitivity hardly decreases even after repeated use, and bisamine compounds and intermediates used therein, and methods for producing these intermediates and bisamine compounds I will provide a.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically illustrating a layer configuration of an electrophotographic photosensitive member using a bisamine compound of the present invention.

FIG. 2 is a cross-sectional view schematically illustrating a layer configuration of an electrophotographic photoreceptor using the bisamine compound of the present invention.

FIG. 3 is a cross-sectional view schematically illustrating a layer configuration of an electrophotographic photosensitive member using the bisamine compound of the present invention.

FIG. 4 is a cross-sectional view schematically illustrating a layer configuration of an electrophotographic photosensitive member using the bisamine compound of the present invention.

FIG. 5 is a cross-sectional view schematically illustrating a layer configuration of an electrophotographic photoreceptor using the bisamine compound of the present invention.

FIG. 6 is a cross-sectional view schematically showing a layer configuration of an electrophotographic photoreceptor using the bisamine compound of the present invention.

FIG. 7 is a 1H-NMR spectrum of an exemplary compound of the present invention.

FIG. 8 shows a typical 13C in one exemplified compound of the present invention.
-It is an NMR spectrum figure.

FIG. 9 shows DEPT135 in one exemplary compound of the present invention.
FIG. 13 is a 13C-NMR spectrum diagram of FIG.

FIG. 10 is an IR spectrum of an exemplary compound of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2 Carrier generating material 3 Carrier moving material 4, 4 'photosensitive layer 5 Carrier generating layer 6 Carrier moving layer

Claims (11)

[Claims] 1. A carrier transfer material according to the following general formula (1): [In the formula, Ar1 and Ar2 represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, or a heterocyclic-substituted alkyl group. And Z is an O, S, or Se atom. R1, R2
Is an alkyl group having 1 to 3 carbon atoms which may have a substituent, an alkoxy group having 1 to 3 carbon atoms,
Represents a dialkylamino group, a halogen atom or a hydrogen atom, wherein m is an integer of 1 to 4, and n is an integer of 1 to 3. However, when n and m are 2 or more, R1
And R2 may be the same or different, and may form a ring with each other. ] An electrophotographic photoreceptor comprising the bisamine compound of [1]. 2. The bisamine compound represented by the general formula (1) is represented by the following structural formula (2): The electrophotographic photoreceptor according to claim 1, wherein Ar 1, Ar 2, R 1, R 2, m, and n are the same as defined in the general formula (1). 3. The bisamine compound represented by the general formula (1) is represented by the following structural formula (3): [In the formula, R3 and R4 each represent an optionally substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, or a hydrogen atom. And l and k are integers of 1 to 3. R1, R2, m and n have the same meanings as in the above formula (1)]. 4. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer comprises a layer containing the carrier transfer material and the carrier generation material. 5. The photosensitive layer according to claim 1, wherein the photosensitive layer comprises a laminate of a carrier transporting layer containing the carrier transporting substance and a carrier generating layer containing the carrier transporting substance. Electrophotographic photoreceptor. 6. A compound represented by the following general formula (4): [Wherein, Ar1, Ar2, Z, R1, R2, m, and n have the same meaning as in the above general formula (1). A bisamine compound represented by the formula: 7. A compound represented by the general formula (5): [Wherein, X represents a Cl, Br, I atom, and R1, R2,
m and n have the same meanings as in the above general formula (1). ] A halogenated benzofuran, benzothiophene or benzoselenophene derivative represented by the formula: 8. A compound represented by the following general formula (6): [Wherein, Ar1, Z, R1, R2, m, and n have the same meaning as in the above general formula (1). And a bisamine compound having a secondary amino group. 9. A compound represented by the general formula (7): [Wherein, Z, R1, R2, m and n have the same meanings as in the above general formula (1). The method for producing a halogenated derivative according to claim 7, wherein the amino compound represented by the formula (1) is converted into a halide by a Sandmeyer reaction. 10. The method for producing a bisamine compound having a secondary amino group according to claim 8, wherein the halogenated derivative according to claim 7 and an aniline derivative are coupled by an Ullmann reaction. 11. A bisamine compound having a secondary amino group according to claim 8 or an amine compound represented by the general formula (7) and an aryl halide are coupled by an Ullmann reaction. Item 6
The method for producing a bisamine compound according to the above.