JPH1135540A - Organic photoconductive compound and electrophotographic photoreceptor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful for electrophotographic photoreceptors and sensor materials, electrostatic recording devices, etc., which are highly sensitive, high in electrification voltage, and capable of exhibiting stable performance with their various properties invariant even if used repeatedly. SOLUTION: This new compound is an organic photoconductive compound of formula I or formula II [X is oxygen or sulfur; R<1> is a (substituted) alkyl, (substituted) aralkyl, etc.; R<2> is H, a (substituted) alkyl, etc.; R<3> and R<4> are each H, a (substituted) alkyl, etc.; Ar<1> is a (substituted) aryl, (substituted) heterocycle, etc.], e.g. a stilbene-based compound of formula III. This new compound is obtained, for example, in the case of the compound of formula III, by adding potassium t-butoxide to an N,N-dimethylformamide solution with an aldehyde of formula IV and a phosphonate of formula V dissolved therein under stirring at room temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic photoconductive compound and an electrophotographic photosensitive member using the same.

[0002]

2. Description of the Related Art In recent years, the use of electrophotography is not limited to the field of copiers, but has spread to fields where photographic technology was conventionally used, such as printing plate materials, slide films, and microfilms. Also, application to a high-speed printer using a CRT as a light source is being studied. Recently, the use of a photoconductive material for applications other than the electrophotographic photoreceptor, for example, an electrostatic recording element, a sensor material, an EL element, and the like has been studied. Accordingly, demands for photoconductive materials and electrophotographic photoreceptors using the same are becoming higher and wider. Heretofore, inorganic photoconductive materials such as selenium, cadmium sulfide, zinc oxide, and silicon have been known as electrophotographic photosensitive members, and have been widely studied and put to practical use. While these inorganic materials have many advantages, they also have various disadvantages. For example, selenium has drawbacks in that the production conditions are difficult and it is easy to crystallize due to heat and mechanical shock, and cadmium sulfide and zinc oxide have poor moisture resistance and durability. It has been pointed out that silicon is insufficient in chargeability and difficult to manufacture. Furthermore,
Selenium and cadmium sulfide also have toxicity problems.

On the other hand, organic photoconductive materials have good film-forming properties, excellent flexibility, are lightweight, have good transparency, and are sensitive to a wide wavelength range by an appropriate sensitization method. Due to its advantages such as easy design of the body, its practical use is gradually attracting attention.

Incidentally, the photoreceptor used in the electrophotographic technology is generally required to have the following basic properties. That is, (1) high chargeability against corona discharge in a dark place, (2) little leakage (dark decay) of the obtained charge in a dark place, and (3) charge charge by light irradiation. (4) The residual charge after light irradiation is small.

However, many studies have been made on photoconductive polymers such as polyvinyl carbazole as organic photoconductive substances to date, but these have not always had sufficient film-forming properties, flexibility and adhesiveness. Also, it is difficult to say that the above-mentioned basic properties of the photoreceptor are sufficiently provided.

On the other hand, as for the organic low-molecular-weight photoconductive compound, by selecting a binder or the like used for forming the photoreceptor, the photoreceptor having excellent mechanical strength such as film property, adhesiveness and flexibility can be obtained. Can be obtained, but it is difficult to find a compound suitable for maintaining high-sensitivity properties.

In order to improve such a point, an organic photoreceptor having a higher sensitivity characteristic has been developed in which the charge generation function and the charge transport function are shared by different substances. The feature of such a photoreceptor, which is called a function-separated type, is that a material suitable for each function can be selected from a wide range, and a photoreceptor having an arbitrary performance can be easily manufactured. Has been advanced.

Among them, various substances such as phthalocyanine pigments, squarium dyes, azo pigments, and perylene pigments have been studied as substances in charge of the charge generation function. Among them, azo pigments can have various molecular structures. Also, since high charge generation efficiency can be expected, it has been widely studied, and its practical use has been advanced. However, in this azo pigment, the relationship between the molecular structure and the charge generation efficiency has not been clarified yet. The fact is that we are searching for the optimal structure through extensive synthesis research, but it fully satisfies the basic properties and high durability demands of the photoconductors listed above. Things have not yet been obtained.

[0009] On the other hand, the substances in charge of the charge transport function include a hole transport substance and an electron transport substance. Various kinds of substances such as hydrazone compounds and stilbene compounds have been studied as hole transport substances, and 2,4,7-trinitro-9-fluorenone and diphenoquinone derivatives have been studied as electron transport substances.
Practical application is also progressing, but the fact is that we are also pursuing a huge amount of synthetic research to search for the optimal structure. In fact, many improvements have been made so far, but none of the above-mentioned photoconductors sufficiently satisfy the requirements such as the basic properties and high durability required for the photoconductors.

As described above, various improvements have been made in the production of electrophotographic photoreceptors, but the requirements for the basic properties and high durability required for the above-mentioned photoreceptors have not been sufficiently satisfied. At present, there is no satisfactory product yet.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photoreceptor, a sensor material, and an EL element which exhibit a high charge potential, high sensitivity, stable performance even when used repeatedly without changing various characteristics. Another object of the present invention is to provide an organic photoconductive compound which can be used for an electrostatic recording element and the like.

[0012]

Means for Solving the Problems The present inventors have studied photoconductive compounds to achieve the above object, and as a result, have found that an organic photoconductive compound having a specific structure is effective. Invented the invention. The organic photoconductive compound having the above specific structure is a stilbene compound represented by the following general formula (1) or (2) or a hydrazone compound represented by the following general formula (6) or (7) Compound. Among them, stilbene compounds represented by the following general formula (3) or hydrazone compounds represented by the following general formula (8) are preferred in the present invention, and more preferred are those represented by the following general formula (4). A stilbene-based compound represented by the following general formula (9); and a stilbene-based compound represented by the following general formula (5), and particularly preferably a stilbene-based compound represented by the following general formula (5). And a hydrazone compound represented by the formula:

[0013]

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[0014]

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In the general formula (1) or (2), X
Represents an oxygen atom or a sulfur atom; R ¹ represents an alkyl group optionally having a substituent, an aralkyl group optionally having a substituent, an aryl group optionally having a substituent,
Or substituted indicates also heterocyclic group, R ²
Is a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or may have a substituent Shows a heterocyclic group. R ³ and R ⁴ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom. Ar ¹ represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a styryl group which may have a substituent.

Here, specific examples of R ¹ include a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, 3-methoxypropyl group, 2-chloro-3-
An unsubstituted or substituted alkyl group such as a methylhexyl group,
Benzyl group, phenethyl group, 3-phenylpropyl group,
p-methylbenzyl group, o-methoxybenzyl group, 3,
An unsubstituted or substituted aralkyl group such as a 5-dichlorobenzyl group, a 2,4-dimethylphenethyl group, a p-methoxyphenethyl group, and a 2-methyl-3-phenylpropyl group;
Phenyl group, p-tolyl group, m-tolyl group, p-methoxyphenyl group, o-methoxyphenyl group, p-chlorophenyl group, 3,5-dimethylphenyl group, 4-methoxy-2-chlorophenyl group, 3 , 5-dimethoxyphenyl group, 1-naphthyl group, 1-methyl-2-naphthyl group, 9
An unsubstituted or substituted aryl group such as a phenanthryl group or a 1-pyrenyl group, or a 2-furyl group, a 2-thienyl group, a 2-pyridyl group, a 2,6-dimethyl-4-pyridyl group, a 3-indolyl group, And unsubstituted or substituted heterocyclic groups such as -quinolyl group.

Specific examples of R ² include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, n-hexyl group, n-octyl group, 2-
Unsubstituted or substituted alkyl groups such as ethylhexyl group, 3-methoxypropyl group, 2-chloro-3-methylhexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, p-methylbenzyl group, o-methoxybenzyl group , 3,5-dichlorobenzyl group, 2,4-dimethylphenethyl group, p-methoxyphenethyl group, 2-methyl-
Unsubstituted or substituted aralkyl groups such as 3-phenylpropyl group, phenyl group, p-tolyl group, m-tolyl group, p
-Methoxyphenyl group, o-methoxyphenyl group, p-
Chlorophenyl group, 3,5-dimethylphenyl group, 4-
Unsubstituted or substituted aryl groups such as methoxy-2-chlorophenyl group, 3,5-dimethoxyphenyl group, 1-naphthyl group, 1-methyl-2-naphthyl group, 9-phenanthryl group, 1-pyrenyl group, or 2 -Furyl group, 2-
Thienyl group, 2-pyridyl group, 2,6-dimethyl-4-
Examples include unsubstituted or substituted heterocyclic groups such as a pyridyl group, a 3-indolyl group, and a 2-quinolyl group.

Specific examples of R ³ and R ⁴ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-hexyl group, a 2-ethylpentyl group and a 2-ethylpentyl group. Unsubstituted or substituted alkyl groups such as methoxyethyl group and 3-chloropropyl group, unsubstituted or substituted groups such as methoxy group, ethoxy group, n-propoxy group, n-butoxy group, 2-methoxyethoxy group and 4-chlorobutoxy group A substituted alkoxy group, or a fluorine atom, a chlorine atom,
Examples thereof include a halogen atom such as a bromine atom.

Specific examples of Ar ¹ include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, an o-methoxyphenyl group, a p-chlorophenyl group, and a 3,5-dimethylphenyl group. , 4-methoxy-2-
Chlorophenyl group, 3,5-dimethoxyphenyl group, 1
An unsubstituted or substituted aryl group such as -naphthyl group, 1-methyl-2-naphthyl group, 9-phenanthryl group, 1-pyrenyl group, 2-furyl group, 2-thienyl group, 2-pyridyl group, 2,6- Unsubstituted or substituted heterocyclic groups such as dimethyl-4-pyridyl group, 3-indolyl group and 2-quinolyl group, and unsubstituted or substituted heterocyclic groups such as 2-styryl group, 2-p-methylstyryl group and 2-m-methoxystyryl group Examples include a substituted or substituted styryl group.

In the general formula (6) or (7), Z represents an oxygen atom or a sulfur atom, and R ⁷ and R ⁸
Is an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent Is shown. R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom. Ar ² represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

Here, specific examples of R ⁷ and R ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
An unsubstituted or substituted alkyl group such as -butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, 3-methoxypropyl group, 2-chloro-3-methylhexyl group, benzyl group, phenethyl group, 3 -Phenylpropyl group, p-methylbenzyl group, o-methoxybenzyl group, 3,5-dichlorobenzyl group, 2,4-dimethylphenethyl group, p-methoxyphenethyl group, 2-methyl-
Unsubstituted or substituted aralkyl groups such as 3-phenylpropyl group, phenyl group, p-tolyl group, m-tolyl group, p
-Methoxyphenyl group, o-methoxyphenyl group, p-
Chlorophenyl group, 3,5-dimethylphenyl group, 4-
Unsubstituted or substituted aryl groups such as methoxy-2-chlorophenyl group, 3,5-dimethoxyphenyl group, 1-naphthyl group, 1-methyl-2-naphthyl group, 9-phenanthryl group, 1-pyrenyl group, or 2 -Furyl group, 2-
Thienyl group, 2-pyridyl group, 2,6-dimethyl-4-
Examples include unsubstituted or substituted heterocyclic groups such as a pyridyl group, a 3-indolyl group and a 2-quinolyl group.

Specific examples of R ⁹ and R ¹⁰ include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, 2-ethylpentyl, 2-ethylpentyl, Unsubstituted or substituted alkyl groups such as methoxyethyl group and 3-chloropropyl group, unsubstituted or substituted groups such as methoxy group, ethoxy group, n-propoxy group, n-butoxy group, 2-methoxyethoxy group and 4-chlorobutoxy group Examples include a substituted alkoxy group or a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom.

Specific examples of Ar ² include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, an o-methoxyphenyl group, a p-chlorophenyl group, and a 3,5-dimethylphenyl group. , 4-methoxy-2-
Chlorophenyl group, 3,5-dimethoxyphenyl group, 1
An unsubstituted or substituted aryl group such as -naphthyl group, 1-methyl-2-naphthyl group, 9-phenanthryl group, 1-pyrenyl group, 2-furyl group, 2-thienyl group, 2-pyridyl group, 2,6- Unsubstituted or substituted heterocyclic groups such as dimethyl-4-pyridyl group, 3-indolyl group and 2-quinolyl group, and unsubstituted or substituted heterocyclic groups such as 2-styryl group, 2-p-methylstyryl group and 2-m-methoxystyryl group Examples include a substituted or substituted styryl group.

In the general formula (3), R ¹ , R ² and Ar
¹ is the same as in the general formula (2). In the general formula (4), R ¹ is the same as in the general formula (2). R ⁵ is a hydrogen atom,
It represents a lower alkyl group, a lower alkoxy group, or a halogen atom. Y ¹ represents a hydrogen atom, a lower alkyl group or an aryl group, and the aryl group may be substituted with a lower alkyl group, a lower alkoxy group, or a halogen atom.

Here, specific examples of R ⁵ include a hydrogen atom,
Lower alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, methoxy group,
Examples thereof include lower alkoxy groups such as ethoxy group, n-propoxy group and n-butoxy group, and halogen atoms such as fluorine atom, chlorine atom and bromine atom.

Specific examples of Y ¹ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
lower alkyl groups such as n-butyl group, or phenyl group, p-tolyl group, m-tolyl group, p-methoxyphenyl group, o-methoxyphenyl group, p-chlorophenyl group, 3,5-dimethylphenyl group, 4-methoxy-2-
Chlorophenyl group, 3,5-dimethoxyphenyl group, 1
An unsubstituted or lower alkyl group, a lower alkoxy group, or an aryl group substituted with a halogen atom, such as a -naphthyl group, a 1-methyl-2-naphthyl group, a 9-phenanthryl group, or a 1-pyrenyl group. I can do it.

In the general formula (5), R ⁶ is a hydrogen atom,
Indicates a methyl group or a chlorine atom. Y ² represents a hydrogen atom, a methyl group, a phenyl group, a p-tolyl group, a p-methoxyphenyl group, or a p-chlorophenyl group.

In the general formula (8), R ⁷ , R ⁸ and Ar ² are the same as in the general formula (7). In the general formula (9), R ⁷ and R ⁸ are the same as in the general formula (7). R ¹¹ represents a hydrogen atom, a methyl group, or a chlorine atom.

In the general formula (10), R ¹¹ is the same as in the general formula (9). U is a methyl group, a phenyl group, p
-Represents a tolyl group, a p-methoxyphenyl group, or a p-chlorophenyl group.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (1) according to the present invention,
Alternatively, specific examples of the organic photoconductive compound represented by (2) include the following stilbene compounds of S-01 to S36, and the organic photoconductive compound represented by the general formula (6) or (7). Specific examples of the compound include H-01 shown below.
To 36 hydrazone-based compounds,
It is not limited to these.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The photosensitive layer of the present invention containing the organic photoconductive compound represented by the general formula (1) or (2) or the organic photoconductive compound represented by the general formula (6) or (7) Any of those forms can be used as the form of the electrophotographic photosensitive member containing. For example, there is one in which a photosensitive layer made of a charge generating substance, a charge transporting substance, and a film-forming binder resin is provided on a conductive support. Further, on a conductive support, a charge generation layer composed of a charge generation substance and a binder resin,
Laminated photoconductors provided with a charge transport layer made of a charge transport material and a binder resin are also known. Either of the charge generation layer and the charge transport layer may be an upper layer. In addition, if necessary, an undercoat layer is provided between the conductive support and the photosensitive layer, an overcoat layer is provided on the surface of the photosensitive member, and in the case of a laminated photosensitive member, an intermediate layer is provided between the charge generation layer and the charge transport layer. Can also be provided. As a support for producing a photoreceptor by using the compound of the present invention, a metal drum, a metal plate, a sheet-like or drum-like or belt-like support of paper or plastic film subjected to conductive processing, and the like are used. You.

The electrophotographic photoreceptor of the present invention contains one kind of each of the organic photoconductive compound represented by the general formula (1) or (2) or the general formula (6) or (7), and a charge generating substance. Alternatively, it is obtained by containing two or more types. The charge generating substance includes an inorganic charge generating substance and an organic charge generating substance. Examples of the former include selenium, selenium-tellurium alloy, selenium-arsenic alloy, cadmium sulfide, zinc oxide, amorphous silicon, and the like. Examples of organic charge generating substances include, for example, methyl violet, brilliant green, triphenylmethane dyes such as crystal violet, thiazine dyes such as methylene blue, quinone dyes such as quinizarin, cyanine dyes, acridine dyes, pyrylium dyes,
Thiapyrylium dyes, squarium dyes, perinone-based pigments, anthraquinone-based pigments, perylene-based pigments, metal-containing or metal-free phthalocyanine-based pigments, and the like, and azo pigments are also used.

As the azo pigment, for example, JP-A-47-3
7543, JP-A-53-95033, JP-A-53-132347, JP-A-53-13344
No. 5, JP-A-54-12742, JP-A-54-12742
No.-20736, JP-A-54-20737,
JP-A-54-21728, JP-A-54-22283
No. 4, JP-A-55-69148, JP-A-55-69148
-69654, JP-A-55-79449,
JP-A-55-117151, JP-A-56-462
No. 37, JP-A-56-116039, JP-A-56-116040, JP-A-56-119134
JP, JP-A-56-143437, JP-A-57-143637
-63537, JP-A-57-63538,
JP-A-57-63541, JP-A-57-6354
No. 2, JP-A-57-63549, JP-A-57-63549
-66438, JP-A-57-74746,
JP-A-57-78542, JP-A-57-7854
No. 3, JP-A-57-90056, JP-A-57-90056
-90057, JP-A-57-90632,
JP-A-57-116345, JP-A-57-202
349, JP-A-58-4151, and JP-A-5-5
JP-A-8-90644, JP-A-58-144358, JP-A-58-177555, JP-A-59-3
1962, JP-A-59-33253, JP-A-59-71059, JP-A-59-72448, JP-A-59-78356, JP-A-59-1
No. 36351, JP-A-59-201060,
JP-A-60-15624, JP-A-60-1403
No. 51, JP-A-60-179746, JP-A-61-11754, JP-A-61-90164, JP-A-61-90165, JP-A-61-90
166, JP-A-61-112154, JP-A-61-269165, and JP-A-61-28124.
No. 5, JP-A-61-51063, JP-A-62
-267363, JP-A-63-68844, JP-A-63-89866, JP-A-63-13
No. 9355, JP-A-63-142033, JP-A-63-183450, JP-A-63-2827
No. 43, JP-A-64-21455, JP-A-6-21
JP-A-4-78259, JP-A-1-200267, JP-A-1-202775, JP-A-1-319
754, JP-A-2-72372, JP-A-2-72372
-254467, JP-A-3-95561,
JP-A-3-278063, JP-A-4-96068
JP, JP-A-4-96069, JP-A-4-14
Compounds described in JP-A-7265, JP-A-5-142841, JP-A-5-303226, JP-A-6-324504, JP-A-7-168379 are exemplified.

The structure of the coupler component used in these azo pigments varies widely. For example, JP-A-54-17
735, JP-A-54-79632, JP-A-57-176055, JP-A-59-197043
JP, JP-A-60-130746, JP-A-60-130746
JP-153050, JP-A-60-103048, JP-A-60-189759, JP-A-63-1
No. 31146, JP-A-63-155052,
JP-A-2-110569, JP-A-4-14944
No. 8, JP-A-6-27705, JP-A-6-3
Compounds described in 48047 and the like can be mentioned.

Specific examples of the azo pigment include the compounds shown in Tables 1 to 45 below, but are not limited thereto. Further, these compounds can be used in combination with other charge generating substances.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

[0052]

[Table 5]

[0053]

[Table 6]

[0054]

[Table 7]

[0055]

[Table 8]

[0056]

[Table 9]

[0057]

[Table 10]

[0058]

[Table 11]

[0059]

[Table 12]

[0060]

[Table 13]

[0061]

[Table 14]

[0062]

[Table 15]

[0063]

[Table 16]

[0064]

[Table 17]

[0065]

[Table 18]

[0066]

[Table 19]

[0067]

[Table 20]

[0068]

[Table 21]

[0069]

[Table 22]

[0070]

[Table 23]

[0071]

[Table 24]

[0072]

[Table 25]

[0073]

[Table 26]

[0074]

[Table 27]

[0075]

[Table 28]

[0076]

[Table 29]

[0077]

[Table 30]

[0078]

[Table 31]

[0079]

[Table 32]

[0080]

[Table 33]

[0081]

[Table 34]

[0082]

[Table 35]

[0083]

[Table 36]

[0084]

[Table 37]

[0085]

[Table 38]

[0086]

[Table 39]

[0087]

[Table 40]

[0088]

[Table 41]

[0089]

[Table 42]

[0090]

[Table 43]

[0091]

[Table 44]

[0092]

[Table 45]

As the phthalocyanine pigment used in the present invention, any of the phthalocyanines and derivatives thereof known per se can be used. Specifically, metal-free phthalocyanines, titanyloxy phthalocyanines, copper phthalocyanines, aluminum phthalocyanines , Diphenoxygermanium phthalocyanines, germanium phthalocyanines, gallium phthalocyanines, chlorogallium phthalocyanines, bromogallium phthalocyanines, chloroindium phthalocyanines, bromoindium phthalocyanines, iodoindium phthalocyanines, magnesium phthalocyanines, chloroaluminum phthalocyanines, bromo Aluminum phthalocyanines, tin phthalocyanines, dichlorotin phthalocyanines, Ziroxy phthalocyanines, zinc phthalocyanines, cobalt phthalocyanines, nickel phthalocyanines, hydroxygallium phthalocyanines, dihydroxygallium phthalocyanines, barium phthalocyanines, beryllium phthalocyanines, cadmium phthalocyanines, chlorocobalt phthalocyanines, dichlorotitanyl phthalocyanines, iron Examples include phthalocyanines, silicon phthalocyanines, lead phthalocyanines, platinum phthalocyanines, metal-free naphthalocyanines, aluminum naphthalocyanines, titanyloxynaphthalocyanines, ruthenium phthalocyanines, and palladium phthalocyanines. In particular, among them, metal-free phthalocyanine, titanyloxyphthalocyanine, copper phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, vanadyloxyphthalocyanine, diphenoxygermanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferably used in the present invention.

The phthalocyanine-based pigment is known as a polymorphic compound, and various crystal-type phthalocyanine-based pigments have been found. For a description of these crystal forms and production methods, metal-free phthalocyanine is described in
4338, JP-A-58-182639, JP-A-60-19151, JP-A-62-47054
JP, JP-A-62-143058 and JP-A-63
JP-A-286857, JP-A-1-138563, JP-A-1-230581, JP-A-2-233
No. 769, furthermore, J.I. Phys. Chem. 72 ,
3230 (1968).

Titanyloxyphthalocyanine is disclosed in JP-A-61-217050, JP-A-62-67094, JP-A-62-2229253, and JP-A-63-229253.
364, JP-A-63-365, JP-A-63
-366, JP-A-63-37163, JP-A-63-80263, JP-A-63-116158
JP, JP-A-63-198067, JP-A-63-198167
JP-A-218768, JP-A-64-17066, JP-A-1-123868, JP-A-1-138
No. 562, Japanese Unexamined Patent Publication No. 1-153775, Japanese Unexamined Patent Publication No. 1-172459, Japanese Unexamined Patent Publication No. 1-172462, Japanese Unexamined Patent Publication No. 1-189200, Japanese Unexamined Patent Publication No. 1-204
969, JP-A-1-207755, JP-A-1-299874, JP-A-2-8256,
JP-A-2-99969, JP-A-2-131243
JP, JP-A-2-165156, JP-A-2-1-1
65157, JP-A-2-215866, JP-A-2-267563, JP-A-2-297560
JP, JP-A-3-35064, JP-A-3-54
264, JP 3-84068, JP 3
-94264, JP-A-3-100658,
JP-A-3-100659, JP-A-3-12335
9, JP-A-3-199268, JP-A-3-199268
2007790, JP-A-3-269064,
JP-A-4-145166, JP-A-4-14516
7, JP-A-4-153273, JP-A-4-153273
159373, JP-A-4-179964,
JP-A-5-202309, JP-A-5-27959
JP-A-5-289380, JP-A-5-289380,
JP-A-336554, JP-A-7-82503, JP-A-7-82505, and JP-A-8-1106
No. 49 can be mentioned.

Further, copper phthalocyanine is disclosed in
No. 1667, JP-A-51-108847, JP-A-55-60958,
Furthermore, γ-type, π-type, χ-type, and ρ-type are known, and these can be mentioned. Chloroaluminum phthalocyanine is disclosed in JP-A-58-158649 and JP-A-58-158649.
JP-A-2-133462, JP-A-62-163060, JP-A-63-43155, and JP-A-6-163155.
JP-A-4-70762 discloses chloroindium phthalocyanine as disclosed in JP-A-59-44054 and JP-A-60-5.
No. 9355, JP-A-61-45249 and JP-A-7-13375, vanadyloxyphthalocyanine is disclosed in JP-A-63-18361, JP-A-1-204968, and JP-A-1-204968. JP-A-268763, JP-A-3-269063, and JP-A-7-26963.
No. 247442, diphenoxygermanium phthalocyanine is disclosed in JP-A-4-360150, and chlorogallium phthalocyanine is disclosed in JP-A-5-194523.
JP-A-7-102183 discloses hydroxygallium phthalocyanine.
No. 07, and further, those described in JP-A-7-53892.

A film-forming binder used for forming a photosensitive layer containing the organic photoconductive compound represented by the general formula (1) or (2) or the general formula (6) or (7) of the present invention Various resins can be used depending on the field of use. For example, in photoreceptor applications for copying, polystyrene resin, polyvinyl acetal resin, polysulfone resin,
Examples include polycarbonate resin, vinyl acetate / crotonic acid copolymer resin, polyester resin, polyphenylene oxide resin, polyarylate resin, alkyd resin, acrylic resin, methacrylic resin, phenoxy resin, and polyvinyl chloride resin. Among them, polystyrene resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, polyarylate resin, and the like have excellent potential characteristics as a photoconductor. These resins may be used alone or in the form of a copolymer. These resins may be used alone or in combination of two or more. The amount of the binder resin to be added to the photoconductive compound is preferably 20 to 1000% by weight, and 50 to 5% by weight.
00% by weight is more preferred.

In the case of a laminated photoreceptor, these resins contained in the charge generation layer are 10 to 50 with respect to the charge generation substance.
0% by weight is preferable, and 50 to 150% by weight is more preferable. If the ratio of the resin is too high, the charge generation efficiency is lowered, and if the ratio of the resin is too low, there is a problem in film formability. Further, the content of these resins contained in the charge transport layer is preferably from 20 to 1,000% by weight, more preferably from 50 to 500% by weight, based on the charge transport material. If the ratio of the resin is too high, the sensitivity is lowered, and if the ratio of the resin is too low, the repetition characteristics may be deteriorated or the coating film may be damaged.

Some of these resins include tension, bending,
Some have weak mechanical strength such as compression. To improve this property, substances which impart plasticity can be added. Specifically, phthalic acid esters (eg, DOP, DOP
BP), phosphoric acid esters (eg, TCP, TOP, etc.), sebacic acid esters, adipic acid esters, nitrile rubber, chlorinated hydrocarbons and the like. If these substances are added unnecessarily, they adversely affect the electrophotographic properties. Therefore, the ratio is preferably 20% by weight or less based on the binder resin.

In addition, as an additive to the photoreceptor, a leveling agent or the like for improving coating properties, such as an antioxidant or an anti-curl agent, can be added as needed.

The compound represented by the general formula (1) or (2) or the general formula (6) or (7) can be used in combination with another charge transporting substance. The charge transport materials include a hole transport material and an electron transport material. Examples of the former include, for example, oxadiazoles disclosed in JP-B-34-5466, triphenylmethanes disclosed in JP-B-45-555, and JP-B-52-4188. And the like, hydrazones described in JP-B-55-42380, oxadiazoles described in JP-A-56-123544, and the like. On the other hand, examples of the electron transporting substance include chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone,
4,5,7-tetranitro-9-fluorenone, 2,
4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 1,3,7-trinitrodibenzothiophene, 1,3,7-trinitrodibenzothiophene-5,5-dioxide and the like . These charge transport materials can be used alone or in combination of two or more.

Further, as a sensitizer which forms a charge transfer complex with the compound represented by the general formula (1) or (2) or the general formula (6) or (7) and further increases the sensitizing effect, Certain electron withdrawing compounds can also be added. Examples of the electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, and phenanthrenequinone; Aldehydes such as benzaldehyde, 9-benzoylanthracene, indandione,
3,5-dinitrobenzophenone, 3,3 ', 5,5'
Ketones such as tetranitrobenzophenone, phthalic anhydride, acid anhydrides such as 4-chloronaphthalic anhydride,
Cyano compounds such as terephthalalmalononitrile, 9-anthrylmethylidenemalononitrile, 4-nitrobenzalmalonenitrile, 4- (p-nitrobenzoyloxy) benzalmalononitrile, 3-benzalphthalide, 3- (α-cyano -P-nitrobenzal) phthalide, 3- (α-cyano-p-nitrobenzal) -4,
Phthalides such as 5,6,7-tetrachlorophthalide and the like can be mentioned.

The organic photoconductive compound of the present invention is dissolved or dispersed in a suitable solvent together with the various additives described above depending on the form of the photoreceptor, and the coating solution is applied onto the above-mentioned conductive support. And dried to produce a photoreceptor.

Examples of the coating solvent include halogenated hydrocarbons such as chloroform, dichloroethane, dichloromethane, trichloroethane, trichloroethylene, chlorobenzene and dichlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, dioxane, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, and the like. Ether solvents such as ethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone and cyclohexanone, ester solvents such as ethyl acetate, methyl formate, methyl cellosolve acetate, N, N-dimethylformamide, acetonitrile, Aprotic polar solvents such as N-methylpyrrolidone, dimethylsulfoxide and n-butanol, 2-propanol; , And the like alcohol solvents such Lumpur. These solvents may be used alone or
It can be used as a mixed solvent of at least one kind.

[0105]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0106]

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[0107]

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Synthesis Example 1 Synthesis of Exemplified Compound (S-07) 1.59 g of the aldehyde compound represented by the above (11),
To a solution of 1.07 g of the phosphonate compound represented by the above (12) and 50 ml of N, N-dimethylformaldehyde (DMF), 0.72 g of potassium t-butoxide was slowly added at room temperature with stirring. After stirring at room temperature overnight, the reaction solution was poured into 300 ml of ice water to stop the reaction, and the organic component was extracted with ethyl acetate. The separated organic layer was dried over anhydrous magnesium sulfate,
The solvent was distilled off under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain 1.15 g of the desired compound (S-07). Its melting point was 77.0-79.0 ° C.

[0109]

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Synthesis Example 2 Synthesis of Exemplified Compound (S-12) 1.77 g of the aldehyde compound represented by the above (11),
0.87 g of potassium t-butoxide was slowly added to a 50 ml solution of DMF in which 1.72 g of the phosphonate compound represented by the above (13) was dissolved at room temperature with stirring. After stirring at room temperature overnight, the reaction solution was
The reaction was stopped by pouring into 1 l of ice water, and the organic component was extracted with ethyl acetate. The separated organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain 1.33 g of the desired compound (S-12). Its melting point was 89.5-91.5 ° C.

Example 1 1 part by weight of an azo pigment (K-1) and 1 part by weight of a polyester resin (Vylon 200 manufactured by Toyobo) were mixed with 100 parts by weight of tetrahydrofuran, and dispersed together with glass beads for 2 hours using a paint conditioner. The dispersion thus obtained was applied on an aluminum-evaporated polyester using an applicator and dried to form a charge generation layer having a thickness of about 0.2 μm. Next, the exemplary compound (S-07) was mixed with a polyarylate resin (U-Polymer manufactured by Unitika) at a weight ratio of 1: 1 to prepare a 10% by weight solution using dichloroethane as a solvent. The resultant was applied with an applicator to form a charge transport layer having a thickness of about 20 μm.

The electrophotographic characteristics of the laminated photoreceptor thus manufactured were evaluated using an electrostatic recording tester (SP-428 manufactured by Kawaguchi Electric). Measurement conditions: applied voltage -6 kV, static No. 3 (turntable rotation speed mode: 10 m / min)
). As a result, the charge potential (V ₀ ) was -780 V, and the half-exposure amount (E1 / 2) showed a value of 1.1 lux · sec, which was a high sensitivity value.

Further, the same apparatus was used to evaluate characteristics for repeated use in which charging-discharging (discharging light: irradiation with white light at 400 lux × 1 second) was performed in one cycle. 5000
The change in the charged potential due to the repetition of
To times th charge potential (V ₀₎ -780V, 5000-th charge potential (V ₀₎ is -770V, reduction in potential due to repetitive showed almost no stable characteristics. The first half-exposure dose (E1 / 2) is 1.1 lux / sec, whereas the 5000th half-exposure dose (E1 / 2) is 1.1.
It showed excellent characteristics without change in looks and seconds.

Examples 2 to 49 The azo pigment (K-1) of Example 1 and the exemplified compound (S-0)
A photoconductor was prepared and the characteristics were evaluated in the same manner as in Example 1, except that the azo pigments shown in Tables 46 and 47 and the compound of the present invention were used instead of 7). The results are shown in Tables 46 and 47.

[0115]

[Table 46]

[0116]

[Table 47]

Example 50 1 part by weight of azo pigment (I-2) and tetrahydrofuran 40
Parts by weight were dispersed for 8 hours together with glass beads in a paint conditioner. In the dispersion thus obtained,
2.5 parts by weight of the exemplified compound (S-12), 10 parts by weight of a polycarbonate resin (PCZ-200 manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 60 parts by weight of tetrahydrofuran were added, and the mixture was subjected to a dispersion treatment with a paint conditioner for 30 minutes. The composition was applied on an aluminum-evaporated polyester by an applicator to form a photosensitive layer having a thickness of about 15 μm. The electrophotographic characteristics of this photoreceptor were evaluated in the same manner as in Example 1. However, only the applied voltage was changed to +5 kV. As a result, 1
The second charging potential (V ₀ ) +480 V, half-exposure amount (E1 /
2) Charged potential (V ₀ ) + 475 V after 5,000 repetitions, half-exposure (E1 / 2) of 1.4 lux / sec after 5,000 repetitions, high sensitivity and excellent characteristics with little change Indicated.

Examples 51 to 92 The azo pigment (I-2) and the exemplified compound (S-
A photoconductor was prepared in the same manner as in Example 50 except that the azo pigments and the compounds of the present invention shown in Tables 48 and 49 were used instead of 12), and the characteristics of the photoconductor were evaluated. The results are shown in Tables 48 and 49.

[0119]

[Table 48]

[0120]

[Table 49]

Examples 93 to 103 In place of the azo pigment of Example 1, CuKα 1.541 angstroms X-ray Bragg angle (2θ ± 0.2 °)
Are 9.5 °, 9.7 °, 11.7 °, 15.0 °, 2
Titanyloxyphthalocyanine (Y-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing main peaks at 3.5 °, 24.1 °, and 27.3 ° are shown in Tables in place of the exemplary compound (S-07), respectively. A photoconductor was prepared in the same manner as in Example 1 except that the compound of the present invention shown in No. 50 was used, and its characteristics were evaluated. The results are shown in Table 50.

[0122]

[Table 50]

Examples 104 to 114 The procedure of Example 50 was repeated except that the azo pigment of Example 50 was replaced with Y-type titanyloxyphthalocyanine and the compound of the present invention shown in Table 51 was used instead of the exemplified compound (S-12). A photoconductor was prepared in the same manner as in Example 50, and the characteristics were evaluated. The results are shown in Table 51.

[0124]

[Table 51]

[0125]

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Comparative Example Example 1 was repeated except that the comparative compound (14) shown above was used instead of the exemplary compound (S-07) as the charge transporting substance.
As a result of preparing a photoreceptor in the same manner as described above and evaluating the characteristics, a reduction in sensitivity was observed, with the charging potential (V ₀ ) being -640 V and the half-life exposure amount (E1 / 2) being 4.1 lux · sec.

[0127]

As is apparent from the above, the use of the organic photoconductive compound of the present invention has high sensitivity and high durability.
An excellent electrophotographic photosensitive member can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 409/12 C07D 409/12 G03G 5/06 324 G03G 5/06 324A 324B

Claims (12)

[Claims] 1. An organic photoconductive compound represented by the following general formula (1) or (2). Embedded image (In the general formula (1) or (2), X represents an oxygen atom or a sulfur atom, and R ¹ represents an alkyl group which may have a substituent or an aralkyl group which may have a substituent. Represents an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ² represents a hydrogen atom, an alkyl group which may have a substituent, R ³ and R ⁴ represent an aralkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent; Ar ¹ represents an optionally substituted alkyl group, an optionally substituted alkoxy group, or a halogen atom, and Ar ¹ represents an optionally substituted aryl group or an optionally substituted substituent. It represents a heterocyclic group or a styryl group which may have a substituent.) 2. The organic photoconductive compound according to claim 1, represented by the following general formula (3). Embedded image (In the general formula (3), R ¹ , R ² and Ar ¹ are the same as those in the general formula (2).) 3. The organic photoconductive compound according to claim 1, represented by the following general formula (4). Embedded image (In the general formula (4), R ¹ is the same as the general formula (2). R ⁵ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom. Y ¹ represents a hydrogen atom, a lower alkyl group. Or an aryl group, which may be substituted with a lower alkyl group, a lower alkoxy group, or a halogen atom.) 4. The organic photoconductive compound according to claim 1, represented by the following general formula (5). Embedded image (In the general formula (5), R ⁶ represents a hydrogen atom, a methyl group,
Or a chlorine atom. Y ² represents a hydrogen atom, a methyl group, a phenyl group, a p-tolyl group, a p-methoxyphenyl group, or a p-chlorophenyl group. ) 5. The method according to claim 1, wherein said conductive support has a general formula (1)
An electrophotographic photoreceptor comprising a photosensitive layer containing at least one of the organic photoconductive compounds represented by (5). 6. The photosensitive layer contains a charge-generating substance and a charge-transporting substance, wherein the charge-transporting substance has the general formula (1)
The electrophotographic photoreceptor according to claim 5, wherein the electrophotographic photoreceptor is at least one kind of the organic photoconductive compound represented by (5). 7. An organic photoconductive compound represented by the following general formula (6) or (7). Embedded image (In the general formula (6) or (7), Z represents an oxygen atom or a sulfur atom, and R ⁷ and R ⁸ may be an alkyl group which may have a substituent, or may have a substituent. A good aralkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, wherein R ⁹ and R ¹⁰ are a hydrogen atom or an optionally substituted group; Ar ² represents an alkyl group, an optionally substituted alkoxy group, or a halogen atom, and Ar ² represents an optionally substituted aryl group, or an optionally substituted heterocyclic group. Shown.) 8. The organic photoconductive compound according to claim 7, represented by the following general formula (8). Embedded image (In the general formula (8), R ⁷ , R ⁸ and Ar ² are the same as those in the general formula (7).) 9. The organic photoconductive compound according to claim 7, represented by the following general formula (9). Embedded image (In the general formula (9), R ⁷ and R ⁸ are the same as those in the general formula (7). R ¹¹ represents a hydrogen atom, a methyl group, or a chlorine atom.) 10. The organic photoconductive compound according to claim 7, represented by the following general formula (10). Embedded image (In the general formula (10), R ¹¹ is the same as in the general formula (9). U is a methyl group, a phenyl group, a p-tolyl group, a p-
-A methoxyphenyl group or a p-chlorophenyl group. ) 11. The method according to claim 1, wherein the conductive support has the general formula (7)
At least one of the organic photoconductive compounds represented by (10)
An electrophotographic photosensitive member comprising a photosensitive layer containing a seed. 12. The photosensitive layer contains a charge-generating substance and a charge-transporting substance, wherein the charge-transporting substance has the general formula (7)
At least one of the organic photoconductive compounds represented by (10)
The electrophotographic photosensitive member according to claim 11, which is a seed.