JPH09297416A - Organic photoconductive material and electrophotographic photoreceptor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic photoreceptor having high potential by electrification and high sensitivity, undergoing no change in various characteristics even after repeated use and exhibiting stable performance by imparting a specified structure. SOLUTION: This org. photoconductive material is a compd. represented by formula I or II. In the formulae I, II, each of R1 and R4 is alkyl which may have a substituent, aryl, aralkyl, or alkoxy, each of (m) and (n) is an integer of 0-4, each of R2 and R3 is alkyl which may have a substituent, alkenyl, alkynyl, aralkyl, aryl or a heterocyclic group, R2 and R3 may form a hetero ring by bonding to each other, each of R5 and R6 is H, alkyl which may have a substituent, alkenyl, aryl or a heterocyclic group and R5 and R6 may form a hetero ring by bonding to each other. When this photoconductive material is used, the objective electrophotographic photoreceptor having high potential by electrification and high sensitivity, undergoing no change in various characteristics even after repeated use and capable of exhibiting stable performance is obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic photoconductive material and an electrophotographic photoreceptor using the same, and more particularly, to an electrophotographic photoreceptor containing a specific organic photoconductive material. It is.

[0002]

2. Description of the Related Art In recent years, the use of the electrophotographic method has spread not only in the field of copying machines but also in fields in which photographic technology has been conventionally used, such as printing plate materials, slide films, and microfilms. Application to a high-speed printer using a light source is also being studied. Recently, the use of a photoconductive material other than an electrophotographic photosensitive member, for example, an application to an electrostatic recording element, a sensor material, an EL element, and the like has begun to be 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 that it is difficult to produce under conditions and is easily crystallized by heat or 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. In addition, selenium and cadmium sulfide 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 yet been clarified. 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. A variety of materials such as hydrazone compounds and stilbene compounds have been studied as hole transport materials, and 2,4,7-trinitro-9-fluorenone and diphenoquinone derivatives have been studied as electron transport materials. The fact is that they are conducting extensive 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 photoconductors, but the basic properties and high durability required for the photoconductors listed above are sufficiently met. The current situation is that nothing has been obtained that satisfies them.

[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 material that can be used for an electrostatic recording element and the like.

[0012]

Means for Solving the Problems The present inventors have studied photoconductive materials to achieve the above object, and as a result, have found that an organic photoconductive material having a specific structure is effective. Invented the invention. The above-mentioned organic photoconductive material having a specific structure is a compound represented by the following general formulas (1) and (2).

[0013]

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In the general formulas (1) and (2), R ₁ and R ₄
Each represents an alkyl group, an aryl group, an aralkyl group, or an alkoxy group which may have a substituent, and m and n each represent an integer of 0 to 4. R ₂ and R ₃ each represent an optionally substituted alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group,
They may together form a heterocycle. R ₅ and R ₆ each represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an aryl group or a heterocyclic group, which may together form a ring.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of R ₁ and R ₄ include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, aryl groups such as phenyl group and naphthyl group, benzyl group, β Examples thereof include an aralkyl group such as a phenylethyl group, an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group. R ₁ and R ₄ may have a substituent, and specific examples of the substituent include halogen atoms such as fluorine atom, bromine atom, chlorine atom and iodine atom.

Specific examples of R ₂ and R ₃ include alkyl groups such as methyl group, ethyl group, propyl group and butyl group,
Allyl group, 1-propenyl group, 2-butenyl group, alkenyl group such as methallyl group, alkynyl group such as propargyl group, benzyl group, β-phenylethyl group, aralkyl group such as α-naphthylmethyl group, phenyl group, naphthyl group Base,
Examples thereof include an aryl group such as an anthryl group and a heterocyclic group such as a pyridyl group. R ₂ and R ₃ may have a substituent, and specific examples of the substituent include a hydrogen atom,
Examples thereof include a halogen atom such as a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, the above alkyl group and an aryl group. Examples of R ₂ and R ₃ which together form a heterocycle include a piperidine ring, a morpholine ring and an indoline ring.

Specific examples of R ₅ and R ₆ include a hydrogen atom, a heterocyclic group such as a furyl group, a thienyl group and a pyridyl group, and the above-mentioned alkyl group, alkenyl group and aryl group. R ₅ and R ₆ may have a substituent, and specific examples of the substituent include aryloxy groups such as phenoxy group, arylthio groups such as phenylthio group, the above-mentioned halogen atom, alkoxy group and aralkyl. Group, alkyl group, alkenyl group, aryl group and the like. Examples of R ₅ and R ₆ which together form a ring include a fluorene ring, an indane ring and a xanthene ring.

Specific examples of the organic photoconductive material represented by the general formulas (1) and (2) according to the present invention include, but not limited to, those having the following structural formulas. .

[0019]

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[0020]

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[0021]

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[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

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[Chemical 12]

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[0032]

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[Chemical 21]

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

[Chemical formula 26]

[0043]

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[0045]

[Chemical 29]

[0046]

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[0047]

[Chemical 31]

[0048]

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[Chemical 33]

[0050]

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[0065]

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[Chemical 51]

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[0075]

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[0076]

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[0077]

[Chemical formula 61]

[0078]

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[0080]

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[0081]

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[0082]

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[0100]

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[0101]

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[0102]

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[0103]

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[0115]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

[Chemical formula 106]

[0123]

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[0124]

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[0125]

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[0126]

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[0127]

[Chemical 111]

[0128]

[Chemical 112]

[0129]

[Chemical 113]

[0130]

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[0131]

[Chemical 115]

[0132]

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[0133]

[Chemical 117]

[0134]

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[0135]

[Chemical formula 119]

[0136]

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The electrophotographic photoreceptor of the present invention has the general formula (1):
It can be obtained by containing one kind or two or more kinds of the organic photoconductive material and the charge generating substance shown in (2). 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 pigments, anthraquinone pigments, metal-containing or metal-free phthalocyanine pigments, perylene pigments, and the like.
Azo pigments are also used.

Examples of azo pigments include JP-A-47-3
7543, JP-A-53-95033, JP-A-53-95033
132347, JP-A-53-133445, JP-A-54-12742, JP-A-54-20736, JP-A-54-20737, JP-A-54-21728, JP-A-54-22834 JP-A-55-69148,
JP-A-55-69654 and JP-A-55-79449.
JP-A-55-117151, JP-A-56-462
No. 37, JP-A-56-116039, JP-A-56-1
No. 16040, JP-A-56-119134, JP-A-5-119134
6-143437, JP-A-57-63537, JP-A-57-63538, JP-A-57-63541, JP-A-57-63542, JP-A-57-63549,
JP-A-57-66438, JP-A-57-74746
JP-A-57-78542 and JP-A-57-7854.
3, JP-A-57-90056, JP-A-57-90056
No. 57, JP-A-57-90632, JP-A-57-11
6345, JP-A-57-202349, JP-A-58
-4151, JP-A-58-90644, JP-A-58-9064
JP-A-144358, JP-A-58-177555, JP-A-59-31962, JP-A-59-33253, JP-A-59-71059, JP-A-59-72448,
JP-A-59-78356, JP-A-59-136351
JP-A-59-201060, JP-A-60-156
No. 42, JP-A-60-140351, JP-A-60-1
No. 79746, JP-A-61-11754, JP-A-61-11654
-90164, JP-A-61-90165, JP-A-6
1-90166, JP-A-61-112154, JP-A-61-281245, JP-A-61-51063,
JP-A-62-267363, JP-A-63-68844
JP-A-63-89866, JP-A-63-1393
No. 55, JP-A-63-142063, JP-A-63-1
No. 83450, JP-A-63-282743, JP-A-6-282743
JP-A-4-21455, JP-A-64-78259, JP-A-1-200267, JP-A-1-202775, JP-A-1-319754, JP-A-2-72372, JP-A-2-254467, JP-A-2-254467 JP-A-3-27863, JP-A-4-96068, JP-A-4-96069, JP-A-4-147265, JP-A-5-142841, JP-A-5-303226, JP-A-6-324504,
Compounds described in JP-A-7-168379 and the like can be mentioned.

The structure of the coupler component used in these azo pigments is diverse. For example, Japanese Patent Application Laid-Open
No. 17735, JP-A-54-79632 and JP-A-57
-176055, JP-A-59-197043, JP-A-60-130746, JP-A-60-153050
JP-A-60-103048, JP-A-60-189
759, JP-A-63-131146, JP-A-63-131146
155052, JP-A-2-110569, JP-A-4
-149448, JP-A-6-27705, JP-A-6-27705
And the compounds described in JP-A-348047 and the like.

Specific examples of the azo pigment include the compounds shown in the following table, but the invention is not limited thereto. Further, these compounds can be used in combination with other charge generating substances.

[0141]

[Table 1]

[0142]

[Table 2]

[0143]

[Table 3]

[0144]

[Table 4]

[0145]

[Table 5]

[0146]

[Table 6]

[0147]

[Table 7]

[0148]

[Table 8]

[0149]

[Table 9]

[0150]

[Table 10]

[0151]

[Table 11]

[0152]

[Table 12]

[0153]

[Table 13]

[0154]

[Table 14]

[0155]

[Table 15]

[0156]

[Table 16]

[0157]

[Table 17]

[0158]

[Table 18]

[0159]

[Table 19]

[0160]

[Table 20]

[0161]

[Table 21]

[0162]

[Table 22]

[0163]

[Table 23]

[0164]

[Table 24]

[0165]

[Table 25]

[0166]

[Table 26]

[0167]

[Table 27]

[0168]

[Table 28]

[0169]

[Table 29]

[0170]

[Table 30]

[0171]

[Table 31]

[0172]

[Table 32]

[0173]

[Table 33]

[0174]

[Table 34]

[0175]

[Table 35]

[0176]

[Table 36]

[0177]

[Table 37]

[0178]

[Table 38]

[0179]

[Table 39]

[0180]

[Table 40]

[0181]

[Table 41]

[0182]

[Table 42]

[0183]

[Table 43]

[0184]

[Table 44]

[0185]

[Table 45]

Various types of photoreceptors are known, and any of them can be used. For example, there is one in which a photosensitive layer comprising 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 using the compound of the present invention, a metal drum,
A metal plate, a paper subjected to conductive processing, a plastic film sheet, a drum-shaped or belt-shaped support, and the like are used.

As the film-forming binder resin used for forming the photosensitive layer on these supports, various ones can be mentioned depending on the field of use. 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 and the like. Among these, polystyrene resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, polyarylate resin, and the like are excellent in potential characteristics as a photoconductor. Also, these resins are
One type or a mixture of two or more types may be used alone or as a copolymer. 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 generating layer are contained in an amount of 10 to 50 relative to the charge generating substance.
0 wt% is preferable, and 50 to 150 wt% 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, the film formability becomes a problem. 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, etc.), phosphate esters (eg, TCP, TOP
Etc.), sebacic esters, adipic esters, nitrile rubbers, chlorinated hydrocarbons and the like. If these substances are added unnecessarily, they adversely affect the electrophotographic properties. Therefore, the ratio is preferably 20% or less based on the binder resin.

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

The compounds represented by the general formulas (1) and (2) can be used in combination with other charge transport materials. The charge transport materials include a hole transport material and an electron transport material. Examples of the former include oxadiazoles disclosed in JP-B-34-5466 and JP-B-45-466.
-555, etc .; pyrazolines shown in JP-B-52-4188, hydrazones shown in JP-B-55-42380, etc .; Oxadiazoles disclosed in JP-A-56-123544 and the like can be mentioned. On the other hand, examples of the electron transport material include chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,
4,5,7-tetranitro-9-fluorenone, 2,
There are 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.

It is also possible to add a certain electron-withdrawing compound as a sensitizer which forms a charge transfer complex with the organic conductive material of the present invention and further enhances the sensitizing effect. Examples of the electron-withdrawing compound include 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone,
Quinones such as 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone and phenanthrenequinone;
Aldehydes such as -nitrobenzaldehyde, ketones such as 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, 3,3 ', 5,5'-tetranitrobenzophenone, phthalic anhydride and 4-chloronaphthalic anhydride Acid anhydrides, terephthalalmalononitrile, 9-anthrylmethylidenemalononitrile,
Cyano compounds such as 4-nitrobenzalmalonenitrile, 4- (p-nitrobenzoyloxy) benzalmalonenitrile, 3-benzalphthalide, 3- (α-cyano-p
-Nitrobenzal) phthalide, 3- (α-cyano-p-
And phthalides such as nitrobenzal) -4,5,6,7-tetrachlorophthalide.

The organic photoconductive material of the present invention is dissolved or dispersed in a suitable solvent together with the above-mentioned various additives according to the form of the photoreceptor, and the coating solution is applied to the above-mentioned conductive support. It is possible to produce a photoconductor by applying the composition onto a substrate and drying it.

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, 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 and methyl cellosolve acetate, N, N-dimethylformamide, acetonitrile, Aprotic polar solvents such as N-methylpyrrolidone and dimethylsulfoxide, alcohol solvents and the like can be mentioned. These solvents can be used alone or as a mixed solvent of two or more kinds.

[0195]

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

Synthesis Example 1 Synthesis of Exemplified Compound 6 Phenanthrene-9-carboxaldehyde (1.65 g), 1-methyl-1-phenylhydrazine (1.17 g), acetic acid (0.3 ml) and ethanol (30 ml) were mixed and heated under reflux for 30 minutes. After cooling, the precipitated crystals were collected by filtration and recrystallized from 170 ml of isopropanol to obtain 2.16 g of Compound 5. The melting point of the obtained compound 5 was 136.6 to 136.9 ° C.

Synthesis Example 2 Synthesis of Exemplified Compound 66 Phenanthrene-9-carboxaldehyde (1.44 g), diethyl benzohydrylphosphonate (2.34 g) and ethylene glycol dimethyl ether (20 ml) were mixed, and the mixture was stirred on an ice bath.
1.18 g of potassium-t-butoxide was added. 1 more at room temperature
After continuously stirring for 150 hours, 150 ml of water was added, the organic component was extracted with chloroform, and washed successively with diluted hydrochloric acid and saturated brine. After drying over anhydrous sodium sulfate, concentrate under reduced pressure,
The obtained oily substance was purified by silica gel chromatography to obtain 0.92 g of white crystals of Compound 66. The melting point of the obtained compound 66 was 126.6 to 127.0 ° C.

Synthesis Example 3 Synthesis of exemplified compound 82 Phenanthrene-9-carboxaldehyde (1.17 g), diethyl benzylphosphonate (1.43 g) and ethylene glycol dimethyl ether (15 ml) were mixed, and potassium-t-butoxide (0.90) was stirred under stirring on an ice bath. g was added. After continuing stirring at room temperature for an additional 1 hour, 150 ml of water was added, the organic component was extracted with chloroform, and washed successively with diluted hydrochloric acid and saturated saline. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the obtained oily substance was purified by silica gel chromatography to obtain 1.10 g of white crystals of Compound 82. The melting point of the obtained compound 82 was 111.9 to 113.2 ° C.

Example 1 1 part by weight of the azo pigment (A-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 the mixture was dispersed together with glass beads for 2 hours in a paint conditioner device. 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 hydrazone compound (exemplified compound 6) was mixed with a polyarylate resin (Unitika U-polymer) in a ratio of 1: 1.
At a weight ratio of 10% using dichloroethane as a solvent.
Was prepared and applied on the above-mentioned charge generation layer with an applicator to form a charge transport layer having a thickness of about 20 μm.

The electrophotographic characteristics of the thus-prepared laminated type photoreceptor were evaluated by using an electrostatic recording tester (SP-428 manufactured by Kawaguchi Denki Co., Ltd.). Measurement conditions: applied voltage -6 kV, static No. 3 (turntable rotation speed mode: 10 m / min)
). As a result, the charging potential (Vo) was -800 V, and the half-dose exposure amount (E1 / 2) was 1.0 lux · sec, which was a high sensitivity value.

Further, using the same apparatus, characteristic evaluation was carried out for repeated use in which one cycle of charging-discharging (eliminating light: irradiation with white light of 400 lux × 1 second) was set as one cycle. 5000
The change in the charged potential due to the repetition of
The 5000th charging potential (Vo) was -790 V with respect to the charging potential (Vo) of -800 V at the time, and showed a stable characteristic without a decrease in potential due to repetition. Further, the half-time exposure amount (E1 / 2) of the first time was 1.0 lux · second, whereas the half-time exposure amount of the 5,000th time (E1 / 2) was 1.0 lux · second, showing excellent characteristics. .

Examples 2 to 9 In the same manner as in Example 1, except that the azo pigments and hydrazone compounds shown in Table 46 were used instead of the azo pigment (A-1) and the exemplified compound 6 of Example 1, respectively. A photoreceptor was prepared and its characteristics were evaluated. The results are shown in Table 46.

[0203]

[Table 46]

Examples 10 to 18 Similar to Example 1 except that X-type metal-free phthalocyanine is used in place of the azo pigment of Example 1 and hydrazone compounds shown in Table 47 are used in place of Exemplified Compound 6, respectively. A photoreceptor was prepared and its characteristics were evaluated. The results are shown in Table 47.

[0205]

[Table 47]

Example 19 1 part by weight of azo pigment (A-1) and 40 parts of tetrahydrofuran
Parts by weight were dispersed for 4 hours together with glass beads in a paint conditioner. In the dispersion thus obtained,
2.5 parts by weight of a hydrazone compound (exemplified compound 6),
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 dispersion treatment was further performed by a paint conditioner device for 30 minutes, and then applied on aluminum vapor-deposited polyester with an applicator to form a film. A photoconductor having a thickness of about 15 μm was formed. 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, the first charge potential (Vo) + 450V,
Half-exposure amount (E1 / 2) 1.3 lux.sec., Charging potential (Vo) + 440V after repeating 5000 times, half-exposure amount (E1 / 2) 1.2 lux.sec., With high sensitivity and little change , Showed excellent characteristics.

Examples 20 to 27 In the same manner as in Example 19 except that the azo pigment and the hydrazone compound shown in Table 48 were used instead of the azo pigment (A-1) and the exemplified compound 6 of Example 19, respectively. A photoreceptor was prepared and its characteristics were evaluated. The results are shown in Table 48.

[0208]

[Table 48]

Example 28 A photoreceptor was prepared in the same manner as in Example 1 except that Exemplified Compound 66 was used in place of Exemplified Compound 6 in Example 1, and the characteristics thereof were evaluated. As a result, the charging potential (Vo) is -8.
It showed a high sensitivity value of 15 V and a half exposure (E1 / 2) of 0.9 lux.sec.

[0210] Further, using the same apparatus, characteristic evaluation was carried out for repeated use in which one cycle of charging-discharging (eliminating light: irradiation with white light of 400 lux x 1 second) was made one cycle. 5000
The change in the charged potential due to the repetition of
The charging potential (Vo) at the 5000th time was −795V, whereas the charging potential (Vo) at the 5000th time was −795V. Also, 1
The half-time exposure amount (E1 / 2) at the fifth time was 0.9 lux.sec., But the half-time exposure amount at the 5000th time (E1 / 2) was 0.9 lux.sec.

Examples 29 to 36 In the same manner as in Example 1 except that the azo pigments and stilbene compounds shown in Table 49 are used instead of the azo pigment (A-1) and the exemplified compound 6 of Example 1, respectively. A photoreceptor was prepared and its characteristics were evaluated. The results are shown in Table 49.

[0212]

[Table 49]

Examples 37 to 45 In the same manner as in Example 1 except that X-type metal-free phthalocyanine was used in place of the azo pigment of Example 1 and stilbene compounds shown in Table 50 were used in place of Exemplified Compound 6, respectively. A photoreceptor was prepared and its characteristics were evaluated. The results are shown in Table 50.

[0214]

[Table 50]

Example 46 A photoconductor was prepared in the same manner as in Example 19 except that Exemplified Compound 66 was used instead of Exemplified Compound 6 in Example 19, and the characteristics thereof were evaluated. As a result, the charge potential (Vo) of the first time +405 V, the half-exposure amount (E1 / 2) 1.4 lux · sec, and the charge potential (Vo) after repeating 5000 times
It showed excellent characteristics with high sensitivity and little change, such as +390 V and half exposure (E1 / 2) 1.3 lux.sec.

Examples 47 to 54 In the same manner as in Example 19 except that the azo pigments and stilbene compounds shown in Table 51 are used instead of the azo pigment (A-1) and Exemplified Compound 6 of Example 19, respectively. A photoreceptor was prepared and its characteristics were evaluated. The results are shown in Table 51.

[0219]

[Table 51]

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1 except that Comparative Compound 121 was used instead of Exemplified Compound 6 as the charge transport material, and the characteristics thereof were evaluated. As a result, the first charge potential was (Vo) -750V, and the half-exposure amount (E1 / 2) was 1.
The sensitivity is as low as 8 lux · sec, the charging potential (Vo) at the 5000th time is −525 V, and the half exposure amount (E1 / 2) is 1.
It was 7 lux · sec, and a large decrease in potential was observed with repetition.

Comparative Example 2 A photoconductor was prepared in the same manner as in Example 10 except that Comparative Compound 122 was used instead of Exemplified Compound 6 as the charge transport material, and the characteristics thereof were evaluated. As a result, the charge potential (Vo) at the first time was -720 V, and the half-exposure amount (E1 / 2) was 1.3 lux · sec, which were relatively good results.
The charging potential (Vo) at the 000th time was −325 V and the half-exposure amount (E1 / 2) was 1.0 lux · second, and a large decrease in the potential was observed with repetition.

Comparative Example 3 A photoconductor was prepared in the same manner as in Example 19 except that Comparative Compound 123 was used instead of Exemplified Compound 6 as the charge transport material, and the characteristics thereof were evaluated. As a result, the charging potential (Vo) was 375 V and the half-exposure amount (E1 / 2) was 6.7 lux · sec, which was insufficient sensitivity.

[0221]

[Chemical 121]

[0222]

[Chemical formula 122]

[0223]

Embedded image

[0224]

As is apparent from the above, an electrophotographic photosensitive member having high sensitivity and high durability can be provided by using the organic photoconductive material of the present invention.

Claims (3)

[Claims] 1. An organic photoconductive material represented by the following general formulas (1) and (2). Embedded image (In the general formulas (1) and (2), R ₁ and R ₄ each represent an alkyl group which may have a substituent, an aryl group, an aralkyl group or an alkoxy group, and m and n are 0 to 4 respectively. R ₂ and R ₃ each represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group which may have a substituent, and which together form a heterocycle. R ₅ and R ₆ are each a hydrogen atom,
An alkyl group which may have a substituent, an alkenyl group,
It represents an aryl group or a heterocyclic group, and may together form a ring. ) 2. An electrophotographic photoreceptor having a photosensitive layer containing an organic photoconductive material represented by the general formula (1) or (2) on a conductive support. 3. The photosensitive layer contains a charge generating substance and a charge transporting substance, and the charge transporting substance is an organic photoconductive material represented by the general formula (1) or (2). The electrophotographic photosensitive member according to claim 2.