JPH1138657A - Electrophotographic photoreceptor and bisenamine compound, amine compound and nitro compound and method for manufacturing these compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoreceptor superior in stability against temperature and humidity and high in static charge characteristic and hard in occurrence of sensitivity deterioration due to repeated uses. SOLUTION: Th photosensitive layer of the photoreceptor formed on an electrically conductive substrate contains the enamine compound represented by the formula, in which Ar1 is an aryl, aralkyl or alkyl group; R1 is a 1-3C alkyl, such alkoxy or such dialkyl-amino group or a halogen or H atom; Y is an O or S or monosubstituted N atom; (m) is an integer of 1-8; and (n) is 1, 2, or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a specific bisenamine compound contained in a photosensitive layer formed on a conductive support. is there.

[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) chargeability of a charge by corona discharge in a dark place. 2) The obtained charge due to corona discharge is less attenuated in a dark place. 3) The charge is quickly dissipated by light irradiation. 4) The residual charge after light irradiation is small. 5) Repetition. And 6) little change in electrophotographic characteristics due to temperature and humidity, and the like.

As such materials, inorganic photoconductive materials such as zinc oxide (Japanese Patent Publication No. 57-19780), cadmium sulfide (Japanese Patent Publication No. 58-46018), and amorphous selenium alloy have been conventionally 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.

[0004] From a future perspective, electrophotography made of an organic material rather than an inorganic material, which has production problems due to resource depletion, concerns about pollution due to toxicity, and environmental problems. 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 charge generation layer and a hole-transport charge-transport layer on a conductive layer. Are stacked in order, and the charge transfer surface is negatively charged.

[0005] As described above, by separating the functions, it becomes possible to independently develop materials having the functions of charge generation and charge transfer, respectively. As a result, charges having various molecular structures can be obtained. Many generators, as well as charge transfer materials, have been developed.

[0006] Electrophotographic photoreceptors using these organic compounds are produced 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 charge transfer materials, a typical one of them is classified according to the structural characteristics. The hydrazone type (JP-A-54-59143) and the stilbene-styryl type (JP-A-54-59143) JP-A-58-198043), triarylamines (JP-B-58-32372).
), Phenothiazines, triazoles, quinoxalines, oxadiazoles, oxazoles, pyrazolines, triphenylmethanes, dihydronicotinamide compounds, indoline compounds, semicarbazone compounds, and the like.

[0008]

However, in spite of the fact that many organic compounds have been developed as charge transfer materials as described above, 1) low compatibility with a binder, and 2) easy precipitation of crystals. 3) There is no organic compound that satisfies the following problems: 3) a change in sensitivity occurs when used repeatedly; 4) poor charging ability and repetition characteristics; 5) poor residual potential characteristics. At present, those which satisfy the basic properties required as well as mechanical strength, high durability and the like have not yet been sufficiently obtained.

An object of the present invention is to provide an electrophotographic photosensitive member having high sensitivity and high durability, an organic compound used as a carrier transfer material of the electrophotographic photosensitive member, and a compound intermediate necessary for synthesizing the carrier transfer material. It is an object of the present invention to provide an efficient method for synthesizing the compound and the compound. In particular, the photoreceptor of the present invention has excellent stability against temperature and humidity,
Another object of the present invention is to provide a photoreceptor which has high charging characteristics and hardly causes a decrease in sensitivity even when used repeatedly.

[0010]

Means for Solving the Problems The present inventors have studied the above-mentioned photoconductive substance having high sensitivity and high durability, and as a result, the following general formulas (I), (V), (I
The present inventors have found that the bisenamine compounds represented by X) and (XV) are effective, and have reached the present invention.

That is, the electrophotographic photoreceptor according to the present invention (claim 1) achieves the above object by the fact that the photosensitive layer formed on the conductive support contains the bisenamine compound represented by the general formula (I). To achieve.

[0012]

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(Wherein, Ar 1 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. R1 is an optionally substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms.
Represents a dialkylamino group, a halogen atom or a hydrogen atom, Y represents an oxygen atom, a sulfur atom, or a monosubstituted nitrogen atom, m is an integer of 1 to 8, and n is an integer of 1 to 3. However, when m is 2 or more, R1 may be the same or different. In the general formula (I), Ar1 is specifically an aryl group such as phenyl, tolyl, methoxyphenyl, naphthyl, pyrenyl, biphenyl, benzofuryl, benchazolyl,
Heterocyclic groups such as benzoxazolyl and N-ethylcarbazolyl; aralkyl groups such as methylbenzyl and methoxybenzyl; and the like. R1 is specifically methyl, ethyl, n-propyl, Iso-propyl and the like. An alkyl group of
Examples thereof include alkoxy groups such as methoxy, ethoxy, n-propoxy and iso-propoxy, dialkylamino groups such as dimethylamino, diethylamino and di-iso-propylamino, and halogen atoms such as fluorine, chlorine and bromine. Generally, an electron donating substituent is effective.

Here, general formulas (II), (III),
It is more preferable to use the bisenamine compound represented by (IV).

[0015]

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(Wherein, Ar1, R1, m and n are as defined in claim 1)
Is synonymous with )

[0017]

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(Wherein, Ar1, R1, and m are as defined in claim 1).

[0019]

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(Wherein, R 2 represents an optionally substituted alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms,
Represents a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and 1 represents a positive number from 1 to 5.
However, when 1 is 2 or more, R2 may be the same or different. R1 and m are as defined in claim 1. The electrophotographic photoreceptor according to the present invention (claim 2)
The above object is achieved when the photosensitive layer formed on the conductive support contains the bisenamine compound represented by the general formula (V).

[0021]

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(Wherein Ar2 and Ar3 are 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. , Or a hydrogen atom (where Ar2, A
R2 is an 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 which may have a substituent. Alternatively, it represents a hydrogen atom, and 1 is an integer of 1 to 4. However, when 1 is 2 or more, R2 may be the same or different. R3 represents an aryl group which may have a substituent, a heterocyclic ring which may have a substituent, an aralkyl group which may have a substituent, an alkyl group or a hydrogen atom. R1, m, n and Y have the same meaning as in claim 1. In the general formula (V), Ar2 and Ar3 are specifically an aryl group such as phenyl, tolyl, methoxyphenyl, naphthyl, pyrenyl, biphenyl, or a complex such as benzofuryl, benchazolyl, benzoxazolyl, N-ethylcarbazolyl or the like. A ring group, an aralkyl group such as methylbenzyl, methoxybenzyl and the like, and R1 and R2 are specifically an alkyl group such as methyl, ethyl, n-propyl and Iso-propyl, methoxy, ethoxy, n-propoxy,
Examples thereof include an alkoxy group such as iso-propoxy, a dialkylamino group such as dimethylamino, diethylamino and di-iso-propylamino, and a halogen atom such as fluorine, chlorine and bromine. R3 is, specifically, an alkyl group such as methyl, ethyl, n-propyl, and iso-propyl. Generally, an electron donating substituent is effective.

Here, the general formulas (VI), (VII),
It is preferable to use the bisenamine compound represented by (VIII).

[0024]

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(Wherein, Ar2, Ar3, R1, R2,
1, m, and n have the same meaning as in claim 2. )

[0026]

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Wherein Ar2, Ar3, R1, R2,
l and m have the same meaning as in claim 2. )

[0028]

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(Wherein, R 4 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 having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and p represents a positive number from 1 to 5.
However, when p is 2 or more, R2 may be the same or different. Ar3, R1, R2, 1, and m have the same meaning as in claim 2. Further, the electrophotographic photoreceptor according to the present invention (claim 3) is:
The object is achieved by the fact that the photosensitive layer formed on the conductive support contains the bisenamine compound represented by the general formula (IX).

[0030]

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(Wherein, Ar 4 and Ar 5 are 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 an alkyl group which is substituted with a heterocyclic group. , Or a hydrogen atom, and may form a ring with each other directly or through a divalent linking group (methylene, ethylene, vinylene, oxygen atom, sulfur atom).
R1, R2, R3, m, n, 1, Y are as defined in claim 2. In the general formula (IX), Ar4 and Ar5 are specifically an aryl group such as phenyl, tolyl, methoxyphenyl, naphthyl, pyrenyl, biphenyl, or a complex such as benzofuryl, benchazolyl, benzoxazolyl, N-ethylcarbazolyl or the like. A ring group, an aralkyl group such as methylbenzyl, methoxybenzyl and the like, and R1 and R2 are specifically an alkyl group such as methyl, ethyl, n-propyl and Iso-propyl, methoxy, ethoxy, n-propoxy,
Examples thereof include an alkoxy group such as iso-propoxy, a dialkylamino group such as dimethylamino, diethylamino and di-iso-propylamino, and a halogen atom such as fluorine, chlorine and bromine. R3 is, specifically, an alkyl group such as methyl, ethyl, n-propyl, and iso-propyl. Generally, an electron donating substituent is effective.

Here, the general formulas (X), (XI) and (XI)
It is preferable to use bisenamine compounds represented by I), (XIII) and (XIV).

[0033]

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(Wherein, Ar4, Ar5, R1, R2,
l, m, and n have the same meaning as in claim 3. )

[0035]

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(Wherein, Ar4, Ar5, R1, R2,
l and m have the same meaning as in claim 3. )

[0037]

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(Wherein R5 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 having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and q represents a positive number from 1 to 5.
However, when q is 2 or more, R2 may be the same or different. Ar5, R1, R2, 1, and m have the same meaning as in claim 3. )

[0039]

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(Wherein R5 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 having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and r represents a positive number from 1 to 8.
However, when r is 2 or more, R4 may be the same or different. R1, R2, l, and m have the same meaning as in claim 3. )

[0041]

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(Wherein R5 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 having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and s represents a positive number from 1 to 10. However, when s is 2 or more, R4 may be the same or different. R1, R2, l, and m have the same meaning as in claim 3. Further, the electrophotographic photoreceptor according to the present invention (claim 4) is:
The object is achieved by the fact that the photosensitive layer formed on the conductive support contains the bisenamine compound represented by the general formula (XV).

[0043]

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(Wherein R5 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 having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, t represents a positive number from 1 to 10, and Z represents a divalent linking group which may have a substituent (methylene, ethylene, Vinylene, oxygen atom, sulfur atom). However, when t is 2 or more, R4 may be the same or different. R1, R2, R3, l, m, n, and Y are as defined in claim 2.
Is synonymous with In the general formula (XV), R1, R2, and R5 are specifically alkyl groups such as methyl, ethyl, n-propyl, and iso-propyl, methoxy, ethoxy, n-propoxy, i
alkoxy groups such as so-propoxy, dimethylamino,
Examples thereof include dialkylamino groups such as diethylamino and di-iso-propylamino, and halogen atoms such as fluorine, chlorine, and bromine. R3 is specifically methyl, ethyl, n
And alkyl groups such as -propyl and Iso-propyl. Generally, an electron donating substituent is effective.

Here, the general formulas (XVI) and (XVI
It is preferable to use bisenamine compounds represented by I), (XVIII) and (XIX).

[0046]

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(Wherein, R 6 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 having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, t represents a positive number from 1 to 10, and Z represents a divalent linking group which may have a substituent (methylene, ethylene, Vinylene, oxygen atom, sulfur atom). However, when t is 2 or more, R5 may be the same or different. R1, R2, 1, m, and n have the same meaning as in claim 3. )

[0048]

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(Wherein R 6 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 having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, t represents a positive number from 1 to 10, and Z represents a divalent linking group which may have a substituent (methylene, ethylene, Vinylene, oxygen atom, sulfur atom). However, when t is 2 or more, R5 may be the same or different. R1, R2, l, and m have the same meaning as in claim 3. )

[0050]

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(Wherein, R 6 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 having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and t represents a positive number from 1 to 10. However, when t is 2 or more, R4 may be the same or different. R1, R2, l, and m have the same meaning as in claim 3. )

[0052]

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(Wherein R 6 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 having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and u represents a positive number from 1 to 10. However, when u is 2 or more, R5 may be the same or different. R1, R2, l, and m have the same meaning as in claim 3. The bisenamine compound of the general formula (I) according to the present invention can be synthesized by various methods, but is usually easily synthesized by the following synthesis process. That is, the following general formula (XX)
(In the formula, R1, m, n, and Y have the same meaning as in claim 1.)
An aldehyde compound represented by the formula (2.0-2.8 equivalents)
And the following general formula (XXIII)

[0054]

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In the presence of an amine compound represented by the formula (1.0 equivalent) and an acid catalyst such as p-toluenesulfonic acid, camphorsulfonic acid, pyridinium-p-toluenesulfonic acid, toluene, xylene, chlorobenzene, chloroform, It can be easily synthesized by heating and stirring in an organic solvent such as those described above for 2 to 18 hours and removing by-produced water by reaction.

The bisenamine compound of the general formula (V) according to the present invention can be synthesized by various methods, but is usually easily synthesized by the following synthesis process. That is, an aldehyde compound represented by the following general formula (XX) (wherein R1, m, n, and Y are as defined in claim 1) (2.0-
2.8 equivalents) and the following general formula (XXV)

[0057]

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(Wherein Ar 2, Ar 3, R 2, and R 31 are as defined in claim 2) (1.0 equivalent) and p-toluenesulfonic acid, camphorsulfonic acid, pyridinium-p -Easily synthesized by heating and stirring in an organic solvent such as toluene, xylene, chlorobenzene, chloroform, etc. for 2-18 hours in the presence of an acid catalyst such as toluenine sulfonic acid to boil off water by-produced by the reaction. it can.

The bisenamine compound of the general formula (IX) according to the present invention can be synthesized by various methods, but is usually easily synthesized by the following synthesis steps. That is, an aldehyde compound represented by the following general formula (XX) (wherein R1, m, n, and Y are as defined in claim 1) (2.0-
2.8 equivalents) and the following general formula (XXIX)

[0060]

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(Wherein Ar 4, Ar 5, R 2, and R 31 are as defined in claim 3) and p-toluenesulfonic acid, camphorsulfonic acid, pyridinium-p. -Easily synthesized by heating and stirring in an organic solvent such as toluene, xylene, chlorobenzene, chloroform, etc. for 2-18 hours in the presence of an acid catalyst such as toluenine sulfonic acid to boil off water by-produced by the reaction. it can.

The bisenamine compound of the general formula (XV) according to the present invention can be synthesized by various methods, but is usually easily synthesized by the following synthesis process. That is, an aldehyde compound represented by the following general formula (XX) (wherein R1, m, n, and Y are as defined in claim 1) (2.0-
2.8 equivalents) and the following general formula (XXXII)

[0063]

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(Wherein R5, R2, R3, l, t, and Z have the same meanings as in claim 4) and p-toluenesulfonic acid and camphorsulfonic acid. , Pyridinium-p-toluenesulfonic acid, etc., in the presence of an acid catalyst such as toluene, xylene, chlorobenzene, chloroform, etc. for 2 to 18 hours while stirring to boil off water by-produced by the reaction. And can be easily synthesized.

The aldehyde compound of the general formula (XX) according to the present invention can be synthesized by various methods, but is usually easily synthesized by the following synthesis process. That is, a carbonyl compound (1.0 equivalent) represented by the following general formula (XXI) (wherein R1, m, n, and Y are as defined in claim 1) and the following general formula (XXII)

[0066]

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(Wherein R4 represents a lower alkyl group;
Represents a halogen atom. ) With a base (1.0-3.5 equivalents) such as sodium alkoxide and potassium alkoxide.
Equivalent) in the presence of an organic solvent such as toluene, xylene, etc.
The reaction is carried out at a temperature of -5 to +5 degrees for 2-8 hours. Then, the glycidyl ester compound obtained by this reaction is converted into a hydroxide compound such as sodium hydroxide or potassium hydroxide (based on the weight of the glycidyl ester compound) in an organic solvent such as methanol, ethanol, butanol, tetrahydrofuran, or 1,4-dioxane. 2-4 times the amount)
The mixture is heated and stirred at a temperature of 50-80 degrees for 2-8 hours to hydrolyze the ester moiety. Then, an organic solvent such as toluene, xylene and chlorobenzene is added, and an acid such as 10-20% hydrochloric acid or sulfuric acid is gradually added, and the pH of the solution is changed to 2-4.
And The organic layer can be synthesized by separating the organic layer, washing with water, distilling the organic layer, and distilling the crude product under reduced pressure.

The amine compound of the general formula (XXV) according to the present invention can be synthesized by various methods, but is usually easily synthesized by the following synthesis process. That is, a carbonyl compound (1.0 equivalent) represented by the following general formula (XXVI) (wherein R2, R3, and l are as defined in claim 2) and the following general formula (XXVII)

[0069]

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(Wherein R5 represents a lower alkyl group or an aryl group which may have a substituent, and Ar2 and Ar3 have the same meanings as in claim 2).
1.5 equivalents) in the presence of a base (1.0-2.0 equivalents) such as sodium alkoxide, potassium alkoxide, etc., in N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, 1,4-dioxane, etc. In an organic solvent at a temperature of -5 to +5 degrees for 2 to 8 hours. Then, the obtained compound represented by the following general formula (XXIV)

[0071]

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(Wherein Ar2, Ar3, R2, R3, l
Has the same meaning as in claim 2. ) In a mixed solvent such as tetrahydrofuran / water, 1,4-dioxane / water and the like.
The amine compound represented by the general formula (XXV) can be easily synthesized by performing a reduction reaction with an equivalent ratio of −20 and vigorous heating and stirring.

The amine compound of the general formula (XXIX) according to the present invention can be synthesized by various methods, but is usually easily synthesized by the following synthesis process. That is, an aldehyde compound (1.0 equivalent) represented by the following general formula (XXVI) (wherein R1, R3, and l have the same meanings as in claim 3) and the following general formula (XXX)

[0074]

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(Wherein Ar4 and Ar5 have the same meaning as in claim 3) (1.0-1.
5 eq.) In an organic solvent such as methanol, ethanol, propanol or the like, and heated to a temperature of 60-80 ° C. for 2-8 hours. Then, the obtained compound represented by the following general formula (XXVII) was obtained.
I)

[0076]

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(Wherein R 6, R 2, R 3, l, t, and z have the same meaning as in claim 4) in a mixed solvent such as tetrahydrofuran / water and 1,4-dioxane / water. 100-200 mesh iron powder 1: 10-
An amine compound of the general formula (XXIX) can be easily synthesized by performing a reduction reaction in which the mixture is added at an equivalent ratio of 20 and heated and stirred vigorously.

The amine compound of the general formula (XXXII) according to the present invention can be synthesized by various methods, but is usually easily synthesized by the following synthesis process. That is, the following general formula (XXVI) (wherein R1, R3, and l are
Is synonymous with Aldehyde compound (1.0)
Equivalent) and the following general formula (XXXIII)

[0079]

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(Wherein R 6, t and Z have the same meanings as in claim 4) (1.0 to 1.5)
Is heated in an organic solvent such as methanol, ethanol, propanol or the like to a temperature of 60-80 ° C. and reacted for 2-8 hours. Then, the obtained compound represented by the following general formula (XXXI)

[0081]

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(Wherein R 6, R 2, l, t, and z have the same meanings as in claim 4) in a mixed solvent such as tetrahydrofuran / water or 1,4-dioxane / water. An amine compound of the general formula (XXXII) can be easily synthesized by adding -200 mesh iron powder at an equivalent ratio of 1: 10-20 and performing a reduction reaction with vigorous heating and stirring.

Next, the general formulas (I), (V) and (I)
Specific examples of the bisenamine compounds of the present invention represented by X) and (XV) include those having the structures shown in the following Tables 1 to 5, which limit the bisenamine compounds of the present invention. Not something.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

The electrophotographic photoreceptor according to the present invention can be obtained by containing one or more of the above-described bisenamine compounds. In some cases, as another charge transporting material, 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},
Alternatively, the following hydrazone compound {for example, 4- (dibenzylamino) benzaldehyde-N, N-diphenylhydrazone, 4- (ethylphenylamino) benzaldehyde-N, N-diphenylhydrazone, 4-di (p-tolylamino) benzaldehyde- N, N-diphenylhydrazone, 3,3-bis- (4′-diethylaminophenyl) -acrolein-N, N-diphenylhydrazone or the following triphenylamine compound {for example, 4-methoxy-4 ′-(4- (Methoxystyryl) triphenylamine, 4-methoxy-4'-styryltriphenylamine} and the like.

Various methods can be considered for using these bisenamine compounds as an electrophotographic photosensitive member. For example, a photoconductor formed by dissolving or dispersing a bisenamine compound and a sensitizing dye in a binder resin by adding a chemical sensitizer or an electron-withdrawing compound as necessary, and providing the resultant on a conductive support. Or, in the form of a laminated structure composed of a carrier generation layer and a carrier transfer layer having a high charge carrier generation efficiency, a sensitizing dye or an azo pigment, a pigment represented by a phthalocyanine pigment is mainly used on a conductive support. The bisenamine compound of the present invention is dissolved or dispersed in a binder by adding an antioxidant compound or an electron-withdrawing compound, if necessary, on the provided carrier generating layer, and is provided as a carrier transfer layer. There is a body and the like, but it is possible to apply in any case.

In preparing a photoreceptor using the compounds of the present invention, the aid of a polymer film-forming binder on a support such as a metal drum, metal plate, electrically processed paper, or 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. Among them, resins such as polystyrene, polycarbonate, polyarylate, and polyphenylene oxide have a volume resistivity of 10 ¹³ Ω or more, and are excellent in film properties, potential characteristics, and the like.

The amount of these binders to be added to the bisenamine compound of the present invention is 0.2 to 20 times by weight, preferably 0.5 to 5 times, and less than 0.2. When this happens, the disadvantage that the bisenamine compound precipitates from the surface of the photoreceptor occurs, and when it becomes 20 times or more, the sensitivity is remarkably reduced.

For use in a printing plate, 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 charge carriers with extremely high efficiency by light absorption in the photosensitive layer include phthalocyanine pigments such as various metal phthalocyanines, metal-free phthalocyanines, halogen-free metal phthalocyanines, perylene imides, and the like. Examples include perylene acid pigments such as perylene anhydride, 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 the pigment that generates charge carriers exhibit high sensitivity. Provide an electrophotographic photoreceptor.

Further, the above-mentioned dye may be used as a charge carrier generating substance. These dyes may be used alone, but they often generate charge 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 the residual potential, a decrease in the charged potential, a decrease in the sensitivity and the like 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-nitrobenzalmalone dinitrile, ethyl α-cyano-β- (p-cyanophenyl) acrylate 9-anthracenylmethylmalondinitrile 1-cyano-1- (p-nitrophenyl) -2- (p-chlorophenyl) ethylene, 2,7-
Electron-withdrawing compounds such as dinitrofluorenone; In addition, antioxidants,
An anti-curl agent, a leveling agent and the like can be added as needed.

The bisenamine compound of the present invention is dissolved or dispersed in a suitable solvent together with the above-mentioned various additives depending on the form of the photoreceptor, and the coating solution is coated on the conductive support described above. 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 bisenamine compound represented by the general formula (I) as a carrier transfer material, and various embodiments can be considered in the embodiment. 6 is schematically shown in FIG.

FIG. 1 shows a photosensitive layer 4 as a photosensitive layer 4 on a conductive support 1, in which a carrier generating layer 5 containing a carrier generating substance 2 as a main component and dispersed in a binder, and a carrier transferring substance 3 as a main component. A function-separated type photoconductor comprising a layered structure with a dispersed carrier moving layer 6, wherein the carrier moving layer 6 is formed on the surface of the carrier generating layer 5,
In the carrier transfer layer 6, as a carrier transfer substance 3,
1 shows a configuration of a photoreceptor using the bisenamine compound of the present invention.

FIG. 2 shows the same carrier generation layer 5 as in FIG.
And a carrier transfer layer 6, a carrier separation layer is formed on the surface of the carrier transfer layer 6, contrary to FIG. 3 shows a configuration of a photoreceptor using the bisenamine compound of the present invention as the carrier transfer material 3.

FIG. 3 shows the structure of a photoreceptor composed of a single layer in which a carrier generating substance 2 and a carrier transfer substance 3 are dispersed in a binder as a photosensitive layer 4 on a conductive support 1.

FIG. 4 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.

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 in FIG. 3, and shows the structure of a single-layer photosensitive member.

The intermediate layer 8 provided between the conductive support 1 and the photosensitive layer 4 has a protective function and an adhesive function.
It is intended to improve coatability and further improve charge injection from the substrate to the photosensitive layer.
Suitable are casein, 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.

[0106]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Synthesis Example 1 15.0 g (1.0 equivalent) of 4-formyl roman 4-chromanone and 24.8 g (2.0 equivalents) of ethyl monochloroacetate were combined with 11.5 g (2 equivalents) of sodium methoxide. (1 equivalent) in a 300 ml toluene solvent at a temperature of -5 to +5 degrees for 8 hours. After the completion of the reaction, excess sodium methoxide was crushed by adding water and neutralized with a 1N hydrochloric acid solution, and then the toluene layer was separated.
Extract twice with 0 ml of toluene. All the toluene is combined and concentrated by an evaporator to obtain 14.3 g of a glycidyl ester compound as a crude product.

Then, the glycidyl ester compound was treated with sodium hydroxide 5.0 in 120 ml of methanol solvent.
0 g is added, and the mixture is heated and stirred at a temperature of 60 ° C. for 4 hours to hydrolyze the ester portion. Then, 200 ml of toluene solvent was added, and 10% sulfuric acid was gradually added to adjust the pH of the solution to 3. After separating the organic layer, the organic layer was distilled off after washing with water, and the crude product was distilled under reduced pressure of 0.1 mmHg to obtain a crude product.
8.4 g (yield = 50.6%) of the desired 4-formyl roman is obtained as a 6-9 degree fraction.

The compound obtained in this manner is 1H-N
MR spectrum, normal 13C-NMR spectrum, D
The 13C-NMR spectrum by EPT-135 confirmed that it was the desired 4-formyl roman.

FIG. 6 shows the 1H-NMR spectrum of 4-formyl roman in deuterated chloroform. FIG. 7 shows 13C-NM of 4-formyl roman in deuterated chloroform.
2 shows an R spectrum. FIG. 8 shows 4-
13C-NMR of formyl roman on DEPT135
The spectrum is shown.

Synthesis Example 2 10.0 g of 3-aminobenzaldehyde-N, N-diphenylhydrazone 3-nitrobenzaldehyde and 15.04 g of N, N-diphenylhydrazine hydrochloride (1.03 equivalent)
Is heated to a temperature of 80 degrees in 200 ml of ethanol,
Incubate for 8 hours. The crystals obtained by the reaction are filtered off,
After washing with ethanol, dry thoroughly. Then, 200 mesh iron powder was added to 3 ml of the obtained 3-nitrobenzaldehyde-N, N-diphenylhydrazone compound in 300 ml of a mixed solvent of 1,4-dioxane / water 1: 1.
Add 0.0 g (8.0 equivalents), and vigorously heat and stir for 2 hours. After completion of the reaction, the mixture was filtered through hot celite and the filtrate was concentrated to obtain the desired 3-aminobenzaldehyde-N,
17.2 g of N-diphenylhydrazone (yield = 90.
8%).

The compound obtained in this way is 1H-N
MR spectrum, normal 13C-NMR spectrum, D
The 13C-NMR spectrum using EPT-135 confirmed that the target product was 3-aminobenzaldehyde-N, N-diphenylhydrazone.

FIG. 9 shows 1H of 3-aminobenzaldehyde-N, N-diphenylhydrazone in deuterated chloroform.
-Shows an NMR spectrum. FIG. 10 shows a 13 C-NMR spectrum of 3-aminobenzaldehyde-N, N-diphenylhydrazone in deuterated chloroform. FIG.
3-aminobenzaldehyde in deuterated chloroform
1 of N, N-diphenylhydrazone at DEPT135
3 shows a 3C-NMR spectrum.

(Synthesis Example 3) 7.0 g of 4'-aminobenzaldehyde-1-amino-1,2,3,4-tetrahydroquinolinehydrazone 4-nitrobenzaldehyde and 1-amino-
6.95 g of 1,2,3,4-tetrahydroquinoline
(1.01 eq.) Is heated to a temperature of 80 ° C. in 150 ml of ethanol and reacted for 8 hours. The crystals obtained by the reaction are separated by filtration, washed with ethanol and dried sufficiently.
Then, the obtained 4'-nitrobenzaldehyde-1-
13.0 g of the amino-1,2,3,4-tetrahydroquinoline hydrazone compound was mixed with 200 mesh iron powder in 250 ml of a 1: 1 solvent mixture of 1,4-dioxane / water.
5.85 g (10.0 equivalents) were added, and the mixture was vigorously stirred with heating.
Do time. After completion of the reaction, the solution was filtered through celite while hot and the filtrate was concentrated to obtain 9.11 g of the desired 4'-aminobenzaldehyde-1-amino-1,2,3,4-tetrahydroquinoline hydrazone (yield = 78.36%). obtain.

The compound obtained in this manner is 1H-N
MR spectrum, normal 13C-NMR spectrum, D
The target 4'-aminobenzaldehyde-1-amino- was determined by 13C-NMR spectrum using EPT-135.
It was confirmed to be 1,2,3,4-tetrahydroquinoline hydrazone.

FIG. 12 shows the 1H-NMR spectrum of 4'-aminobenzaldehyde-1-amino-1,2,3,4-tetrahydroquinoline hydrazone in deuterated chloroform. FIG. 13 shows a 13 C-NMR spectrum of 4′-aminobenzaldehyde-1-amino-1,2,3,4-tetrahydroquinoline hydrazone in deuterated chloroform. FIG. 14 shows 13 ′ of 4′-aminobenzaldehyde-1-amino-1,2,3,4-tetrahydroquinoline hydrazone in DEPT135 in deuterated chloroform.
1 shows a C-NMR spectrum.

(Synthesis Example 4) 15.8 g of diethyl 4- (N, N-dimethylamino) -4'-aminostilbene p-nitrobenzylphosphonate
(1.08 equivalents) was dissolved in a mixed solvent of 100 ml of tetrahydrofuran and 50 ml of dimethylformamide, and the internal temperature was cooled to 0 ° C with an ice bath. Then, 8.0 g (1.2 equivalents) of potassium t-butoxide was added, and the mixture was stirred for about 30 minutes. Thereafter, a solution in which 8.0 g of 4-dimethylaminobenzaldehyde is dissolved in 40 ml of tetrahydrofuran is gradually added at the same temperature. When the addition is complete, remove the ice bath and leave it overnight. For the post-treatment of the reaction, a saturated aqueous solution of citric acid is added into the reaction system, the excess base is neutralized, and then the solvent tetrahydrofuran is removed by an evaporator, and the resulting solid is filtered. The obtained solid is sufficiently washed with ethanol and dried under reduced pressure.
4- (N, N-dimethylamino) thus obtained
14.0 g of -4'-nitrostilbene was added to 30.0 g (10.0 equivalents) of 200 mesh iron powder in 300 ml of a 1: 1 solvent mixture of 1,4-dioxane / water, and the mixture was vigorously heated and stirred for 2 hours. . After completion of the reaction, the mixture was filtered through hot celite and the filtrate was concentrated to give 12.6 g of the desired 4- (N, N-dimethylamino) -4'-aminostilbene.
(Yield = 98.7%).

The compound obtained in this manner is 1H-N
MR spectrum, normal 13C-NMR spectrum, D
The 13C-NMR spectrum using EPT-135 confirmed that the target compound was 4- (N, N-dimethylamino) -4′-aminostilbene. FIG. 15 shows the 1H-NMR spectrum of 4- (N, N-dimethylamino) -4′-aminostilbene in deuterated chloroform. FIG.
FIG. 6 shows the 13C-NMR spectrum of 4- (N, N-dimethylamino) -4′-aminostilbene in deuterated chloroform. FIG. 17 shows 4- (N,
DE of N-dimethylamino) -4'-aminostilbene
13 shows a 13C-NMR spectrum of PT135.

(Synthesis Example 5) 10.85 g of diethyl 4-methoxy-4'-aminostilbene p-nitrobenzylphosphonate
(1.08 equivalents) was dissolved in a mixed solvent of 80 ml of tetrahydrofuran and 40 ml of dimethylformamide, and the internal temperature was cooled to 0 ° C with an ice bath. Then, 4.95 g (1.2 equivalents) of potassium-t-butoxide was added, and the mixture was stirred for about 30 minutes. Thereafter, 4-dimethylaminobenzaldehyde5.
A solution prepared by dissolving 0 g in 30 ml of tetrahydrofuran is gradually added at 0 degree. When the addition is complete, remove the ice bath and leave it overnight. For the post-treatment of the reaction, a saturated aqueous solution of citric acid is added into the reaction system, the excess base is neutralized, and then the solvent tetrahydrofuran is removed by an evaporator, and the resulting solid is filtered. The obtained solid is sufficiently washed with ethanol and dried under reduced pressure. 9.3 g of 4-methoxy-4'-nitrostilbene thus obtained was mixed with 20.5 g (10.5 g) of 200 mesh iron powder in 250 ml of a 1: 1 solvent mixture of 1,4-dioxane / water.
0.0 equivalent) and vigorously heat and stir for 2 hours. After completion of the reaction, the mixture was filtered through hot celite and the filtrate was concentrated to give the desired 4-amino-4'-aminostilbene in 8.0.
g (yield = 96.7%).

The compound obtained in this manner is 1H-N
MR spectrum, normal 13C-NMR spectrum, D
The 13C-NMR spectrum using EPT-135 confirmed that the target compound was 4-amino-4′-aminostilbene.

FIG. 18 shows the 1 H-NMR spectrum of 4-amino-4'-methoxystilbene in chloroform-d.
3 shows a 13 C-NMR spectrum of 4′-methoxystilbene. FIG. 20 shows 4-amino- in deuterated chloroform.
13C of 4'-methoxystilbene on DEPT135
-Shows an NMR spectrum.

(Synthesis Example 6) 2 1.0 g of p-toluidine P and 4-
1.59 g (1.05 equivalents) of formyl roman are dissolved in 50 ml of toluene. Then, at room temperature, the amount of catalyst (about 50
mg) of p-toluenesulfonic acid, and the mixture is stirred and gradually heated. Water by-produced by the reaction is distilled out of the reaction system by azeotropic distillation with toluene. Further, 1.97 g (1.30 equivalents) of 4-formyl roman was added and reacted in the same manner. Water produced as a by-product of the reaction was distilled out of the reaction system by azeotropic distillation with toluene. After the azeotropic toluene is no longer cloudy, heating and stirring are continued for another 3 hours. After completion of the reaction, toluene was removed by an evaporator, and the residue was recrystallized from a mixed solvent of ethanol / ethyl acetate to obtain 2.1 g (yield: 57.0%) of the desired Exemplified Compound No. 2.

The compound obtained in this manner is 1H-N
MR spectrum, normal 13C-NMR spectrum, D
From the 13C-NMR spectrum of EPT-135, the desired Exemplified Compound No. was obtained. 2 was confirmed.

FIG. 21 shows an example compound No. in deuterated chloroform. 2 shows the 1H-NMR spectrum of 2. FIG. 22 shows an example compound No. in deuterated chloroform. 2 of 13C-NM
2 shows an R spectrum. FIG. 23 shows an example compound No. in deuterated chloroform. 2 shows a 13C-NMR spectrum with DEPT135 of No. 2.

By changing the amine compound of Synthesis Example 6 to the corresponding amine compound, Compound No. 1 was prepared. 1, N
o. Compounds of 3 to 48 can also be easily synthesized.

(Examples 1 to 5) A 1% THF solution of a phenoxy resin (manufactured by Union Carbide: PKHH) with a bisazo pigment represented by the following structural formula was used on a support made of an aluminum-deposited polyester film (thickness: 80 μm). The same amount as the resin was added to the solution in the same weight ratio, then dispersed in a paint conditioner (manufactured by Red Devil Co., Ltd.) with glass beads having a diameter of 1.5 mm for about 2 hours, and applied and dried by a doctor blade method. did. 0.2μ after drying
m.

[0127]

Embedded image

On the pigment layer (charge generation layer), Exemplified Compound No. 2, No. 5, no. 23, no. 2
9 or No. 42 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 ( (A charge transfer 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)
The exposure amount E100 (lux · second) and the initial potential V0 (−volt) required to attenuate to 00V were measured, and the values are shown in Table 6. Further, using the same apparatus, the same operation was performed 10,000 times with one cycle of charge-discharge (discharge light: irradiation of white light of 40 lux for 1 second), and exposure amount E100 after 10,000 times was performed.
(Looks-seconds) and the initial potential V0 (−volt) were measured, and changes in E100 and V0 were examined.

[0130]

[Table 6]

As is clear from Table 6, the bisenamine compound of the present invention was found to have good sensitivity repetition characteristics.

Example 6 An x-type metal-free phthalocyanine represented by the following structural formula (Fastgen Blue 812, manufactured by Dainippon Ink) on an aluminum-evaporated polyester film.
0) 0.4 g was added to 30 ml of an ethyl acetate solution in which 0.3 g of a polyvinyl chloride: vinyl acetate copolymer resin (manufactured by Sekisui Chemical Co., Ltd .: Eslex M) was dissolved.
Disperse for 0 minutes, apply by doctor blade method,
The charge generation layer was formed so that the film thickness after drying was 0.4 μm.

[0133]

Embedded image

On the charge generation layer, the exemplary compound No. A two-layer photoreceptor was prepared by laminating a polyarylate layer containing 50% by weight of a bisenamine compound of No. 21.

The energy required for halving the potential (E50) and the initial potential (−V
0), V0 = −755 (volts), E5
0 = 0.24 (uJ), indicating that the photosensitive member had a very high sensitivity and a high chargeability.

A laser printer manufactured by Sharp (WD)
-580P), the photoreceptor was stuck to the drum part, and continuous empty copy (Non Copy Aging) was performed 10,000 times, and then the initial potential reduction and the degree of sensitivity reduction were also examined. As a result, V0 = −730 (volt), E
50 = 0.26 (uJ), almost no change in value compared to the first time.

(Examples 7 to 10) Exemplified Compound No. of the present invention was placed on a support having an aluminum base surface subjected to alumite processing (alumite layer: 7 μm). 9, No. 32, no. 39,
Or No. 43, 1 g, a polyarylate resin 1.1 g represented by the following structural formula, N, N-3,5-xylyl-
A solution in which 0.15 g of 3,4,9,10-perylenetetracarboximide and 0.05 g of an ultraviolet absorber were dissolved in methylene chloride (an imide compound was partially dispersed) was applied by an applicator, and a single layer having a dry film thickness of 20 μm was applied. A layer photoreceptor was obtained.

[0138]

Embedded image

The electrophotographic characteristics of the photoreceptor prepared as described above were evaluated using an electrostatic recording paper test apparatus. The measurement conditions were as follows: applied voltage: -5.5 kV, static: No. 3 was performed. The exposure amount E100 (lux · second) required to attenuate from +700 V to +100 V by white light irradiation was measured, and the value is shown in Table 7. Further, the empty copy test was performed 10,000 times, and the degree of decrease in sensitivity (E100) is shown in Table 7.

[0140]

[Table 7]

Table 7 shows that the photoreceptor using the bisenamine compound of the present invention has excellent sensitivity and repetition characteristics even in positive charging.

[0142]

According to the method for producing a bisenamine compound of the present invention and the method for producing an intermediate thereof, the bisenamine compound of the present invention can be produced very easily in high yield.

Further, the photoreceptor containing the bisenamine compound of the present invention is an organic electrophotographic photoreceptor having high sensitivity and high durability, and is nontoxic and has no problem in resources as compared with inorganic ones. It has good transparency, light weight, excellent film formability, has both positive and negative chargeability, and has the advantages of organic photoreceptor that photoreceptor is easy to manufacture. It has excellent characteristics that hardly decreases.

[Brief description of the drawings]

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

FIG. 2 is a cross-sectional view schematically illustrating a layer structure of an electrophotographic photosensitive member using the bisenamine compound of the present invention.

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

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

FIG. 5 is a cross-sectional view schematically showing a layer structure of an electrophotographic photosensitive member using the bisenamine compound of the present invention.

FIG. 6 is a 1 H-NMR spectrum of 4-formyl roman in deuterated chloroform.

FIG. 7 is a 13 C-NMR spectrum of 4-formyl roman in deuterated chloroform.

FIG. 8 is a 13 C-NMR spectrum of 4-formyl roman with DEPT135 in deuterated chloroform.

FIG. 9 is a 1 H-NMR spectrum of 3-aminobenzaldehyde-N, N-diphenylhydrazone in deuterated chloroform.

FIG. 10. 13C-NM of 3-aminobenzaldehyde-N, N-diphenylhydrazone in deuterated chloroform.
It is an R spectrum.

FIG. 11. DEPT13 of 3-aminobenzaldehyde-N, N-diphenylhydrazone in deuterated chloroform
5 is a 13 C-NMR spectrum.

FIG. 12 is a 1 H-NMR spectrum of 4′-aminobenzaldehyde-1-amino-1,2,3,4-tetrahydroquinoline hydrazone in deuterated chloroform.

FIG. 13 is a 13 C-NMR spectrum of 4′-aminobenzaldehyde-1-amino-1,2,3,4-tetrahydroquinoline hydrazone in deuterated chloroform.

FIG. 14: 13C-NM of 4′-aminobenzaldehyde-1-amino-1,2,3,4-tetrahydroquinoline hydrazone in deuterochloroform with DEPT135
It is an R spectrum.

FIG. 15 is a 1 H-NMR spectrum of 4- (N, N-dimethylamino) -4′-aminostilbene in chloroform-d.

FIG. 16: 13C-NMR of 4- (N, N-dimethylamino) -4′-aminostilbene in deuterated chloroform
It is a spectrum.

FIG. 17. DEPT135 of 4- (N, N-dimethylamino) -4′-aminostilbene in deuterated chloroform
Is a 13C-NMR spectrum.

FIG. 18 is a 1 H-NMR spectrum of 4-amino-4′-methoxystilbene in deuterated chloroform.

FIG. 19 is a 13 C-NMR spectrum of 4-amino-4′-methoxystilbene in deuterated chloroform.

FIG. 20 is a 13 C-NMR spectrum of DEPT135 of 4-amino-4′-methoxystilbene in deuterated chloroform.

FIG. 21 illustrates an exemplary compound No. in deuterated chloroform. 2 is a 1H-NMR spectrum.

FIG. 22 illustrates an example compound No. in deuterated chloroform. 2 is a 13C-NMR spectrum.

FIG. 23 illustrates Compound No. 1 in deuterated chloroform. 2 is a 13C-NMR spectrum with DEPT135 of No. 2.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2 Charge generation material 3 Charge transfer material 4, 4 'Photosensitive layer 5 Charge generation layer 6 Charge transfer layer 7 Intermediate layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 251/86 C07C 251/86 C07D 215/12 C07D 215/12 277/64 277/64 307/81 307/81 311/58 311 / 58 313/08 313/08 335/06 335/06 401/14 215 401/14 215 405/14 209 405/14 209 215 215 219 219 407/14 311 407/14 311 409/14 335 409/14 335 413/14 311 413/14 311 417/14 311 417/14 311 (72) Inventor Hiroshi Sugimura Sharp Corporation 22-22 Nagaikecho, Abeno-ku, Osaka City, Osaka Prefecture

Claims (26)

[Claims] 1. An electrophotographic photoreceptor comprising a bisenamine compound represented by the following general formula (I) in a photosensitive layer formed on a conductive support. Embedded image (In the formula, Ar1 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 an alkyl group. R1 represents a substituent. Represents an 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, and Y represents an oxygen atom, a sulfur atom, Represents a substituted nitrogen atom, m is an integer of 1 to 8, and n is an integer of 1 to 3. However, when m is 2 or more,
R1 may be the same or different. ) 2. An electrophotographic photoreceptor comprising a bisenamine compound represented by the following general formula (V) in a photosensitive layer formed on a conductive support. Embedded image (Wherein, Ar 2 and Ar 3 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 an alkyl group, or a hydrogen atom. (However, unless Ar2 and Ar3 are hydrogen atoms at the same time) R2 has 1 to 1 carbon atoms which may have a substituent.
Represents an alkyl group having 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, and l is an integer of 1 to 4. Where l is 2
In the above, R2 may be the same or different. R3 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, an alkyl group, or a hydrogen atom. Where R1, m,
n and Y have the same meaning as in claim 1. ) 3. An electrophotographic photoreceptor comprising a bisenamine compound represented by the following general formula (IX) in a photosensitive layer formed on a conductive support. Embedded image (In the formula, Ar4 and Ar5 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 an alkyl group, or a hydrogen atom. Further, a ring may be formed directly or by a divalent linking group (methylene, ethylene, vinylene, oxygen atom, sulfur atom), wherein R1, R2, R
3, m, n, l, and Y are as defined in claim 2. ) 4. An electrophotographic photosensitive member, characterized in that a photosensitive layer formed on a conductive support contains a bisenamine compound represented by the following general formula (XV). Embedded image (Wherein, R 6 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, t represents a positive number from 1 to 10, and Z represents a divalent linking group which may have a substituent (methylene, ethylene, vinylene, oxygen atom, (Sulfur atom). However, when t is 2 or more, R4 may be the same or different. Where R
1, R2, R3, l, m, n and Y have the same meaning as in claim 4. ) 5. An aldehyde compound represented by the general formula (XX). Embedded image (In the formula, R1, m, n, and Y have the same meaning as in claim 1.) 6. The method for producing an aldehyde compound according to claim 5, wherein the carbonyl compound represented by the general formula (XXI) is reacted with an ester compound represented by the general formula (XXII). Embedded image (In the formula, R4 represents a lower alkyl group, X represents a halogen atom, and R1, m, n, and Y have the same meaning as in claim 1.) 7. A bisenamine compound represented by the general formula (I): Embedded image (Wherein, Ar1, R1, R2, m, n, and Y are as defined in claim 1)
Is synonymous with ) 8. The process for producing a bisenamine compound according to claim 7, wherein the aldehyde compound represented by the general formula (XX) is reacted with an amine compound represented by the general formula (XXIII). Embedded image (In the formula, Ar1, R1, m, n, and Y have the same meaning as in claim 1.) 9. A nitro compound represented by the general formula (XXIV): Embedded image (In the formula, Ar2, Ar3, R2, and R31 have the same meaning as in claim 2.) 10. An amine compound represented by the general formula (XXV). Embedded image (In the formula, Ar2, Ar3, R2, R3, 1 have the same meaning as in claim 2.) 11. A bisenamine compound represented by the general formula (V): Embedded image (Wherein, Ar2, Ar3, R1, R2, R3, 1, m,
n and Y are as defined in claim 2. ) 12. The method for producing a nitro compound according to claim 9, wherein the carbonyl compound represented by the general formula (XXVI) is reacted with a phosphorus compound represented by the general formula (XXVII). Embedded image (In the formula, R5 represents a lower alkyl group or an aryl group which may have a substituent, and Ar2, Ar3, R2, and R31 have the same meaning as in claim 2.) 13. The method for producing an amine compound according to claim 10, wherein the nitro compound represented by the general formula (XXIV) is reduced. Embedded image (In the formula, Ar2, Ar3, R2, R3, 1 have the same meaning as in claim 2.) 14. The method for producing a bisenamine compound according to claim 2, wherein the aldehyde compound represented by the general formula (XX) is reacted with an amine compound represented by the general formula (XXV). Embedded image (Wherein, Ar2, Ar3, R1, R2, R3, 1, m,
n and Y are as defined in claim 2. ) 15. A nitro compound represented by the general formula (XXVIII). Embedded image (Wherein, Ar4, Ar5, R2, and R31 have the same meaning as in claim 3.) 16. An amine compound represented by the general formula (XXIX): Embedded image (Wherein, Ar4, Ar5, R2, and R31 have the same meaning as in claim 3.) 17. A bisenamine compound represented by the general formula (IX): Embedded image (Wherein, Ar4, Ar5, R1, R2, R3, 1, m,
n and Y are as defined in claim 3. ) 18. The method for producing a nitro compound according to claim 15, wherein the carbonyl compound represented by the general formula (XXVI) is reacted with a hydrazine compound represented by the general formula (XXX). Embedded image (In the formula, Ar4, Ar5, R1, R3, and 1 have the same meaning as in claim 3.) 19. The method for producing an amine compound according to claim 16, wherein the nitro compound represented by the general formula (XXVIII) is reduced. Embedded image (In the formula, Ar4, Ar5, R2, and R31 have the same meaning as in claim 2.) 20. The method for producing a bisenamine compound according to claim 17, wherein the aldehyde compound represented by the general formula (XX) is reacted with an amine compound represented by the general formula (XXIX). Embedded image (Wherein, Ar4, Ar5, R1, R2, R3, 1, m,
n and Y are as defined in claim 2. ) 21. A nitro compound represented by the general formula (XXXI). Embedded image (In the formula, R6, R2, R3, l, t, and Z have the same meaning as in claim 4.) 22. An amine compound represented by the general formula (XXXII). Embedded image (In the formula, R6, R2, R3, l, t, and Z have the same meaning as in claim 4.) 23. A bisenamine compound represented by the general formula (XV): Embedded image (Where R6, R1, R2, R3, 1, m, n, t,
Y and Z have the same meaning as in claim 4. ) 24. The method for producing a nitro compound according to claim 21, wherein the carbonyl compound represented by the general formula (XXVI) is reacted with a hydrazine compound represented by the general formula (XXXIII). Embedded image (In the formula, R6, R2, R3, l, t, and Z have the same meaning as in claim 4.) 25. The method for producing an amine compound according to claim 22, wherein the nitro compound represented by the general formula (XXXI) is reduced. Embedded image (In the formula, R6, R2, R3, l, t, and Z have the same meaning as in claim 4.) 26. The method for producing a bisenamine compound according to claim 23, wherein the aldehyde compound represented by the general formula (XX) is reacted with an amine compound represented by the general formula (XXXII). Embedded image (Where R6, R1, R2, R3, 1, m, n, t,
Y and Z have the same meaning as in claim 4. )