JP2000219677A - Organic photoconductive compound and electrophotographic photoreceptor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound comprising a specific bisindole- based compound, having a high electrification potential and a high sensitivity, capable of manifesting stable performances without changing characteristics even when repetitively used and useful as a sensor material, an EL element, an electrostatic recording element, etc. SOLUTION: This compound is represented by formula I (R1 is H, a lower alkyl or the like; (m) is 3-6; and (n) is 1 or 2), e.g. a compound represented by formula II. The compound represented by formula I is obtained by reacting an indole compound represented by formula III with a p-dihalogen-substituted benzene represented by formula IV or a p,p'-dihalogen-substituted biphenyl represented by formula V (X is bromine, iodine or the like) in an amount of 0.5 mol (equivalent) of the indole compound represented by formula III without or using a high-boiling point solvent)((e.g. nitrobenzene or sulfolane) by adding 1.0-1.5 mol of a base (e.g. potassium carbonate or sodium carbonate) and further adding a catalyst (e.g. metallic copper or a monovalent copper salt such as a cuprous chloride) under heating at a high temperature of 200-300 deg.C for 5-24 h.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel 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 characteristics.

In order to improve such a point, an organic photoreceptor having higher sensitivity characteristics in which a charge generation function and a charge transport function are shared by different substances has been developed. 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 by accumulating a huge amount of synthetic research, but until now,
A photoreceptor that sufficiently satisfies the basic properties and high durability required for the photoreceptor has 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 a material for an electrophotographic photoreceptor which has a high charging potential, high sensitivity, does not change various characteristics even when used repeatedly, and has stable performance. Another object of the present invention is to provide a novel organic photoconductive compound that can be used for a sensor material, an EL element, an electrostatic recording element, and the like.

[0012]

Means for Solving the Problems The present inventors have studied organic photoconductive compounds to achieve the above object, and as a result,
The present inventors have found that an organic photoconductive compound having a specific structure is effective, and have reached the present invention. The organic photoconductive compound having a specific structure as described above includes a bisindole compound represented by the following general formula (1).

[0013]

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In the general formula (1), R ₁ is a hydrogen atom,
A lower alkyl group, a lower alkoxy group, or a halogen atom, m represents an integer of 3 to 6, and n represents 1 or 2.

Further, as the organic photoconductive compound having a specific structure of the present invention, a bisindoline-based compound represented by the following general formula (2) can be mentioned.

[0016]

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In the general formula (3), R ₂ is a hydrogen atom,
It represents a lower alkyl group, a lower alkoxy group or a halogen atom, p represents an integer of 3 to 6, and q represents 1 or 2.

Here, specific examples of R ₁ and R ₂ include a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group, a methoxy group, an ethoxy group, Examples include lower alkoxy groups such as n-propoxy group and n-butoxy group, and halogen atoms such as fluorine atom, chlorine atom and bromine atom.

M and p each represent an integer of 3 to 6, and n and q each represent 1 or 2.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the organic photoconductive compound represented by the general formula (1) according to the present invention include the following bisindole compounds of EA-01 to EA-20. It is not limited to these.

[0021]

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[0022]

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[0023]

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[0024]

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Further, specific examples of the organic photoconductive compound represented by the general formula (2) according to the present invention include the following bisindoline compounds of EB-01 to EB-20. It is not limited.

[0026]

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[0027]

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[0028]

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[0029]

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The bisindole compound represented by the general formula (1) in the present invention is easily synthesized by the following synthesis route.

That is, an indole compound represented by the following general formula (3) and a p-dihalogen-substituted benzene represented by the following general formula (4) in an amount of 0.5 molar equivalents relative to (3) or the following general formula: The p, p'-dihalogen-substituted biphenyl represented by the formula (5) may be used in the absence of a solvent or a high boiling solvent such as nitrobenzene or sulfolane in an amount of 1.0 molar equivalent to
Add 1.5 molar equivalents of a base such as potassium carbonate or sodium carbonate, and further as a catalyst, metallic copper or cuprous chloride,
A monovalent copper salt such as cuprous bromide or cuprous iodide is added, and 200
It can be easily synthesized by reacting at a high temperature of up to 300 ° C. under heating for about 5 to 24 hours.

[0032]

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[0033]

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[0034]

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R ₁ and m in the general formula (3) are
It is the same as the bisindole compound represented by the general formula (1), and X in the general formulas (4) and (5) represents a bromine atom or a halogen atom of an iodine atom.

The bisindoline compound represented by the general formula (2) in the present invention is obtained by using the indoline compound represented by the following general formula (6) in place of the indole compound represented by the above general formula (3). The compound can be easily synthesized by performing the same reaction as described above.

[0037]

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The bisindolinic compound represented by the general formula (2) can be obtained by converting the corresponding bisindole compound represented by the general formula (1) into an alcoholic solvent such as methanol or ethanol, or a dioxane or dioxolane. Using a cyclic ether-based solvent and a catalyst such as 5% palladium carbon as a catalyst, catalytic reduction with hydrogen gas is performed under normal pressure or under pressure to reduce the double bond of the two indole moieties of the general formula (1). In some cases, it can be easily synthesized.

R ₂ and p in the general formula (6) are
It is the same as the bisindoline compound represented by the general formula (2).

The indole compound represented by the general formula (3), which is used as a raw material for the above reaction, is obtained from Journal of
Chemical Society, 1923, 12
According to the method described in Volume 3, pages 3242 to 3247,
The indoline compound of the general formula (6) can be obtained in good yield, and can be obtained from the Journal of Chemical So
Citiy, 1958, pp. 2302-2311. Regarding the compounds of the general formulas (4) and (5), which are one raw material for synthesis, both those in which X is a bromine atom and those in which the iodine atom is X are both commercially available.

In the present invention, any of the electrophotographic photosensitive members having a photosensitive layer containing the organic photoconductive compound represented by the general formula (1) or (2) can be used. 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, a laminated photoreceptor in which a charge generation layer composed of a charge generation substance and a binder resin and a charge transport layer composed of a charge transport substance and a binder resin are provided on a conductive support is 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 has the general formula (1)
Alternatively, it can be obtained by containing one kind or two or more kinds of the organic photoconductive compound represented by (2) and the charge generating substance. Charge generation materials include inorganic charge generation materials and organic charge generation materials.Examples of the former include, for example, selenium, selenium-tellurium alloy, selenium-arsenic alloy,
Cadmium sulfide, zinc oxide, amorphous silicon, and the like can be given. Examples of organic charge generating substances include, for example, triphenylmethane dyes such as methyl violet, brilliant green, and crystal violet; thiazine dyes such as methylene blue; quinone dyes such as quinizarin; cyanine dyes; acridine dyes; pyrylium dyes; , Squarium dye, perinone pigment, anthraquinone pigment, perylene pigment,
Metal-containing or non-metallic phthalocyanine 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.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

[Table 9]

[0055]

[Table 10]

[0056]

[Table 11]

[0057]

[Table 12]

[0058]

[Table 13]

[0059]

[Table 14]

[0060]

[Table 15]

[0061]

[Table 16]

[0062]

[Table 17]

[0063]

[Table 18]

[0064]

[Table 19]

[0065]

[Table 20]

[0066]

[Table 21]

[0067]

[Table 22]

[0068]

[Table 23]

[0069]

[Table 24]

[0070]

[Table 25]

[0071]

[Table 26]

[0072]

[Table 27]

[0073]

[Table 28]

[0074]

[Table 29]

[0075]

[Table 30]

[0076]

[Table 31]

[0077]

[Table 32]

[0078]

[Table 33]

[0079]

[Table 34]

[0080]

[Table 35]

[0081]

[Table 36]

[0082]

[Table 37]

[0083]

[Table 38]

[0084]

[Table 39]

[0085]

[Table 40]

[0086]

[Table 41]

[0087]

[Table 42]

[0088]

[Table 43]

[0089]

[Table 44]

[0090]

[Table 45]

As the phthalocyanine pigment used in the present invention, any of 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. Among them, metal-free phthalocyanine, titanyloxyphthalocyanine, copper phthalocyanine, chloroaluminum phthalocyanine, chloroindium phthalocyanine, vanadyloxyphthalocyanine, diphenoxygermanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are particularly preferably used in the present invention.

The phthalocyanine pigment is known as a polymorphic compound, and various crystalline phthalocyanine 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
No. 2, 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.

As the film-forming binder resin used for forming the photosensitive layer containing the organic photoconductive compound represented by the general formula (1) or (2) of the present invention, various resins may be used depending on the field of use. can give. For example, for photoreceptors for copying, polystyrene resin, polyvinyl acetal resin, polysulfone resin, polycarbonate resin, vinyl acetate / crotonic acid copolymer resin, polyester resin, polyphenylene oxide resin, polyarylate resin, alkyd resin, acrylic resin, methacrylic resin Phenoxy resin or 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 as a copolymer, and one or more of these resins may be used in combination. The amount of the binder resin added to the photoconductive compound is preferably 20 to 1000% by weight, more preferably 50 to 500% by weight.

In the case of a laminated type 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.

Among these resins, there are 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, a leveling agent or the like for improving coating properties, such as an antioxidant or an anti-curl agent, may be added as necessary to the photoreceptor.

The compound represented by formula (1) or (2) can be used in combination with another charge transporting substance. The charge transport materials include a hole transport material and an electron transport material. An example of the former is, for example, Japanese Patent Publication No. 34-54.
No. 66, etc., oxadiazoles disclosed in Japanese Patent Publication No. 45-555, etc., pyrazolines described in Japanese Patent Publication No. 52-4188, etc., Hydrazones disclosed in JP-A-55-42380, JP-A-56-1235.
Oxadiazoles disclosed in JP-A-44-44 and the like can be mentioned. On the other hand, as electron transport materials,
For example, chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone , 2,
Examples include 4,8-trinitrothioxanthone, 1,3,7-trinitrodibenzothiophene, and 1,3,7-trinitrodibenzothiophene-5,5-dioxide. These charge transport materials can be used alone or in combination of two or more.

It is also possible to form a charge transfer complex with the compound represented by the general formula (1) or (2) and to add a certain electron-withdrawing compound as a sensitizer for further enhancing the sensitizing effect. it can. 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,
Ketones such as 3 ', 5,5'-tetranitrobenzophenone, acid anhydrides such as phthalic anhydride and 4-chloronaphthalic anhydride, terephthalalmalononitrile, 9-anthrylmethylidenemalononitrile, 4-nitroben Salmalononitrile, 4- (p-nitrobenzoyloxy)
Cyano compounds such as benzalmalononitrile, 3-benzalphthalide, 3- (α-cyano-p-nitrobenzal) phthalide, 3- (α-cyano-p-nitrobenzal) -4,5,6,7-tetrachlorophthalide And the like.

The organic photoconductive 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 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.

[0103]

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.

[0104]

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[0105]

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Synthesis Example 1 Synthesis of Exemplified Compound (EA-11) 5.1 g of the diiodide compound represented by the above (7), 4.72 g of the indole compound represented by the above (8), 4.9 g of potassium carbonate, and bromide After well mixing 0.16 g of cuprous copper, 25 ml of sulfolane was added, and the mixture was stirred for 2 hours.
Heat at 00 ° C. for 7 hours. After returning the reaction solution to room temperature, it is poured into 300 ml of water, and the insoluble crystals are collected by filtration. This was thoroughly dispersed and washed with ethyl acetate, purified by silica gel column chromatography (elution solvent: chloroform), and recrystallized from chloroform to obtain 1.77 g of the desired compound (EA-11). The yield is 30.2%,
Melting point was 259-266 ° C.

Synthesis Example 2 Synthesis of Exemplified Compound (EB-11) 1.13 g of (EA-11) synthesized in Synthesis Example 1 and 5
0.17 g of palladium carbon in 50 m of dioxane
The mixture is suspended in a mixed solution of 1 ml of methanol and 20 ml of methanol, and while being stirred at room temperature, hydrogen gas is introduced under normal pressure to perform catalytic reduction. (Reaction time: 72 hours) After confirming the completion of the reaction by gas chromatography, the reaction solution is filtered, the solvent of the filtrate is distilled off under reduced pressure, and the obtained oil is left to crystallize.
This was dispersed and washed with ethanol, and dried to obtain 0.37 g of the target compound (EB-11). The yield is 33%,
Melting point was 186-190 ° 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 by a paint conditioner for 2 hours. 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 exemplified compound (EA-11) 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 charging potential (V ₀ ) was -720 V, and the half-exposure dose (E1 / 2) was 1.5 lux / sec, which was a high sensitivity value.

Further, the same apparatus was used to evaluate the characteristics with respect to repeated use in which one cycle was charging-discharging (discharging light: irradiation with white light at 400 lux × 1 second). 5000
The change in the charged potential due to the repetition of
The 5000th charging potential (V ₀ ) was −715 V compared to the charging potential (V ₀ ) of −720 V for the 5000 th charging, and showed stable characteristics with almost no decrease in potential due to repetition. In addition, while the first half-exposure dose (E1 / 2) is 1.5 lux / second, the 5000th half-exposure dose (E1 / 2) is 1.5 times.
It showed excellent characteristics without change in looks and seconds.

Examples 2 to 21 The azo pigment (K-1) and the exemplified compound (EA-
A photoconductor was prepared in the same manner as in Example 1 except that the azo pigments shown in Tables 46 to 47 and the compounds of the present invention were used instead of 11), and the characteristics were evaluated. The results are shown in Tables 46 to 47.

[0112]

[Table 46]

[0113]

[Table 47]

Example 22 1 part by weight of azo pigment (J-1) 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 (EA-11), 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 further subjected to a dispersion treatment for 30 minutes by a paint conditioner. 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
Second charging potential (V ₀ ) +450 V, half-exposure amount (E1 /
2) 1.6 lux / sec, charging potential (V ₀ ) after 5,000 repetitions + 440 V, half-exposure (E1 / 2) of 1.6 lux / sec, providing excellent characteristics with high sensitivity and little change Indicated.

Examples 23 to 42 The azo pigment (J-1) of Example 22 and the exemplified compound (EA)
A photoconductor was prepared and the characteristics were evaluated in the same manner as in Example 22, except that the azo pigments and the compounds of the invention shown in Tables 48 to 49 were used instead of -11). The results are shown in Tables 48 to 49.

[0116]

[Table 48]

[0117]

[Table 49]

Examples 43 to 52 Instead of the azo pigment (K-1) of Example 1, CuKα1.
541 angstroms of X-ray Bragg angle (2θ ±
0.2 °) is 9.5 °, 9.7 °, 11.7 °, 1
Titanyloxyphthalocyanine (Y-type titanyloxyphthalocyanine) having an X-ray diffraction spectrum showing main peaks at 5.0 °, 23.5 °, 24.1 °, and 27.3 ° was prepared by using the exemplified compound (EA-11). Were prepared in the same manner as in Example 1 except that the compounds of the present invention shown in Tables 50 to 51 were used instead of, respectively, and the characteristics thereof were evaluated. The results are shown in Tables 50 to 51.

[0119]

[Table 50]

[0120]

[Table 51]

Examples 53 to 62 In place of the azo pigment (J-1) of Example 22, Y-type titanyloxyphthalocyanine was replaced with the exemplified compound (EA-11)
Was replaced with the compounds of the present invention shown in Tables 52 to 53, respectively, to produce a photoreceptor in the same manner as in Example 22, and to evaluate its characteristics. The results are shown in Tables 52 to 53.

[0122]

[Table 52]

[0123]

[Table 53]

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1, except that the following comparative compound (R-1) was used in place of the exemplary compound (EA-11) as the charge transporting substance. Of the first charging potential (V ₀ ) -620 V
The charging potential (V ₀ ) at the 00th time was −430 V, and the initial charging potential was not only poor, but also a drastic decrease in potential due to repetition was observed. The first half-exposure amount (E1 / 2) 2.
5000th half-exposure dose (E
1/2) was 5.5 lux / sec, and a decrease in sensitivity was also observed.

[0125]

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Comparative Example 2 Similarly, the exemplified compound (EA-1) was used as a charge transport material.
A photoconductor was prepared in the same manner as in Example 1, except that the following comparative compounds (R-2 to 5) were used in place of 1), and the characteristics were evaluated. As shown in Table 54, as shown in Table 54, all samples showed a decrease in sensitivity and a decrease in charge potential due to repetition.

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

[Table 54]

[0132]

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.

Claims (4)

[Claims] 1. An organic photoconductive compound represented by the following general formula (1). Embedded image (In the general formula (1), R ₁ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom;
m represents an integer of 3 to 6, and n represents 1 or 2. ) 2. An organic photoconductive compound represented by the following general formula (2). Embedded image (In the general formula (2), R ₂ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom;
p represents an integer of 3 to 6, and q represents 1 or 2. ) 3. An organic photoconductive compound represented by the above general formula (1) or (2) on a conductive support.
An electrophotographic photosensitive member having a photosensitive layer containing a seed. 4. The photosensitive layer contains a charge generating substance and a charge transporting substance, and the charge transporting substance is at least one kind of the organic photoconductive compound represented by the general formula (1) or (2). The electrophotographic photosensitive member according to claim 3, wherein: