JPH071394B2 - Photoconductive composition and electrophotographic photoreceptor using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Use of the Invention) The present invention has a photoconductive composition containing a parent bisazo compound, and an electrophotographic photosensitive layer containing the bisazo compound. The present invention relates to an electrophotographic photoreceptor.

(Prior Art) The photoconductive process of an electrophotographic photosensitive member includes (1) a process of generating electric charges by exposure, and (2) a process of transporting electric charges.

An example of performing (1) and (2) with the same substance is a selenium photosensitive plate. On the other hand, a combination of amorphous selenium and poly-N-vinylcarbazole is well known as an example in which (1) and (2) are performed with different substances. The method in which (1) and (2) are performed with different substances expands the selection range of materials used for the electrophotographic photosensitive member, and accordingly, the electrophotographic characteristics such as sensitivity and receptive potential of the electrophotographic photosensitive member are improved. It has the advantage of being able to select from a wide range of substances that are convenient for producing a coating film for an electrophotographic photoreceptor.

Conventionally, selenium has been used as a photoconductive material for electrophotographic photoreceptors used in electrophotographic systems.
There are inorganic substances such as cadmium sulfide and zinc oxide.

The electrophotographic method, as already disclosed by Carlson in U.S. Pat.No. 2,297,691, has a support coated with an insulating material in the dark, the electric resistance of which changes depending on the amount of irradiation received during image exposure. The photoconductive material is used. This photoconductive material generally undergoes dark adaptation for a suitable period of time,
In the dark, first a uniform surface charge is applied. The material is then imagewise exposed to a pattern of radiation which has the effect of reducing surface charge depending on the relative energies contained in the various parts of the radiation pattern. The surface charge or electrostatic latent image remaining on the surface of the photoconductive material layer (electrophotographic photosensitive layer) in this manner is then made into a visible image by contacting the surface with an appropriate electrophoretic display material, that is, toner. .

The toner is contained in the insulating liquid or in the dry carrier, and in either case, it can be deposited on the surface of the electrophotographic photosensitive layer depending on the charge pattern. The attached display substance is
It can be fixed by known means such as heat, pressure or solvent vapor. Also, the electrostatic latent image is formed on the second support (for example, paper,
Film). Similarly, the electrostatic latent image can be transferred to the second support and developed there. The electrophotographic method is one of image forming methods for forming an image in this way.

The basic characteristics required for an electrophotographic photosensitive member in such an electrophotographic method are (1) being capable of being charged to an appropriate electric potential in a dark place, (2) being less in dissipation of a charge in a dark place, ( 3) It is possible to rapidly dissipate the charge by light irradiation.

It is true that the conventionally used inorganic materials have many advantages and at the same time have various drawbacks. For example, selenium, which is widely used at present, sufficiently satisfies the above conditions (1) to (3), but the manufacturing conditions are difficult, the manufacturing cost is high, the selenium is not flexible, and it is processed into a belt shape. It is difficult to handle, and it is sensitive to heat and mechanical shocks, so it requires careful handling. Cadmium sulfide and zinc oxide are dispersed in a resin as a binder and used as an electrophotographic photosensitive member.However, since they have mechanical defects such as smoothness, hardness, tensile strength, and abrasion resistance, they cannot be used as they are. Cannot be used in duplicate.

In recent years, in order to eliminate the drawbacks of these inorganic substances, electrophotographic photoreceptors using various organic substances have been proposed and some have been put to practical use. For example, an electrophotographic photoreceptor composed of poly-N-vinylcarbazole and 2,4,7-trinitrofluoren-9-one (US Pat. No. 3,484,237) and poly-N-vinylcarbazole sensitized with a pyrylium salt dye. (JP-B-48-25658), an electrophotographic photoreceptor mainly composed of a eutectic complex composed of a dye and a resin (JP-A-47-107).
35) and so on. In addition, electrophotographic photoreceptors containing the following azo pigments as main components have been actively researched recently and many proposals have been made.

(Bisazo pigment) JP-A-47-37543, JP-B-60-5941, JP-B-60-45664, JP-A-56-116039, JP-A-58-123541, JP-A-61-260250,
JP-A-61-228453, JP-A-61-275849, JP-A-61-27585
0, (Trisazo pigment) US Pat. Nos. 4,436,800 and 4,439,506, JP-A-53-13234
7, JP-A-55-69148, JP-A-57-195767, JP-A-57-20004
5, JP-A-57-204556, JP-A-58-31340, JP-A-58-3134
1, JP-A-58-154560, JP-A-58-160358, JP-A-58-1603
59, JP 59-127044, JP 59-196366, JP 59-204
046, JP 59-204841, JP 59-218454, JP 60-11
1249, JP-A-60-111250, JP-A-61-11754, JP-A-61-22
346, JP 61-35451, JP 61-67865, JP 61-1210
59, JP 61-163969, JP 61-179746, JP 61-230
157, JP 61-251862, JP 61-251865, JP 61-26
9164, JP 62-21157, JP 62-78563, JP 62-115
452, (Tetrakisazo pigment) US Pat. No. 4,447,513, JP-A-60-108857, JP-A-60-108
858, JP-A-60-111247, JP-A-60-111248, JP-A-60-11
8843, JP60-176046, JP61-103157, JP61-1
17559, JP 61-182051, JP 61-194447, JP 61-
196253, JP 61-212848, JP 61-240246, JP 61
-273548, JP 61-284769, JP 62-18565, JP 62
-18566, JP-A-62-19875, (Problems to be Solved by the Invention) These organic electrophotographic photoreceptors have improved mechanical properties and flexibility of the inorganic electrophotographic photoreceptors to some extent. In general, it has low photosensitivity and is not suitable for repeated use many times, so that it does not always satisfy the requirements as an electrophotographic photoreceptor.

(Object of the Invention) An object of the present invention is to provide a novel electrophotographic photoreceptor having high sensitivity and high durability. Another object of the present invention is to provide a novel electrophotographic photosensitive member which causes little reduction in photosensitivity even if it is repeatedly used. Still another object is to provide a novel photoconductive composition applicable to various photoconductors.

(Structure of the Invention) The present invention comprises a photoconductive composition containing a novel bisazo compound (bisazo pigment) represented by the following general formula [1], and an electrophotography containing the bisazo compound. The present invention relates to an electrophotographic photosensitive member having a photosensitive layer.

(1) The present invention is a photoconductive composition containing at least one bisazo compound represented by the following general formula [1].

In the general formula [1], Z is Represents R ¹³ represents an alkyl group which may have a substituent, an aryl group, an acyl group, a hydrogen atom or a nitroso group. R ¹¹ and R ¹² represent an alkyl group, an aryl group or an acyl group which may have a substituent. R ¹¹ and R ¹² may be the same group or different groups. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each represent an arylene group which may have a substituent.

A is Represents

X is an atom necessary for forming an aromatic ring or a heterocycle (these rings may be substituted or unsubstituted) by condensing with the benzene ring in the above formula in which the hydroxy group and Y are bonded. Represents a group, Y is R ¹ represents an alkyl group, a phenyl group or a substituted product thereof, R ² represents a hydrogen atom, a lower alkyl group, a carbamoyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a substituted or unsubstituted group. Represents an amino group, R ³ represents an alkyl group, an aromatic ring group, a heteroaromatic ring group or a substituted product thereof, and R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group, an aromatic ring group, a heteroaromatic ring Represents a group or a substitution product thereof. However, R ⁴ and R ⁵
Are not hydrogen atoms at the same time.

Also, Y is When, R ⁵ is not a hydrogen atom.

B represents a divalent group of an aromatic hydrocarbon or a heterocyclic divalent group containing a nitrogen atom in the ring. (These rings may be substituted or unsubstituted).

(2) The present invention comprises an electrophotographic photosensitive layer comprising a layer containing a charge carrier transporting compound and a charge carrier generating compound on a conductive support, or a layer containing a charge carrier transporting compound and a layer containing a charge carrier generating compound. In the body, the electrophotographic photoreceptor is characterized by containing the bisazo compound represented by the general formula [1] as a charge carrier generating compound.

The bisazo compound represented by the general formula [1] will be described in more detail.

X is a group that can be condensed with a benzene ring in which a hydroxy group and Y are bonded to form an aromatic ring such as a naphthalene ring anthracene ring or a heterocycle such as an indole ring, a carbazole ring, a benzocarbazole ring, and a dibenzofuran ring. is there.

When X is a substituted aromatic ring or heterocyclic ring system, the substituent is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), a lower alkyl group, preferably a lower alkyl group having 1 to 8 carbon atoms. Groups (for example, methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, etc.), the number of substituents is 1 or 2, and when there are 2 substituents, they are Can be the same or different.

R ¹ is an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms or a phenyl group.

When R ¹ is an unsubstituted alkyl group, specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Examples thereof include a hexyl group, an isopropyl group, an isobutyl group, an isoamyl group, an isohexyl group, a neopentyl group, and a tert-butyl group.

When R ¹ is a substituted alkyl group, a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, a cyano group, an amino group, an alkylamino group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms is used as the substituent. There are two dialkylamino groups, halogen atoms, aryl groups having 6 to 15 carbon atoms, and the like. Examples thereof include hydroxyalkyl groups (eg, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, etc.), alkoxyalkyl groups (eg, methoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, ethoxymethyl group, 2
-Ethoxyethyl group, etc.), cyanoalkyl group (for example,
Cyanomethyl group, 2-cyanoethyl group, etc.), aminoalkyl group (for example, aminomethyl group, 2-aminoethyl group, 3-aminopropyl group, etc.), (alkylamino) alkyl group (for example, (methylamino) methyl group, 2-
(Methylamino) ethyl group, (ethylamino) methyl group etc.), (dialkylamino) alkyl group (eg, (dimethylamino) methyl group, 2- (dimethylamino) ethyl group etc.), halogenoalkyl group (eg fluoro) Examples thereof include a methyl group, a chloromethyl group, a bromomethyl group, etc.) and an aralkyl group (eg, a benzyl group, a phenethyl group, etc.).

When R ¹ is a substituted phenyl group, the substituent is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, a cyano group, an amino group, an alkylamino group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. There are two dialkylamino groups, halogen atoms, alkyl groups having 1 to 6 carbon atoms, nitro groups and the like. Examples thereof include hydroxyphenyl group, alkoxyphenyl group (eg, methoxyphenyl group, ethoxyphenyl group, etc.), cyanophenyl group, aminophenyl group,
(Alkylamino) phenyl group (for example, (methylamino) phenyl group, (ethylamino) phenyl group, etc.),
(Dialkylamino) phenyl group (eg, dimethylamino) phenyl group, etc., halogenophenyl group (eg,
Fluorophenyl group, chlorophenyl group, bromophenyl group, etc., alkylphenyl group (for example, tolyl group, ethylphenyl group, cumenyl group, xylyl group, mesityl group, etc.), nitrophenyl group, and these substituents (same or different from each other) A phenyl group having 2 or 3 groups (the position of the substituent or the positional relationship between the plurality of substituents is arbitrary).

R ² is a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms,
Carbamoyl group, carboxyl group, alkoxycarbonyl group having an alkoxy group having 1 to 12 carbon atoms, 6 to carbon atoms
An aryloxycarbonyl group having 20 aryloxy groups and a substituted or unsubstituted amino group are preferable.

When R ² is a substituted amino group, specific examples thereof include a methylamino group, an ethylamino group, a propylamino group, a phenylamino group, a tolylamino group, a benzylamino group, a phenethylamino group, a dimethylamino group, a diethylamino group and a diphenylamino group. be able to.

When R ² is a lower alkyl group, specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group and an isobutyl group.

When R ² is an alkoxycarbonyl group, specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an isopropoxycarbonyl group and a benzyloxycarbonyl group.

When R ² is an aryloxycarbonyl group, specific examples thereof include a phenoxycarbonyl group and a toloxycarbonyl group.

As R ³ and R ⁵ , an alkyl group having 1 to 20 carbon atoms, a phenyl group, an aromatic ring group such as a naphthyl group, a dibenzofuranyl group, a carbazolyl group, an oxygen atom such as a benzocarbazolyl group, a nitrogen atom, A heteroaromatic ring group containing a sulfur atom or the like or a substitution product thereof is preferable.

When R ³ or R ⁵ is a substituted or unsubstituted alkyl group,
Examples thereof include the same groups as the specific examples of the substituted or unsubstituted alkyl group for R ¹ described above.

R³Or R^FiveIs a substituted phenyl group, substituted naphthyl group, etc.
Aromatic group, substituted dibenzofuranyl group or substituted carbazo
In the case of a substituted heteroaromatic group containing a hetero atom such as a ryl group,
As examples of the substituent, a hydroxy group, a cyano group, a nitro group,
Halogen atom (eg, fluorine atom, chlorine atom, bromine atom)
Etc.), an alkyl group having 1 to 12 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, isopropyl group, etc.), carbon number 1
~ 12 alkoxy groups (eg methoxy, ethoxy
Group, propoxy group, butoxy group, pentyloxy group, a
Sopropoxy group, isobutoxy group, isoamyloxy
Group, tert-butoxy group, neopentyloxy group, etc.),
Mino group, alkylamino group having 1 to 12 carbon atoms (for example,
Cylamino group, ethylamino group, propylamino group
Etc.), a dialkylamino group having 1 to 12 carbon atoms (for example, dialkylamino group).
Methylamino group, diethylamino group, N-methyl-N-
Ethylamino group, etc.), arylamino group having 6 to 12 carbon atoms
(For example, phenylamino group, tolylamino group, etc.), charcoal
Diarylamino having two aryl groups having a prime number of 6 to 15
Groups (eg, diphenylamino group, etc.), carboxyl
Group, alkali metal carboxylato group (alkali metal (positive
Ion) example, Na , K , Li Etc.), alkali metal
Ruphonato group (example of alkali metal (cation), Na , K
, Li Etc.), an alkylcarbonyl group (eg, acetyl
Group, propionyl group, benzylcarbonyl group, etc.), charcoal
Arylcarbonyl group having an aryl group having a prime number of 6 to 12
(For example, benzoyl group, toluoyl group, carbon number 1-12
Alkylthio groups (eg, methylthio group, ethylthio group
Group) or an arylthio group having 1 to 12 carbon atoms (for example,
For example, phenylthio group, tolylthio group, etc.)
The number of substituents is 1 to 3, and the number of substituents is
If substituents are attached, they may be the same or different.
May be any combination of any of the substituents,
The binding position is arbitrary.

R ⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a substitution product thereof.

When R ⁴ is a substituted or unsubstituted alkyl group and a phenyl group, the same groups as the specific examples of the substituted or unsubstituted alkyl group and a phenyl group for R ³ and R ⁵ can be mentioned.

It is possible to substitute at any of the 3 to 8 positions of the naphthalene ring, but it is preferable to substitute at the 8 position.

B represents an aromatic hydrocarbon divalent group or a heterocyclic divalent group containing a nitrogen atom in the ring, which may be substituted with an alkyl group, a halogen atom, a nitro group or a hydroxy group. Good. Examples of the divalent group of aromatic hydrocarbon include o-phenylene, o-naphthylene group, peri-naphthylene group, 1,2-anthraquinonylene group, and 9,10-phenanthrylene group. Examples of the heterocyclic divalent group containing a nitrogen atom in the ring include, for example, 3,4-pyrazoledilyl group, 2,3-pyridiyl group, 4,5-pyrimidinediyl group, 6,7-indazolediyl group, Examples thereof include 5,6-benzimidazolediyl group and 6,7-quinolinediyl group.

Examples of R ¹¹ and R ¹² include an alkyl group such as a methyl group, an ethyl group, a butyl group, a 2-ethyl-hexyl group, a dodecyl group and an octadecyl group, for example, an aryl group such as a phenyl group and a naphthyl group, for example. Acyl groups such as acetyl group, propanoyl group, capryl group, myristoyl group, stearoyl group, benzoyl group and the like can be mentioned.

When R ¹¹ and R ¹² have a substituent, the substituent is a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, a cyano group, an alkylamino group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms. A dialkylamino group having two groups, a halogen atom, an aryl group having 6 to 15 carbon atoms, an acyl group having 18 carbon atoms, and the like.

Examples of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include arylene groups such as phenylene, naphthalene, anthrylene, biphenylene, terphenylene and the like.

When Ar ¹ , Ar ² , Ar ³ and Ar ⁴ have a substituent, the substituent is a hydroxy group, an alkoxy group having 1 to 18 carbon atoms, a cyano group, an alkylamino group having 1 to 18 carbon atoms, or a carbon number. 1 to
Examples thereof include a dialkylamino group having two 18 alkyl groups, a halogen atom, an aryl group having 6 to 15 carbon atoms, and an acyl group having 18 carbon atoms.

Z is Here, as R ¹³ , the same groups as those of R ¹¹ and R ¹² , a hydrogen atom and a nitroso group can be mentioned.

Next, the bisazo compound of the present invention will be described more specifically, but the present invention is not limited thereto.
For example, an example of a bisazo compound is shown in Table 1 by changing the substituents of the following general formula [1 '] and by the general formulas [2] to [40]. A ₁ in the general formulas [2] to [40] is a coupler residue shown in Table 2, Table 3 or Table 4.

The novel bisazo compound of the present invention can be easily produced by a known method. For example, the above general formula [2]
The bisazo compound shown in can be synthesized by the following method, and can be easily obtained by diphenylation and then dimethylation of 4,4'-diaminodiphenyl ether (Mitsui Toatsu Chemicals, Inc.). compounds suitable conditions R ⁷ is hydrogen of the general formula [41] to give compound R ⁷ is a nitro group in the general formula [41] by nitrating example acetic anhydride nitrate. Then, this compound is reduced under suitable conditions, for example, with iron powder and dilute hydrochloric acid or stannous chloride and hydrochloric acid, to give a compound in which R ⁷ in the general formula [41] is —NH ₂ group. Then, it can be easily produced by diazotizing it and then performing a coupling reaction with a corresponding cuppler (eg, naphthol AS). Other compounds can be produced by the same method. Here shows an example of the synthesis of compounds wherein A ₁ is A ₁ -21 in the general formula (2) as a representative example.

4,4'-bis (N-methyl-N-p-nitrophenylamino) -diphenyl ether (1) (9.4 g, 0.02 mol)
200 ml of N, N-dimethylformamide and 11 g of iron powder were mixed,
Concentrated hydrochloric acid (6 ml) and water (16 ml) were added to this mixed solution, and the mixture was heated to 100 ° C. with good stirring. After reacting for 1 hour, the reaction solution was kept at 100 ° C and neutralized with saturated aqueous sodium carbonate solution to pH.
= 8, and the reaction solution was heated. The solution was poured into 2 l of ice water, and the resulting amino compound (2) was precipitated and dried. Yield 4.8 g (59% yield).

Next, 4.1 g (0.01 mol) of amino compound (2) was added to 25 m of concentrated hydrochloric acid.
In addition to dilute hydrochloric acid prepared from 1 and 30 ml of water, the mixture was well stirred on a water bath at 60 ° C for about 30 minutes. The mixture is then cooled to 0 ° C. and 1.52 g (0.022 mol) sodium nitrite are added to 10 m water.
The solution dissolved in 1 was added dropwise at 0 ° C. over about 5 minutes. Then stirred at the same temperature for 1 hour, after another a small amount of unreacted product was prepared liquid into another reaction vessel, the coupler (A ₁ -21) -
The mixture was added dropwise to a mixture of 7.65 g of H, 0.02 mol, and 100 ml of pyridine under ice cooling while stirring. After stirring at room temperature for 2 hours,
The reaction mixture was poured into 500 ml of water, the precipitated crystals were washed with water, and then repeatedly washed with acetone. 4.78
g of compound (3) was obtained as a black powder. Yield 40% based on amino compound (2).

Decomposition temperature 300 ° C or higher Elemental analysis Calculated as C ₇₄ H ₅₆ O ₇ N ₁₀ C74.23%, H4.71%, N11.70% Measured value C74.40%, H4.56%, N11.85% IR absorption Spectrum (KBr tablet method) υNH 3250 to 3450 cm ^-1 υC = O 1665 cm ^-1 The electrophotographic photosensitive member of the present invention has an electrophotographic photosensitive layer containing one or more bisazo compounds represented by the above general formula. Although various types of electrophotographic photoreceptors are known, the electrophotographic photoreceptor of the present invention may be any type of photoreceptor, but usually has an electrophotographic photoreceptor structure of the type illustrated below. .

(I) An electrophotographic photosensitive layer provided by dispersing a bisazo compound in a binder or a charge carrier transport medium on a conductive support.

(II) A structure in which a charge carrier generation layer containing a bisazo compound as a main component is provided on a conductive support, and a charge carrier transport medium layer is provided thereon.

The bisazo compound of the present invention acts as a photoconductive substance,
When light is absorbed, charge carriers are generated with extremely high efficiency, and the generated charge carriers can be transported using a bisazo compound as a medium, but it is more effective to transport the charge carrier transporting compound as a medium.

To prepare a type (I) electrophotographic photosensitive member, fine particles of an azo compound may be dispersed in a binder solution or a solution in which a charge carrier transporting compound and a binder are dissolved, and this may be coated on a conductive support and dried. . At this time, the thickness of the electrophotographic photosensitive layer is 3 to 30 µ, preferably 5 to
20μ is good.

To prepare a type (II) electrophotographic photosensitive member, a bisazo compound is vacuum-deposited on a conductive support, dissolved in a solvent such as amine, and then coated, or fine particles of the bisazo compound are mixed with an appropriate solvent or If necessary, it is obtained by dispersing in a solvent in which a binder is dissolved, coating and drying, and then coating and drying a solution containing a charge carrier transporting compound and a binder. At this time, the thickness of the bisazo compound layer serving as the charge carrier generating layer is 4 μm or less, preferably 2 μm or less, and the thickness of the charge carrier transporting medium layer is 3 to 30 μm, preferably 5 to 20 μm.

The azo compound used in the photoconductors of the types (I) and (II) is pulverized to a particle size of 5 μm or less, preferably 2 μm or less by a dispersing machine such as a ball mill, a sand mill or a vibration mill.

If the amount of the bisazo compound used in the type (I) electrophotographic photosensitive member is too small, the sensitivity will be poor, and if it is too large, the charging property will be poor, or the strength of the electrophotographic photosensitive layer will be weak. The proportion of the bisazo compound in the layer is 0.01 to 2 times the weight of the binder, preferably 0.1.
The amount of the charge carrier transporting compound to be added, if necessary, is 0.1 to 2 times by weight, preferably 0.3 to 1.3 times by weight. In the case of a charge carrier transporting compound which can be used as a binder itself, the addition amount of the bisazo compound is 0.01 to the binder.
It is preferable to use 0.5 times the weight.

When a bisazo compound-containing layer to be a charge carrier generating layer is formed by coating in a type (II) electrophotographic photoreceptor,
The amount of bisazo compound used for the binder resin is 0.1
It is preferable that the amount is more than the weight times, and if it is less than that, sufficient photosensitivity cannot be obtained. The ratio of the charge carrier transporting compound in the charge carrier transporting medium is 0.2 to 2 times the weight of the binder, preferably 0.3 to
1.3 times by weight is preferable. When using a polymeric charge carrier transport compound which itself can be used as a binder, it can be used without other binders.

When preparing the electrophotographic photoreceptor of the present invention, additives such as a plasticizer or a sensitizer may be used together with the binder.

As the conductive support used in the electrophotographic photoreceptor of the present invention, aluminum, copper, a metal plate such as zinc, a plastic sheet such as polyester or aluminum, indium oxide, a conductive material such as SnO ₂ is deposited on the plastic film. Alternatively, a dispersion-coated one, a conductive-treated paper, or the like is used.

As the binder, it is preferable to use a film-forming polymer which is hydrophobic, has a high dielectric constant, and is electrically insulating. Examples of such high molecular weight polymers include, but are not limited to, the following.

Polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-
Vinyl acetate-maleic anhydride copolymer, silicone resin,
Silicon-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole These binders can be used alone or as a mixture of two or more kinds.

Examples of the plasticizer include biphenyl, biphenyl chloride, o-terphenyl, p-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate,
Examples thereof include triphenylphosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, dilaurylthiodipropionate, 3,5-dinitrosalicylic acid and various fluorohydrocarbons.

In addition, silicone oil or the like may be added to improve the surface properties of the electrophotographic photoreceptor.

As the sensitizer, chloranil, tetracyanoethylene,
Examples include methyl violet, rhodamine B, cyanine dye, merocyanine dye, pyrylium dye, thiapyrylium dye.

Compounds that transport charge carriers are generally classified into two types, compounds that transport electrons and compounds that transport holes, and both can be used in the electrophotographic photosensitive member of the present invention. The compound that transports electrons is a compound having an electron-withdrawing group, for example, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 9-dicyanomethylene-2,4. , 7-Trinitrofluorenone, 9-dicyanomethylene-2,4,5,7-tetranitrofluorenone, tetranitrocarbazole chloranil, 2,3-dichloro-5,6-dicyanobenzoquinone, 2,4,
Examples thereof include 7-trinitro-9,10-phenanthrenequinone, tetrachlorophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane and the like.

The compound for transporting holes is a compound having an electron-donating group, for example, a polymer having (1) polyvinylcarbazole and its derivative described in JP-B-34-10966, and (2) JP-B-43-18674. Polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4- (4'-dimethylaminophenyl) described in JP-B-43-19192.
-5-phenyl-oxazole, poly-3-vinyl-N
-Vinyl polymers such as ethylcarbazole, (3) polymers such as polyacenaphthylene, polyindene, copolymerization of acenaphthylene and styrene described in JP-B-43-19193, (4) JP-B-56-13940 Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin described in JP-A-56-90883 and JP-A-56-161550. For triphenyl methane polymer and low molecular weight compounds, (6) triazole derivatives described in US Pat. No. 3,112,197, etc., (7) oxadiazole described in US Pat. No. 3,189,447, etc. Derivatives, (8) imidazole derivatives described in Japanese Examined Patent Publication No. 37-16096, etc. (9) U.S. Pat. Nos. 3615402, 3820989 , The 354254
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32103, U.S. Pat.No. 4,175,961, U.S. Pat.No. 4012376
No. 5, JP-A-55-144250, JP-A-56-119132, JP-B 39
-27577, Japanese Patent Application Laid-Open No. 56-22437, and the like, (13) Amino-substituted chalcone derivatives described in U.S. Pat. No. 3,526,501, (14) U.S. Pat. No. 3,542,546. N, N-bicarbazine derivatives described in the specification, (15) oxazole derivatives described in U.S. Pat. No. 3,257,203, (16) styrylanthracene derivatives described in JP-A-56-46234, etc. 17) Fluorenone derivatives described in JP-A-54-110837, (18) US Pat. No. 3717462, JP-A-54-59143 (corresponding to US Pat. No. 4150987), JP-A-55- 52063, JP-A-5
5-52064, JP-A-55-46760, JP-A-55-85495, JP-A-57-11350, JP-A-57-148749, JP-A-57-104144
Hydrazone derivatives disclosed in the specification, publication, etc., (19) US Pat. No. 4047948, US Pat. No. 4047949, US Pat. No. 4265990, US Pat. No. 4273846, US Pat.
897, benzidine derivatives described in U.S. Pat. No. 4,306,008 and the like, (20) JP-A-58-190953, JP-A-59-95540, and JP-A-5-95540
9-97148, JP-A-59-195658, JP-A-62-36674, and other stilbene derivatives.

In the present invention, the compounds that transport charge carriers are not limited to the compounds described in (1) to (20), and all charge carrier transporting compounds known so far can be used.

These charge transporting materials can be used in combination of two or more, depending on the case.

The photoreceptor obtained as described above may be provided with an adhesive layer or a barrier layer between the conductive support and the photosensitive layer, if necessary. Examples of materials used for these layers include gelatin, casein, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, and high molecular weight polymers used for the binder.
The vinylidene chloride-based polymer latex described in JP-A-59-84247, the styrene-butadiene-based polymer latex described in JP-A-59-114544, or aluminum oxide, etc., and the thickness of these layers is 1 μm or less. preferable.

Although the electrophotographic photoreceptor of the present invention has been described in detail above, the electrophotographic photoreceptor of the present invention generally has the characteristics of high sensitivity and excellent durability.

INDUSTRIAL APPLICABILITY The electrophotographic photoreceptor of the present invention can be widely applied not only to electrophotographic copying machines, but also to the fields of lasers and photoreceptors of printers using a cathode ray tube as a light source.

The photoconductive composition containing the bisazo compound of the present invention is provided as a photoconductive layer of an image pickup tube of a video camera and over the entire surface of a one-dimensionally or two-dimensionally arranged semiconductor circuit for performing known signal transfer and scanning. It can be used as a photoconductive layer of a solid-state imaging device having a light receiving layer (photoconductive layer). Also, AKGhosh, Tom Feng, J.Appl.Phys ,, 49 (12), 5982
As described in (1978), it can also be used as a photoconductive layer of a solar cell.

The bisazo compound of the present invention can also be used as photoconductive colored particles in a photoelectrophoresis system and as colored particles in a dry or wet electrophotographic developer.

Further, the bisazo compound of the present invention can be obtained by using JP-B-37-17162, JP-A-55-19063, JP-A-55-161250, and JP-A-57-147656.
As disclosed in each publication, it is dispersed in an alkali-soluble resin liquid such as a phenol resin together with the above-mentioned charge carrier transporting compound such as an oxadiazole derivative and a hydrazone derivative, and coated on a conductive support such as aluminum. After drying, by image exposure, toner development, and etching with an aqueous alkali solution, a printing plate having high resolution, high durability, and high sensitivity can be obtained, and a printed circuit can be prepared.

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples. In the examples, "part" means "part by weight".

Represented by formula (1) synthesized in Example -1 Synthesis Example, A ₁ is No. (A ₁ -2
5 parts of 1) bisazo compound and 5 parts of polyester resin (trade name: Byron 200, manufactured by Toyobo Co., Ltd.) were dissolved in 50 parts of tetrahydrofuran with a ball mill and dispersed in a ball mill for 20 hours, and then a wire round rod was used. Then, a conductive support (75 μm polyethylene terephthalate film with a vapor deposited aluminum film on its surface. Surface electrical resistance 4 × 10 ² Ω) is applied and dried to form a 0.5 μm thick charge generation layer. It was made.

Next, p- (diphenylamino) benzaldehyde-N'-methyl-N'-phenylhydrazone is formed on the charge generation layer. A solution prepared by dissolving 3.6 parts and 4 parts of bisphenol A polycarbonate in 13.3 parts of dichloromethane and 26.6 parts of 1,2-dichloroethane was applied and dried using a wire round rod to form a charge transport layer having a thickness of 11 μm. An electrophotographic photosensitive member No.-1 having an electrophotographic photosensitive layer consisting of two layers was prepared.

Examples-2 to 10 Electrophotographic photoreceptors Nos. 2 to 10 were prepared in the same manner as in Example 1 except that the bisazo pigment shown in Table 4 was used instead of the bisazo pigment used in Example 1.

Example-11 Electrophotographic photoreceptors Nos. 1 to 10 were subjected to negative charging by a corona discharge of -6 kV using an electrostatic copying paper tester (SP-428 manufactured by Kawaguchi Electric Co., Ltd.). The initial surface potential Vo is measured, then the light from the tungsten lamp is irradiated so that the illuminance on the surface of the photoconductor becomes 30 lux, and the exposure amount E required for the surface potential to decay to half the initial surface potential Vo. ₅₀ (lux · sec) was measured.

The results are shown in Table 5.

Example-12 The operation of Example-11 was repeated 3000 times for the electrophotographic photosensitive member No. 1. The results are shown in Table 6.

From the above, it can be seen that the photoconductor of the present invention has high sensitivity and excellent durability.

Represented by the general formula (2) synthesized in Example -13 Synthesis Example, A ₁ is No. (A ₁ -2
5 parts of the bisazo compound of 1), 40 parts of the hydrazone compound used in Example 1, a copolymer of benzyl methacrylate and methacrylic acid ([μ] 30 ° C. methyl ethyl ketone = 0.
12 and 100 parts of methacrylic acid-containing 32.9%) were added to 660 parts of dichloromethane and ultrasonically dispersed.

This dispersion was applied onto a grained aluminum plate having a thickness of 0.25 mm and dried to prepare an electrophotographic photosensitive printing plate material having an electrophotographic photosensitive layer having a dry film thickness of 6 mm.

The surface potential of the photosensitive layer was charged to approximately +600 V by corona discharge (+6 kV) in the dark, and then the sample surface was exposed to tungsten light with a color temperature of 2854 ° K at an illuminance of 2.0 lux. The exposure amount was 5.2 lux · sec.

Next, this sample was charged to a surface potential of about +400 V in a dark place, and then image-exposed in close contact with a transparent original having a positive image. A liquid containing a toner prepared by adding 5 parts of polymethylmethacrylate (toner) dispersed in fine particles and 0.01 part of soybean oil lecithin to 1000 parts of IsoperH (Ethso Standard Co., Ltd., petroleum solvent). Immersion in a developer made it possible to obtain a clear positive toner image.

Further, the toner image was fixed by heating at 100 ° C. for 30 seconds. This printing plate material was dipped in a solution prepared by dissolving 70 parts of sodium metasilicate hydrate in 140 parts of glycerin, 550 parts of ethylene glycol, and 150 parts of ethanol for about 1 minute and washed with a water stream while lightly brushing to remove the toner. The electrophotographic photosensitive layer on the part not attached was removed to obtain a printing plate.

Further, instead of the liquid developer, the obtained electrostatic latent image was subjected to magnetic brush development using a toner for Zerox 3500 (manufactured by Fuji Zerox Co., Ltd.) and then heated and fixed at 80 ° C. for 30 seconds.
Next, a printing plate was obtained by removing the photosensitive layer in the portion where the toner did not adhere with an alkaline solution.

The plate thus produced was printed by a conventional method using a Hamada Star 600CD offset printing machine, and it was possible to print 50,000 very clear prints without stains.

Claims (2)

[Claims] 1. A photoconductive composition comprising at least one disazo compound represented by the following general formula [1]. In the general formula [1], Z is Represents R ¹³ represents an alkyl group which may have a substituent, an aryl group, an acyl group, a hydrogen atom or a nitroso group. R ¹¹ and R ¹² represent an alkyl group, an aryl group or an acyl group which may have a substituent. R ¹¹ and R ¹² may be the same group or different groups. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each represent an arylene group which may have a substituent. A is Represents X is an atom necessary for forming an aromatic ring or a heterocycle (these rings may be substituted or unsubstituted) by condensing with the benzene ring in the above formula in which the hydroxy group and Y are bonded. Represents a group, Y is R ¹ represents an alkyl group, a phenyl group or a substituted product thereof, and R ² represents a hydrogen atom, a lower alkyl group, a carbamoyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a substituted or unsubstituted group. Represents a substituted amino group, R ³ represents an alkyl group, an aromatic ring group, a heteroaromatic ring group or a substitution product thereof, R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group, an aromatic ring group, a heteroaromatic group Represents a group cyclic group or a substitution product thereof. However, R ⁴ and R ⁵
Are not hydrogen atoms at the same time. Also, Y is When, R ⁵ is not a hydrogen atom. B represents a divalent group of an aromatic hydrocarbon or a heterocyclic divalent group containing a nitrogen atom in the ring. (These rings may be substituted or unsubstituted). 2. An electrophotographic photoreceptor comprising a layer containing a charge carrier transporting compound and a charge carrier generating compound, or a charge carrier transporting compound containing layer and a charge carrier generating compound containing layer on a conductive support. An electrophotographic photoreceptor comprising a bisazo compound represented by the following general formula [1] as a charge carrier generating compound. In the general formula [1], Z is Represents R ¹³ represents an alkyl group which may have a substituent, an aryl group, an acyl group, a hydrogen atom or a nitroso group. R ¹¹ and R ¹² represent an alkyl group, an aryl group or an acyl group which may have a substituent. R ¹¹ and R ¹² may be the same group or different groups. Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each represent an arylene group which may have a substituent. A is Represents X is an atom necessary for forming an aromatic ring or a heterocycle (these rings may be substituted or unsubstituted) by condensing with the benzene ring in the above formula in which the hydroxy group and Y are bonded. Represents a group, Y is R ¹ represents an alkyl group, a phenyl group or a substituted product thereof, R ² represents a hydrogen atom, a lower alkyl group, a carbamoyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a substituted or unsubstituted group. Represents an amino group, R ³ represents an alkyl group, an aromatic ring group, a heteroaromatic ring group or a substituted product thereof, and R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group, an aromatic ring group, a heteroaromatic ring Represents a group or a substitution product thereof. However, R ⁴ and R ⁵
Are not hydrogen atoms at the same time. Also, Y is When, R ⁵ is not a hydrogen atom. B represents a divalent group of an aromatic hydrocarbon or a heterocyclic divalent group containing a nitrogen atom in the ring. (These rings may be substituted or unsubstituted).