JPH02304572A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic sensitive body which has a high sensitivity and high durability and is less degraded in photosensitivity in spite of repetitive use by incorporating a specific trisazo compd. as a charge generating compd. into the photosensitive body. CONSTITUTION:The trisazo compd. expressed by formula I is incorporated as the charge carrier generating compd. into the photosensitive body. In the formula I, Ar<1>, Ar<2>, Ar<3>, Ar<4>, and Ar<5> denote an alylene group, bivalent condensed polycyclic arom. or bivalent arom. heterocyclic group. Cp' denotes a residual coupler group. The photosensitive body which has the excellent sensitivity and durability, is extremely slight in the degradation of the sensitivity after the repetitive use and has the high sensitivity sufficient as the photosensitive body for a semiconductor laser light source is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an electrophotographic photoreceptor characterized by having an electrophotographic photosensitive layer containing a novel trisazo compound.

[Conventional technology]

Conventionally, as photoconductive compositions used in electrophotographic photoreceptors, inimitable substances such as selenium, cadmium sulfide, zinc oxide, and amorphous silicon are well known. These inorganic materials have the advantage of having good electrophotographic properties, that is, very good photoconductivity, charge acceptance in the dark, and insulation properties, but on the other hand, they have various drawbacks, such as: , Selenium photoreceptors have drawbacks such as high production costs, lack of flexibility, and are susceptible to heat and mechanical shock.Cadmium sulfide photoreceptors have pollution problems because they use a toxic substance called cadmium as a material. There is. Zinc oxide has a drawback in image stability when used repeatedly over a long period of time. Furthermore, amorphous silicon photoreceptors have drawbacks such as extremely high manufacturing costs and the need for special surface treatment to prevent deterioration of the photoreceptor surface.

In recent years, electrophotographic photoreceptors using various organic materials have been proposed in order to eliminate the drawbacks of these inorganic materials, and some of them have been put into practical use. For example, poly-N-vinylcarbazole and 2. 4. Electrophotographic photoreceptor consisting of 7-dolinitrofluorenone-9-one (U.S. Patent No. 3,
484,237) Poly N-vinylcarbazole sensitized with pyrylium salt dye (Japanese Patent Publication No. 48-2565
8>.

Examples include an electrophotographic photoreceptor (Japanese Unexamined Patent Publication No. 10,735/1983) whose main component is a eutectic complex consisting of a dye and a resin.

Additionally, perylene pigments (U.S. Pat. No. 3,371.884, etc.), phthalocyanine pigments (U.S. Pat. No. 3,397.0, etc.),
86, No. 4,666.802, etc.), azulenium salt pigments (JP-A-59-53850.61-212,54)
2 etc.) Squarium base pigment (U.S. Pat. No. 4,396,
610, No. 4.644,082, etc.), polycyclic quinone pigments (JP-A-59-184,348.62-28,73)
Recently, active research has been conducted on electrophotographic photoreceptors containing Ja pigments such as 8) and azo pigments as shown below.
Many proposals have been made.

(Bisazo pigment) JP-A-47-37,543, JP-A-60-5゜9411
Special Publication No. 60-45, 664, No. 56, -116
,039, JP-A-58-123,541, JP-A-61-
260,250, JP 61-228,453, JP 61-275,849, JP 61-275,850 (Trisazo-based IF4) U.S. Pat. No. 4,436,800, U.S. Pat. No. 4,439 .5
No. 06, JP-A-53-132,347, JP-A-55-6
9.148. JP-A-57-195゜767, JP-A-57
-200,045, JP-A-57-204,556, JP-A-58-31,340, JP-A-58-31,341. JP-A-58-154゜560, JP-A-58-160,35
8, JP-A-58-160.359, JP-A-59-127
．． 044, JP-A-59-196.366, JP-A-59-
204.046, JP-A-59-204,841, JP-A-59-218. /, 54, JP-A-60-111.249
, JP-A-60-111,250. JP-A-61-11.7
54, JP-A No. 61-22, 346, JP-A No. 61-15,
451. JP-A-61-67.865, JP-A-61-12
1,059, JP-A-61-163.969, JP-A-61
-179°746, JP 61-230,157, JP 61-251.1162, JP 61-251,86
5, JP-A-61-269.164, JP-A-62-21.
157. Unexamined Japanese Patent Publication No. 62-78, 563. Japanese Unexamined Patent Publication No. 62-11
5.452 (Tetrakisazo pigment) U.S. Patent No. 4,447,513, JP-A-60-108
, 857, JP-A-60-108,858, JP-A-60-
111,247, JP-A-60-111.248, JP-A-60-118.843, JP-A-60-176.046,
JP-A-61-103゜157, JP-A-61-117,5
59, JP-A-61-182,051, JP-A-61-19
4,447, JP-A-61-196,253, JP-A-61
-212.848, JP 61-240.246, JP 61-273,548, JP 61-284.769
, JP-A-62-18,565, JP-A-62-18,56
6. Japanese Unexamined Patent Publication No. 1987-19875 On the other hand, in recent years, small, low-cost semiconductor lasers (with oscillation wavelengths of 780 nm to 830 nm) have been put into practical use, and near-infrared light is being used in electrophotographic systems using them as light sources. discloses a highly sensitive photoreceptor.

[Problem to be solved by the invention]

Although these electrophotographic photoreceptors have improved the mechanical properties and flexibility of the inorganic electrophotographic photoreceptors to a certain extent,
Generally, they have low photosensitivity and may not be suitable for repeated use many times, so they do not necessarily fully satisfy the requirements for electrophotographic photoreceptors. In addition, although various photoreceptors have been developed for semiconductor lasers, they are not necessarily sufficient in terms of sensitivity, repeatability, etc., and further improvements have been desired.

[Purpose of the invention]

An object of the present invention is to propose a novel electrophotographic photoreceptor having high sensitivity and high durability. Another object of the invention is to provide a new electrophotographic photoreceptor that exhibits little reduction in photosensitivity even after repeated use. Yet another object is to provide a photoreceptor that is compatible with a semiconductor laser light source.

[Means for Solving the Problems] The present invention comprises 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 charge generating compound. The present invention relates to an electrophotographic photoreceptor comprising a compound-containing layer, which contains a trisazo compound represented by the following general formula [1] as a charge carrier generating compound.

General formula [1] % formula % In general formula [1], Ar', Ar", Ar"
.

Ar' and Ar' represent an arylene group, a divalent condensed polycyclic aromatic group, or a divalent heteroaromatic ring group.

Cp' represents a coupler residue.

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

Ar', Ar'', Ar3.fi, r' and Ar5
Examples include arylene groups such as phenylene, naphthazine, anthrylene, biphenylene, terphenylene, etc., and fused polycyclic aromatic rings such as indene, fluorene, acenaphthene, perylene, fluorenone, anthrone, anthraquinone, benzanthrone, isocoumarin, etc. Divalent groups, divalent groups derived from heteroaromatic rings such as pyridine, quinoline, oxazole, thiazole, oxadiazole, benzoxazole, penzimidasol, benzodi7sol, benzoxazole, dibenzofuran, carbazole, xanthine, etc. can be mentioned.

When Ar' r Ar", Ar", Ar' and ArS have a substituent, the substituent has a carbon number of 1-18
alkyl group having 1 to 18 carbon atoms, dialkylamino group having two alkyl groups having 1 to 18 carbon atoms, acyl group having 1 to 18 carbon atoms, acyloxy group having i to 18 carbon atoms, 1 carbon number ~! 8 amide groups, carbon number 6-15
, a 7-aryloxy group having 6 to 15 carbon atoms, a halogen atom, a hydroxy group, a carboxyl group, a nitro group, a cyano group, a trifluoromethyl group, and the like.

Cp' represents a known coupler residue that reacts with a diazonium salt, and is preferably a known coupler residue of an azo compound used as a charge generating compound for an electrophotographic photoreceptor. Coupler residues shown in the formula are preferred.

RI RI R'0 In the general formula of Cp' above, X is fused with the benzene ring to which the hydroxyl group and Y are bonded to form an aromatic ring such as a naphculene ring or anthracene ring, or an indole ring or a carbazole ring. , represents an atomic group necessary to form a heterocycle such as a benzocarbazole ring, a dibenzofuran ring, etc.

When X is an aromatic ring or a heterocyclic ring having a substituent, the substituent includes a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, etc.), trifluoromethyl group, nitro group, amino group, cyano group, alkoxy group having 1 to 8 carbon atoms (e.g. methoxy group, (ethoxy group, butoxy group, etc.), and the number of substituents and substitution positions are arbitrary.

Y is -CONR'R', -CONHN=CR3R'-
Represents COOR3 or a hetero5Q ring or a hetero6 ring which may have a substituent.

R1 represents an alkyl group or an aryl group having 1 to 18 carbon atoms.

When R1 is an unsubstituted alkyl group, specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, isoamyl group, isohexyl group, neopentyl group, tert-
Examples include butyl group.

When R1 is a substituted alkyl group, examples of the substituent include a hydroxy group, an alkoxy group having 1 to 18 carbon atoms, a cyano group, an amino group, an alkylamino group having 1 to 18 carbon atoms, and a 1- to 18-carbon alkylamino group.
Examples include a dialkylamino group having two 18 alkyl groups, a halogen atom, and an aryl group having 6 to 15 carbon atoms. Examples include hydroxyalkyl groups (e.g., hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, etc.), alkoxyalkyl groups (e.g., methoxymethyl group, 2-methoxymethyl group, 3-methoxypropyl group, ethoxymethyl group, 2-ethoxyethyl group, etc.), cyanoalkyl group (e.g., cyanomethyl group, 2-cyanoethyl group, etc.), aminoalkyl group (e.g., aminomethyl group, 2-aminoethyl group, (3-aminopropyl group, etc.), (alkylamino)alkyl group (e.g. (methylamino)methyl group, 2
-(methylamino)ethyl group, (ethylamino)methyl group, etc.), (dialkylamino)alkyl group (e.g., (
dimethylamino)methyl group, 2-(dimethylamino)ethyl group, etc.), halogenoalkyl group (e.g., fluoromethyl group, trifluoromethyl group, chloromethyl group, etc.),
Aralkyl group (e.g. benzyl group, phenethyl group, etc.)
can be given.

When R1 is an unsubstituted aryl group, specific examples include a phenyl group, a naphthyl group, an anthryl group, and the like.

When R1 is a substituted aryl group, examples of the substituent include a hydroxy group, an alkoxy group having 1 to 18 carbon atoms, a cyano group, an amino group, an alkylamino group having 1 to 18 carbon atoms, and a 1- to 18-carbon alkylamino group.
Examples include a dialkylamino group having two 18 alkyl groups, an arylazo group having 6 to 18 carbon atoms, a halogen atom, an alkyl group having 1 to 18 carbon atoms, a nitro group, and a trifluoromethyl group. Examples include hydroxyphenyl group, alkoxyphenyl group (e.g., methoxyphenyl group, ethoxyphenyl group, etc.), cyanophenyl group, aminophenyl group, (alkylamino)phenyl group (e.g., (methylamino)phenyl group, (ethyl (amino) phenyl group, etc.), (dialkylamino) phenyl group (e.g., (dimethylamino) phenyl group, (diethylamino) phenyl group, etc.), halogenophenyl group (e.g., fluorophenyl group, chlorophenyl group, bromophenyl group, etc.), Alkylphenyl groups (e.g. tolyl group, ethylphenyl group, cumenyl group, xylyl group, mesityl group, etc.), nitrophenyl group, trifluoromethylphenyl group, and substituents thereof (which may be the same or different from each other) 2
Examples include phenyl groups having 1 or 3 phenyl groups. However, the position of the substituent is arbitrary.

nt is a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a carbamoyl group, a carboxyl group, or a carboxyl group having 1 to 18 carbon atoms.
Preferred are an alkoxycarbonyl group having an alkoxy group, an aryloxycarbonyl group having an aryloxy group having 6 to 20 carbon atoms, and a substituted or unsubstituted amino group.

When RZ is an N-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 diethylamino group, a diphenylamino group, and the like.

When R2 is a lower alkyl group, specific examples include a methyl group, an ethyl group, a propyl group, a rutile group, an isopropyl group, an isobutyl group, and the like.

When R2 is an alkoxycarbonyl group, specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, an isopropoxycarbonyl group, a hensyloxycarbonyl group, and the like.

When R8 is an aryloxycarbonyl group, specific examples thereof include a phenoxycarbonyl group and a doloxycarbonyl group.

R] is an alkyl group having 1 to 20 carbon atoms, an aromatic carbocyclic group such as a phenyl group, a naphthyl group, an aromatic heterocyclic group such as a dibenzofuranyl group, a carbazolyl group, a dibenzocarbazolyl group, or any of these. Substituted forms are preferred.

When R3 is a substituted or unsubstituted alkyl group, specific examples thereof include the same groups as the above-mentioned specific examples of the substituted or unsubstituted alkyl group for R1.

When R3 is an aromatic ring group having a substituent or a heteroaromatic ring group having a substituent, specific examples of the substituent include a hydroxy group, a cyano group, a nitro group, a halogen atom (e.g.
fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, etc.), alkoxy groups having 1 to 12 carbon atoms (e.g., methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, impropoxy group, isobutoxy group, isoamyloxy group, terL-butoxy group, neopentyloxy group, etc.), trifluoromethyl group, trimethylsilyl group, methanesulfonyl group, amino group , alkyl 7mino groups having 1 to 12 carbon atoms (e.g., methylamino group, ethylamino group, propylamino group, etc.), dialkylamino groups having 1 to 12 carbon atoms (e.g., dimethylamino group, diethylamino group, N-methyl -N-ethylamino group, etc.), arylamino group having 6 to 12 carbon atoms (e.g., phenylamino group, tolylamino group, etc.), diarylamino group having two aryl groups having 6 to 15 carbon atoms (e.g., diphenylamino group), groups), arylazo groups having 6 to 12 carbon atoms (e.g. phenylazo group, chlorophenylazo group, fluorophenylazo group, bromophenylazo group, cyanophenyl 7zo group, ethoxycarbonylphenylazo group, nitrophenylazo group, acetamidophenyl azo group, methoxyphenylazo group, methylphenylazo group, n-octylphenylazo group, trifluoromethylphenylazo group, trimethylsilylphenylazo group, methanesulfonylphenylazo group, etc.), carboxyl group, carbon number 1 to 18 Alkoxycarbonyl groups having an alkoxy group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl groups having an aryloxy group having 6 to 16 carbon atoms (e.g. phenoxycarbonyl group, naphthoxycarbonyl group, etc.),
Alkali metal carboxylad group (examples of alkali metal cations, R4a 6, K@, LtΦ, etc.), alkali metal sulfonato groups (examples of alkali metal cations, Na[F],
K'SL ie, etc.), a furkylcarbonyl group (e.g., acetyl group, propionyl group, benzylcarbonyl group, etc.), an arylcarbonyl group containing an aryl group having 6 to 12 carbon atoms (e.g., benzoyl group, trioyl group, etc.)
, an alkylthio group having 1 to 12 carbon atoms (e.g., methylthio group, ethylthio group, etc.), or an arylthio S having 1 to 12 carbon atoms (e.g., phenylthio group, tolylthio group, etc.), and the number of substituents is The number is 1 to 5, and when a plurality of substituents are bonded, they may be the same or different from each other, and the bonding positions of the substituents are arbitrary.

As R4, a hydrogen atom or the same group as the above-mentioned specific example of R'' can be mentioned.

When Y represents an unsubstituted 5-membered heterocyclic ring or a 6-membered heterocyclic ring,
Specific examples include an imidazole ring, an oxazole ring, a mithiazole ring, a hensiimidazole ring, a hendithiazole ring, a benzoxazole ring, a pyrimidine ring, and a perimidine ring.

When Y represents a 5-membered or 6-membered heterocyclic ring having a substituent, specific examples of the substituent are the same as the above-mentioned specific examples of the substituent when R3 is an aromatic carbocyclic group having a substituent. I can give you the basics.

can be substituted at any position from the 3rd to 8th positions of the naphthalene ring, but is preferably substituted at the 8th position.

W represents a divalent group of an aromatic hydrocarbon or a divalent group of a heterocycle containing a nitrogen atom in the ring, and these are all alkyl groups, halogen atoms, nitro groups, trifluoromethyl groups,
It may be substituted with a cyano group, a hydroxy group, or the like. Divalent groups of aromatic hydrocarbons include 0-phenylene group, 0
-naphthylene group, peri-naphthylene group, 1,2-anthraquinonylene! , 9.10-phenanthrylene 71
can be given. Examples of heterocyclic divalent groups containing a nitrogen atom in the ring include 3,4-pyrazolesilyl group, 2,3-pyridiyl group, 4,5-pyrimidinediyl group, 6,7-indazolediyl group, Examples include 6-benzimidazolediyl group and 6,7-chiralindiyl group.

Representative examples of the trisazo compounds of the present invention are listed in Table 1, specifically showing the substituents of the general formula [1].

Of course, the present invention is not limited thereby. Cp' in the trisazo compound of general formula [1] is the second
Represents coupler residues shown as specific examples in Table 3 or Table 4.

Table 2 Table 2 (Continued) Table 2 (YE) Table 2 (Continued) Table 2 <'Ift > Table 2 (Continued) Table 2 (Continued) Table 2 (Continued) 2 Table (continued) Table 2 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (continued) Table 4 (Continued) Table 4 (Continued) The novel trisazo compound of the present invention can be easily synthesized by the following method. That is, the trisamino compound represented by the general formula [2] is rehexaazotized by a conventional method and coupled with the corresponding coupler in the presence of an alkali, or the hexazonium salt is converted into a borofluoride salt, zinc chloride double salt, etc. After isolation, it can be easily synthesized by coupling with a coupler in a solvent such as N,N-dimethylformamide or dimethylsulfoxide in the presence of an alkali.

General formula [2] N.H.

Ar'1hN-^r'-C=C-Ar"-N-Ar"-C=C
-Ar'-NllzHowever,Ar',Ar'', Ar3.
Ar' and Ar' are Ar' and Ar' in the general formula [1] above;
”,Ar”.

It has the same meaning as Ar'' and Ar'.

Synthesis Example In Compound Group 1 in Table 1, the coupler is (Cp'-
21) Synthesis of the trisazo compound having the following structural formula [3]
4.90g of trisamino compound (0,Ol
mol) was added to dilute hydrochloric acid prepared from 25 ml of concentrated hydrochloric acid and 30 ml of water and stirred for about 30 minutes on a water bath at 60°C.The mixture was then cooled to 0°C and 3.04 g of sodium nitrite was added to 10 ml of water. The dissolved solution was added dropwise at 0° C. over about 20 minutes. Thereafter, the mixture was stirred at the same temperature for 1 hour, a small amount of unreacted material was filtered off, and the filtrate was placed in a separate container containing 11.5 g of coupler (Cp'-21).
0.03 mol), sodium acetate 4.92 g, water 1
It was added dropwise to a solution consisting of 0 ml of DMF and 300 mff of DMF while stirring under water cooling. After stirring at room temperature for 2 hours, the formed crystals were collected by filtration and purified by repeated washing with water and acetone. 13.7 g of black powder bundle of trisazo compound was obtained.

Yield 82%. Decomposition temperature 270℃ or higher.

Elemental analysis value C1゜6 Hll I'J13 0
*Calculated value based on structural formula [3] C76, 20%, H4, 28%, N 10
．． 90% actual value C76, 01%, H4, 30%,
N 10.75% The electrophotographic photoreceptor of the present invention has an electrophotographic photosensitive layer containing one or two types of trisazo compounds represented by the general formula [1]. Although various types of electrophotographic photoreceptors are known, the electrophotographic photoreceptor of the present invention may be any type of photoreceptor;
+), (■) or (■) type electrophotographic photoreceptor structure.

(An electrophotographic photosensitive layer in which a trisazo compound is dispersed in a binder or a charge air transport medium is provided on an N conductive support.

(“) A charge carrier generation layer containing a trisazo compound as a main component is provided on a conductive support, and a charge carrier transport layer is provided on top of the charge carrier generation layer.

(III) A charge carrier transport layer is provided on a conductive support, and a charge carrier generation layer containing a trisazo compound as a main component is provided thereon.

The trisazo compound of the present invention has the ability to generate charge carriers with extremely high efficiency when it absorbs light.

The generated charge carriers are transported by a charge carrier transport compound.

To produce an electrophotographic photoreceptor of type (H), fine particles of a trisazo compound are dispersed in a binder solution or a solution containing a charge carrier transport compound and a binder solution, and this is coated on a conductive support and then dried. The thickness of the electrophotographic photosensitive layer at this time is preferably 3 to 30 μm, preferably 5 to 20 μm.

To prepare a type (II) photoreceptor, a trisazo compound is vacuum deposited on a conductive support to form a charge carrier generation layer, or fine particles of a trisazo compound are deposited in a suitable solvent in which a binder resin is dissolved. The resulting dispersion is coated and dried to form a charge carrier generation layer, and if necessary, the surface is finished by a method such as puff polishing or the film thickness is adjusted, and then It is obtained by coating a solution containing a charge carrier transporting substance and a binder resin thereon and drying it. The thickness of the charge carrier generation layer at this time is 0. O1μ~4
μ, preferably 0.1 μ to 2 μ, and the thickness of the charge carrier transport layer is preferably 3 μ to 30 μ, preferably 5 μ to 20 μ.

Type (Il!> electrophotographic photoreceptor type CI+)
It can be produced by reversing the stacking order of the electrophotographic photoreceptors.

[1] The trisazo compound used in the photoreceptors of types (■) and (melon) is milled with a particle size of 0.1 to 2 μ, preferably 0
．． It is used after being dispersed to 3μ to 2μ.

If the amount of the trisazo compound used in the type (r) electrophotographic photoreceptor is too small, the sensitivity will be poor, and if it is too large, the charging property will be poor, the film strength of the electrophotographic photosensitive layer will be poor, and the electrophotographic When a binder is used, the proportion of the trisazo compound in the photosensitive layer is preferably 0.01 to 2 times the weight of the binder, preferably 0.05 to 1 times the weight of the binder, and the proportion of the charge carrier transport compound is 0.01 to 2 times the weight of the binder. , i to 2 times by weight, preferably 0.3 to 1.5 times by weight, and in the case of a charge carrier transport compound that can itself be used as a binder, the amount of the trisazo compound added is within the range of i to 2 times by weight, preferably 0.3 to 1.5 times by weight. It is preferable to use 0.01 to 0.5 times the amount by weight.

In addition, when coating and forming a trisazo compound-containing layer that becomes a charge carrier generating compound-containing layer in type (■) and ([[[) electrophotographic photoreceptors, the amount of trisazo compound to be used relative to the binder is 0.1 times or more by weight. Preferably, if it is less than that, sufficient sensitivity cannot be obtained, and it can be used without a binder. The ratio of the charge carrier transport compound in the charge carrier transport compound-containing layer to the binder is from 0.2 to
A polymer that can itself be used as a binder, preferably 0.3 to 1.5 times the weight! If a carrier transport compound is used, the pond binder can be used without it.

The conductive support used in the electrophotographic photoreceptor of the present invention includes a metal plate made of aluminum, copper, zinc, etc., a plastic sheet or plastic film made of polyester, aluminum, indium oxide, tin oxide, etc.
Paper coated with a conductive material such as iodized steel by steaming or dispersed thereon, or paper treated with conductive treatment with an inorganic salt such as sodium chloride or calcium chloride or an organic quaternary ammonium salt is used.

When a binder is used, it is preferable to use a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating. Examples of such a polymer include the following: These examples can be listed, but of course the examples are not limited to these examples.

Polycarbonate, polyester, polyester carbonate, polysulfone, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer Polymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone
Alkyd resin, phenol-formaldehyde resin,
Styrene-alkyd resin, styrene-maleic anhydride copolymer, phenoxy resin, polyvinyl butyral resin, poly-N-vinylcarbazole.

These resin binders can be used alone or as a mixture of two or more.

In the photoreceptor of the present invention, a plasticizer can be used in combination with a resin binder.

Plasticizers include biphenyl, chlorinated biphenyl, O-terphenyl, p-terphenyl, thibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate,
Examples include triphenyl #M, chlorinated paraffin, diuralyl thiodipropionate, and the like.

When producing the electrophotographic photoreceptor of the present invention, additives such as aggravating agents may be used in the photosensitive layer.

Exacerbating agents include triallylmethane dyes such as Brilliant Green, Victoria Blue 81 Methyl Violet, Crystal Bioleft, and Acid Halo B, xanthene dyes such as Rhodamine B, Rhodamine 6G, Rhodamine G Extra, Eosin S1 Erythrosine, Rose Bengal, and Fluorescein. , thiazine dyes such as methylene blue, C91,13asic, Violet7 (C,1
, 48020), cyanine dyes,
Examples include pyrylium dyes such as 2,6-diphenyl-4-(N,N-dimethylaminophenyl)thiapyrylium perchlorate and benzobyrylium salt (described in Japanese Patent Publication No. 48-25.658).

Furthermore, in order to improve the surface properties of the electrophotographic photoreceptor, silicone oil, fluorine surfactant, etc. can be used.

In the present invention, charge carrier transport materials used in the charge carrier transport layer are classified into two types: compounds that transport electrons and compounds that transport holes.

Both can be used in the electrophotographic photoreceptor of the present invention.

Compounds that transport electrons include compounds having an electron-withdrawing group, such as 2, 4.7. -) Rietlow 9-fluorenone, 2.4.5.7-tetranitro-9-fluorenone, 9-dicyanomethylene-2,4,7-)lindrofluorenone, 9-dicyanomethylene-2,4,5,7-
Tetranitrofluorenone, tetranitrocarbazole, chloranil, 2,3-dichloro-5,6-dicyanobenzoquinone, 2,4,7-)dinitro-9,1O-phenanthrenequinone, tetrachlorophthalic anhydride, terracyanoethylene , tetracyanoquinodimethane, etc.

Compounds that transport holes include compounds having an electron-donating group, such as polymer compounds (al.
- Polyvinylcarbazole and its derivatives described in Publication No. 10.966, (bl Japanese Patent Publication No. 43-1111,674, 43-
Vinyl polymers such as polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4-(4°-dimethylaminophenyl)-5-phenyloxazole, poly-3-vinyl-N-ethylcarbazole, etc. described in Publication No. 19゜192 (C) Polymers such as polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in Japanese Patent Publication No. 43-19,193; Condensation resins such as formaldehyde resin, brompyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, (el JP-A-56-90-8113, JP-A-56-1
Various triphenylmethane polymers described in Japanese Patent No. 61.550, and low-molecular ones include triazole derivatives described in (fl U.S. Pat. No. 3,112,197, etc.); Oxadiazole derivatives, th+, described in No. 3,189.447, Mei $ IIl, etc.
16.096, etc.; (4) U.S. Patent No. 3,615. '402, same 3,
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No. 1, No. 4,012,376, West German Patent (DAS)
No. 1,110.518, Special Publication No. 1973-35,702,
No. 39-27,577, JP-A-55-144,250
No. 56-119.132, No. 56-22,437
arylamine derivatives described in the specifications, publications, etc., (-amino-substituted chalcone derivatives described in the specification of US Pat. No. 3,526.501, tn+ described in the specification of US Pat. No. 3,542.546, etc.) (0) Oxazole derivatives described in U.S. Pat. Ql Fluorenone derivatives described in JP-A No. 54-110,837, etc. frl U.S. Patent No. 3.717.462, JP-A-Sho 5
No. 4-59,143 (U.S. Pat. No. 4.150.98)
Corresponding to No. 7), No. 55-52,063, No. 55-52
．． No. 064, No. 55-46, 760, No. 55-85,
No. 495, No. 57-11, 350, No. 57-148.
749, US Patent No. 57-104゜144 specification, publications, etc., fsl U.S. Patent No. 4.047.948, No. 4.0
No. 47.949, No. 4,265,990, No. 4゜27
No. 3.846, No. 4,299,897, No. 4.306
．． Benzidine derivatives described in the specification of No. 008 etc. +1) JP-A-58-190,953, JP-A-59-9
5.540, 59-97, 148, 59-19
Examples include stilbene derivatives described in Japanese Patent No. 5,658 and No. 62-36,674.

In the present invention, the compound that transports charge carriers is ta
The present invention is not limited to the compounds listed in + to [1], and all hitherto known charge carrier transport compounds can be used.

When producing the electrophotographic photoreceptor of the present invention, additives such as a sensitizer may be added to the charge generation layer and the charge transport layer, or a charge transport compound may be added to the charge generation layer. You may also use it.

Sensitizers include chloranil, tetracyanoethylene,
Examples include methylbioleft, rhodamine B1 cyanine dye, merocyanine dye, pyrylium dye, and thiapyrylium dye.

In addition, in the electrophotographic photoreceptor of the present invention, an adhesive layer or a barrier layer can be provided between the conductive support and the photosensitive layer, if necessary. In addition to the polymer used for the resin binder, materials used for these layers include gelatin, casein, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, and JP-A-159-8
Vinylidene chloride polymer latex described in JP-A No. 4,247, styrene-butadiene polymer latex or aluminum oxide described in JP-A-59-114,544, etc., and the thickness of these layers is preferably lIIm or less. .

The photoreceptor obtained as described above may be further provided with measures to prevent interference fringes that occur when coherent light such as a laser is used for exposure, if necessary. Such techniques include the installation of an undercoat layer having a light scattering and reflective surface as described in JP-A No. 60-186.850, and the method described in JP-A-60-184.
Installation of a titanium black-containing subbing layer as described in No. 258, a method for absorbing most of the light from the light source used in a charge carrier generation layer as described in JP-A-58-82-249, JP-A-61-18
, 963, a method of causing a charge carrier transport layer to have a microphase-separated structure, a method of incorporating a substance that absorbs or scatters coherent light into a photoconductive layer, as described in JP-A-60-86゜550; A method of providing a recess having a depth of 1/4 or more of the wavelength of coherent light on the surface of a photoreceptor described in JP-A-63-106.757, JP-A-62-172,371, JP-A-62-
Examples include the method described in No. 174.771, in which a light scattering layer or a light absorption layer is provided on the back side of a transparent support.

The electrophotographic photoreceptor of the present invention has been described in detail above, and the electrophotographic photoreceptor of the present invention is generally characterized by high sensitivity and little change in electrophotographic characteristics upon repeated use.

The electrophotographic photoreceptor of the present invention can be widely applied to photoreceptors for printers using lasers, cathode ray tubes, LEDs, etc. as light sources in addition to electrophotographic copying machines.

The photoconductive composition containing the trisazo compound of the present invention can be used as a photoconductive layer in the image pickup tube of a video camera, and can also be used as a light-receiving M ( It can be used as a photoconductive layer of a solid-state imaging element having photoconductivity (N). Also, A, to
Ghosh.

Tom Fang, J. Appl, Ph5y.

49 (12), 5982 (1978), it can also be used as a photoconductive layer in solar cells.

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

In addition, the trisazo compound of the present invention was
, No. 162, JP-A-55-19.063, JP-A-55
-161.250 and JP-A-57-147.656, oxadiazole derivatives,
It is dispersed in an alkali-soluble resin such as a phenol resin together with the above-mentioned charge carrier transporting compound such as hydrazone mH, coated on a conductive support such as aluminum, dried, and subjected to image exposure, toner development, and etching with an alkaline aqueous solution. In addition to producing printing plates with high resolution, high durability, and high intensity, it is also possible to create printed circuits.

EXAMPLES Next, the present invention will be specifically explained using Examples, but the present invention is not limited to the Examples. In addition,
In the examples, "parts" represent "parts by weight."

Example 1 5 parts of a trisazo compound of Compound Group-1 in Table 1 shown in the Synthesis Example whose coupler is (CG)'-21 in Table 2) and a polyester resin (trade name: Vylon 200.Toyobo ■)
After adding 5 parts of tetrahydrofuran to 50 parts of tetrahydrofuran and dispersing in a ball mill for 12 hours, the dispersion was dispersed using a wire round rod onto a conductive support (a 75 μm polyethylene tereclate support with an aluminum vapor deposited film on it). A charge generation layer having a thickness of about 0.5 μm was obtained by drying the cloth on top of the product (trade name: Metal Me 757S, east side type).

Next, 3.6 parts of p-<diphenylamino)benzaldehyde-No-methyl-N''-phenylhydrazone and a polycarbonate resin (Panlite-13
00, made by strange people) 4 parts, dichloromethane 13.3 parts and 1
A solution prepared by mixing and dissolving 26.6 parts of , 2-dichloroethane was applied using an applicator to form a charge transport layer having a thickness of 17 μm, thereby producing an electrophotographic photoreceptor having a two-layer photosensitive layer.

The electrophotographic properties of these photoreceptors were evaluated using an electrostatic copying paper tester (model 5P-428 manufactured by Nichidenki Seisakusho) as follows (measured using the static method). The initial surface potential Vs when charged by -6 KV corona discharge and the surface potential V0 when left in a dark place for 30 seconds were measured.

Next, the photoreceptor surface was exposed to light from a tungsten lamp at an illuminance of 31 ux, and the surface potential was the initial surface potential ■. The exposure amount E50 required to attenuate by half of
And the surface potential (residual potential vm) after 30 seconds of exposure was measured. Further, similar measurements were repeated 3000 times. The results are shown in Table 5.

Table 5 Synthesis Examples 2 to 25 Two-layer electrophotographic photoreceptors were prepared and carried out in the same manner as in Example 1, except that the trisazo compounds shown in Table 6 were used instead of the trisazo compounds used in Example 1. As in Example 1, E50. Vs, Vo.

■, was measured. The results are shown in Table 6.

Example 26 The electrophotographic photoreceptor produced in Example 1 was irradiated with 780 parts m light of 1 μJ/d using a monochromator, and V was obtained in the same manner as in Example 1. and Ego were measured. The results are shown below.

■. =-730V E,. =0.7 μJ/cd Examples 27 to 35 Instead of the trisazo compound used in Example 1, Example 12. tk15. Vo and E were prepared in the same manner as in Example 26, except that the trisazo compounds used for Ik19 to Ik25 were used.
,. was measured. The results are shown in Table 7.

From Table 7 and above, it can be seen that the photoreceptor of the present invention has sufficiently high sensitivity to near-infrared light and can be used in semiconductor laser printers.

Example 36 7.5 parts of the hydrazone compound shown in Example 1 and 10 parts of bisphenol A polycarbonate were placed on a conductive support made of polyethylene terephthalate film with a vapor-deposited aluminum film on the surface, and 5 parts of dichloromethane was added.
A charge transport layer having a thickness of 12 μm was provided by applying and drying a solution dissolved in 0 parts using a wire round rod.

Next, a solution prepared by dissolving 2 parts of the trisazo compound used in Example 1 and 2 parts of a polyester resin (trade name: Vylon, manufactured by Toyobo Co., Ltd.) in 5 parts of chlorobenzene was then placed on the charge transport layer in a paint shaker for 1 hour. After dispersion, the mixture was coated using a wire round rod and dried to form a charge generation layer with a thickness of 1 μm, thereby producing a positively charging electrophotographic photoreceptor having a two-layer electrophotographic photosensitive layer.

The initial surface potential v0 of the electrophotographic photoreceptor was measured using an electrostatic copying paper tester (Model 5P-428 manufactured by Kawaguchi Denki ■) when the electrophotographic photoreceptor was positively charged by a 6 kV corona discharge.
Next, light from a tungsten lamp is irradiated so that the illumination intensity on the photoreceptor surface is l lux, and the exposure amount Eso (1ux-sec) required for the surface potential to attenuate to half of the initial surface potential v0 is determined. It was measured.

Further, the same operation was repeated 3000 times.

The results are shown in Table 8.

From Table 8 and above, it can be seen that the photoreceptor of the present invention has high sensitivity and excellent durability even when positively charged.

Example 37 Example! 5 parts of the trisazo compound used in , 40 parts of the hydrazone compound, a copolymer of benzyl methacrylate and methacrylic acid ([η] 30°C methyl ethyl ketone =
0.12. 100 parts of methacrylic acid (32.9% content) were added to 660 parts of dichloromethane, and 1
Dispersed for 2 hours.

This dispersion was coated on a grained aluminum plate with a thickness of 0.25 m and dried to produce an electrophotographic printing plate material having an electrophotographic photosensitive layer with a film thickness of 6 μm.

After charging the surface potential of the photosensitive layer to +500V by corona discharge (+6KV) on this sample in a dark place, tungsten light with a color temperature of 2854 was applied to the sample surface at an illuminance of 2.
When exposed at 0 lux, the half-life exposure (Eso) was 2.01 ux-see.

Next, this sample was charged to a surface potential of +500 in a dark place, and then brought into close contact with a transparent original with a positive image and imagewise exposed. This was immersed in a liquid developer consisting of 5 g of polymethyl methacrylate (toner) dispersed in fine particles in 1000 parts of l5operll (1 petroleum solvent manufactured by Esso Standard) and 0.01 g of soybean oil lecithin, resulting in a clear positive image. I was able to obtain a toner image of

The toner image was further fixed by heating at 100° C. for 30 seconds. This printing plate material was immersed in an etching solution in which 70 g of sodium metasilicate hydrate was dissolved in 140 parts of glycerin, 550 parts of ethylene glycol, and 150 parts of ethanol for 1 minute, and washed with a light stream of water while brushing to remove toner adhesion. A printing plate was obtained by removing the photosensitive layer in the unprotected areas.

In addition, instead of a liquid developer, the obtained electrostatic latent image is used as a toner for Xerox 3500 (manufactured by Fuji Xerox (R1)).
After developing with a magnetic brush, heat at 80℃ for 30 seconds,
A printing plate was also obtained by removing portions of the photosensitive layer to which toner was not attached using a fixed zero order alkaline solution.

The printing plate made in this way was used as a Huff Duster 600CD.
It was possible to print 50,000 sheets of extremely clear printed matter with no spot stains by printing using an offset printing machine in a conventional manner.

(Effects of the Invention) As described above, it has been revealed that the novel electrophotographic photoreceptor of the present invention has excellent strength and durability in both positive and negative charging, and shows only a slight decrease in sensitivity upon repeated use. Furthermore, it has been revealed that the photoreceptor has a sufficiently high sensitivity as a photoreceptor for a semiconductor laser light source.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Scope of Claims] An electrophotographic photoreceptor comprising a layer containing a charge transporting compound and a charge generating compound, or a layer containing a charge transporting compound and a layer containing a charge generating compound on a conductive support. , the charge generating compound is represented by the following general formula [1
] An electrophotographic photoreceptor comprising a trisazo compound represented by the following. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In general formula [1], Ar^1, Ar^2, Ar^3
, Ar^4 and Ar^5 represent an arylene group, a divalent condensed polycyclic aromatic group, or a divalent heteroaromatic ring group. Cp' represents a coupler residue.