JPS63142358A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain flat sensitivity in the whole visible light wavelength region and semiconductor laser emission wavelength region by incorporating a specified azo pigment as an effective constituent in a layer formed on a conductive substrate. CONSTITUTION:The layer 15 formed on the conductive substrate 11 contains as an effective constituent one of the bisazo pigments 13 represented by formula I as a charge generating material in which Ar is a coupler residue. As the coupler to be used for preparing the bisazo pigment represented by ArH, aromatic hydrocarbons each having a hydroxy group, such as phenols or naphthols, and heterocyclic groups each having a hydroxy group, aromatic hydrocarbons having each having an amino group, heterocyclic groups each having an amino group, aromatic hydrocarbons or heterocyclic groups each having both of hydroxy and amino groups, such as aminonaphthols, and aliphatic or aromatic enol form ketones are enumerated, thus permitting superior durability to be obtained.

Description

[Detailed Description of the Invention] The present invention relates to a photoreceptor for electrophotography, and more specifically,
The present invention relates to an electrophotographic photoreceptor provided with a photosensitive layer containing a bisazo pigment as a substance that generates charge carriers when irradiated with light (hereinafter referred to as a "charge-generating substance").

Photoreceptors for electrophotography include inorganic photoreceptors made of selenium and its alloys, or photoreceptors with dye-sensitized zinc oxide dispersed in a binder resin, and organic photoreceptors. A typical known example is one using a charge transfer complex of 2゜4.7-)-linitro-9-fluorenone (hereinafter referred to as rTNFJ) and poly-N-vinylcarbazole (hereinafter referred to as f'PVKJ). It is being

However, while these photoreceptors have many advantages, they also have various disadvantages.

For example, the currently widely used selenium photoreceptor has difficult manufacturing conditions and high manufacturing costs, is difficult to process into a belt due to its lack of flexibility, and is sensitive to heat and mechanical shock. Therefore, care must be taken when handling. Zinc oxide photoreceptors are low in cost because they can be manufactured by applying inexpensive zinc oxide to a support, but they generally have low sensitivity and poor surface smoothness, hardness, tensile strength, and abrasion resistance. It has mechanical drawbacks, and as a photoreceptor for plain paper copying machines, which is normally used repeatedly, there are many problems with durability. Furthermore, a photoreceptor using a charge transfer complex of TNF and PVK has low sensitivity and is unsuitable as a photoreceptor for high-speed copying machines.

In recent years, extensive research has been carried out to eliminate the drawbacks of these photoreceptors, and in particular, various organic photoreceptors have been proposed. Among them, a laminated photoreceptor in which a thin film of an organic pigment is formed on a conductive support (charge generation layer), and a layer mainly composed of a charge transport substance (charge transport layer) is formed on top of this, is a layered photoreceptor that is different from conventional organic pigments. Compared to photoconductors, photoconductors are attracting attention as photoconductors for plain paper copying machines because of their high sensitivity and stable charging properties, and some of them are in practical use.

This type of conventional laminated photoreceptor uses (I) a thin layer of vacuum-deposited perylene derivative as the charge generation layer and an oxadiazole derivative as the charge transport layer (U
(See S P 3871882) (2) @Thin layer formed by coating an organic amine solution of chlordian blue as the charge generation layer, and a hydrazone compound used as the charge transport layer (Japanese Patent Publication No. 55-4238
(3) A thin layer formed by coating an organic solvent dispersion of a distyrylbenzene-based bisazo compound as the charge generation layer, and a hydrazone compound used as the charge transport layer (Japanese Unexamined Patent Application Publication No. 1983-1999) 84943) and the like are known.

However, it is true that conventional laminated photoreceptors of this type have many advantages, but also have various drawbacks. That is, it has the following drawbacks.

Although the photoreceptor using the perylene derivative and oxadiazole derivative shown in (I) has no practical problems,
Sensitivity is low for higher speed copying machines. Furthermore, perylene derivatives, which are charge-generating substances that control the spectral sensitivity of this photoreceptor, have no absorption over the entire visible range, making them unsuitable as photoreceptors for color copying machines.

Although the photoreceptor using chlordiane blue and hydrazone compound shown in (2) has relatively high sensitivity, it is necessary to use an organic amine (e.g. ethylenediamine), which is generally difficult to handle, as a coating solvent to form the charge generation layer. There are many drawbacks in making photoreceptors.

The photoreceptor using a distyrylbenzene-based bisazo compound and a hydrazone compound shown in (3) is very advantageous in terms of manufacturing because a charge generation layer can be easily formed by coating a dispersion of the bisazo compound. However, because of its slightly low sensitivity, it is unsatisfactory as a photoreceptor for high-speed copying machines.

On the other hand, the demand for photoreceptors for laser printers has increased in recent years, and the development of highly sensitive photoreceptors in the wavelength range of semiconductor lasers is desired, but the photoreceptors mentioned above are extremely sensitive to these semiconductor lasers. The reality is that it is too low to be put to practical use.

Purpose The present invention provides a photoreceptor for use in electrophotography and laser printers that overcomes the above-mentioned conventional drawbacks, has flat sensitivity over the entire visible range and the oscillation wavelength range of semiconductor lasers, and is easy to manufacture. The purpose is to provide a photoreceptor.

As a result of intensive research to achieve the above object, the present inventor has prepared a material of the general formula (I) as a charge generating substance on a conductive support.
), Ar −N=N−o−(CH=CH), −@−N=N
By providing an electrophotographic photoreceptor characterized in that a layer containing a bisazo pigment represented by -Ar-(I) (wherein Ar represents a coupler residue) as an active ingredient is formed. I found out that the purpose can be achieved.

Ar used in the production of the bisazo compound of general formula (I)
Examples of the coupler represented by H include aromatic hydrocarbon compounds having a hydroxyl group such as phenols and naphthols, heterocyclic compounds having a hydroxyl group, aromatic hydrocarbon compounds having an amino group, and heterocyclic compounds having an amine group. Formula compounds, aromatic hydrocarbon compounds and heterocyclic compounds having a hydroxyl group and an amino group such as aminonaphthols, compounds having an aliphatic or aromatic dinolic ketone group (compounds having an active methylene group), etc. Preferably, the coupler residue Ar has the following general formula (If), (I[I), (IV), (V), (VI)
, (■), (■), (IX), (X), (XI), (
It is represented by the general formula (Xll).

[Formula (n) above, (I[r), (IV) and (V)]
In the formula, X, Yl, Z, m and n each represent the following.

1 (R and R2 represent hydrogen or a substituted or unsubstituted alkyl group, and R1 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.) Yl: hydrogen, halogen, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, carboxy group, sulfo group, substituted or unsubstituted sulfamoyl group, or 100N-Y2 (R4 is hydrogen, alkyl group or its substituent, phenyl group or its substituent represents a hydrocarbon ring group or a substituent thereof, a heterocyclic group or a substituent thereof, R2 a fused hydrogen ring group or a substituent thereof, a heterocyclic group or a substituent thereof, a styryl group or a substituent thereof, R is represents hydrogen, an alkyl group, a phenyl group, or a substituent thereof, or R2 and R1 may form a ring together with the carbon atoms bonded to them. ) Z: a hydrocarbon ring or its substituted product, or a heterocycle or its substituted product n: an integer of 1 or 2 m: an integer of 1 or 2] [In formulas (VI) and (■), R7 is a substituted or unsubstituted It represents a hydrocarbon group, and X is the same as above. ] Ar.

[In the formula, R8 represents an alkyl group, a carbamoyl group, a carboxyl group, or an ester thereof, and Ar represents a hydrocarbon ring group or a substituted product thereof, or is the same as above. ] [In the above formulas (IX) and (X), R9 represents hydrogen or a substituted or unsubstituted hydrocarbon group, and Ar represents a hydrocarbon ring group or a substituted product thereof. ] The above general formula (II), (m), (IV) or (V)
Examples of the hydrocarbon ring for Z include a benzene ring and a naphthalene ring, and examples of the heterocycle include an indole ring, a carbazole ring, and a benzolane ring. Also, Z
Examples of substituents on the ring include halogen atoms such as chlorine atoms and bromine atoms, and alkoxy groups.

Examples of the hydrocarbon ring group in Y2 or Rs include phenyl group, naphthyl group, anthryl group, pyrenyl group, etc.
In addition, examples of heterocyclic groups include pyridyl group, chenyl group, furyl group, and indolyl group.

Examples include a benzofuranyl group, a carbazolyl group, and a dibenzofuranyl group. Further, examples of the ring formed by bonding R6 and R6 include a fluorene ring.

Substituents on the hydrocarbon ring group or heterocyclic group of Y2 or Rs or the ring formed by R8 and R6 include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, propoxy alkoxy groups such as butoxy groups, halogen atoms such as chlorine atoms and bromine atoms, dialkylamino groups such as dimethylamino groups and diethylamino groups, dialkylamino groups such as dibenzylamino groups, and halomethyl groups such as trifluoromethyl groups. , a nitro group, a cyano group, a carboxyl group or its ester, a hydroxyl group, and a sulfonic acid group such as 5o3Na.

Examples of substituents for the phenyl group of R1 include halogen atoms such as chlorine atoms and bromine atoms.

Representative examples of the hydrocarbon group in R7 or R9 are:
Examples include alkyl groups such as a methyl group, ethyl group, propyl group, and butyl group, aralkyl groups such as benzyl group, aryl groups such as phenyl group, and substituted products thereof.

As a substituent in the hydrocarbon group of R7 or R3,
Alkyl groups such as methyl, ethyl, propyl and butyl groups, alkoxy groups such as methoxy, ethyl, propoxy and butoxy groups, halogen atoms such as chlorine and bromine, hydroxyl and nitro groups, etc. I can give an example.

Typical examples of the hydrocarbon ring group in Ar1 or Ar are phenyl group, naphthyl group, etc.
Substituents for these groups include alkyl groups such as methyl, ethyl, propyl, and butyl, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, nitro, chlorine, bromine, etc. halogen atom, cyano group, dimethylamino group, diethylamine 7
Examples include dialkylamino groups such as .

Furthermore, among X, a hydroxyl group is particularly suitable.

Among the above coupler residues, preferred is the general formula (
Ill), (VI), (■), (■), (IX) and (X), and among these, those in which X in the general formula is a hydroxyl group are preferred. Also, among these, a coupler residue represented by the general formula (Summer) ゝ2' (Yl and 2 are the same as above) is preferable, and more preferably a coupler residue represented by the general formula (Z, Y, and R2 are the same as above). It is a coupler residue represented by

Furthermore, among the above preferred coupler residues, general formula (XIII) or (XIV) ゝZ'ゝZ' (Z, R2, R, and R6 are the same as above, and R□. For example, (Examples include substituents for Y2.) Those represented by the following are suitable.

Specific examples of the bisazo pigment used in the present invention as described above are shown in the following structural formula. For simplicity, only the structural formula of Ar, which is a coupler residue, is shown.

Ar-N=:N-■-(CH=CH),,=■-N=N
-Ar-(I)"L
Knee bile--Ice E-''L EJs--Jl--! −−8−− 1 and 1−&−1−と−−と− −と−−＆− −と−−5− 工 ”L = Sea −&−−Oni−−&
- 02N+C 2H1 - By using the bisazo pigment of the present invention such as 51 or more, an electrophotographic photoreceptor with extremely high sensitivity can be easily produced.

The bisazo pigment of the present invention is, for example, 1,12-bis(4-nitrophenyl)-1, which is obtained by Witschich reaction.
1,12-bis(4-aminophenyl)-1,3 obtained by reducing 3,5,7,9,11-dodecahexaene
, 5,7,9,11-dodecahexaene is lydiazotized to give a tetrazonium salt by a conventional method, and the tetrazonium salt and the corresponding coupler are mixed in a suitable organic solvent such as N
, can be easily produced by reacting a base in N-dimethylformamide to carry out a coupling reaction.

As an example, a production example of the bisazo pigment No. 001 is shown below, but other bisazo pigments can also be easily produced according to this production example, except for changing the coupler.

Production example Dilute sulfuric acid consisting of 7 mΩ of concentrated sulfuric acid and 1 oom of water
12-bis(4-aminophenyl)-1,3,5,7,
4.0 g of 9°11-dodecahexaene was added, stirred at 60°C for 2 hours, and then rapidly cooled to -3°C. Then, a solution of 1.74 g of sodium nitrite dissolved in 5 mA of water was added dropwise to the mixture at -3°C to -2°C over 40 minutes.

Thereafter, the mixture was stirred at the same temperature for 20 minutes, and 200 ml of water was added. A trace amount of insoluble matter was removed by filtration. A 42% aqueous solution of borohydrofluoric acid was added to the filtrate, and the precipitated crystals were collected by filtration and dried. , 5.5 g of dark red tetrazonium salt (yield: 87%) was obtained.

In the infrared absorption spectrum, absorption based on N2 stretching vibration was observed at 2220 cm-1. 3-hydroxy-2
- Dissolve 0.35 g of naphthoic acid anilide in 130 mQ of dimethylformamide (DMF), add 0.34 g of the tetrazonium salt obtained as described above, and then add 2.5 mQ of an 86-part aqueous sodium acetate solution at room temperature. 20
6 times dropped over a period of minutes.

After stirring at the same temperature for 3 hours, the produced bisazo pigment was collected by filtration and washed five times with 150 m fl of dimethylformamide, and then twice with water + 50 m Q. Further, it is heated and dried under reduced pressure to obtain a bisazo pigment of compound N001: 1
．． 12-bis(4-(2-hydroxy-3-phenylcarbamoylnaphthyl-1-7zo)]]phenyl-1,3
, 5, 7, 9.11 0.50 g (yield: 89%) of ene was obtained as a blue-black powder.

Decomposition point: 263°C Elemental analysis: (as CssH44Nco4) HN Actual value 78.08 4.89 9.2
0 calculated value 78.35 5.00 9.
45 visible spectrum [ethylenediamine/DMF (I/9: Vol,)]
:λmax 596 nm The infrared absorption spectrum (KBrBr method) of this product is shown in FIG. As you can see from this figure, 1675 cm
``1 has absorption based on the stretching vibration of °C=O, and 103
Absorption based on out-of-plane bending vibration of the trans-olefin was observed at 0 cm''1.

In the electrophotographic photoreceptor of the present invention, a bisazo pigment is used as a charge generating substance in the photosensitive layer.

A typical structure of this photoreceptor is shown in FIGS. 1 and 2.

The photoreceptor shown in FIG. 1 is a laminated type photoreceptor W11 consisting of a charge generation layer 15 mainly composed of a bisazo pigment 13 and a charge transport layer 17 mainly composed of a charge transport substance on a conductive support 11.
91 is provided.

In the photoreceptor shown in FIG. 1, imagewise exposed light passes through the charge transport layer, reaches the charge generation layer 15, and generates charges in the bisazo pigment 13 in that area.

On the other hand, the charge transport layer 17 receives charge injection and transports it, and the mechanism is such that the bisazo pigment 13 generates the charge necessary for light attenuation, and the charge transport layer 17 transports the charge.

The photoreceptor shown in FIG. 2 has a photosensitive layer 192 mainly composed of a bisazo pigment 13, a charge transport substance, and an insulating binder provided on a conductive support 11. The photoreceptor shown in FIG.

Again, the bisazo pigment 13 is a charge generating substance.

In other photoreceptors, the charge generation layer and charge transport layer may be reversed as shown in FIG.

The thickness of the photosensitive layer is as shown in FIG. 1, and the thickness of the charge generation layer 15 is preferably 0.01 to 5μ, more preferably 0.05μ.
~2μ. If the thickness is less than 0.01 μm, charge generation will not be sufficient, and if it is more than 5 μm, the residual potential will be too high for practical use.

The thickness of the charge transport layer 17 is preferably 3 to 50 microns, more preferably 5 to 20 microns. If the thickness is less than 3 μm, the amount of charge will be insufficient, and if it is more than 50 μm, the residual potential will be too high to be practical.

The charge generation layer 15 is mainly composed of a bisazo pigment represented by the above general formula, and may further contain a binder, a plasticizer, and the like. The proportion of bisazo pigment in the charge generation layer is preferably 30% by weight or more, more preferably 50% by weight or more.

The charge transport layer 17 is mainly composed of a charge transport substance and a binder, and may further contain a plasticizer. The proportion of charge transport material in the charge transport layer is from 10 to 95% by weight, preferably from 30 to 90% by weight. When the proportion of the charge transport substance is less than 10% by weight, almost no charge is transported, and when it is more than 95% by weight, the mechanical strength of the photoreceptor film is so poor that it cannot be put to practical use.

In the case of the photoreceptor shown in FIG. 2, the thickness of the photosensitive layer 192 is preferably 3 to 50 microns, more preferably 5 to 20 microns. Further, the proportion of the disazo pigment in the photoreceptor 192 is preferably 50% by weight or less, more preferably 20% by weight.
or less, and the proportion of the charge transport substance is preferably 10
~95% by weight, more preferably 30-90% by weight.

The gist of the present invention is to use a specific bisazo pigment represented by the general formula (I) as a charge generating substance in an electrophotographic photoreceptor, and a conductive support,
Any conventionally known components such as charge transport materials can be used, and these will be specifically explained below.

Examples of the conductive support used in the photoreceptor of the present invention include a metal plate made of aluminum, copper, zinc, etc., a plastic sheet or film made of polyester, etc., on which a conductive material such as aluminum or 5n02 is vapor-deposited;
Alternatively, conductive treated paper or the like may be used.

As a binder, polyamide, polyurethane, polyester, epoxy resin, polyketone, polycarbonate,
Condensation resins such as polyacetal, polyvinyl ketone,
Examples include vinyl polymers such as polystyrene, poly-N-vinylcarbazole, and polyacrylamide.
Any insulating and adhesive resin can be used.

Examples of plasticizers include halogenated paraffins, polychlorinated biphenyls, dimethylnaphthalene, and dibutyl phthalate. In addition, silicone oil or the like may be added to improve the surface properties of the photoreceptor.

Charge transport materials include hole transport materials and electron transport materials.

As the hole transport substance, for example, the following general formulas (I) to
Examples include compounds as shown in (I3).

In formula C, R engineering 1. represents a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-chloroethyl group, a substituted or unsubstituted alkyl group such as a benzyl group, or a substituted or unsubstituted phenyl group; R1□ is a methyl group, an ethyl group; represents a benzyl group or a substituted or unsubstituted phenyl group, Ar represents a substituted or unsubstituted phenyl group or a naphthyl group, and R represents hydrogen, chlorine, bromine, or a group having 1 carbon number.
-4 alkyl group, C1-C4 alkoxyl group, dialkylamino group or nitro group. ] Ar4-CH=N-N-Ar.

[In the formula, Ar4 represents a naphthalene ring, anthracene ring, styryl group, or a substituted product thereof, or a pyridine ring, a furan ring, or a thiophene ring, and R□6 represents an alkyl group containing a substituted alkyl group or a substituted or unsubstituted phenyl group. Ar represents a substituted or unsubstituted phenyl group or a dimethyl group. ]■ IS5 [In the formula, R□3. represents an alkyl group including a substituted alkyl group, a substituted or unsubstituted phenyl group, or a naphthyl group,
R,,s and R□7. represents hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, a dialkylamino group, or a diarylamino group, m and n represent integers of 1 to 4, and m and n is 2
In the above case, R1G5 and R-work 7. may be the same or different. ] [In the formula, R represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group, or a heterocyclic group, and Rxos may be the same or different, and hydrogen, carbon number 1 to 4 alkyl group, hydroxyalkyl group, chloroalkyl group, substituted or unsubstituted aralkyl group or aryl group, and Rg5 and R2° are bonded to each other to form a nitrogen-containing heterocycle. It's okay. R20, which may be the same or different, represents hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen. ] R2□.

[In the formula, R, and s represent hydrogen or a halogen atom, and Ar represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, or carbazolyl group. ] [In the formula, R23 represents hydrogen, halogen, a cyano group, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, and R24K represents an alkyl group containing a substituted alkyl group or a substituted alkyl group. or represents an unsubstituted phenyl group, R2
5s represents hydrogen, halogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a dialkylamino group, n is 1 or 2, and when n is 2, R2
s, may be the same or different, R2G5 and R2□
5 represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. ] (7) R2,,
-HC=HCCH=CH-R2,.

[In the formula, R265 and R23 are a carbazolyl group, a pyridyl group, a chenyl group, an indolyl group, a furyl group, or a substituted or unsubstituted phenyl group, a styryl group,
A naphthyl group or anthryl group, which substituents include a dialkylamino group containing a substituted alkyl group, a substituted or unsubstituted diarylamino group, an alkyl group, an alkoxy group, a carboxy group or an ester thereof, and a halogen atom.

Represents a group selected from the group consisting of a cyano group, an amino group, a nitro group and an acetylamino group] R1□ [wherein R1゜ is an alkyl group including a substituted alkyl group, or a substituted or unsubstituted phenyl group represents R
315 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, a dialkylamino group containing an amino-substituted alkyl group, or a substituted or unsubstituted diarylamino group, and n is an integer of 1 or 2. represent. [In the formula, R32 represents a hydrogen atom, an alkyl group, an alkoxyl group, or a halogen atom, and Ro and R3
□ represents an alkyl group including a substituted alkyl group, or a substituted or unsubstituted aryl group, and R, 2s and R34,
may be the same or different, R1□ represents a substituted or unsubstituted phenyl group, and Ar represents a substituted or unsubstituted aryl group.] Ar.

C=C(CH=CH)nA / I R,,sR,,.

[In the formula, n is an integer of 0 or 1, R3G5 is a hydrogen atom,
represents an alkyl group containing a substituted alkyl group or a substituted or unsubstituted phenyl group, Ars represents a substituted or unsubstituted aryl group, R3ff f represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group. In the formula, A represents a 9-anthryl group or a substituted or unsubstituted carbazolyl group, where R1,.

represents a hydrogen atom, an alkyl group, an alkoxyl group, a halogen atom or an alkyl group containing a substituted alkyl group, a substituted or unsubstituted aryl group, R3, and R4° may be the same or different, R39, and R4, may form a ring), and 1m is an integer of 0, 1.2 or 3, and when 1m is 2 or more, Ro may be the same or different.] [In the formula, R4! , R4□ and R42 represent hydrogen, a lower alkyl group, a lower alkoxy group, a dialkylamino group or a halogen atom, and n represents O or 1.

[In the formula, R44S and R4s represent an alkyl group including a substituted alkyl group, or a substituted or unsubstituted aryl group, and A1 represents a substituted amino group or a substituted or unsubstituted aryl group or allyl group. ] R4GS [In the formula, or represents a hydrogen atom or a halogen atom, R
4 represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A2 represents a substituted amino group, a substituted or unsubstituted aryl group, or an allyl group. ] The compound represented by general formula (I) includes, for example, 9-
Ethylcarbazole-3-aldehyde, 1-methyl-1
-Phenylhydrazone, 9-ethylcarbazole-3-
Aldehyde 1-benzyl-1-phenylhydrazone, 9
-ethylcarbazole-3-aldehyde 1,1-diphenylhydrazone and the like.

Examples of the compound represented by general formula (2) include 4-diethylaminostyrene-β-aldehyde 1-methyl-1
-Phenylhydrazone, 4-methoxynaphthalene-1-
Examples include aldehyde 1-benzyl-1-phenylhydrazone.

Examples of the compound represented by the general formula (3) include 4-methoxybenzaldehyde 1-methyl-1-phenylhydrazone, 2,4-dimethoxybenzaldehyde 1-benzyl-1-phenylhydrazone, and 4-diethylaminobenzaldehyde 1゜1-diphenyl. hydrazone, 4-methoxybenzaldehyde 1-benzyl-1-(4-methoxy)phenylhydrazone, 4-diphenylaminobenzaldehyde 1-benzyl-1-phenylhydrazone,
Examples include 4-dibenzylaminobenzaldehyde-1,1-diphenylhydrazone.

The compound represented by general formula (4) includes, for example, 1,
1-bis(4-dibenzylaminophenyl)propane,
Tris(4-diethylaminophenyl)methane, 1,1
-bis(4-dibenzylaminophenyl)propane,
Examples include 2,2'-dimethyl-4,4'-bis(diethylamino)-triphenylmethane.

The compound represented by general formula (5) includes, for example, 9-
(4-diethylaminostyryl)anthracene, 9-bromo-10-(4-diethylaminostyryl)anthracene, and the like.

The compound represented by general formula (6) includes, for example, 9-
(4-dimethylaminobenzylidene)fluorene, 3
-(9-fluorenylidene)-9-ethylrubazole and the like.

The compound represented by general formula (7) includes, for example, 1,
2-bis(4-diethylaminostyryl)benzene, 1
, 2-bis(2,4-dimethoxystyryl)benzene.

The compound represented by general formula (8) includes, for example, 3-
Examples include styryl-9-ethylcarbazole and 3-(4-methoxystyryl)-9-ethylcarbazole.

The compound represented by the general formula (9) includes, for example, 4-
Diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4
-diphenylaminostyryl) naphthalene, 1- (4
-diethylaminostyryl) naphthylene, etc.

The compound represented by the general formula (I0) includes, for example, 4'
-diphenylamino-α-phenylstilbene, 4′
-methylphenylamino-α-phenylstilbene and the like.

The compound represented by general formula (I1) includes, for example, 1-
Phenyl-3-(4-diethylaminostyryl)-5-
(4-diethylaminophenyl)pyrazoline, 1-phenyl-3-(4-dimethylaminostyryl)-5-(4
-dimethylaminophenyl)pyrazoline, etc.

Compounds represented by general formulas (I2) and (I3) include:
For example, 2,5-bis(4-diethylaminophenyl)
-1,3,4-oxadiazole, 2゜5-bis(4-
(4-diethylaminostyryl)phenyl)-1,3,
4-Oxadiazole, 2-(9-ethylcarbazolyl-3-)-5-(4-diethylaminophenyl)-1
, 3,4-oxadiazole, etc. Other hole transporting substances include oxazoles such as 2-vinyl-4-(2-chlorophenyl)-5-(4-diethylaminophenyl)oxazole and 2-(4-diethylaminophenyl)-4-phenyloxazole. Compound, triphenylamine, tri-P-tolylamine, 4,4'-dimethoxytriphenylamine, N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine, 1゜1-bis(4- Examples include low molecular weight compounds such as triphenylamine compounds such as di-p-tolylaminophenyl)cyclohexane and N,N,N',N'-tetra(p-tolyl)benzidine. Further, polymeric compounds such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, pyrene formaldehyde resin, and ethylcarbazole formaldehyde resin can also be used.

Examples of electron transport substances include chloranil, bromoanil, tetracyanoethylene, tetracyanoquinone dimethane, 2,4.7-trinitro-9-fluorenone, 2,4,5.7-tetranitro-9-fluorenone, 2, 4,5°7-tetranitroxanthone, 2,4.
8-Trinidrothioxanthone, 2,6.8-trinitro-4H-indeno(I,2-b)thiophene-4-
1,3.7-trinitrodibenzothiophene-5
, 5-dioxide, etc.

These charge transport substances may be used alone or in combination of two or more.

In any of the photoreceptors obtained as described above, an adhesive layer or a barrier layer may be provided between the photoreceptors on the conductive support, if necessary.

Suitable materials for these layers include polyamide, nitrocellulose, aluminum oxide, and the like, and the film thickness is preferably 1 μm or less.

To make the photoreceptor of FIG. 1, a bisazo pigment on a conductive support was prepared using tlSP 3,973,959, USP 3.
996,049, or by dispersing fine particles of a bisazo pigment in a suitable solvent in which a binder is dissolved, if necessary, and depositing this on a conductive support. After the coating is dried and, if necessary, the surface is finished by a method such as buffing or flapping as shown in JP-A No. 51-90827, or the film thickness is adjusted, the charge transport material is applied. It is obtained by applying and drying a solution containing a binder and a binder.

The photoreceptor shown in FIG. 2 can be prepared by dispersing a fine powder of bisazo pigment in a solution containing a charge transporting substance and a binder, and applying and drying this onto a conductive support.

In either case, the bisazo pigment used in the present invention is ground to a particle size of 5 μm or less, preferably 2 μm or less, using a ball mill or the like. The coating method is carried out by conventional means such as doctor blade, dipping, wire bar, etc.

To perform copying using the photoreceptor of the present invention, the surface of the photoreceptor layer is charged and exposed, and then developed, and if necessary,
This is achieved by transferring to paper or the like.

The electrophotographic photoreceptor of the present invention has 1,8-diphenyl-1,
By using a bisazo pigment having a 3,5,7-octatetraene skeleton as a charge generating substance, it is easier to manufacture than conventional photoreceptors, and has high sensitivity, and is suitable for use in the entire visible range and semiconductor lasers. It has excellent properties such as exhibiting flat sensitivity over the oscillation wavelength range and stable characteristics even when the photoreceptor is used repeatedly.

EXAMPLES Next, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereby.

Example 1 7.5 parts by weight of bisazo pigment Nα1 and 500 parts by weight of a tetrahydrofuran solution (solid content concentration 0.5%) of polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) were pulverized and mixed in a ball mill. The dispersion was applied using a doctor blade onto the aluminum surface of an aluminum-deposited polyester base (conductive support), air-dried,
A charge generation layer having a thickness of about 1 μm was formed.

On this charge generation layer, 2 parts by weight of 9-ethylcarbazole-3-aldehyde 1-methyl-1-phenylhydrazone, 2 parts by weight of polycarbonate resin (Panlite -1300 manufactured by Kijinsha Co., Ltd.) and 16 parts by weight of tetrahydrofuran were added as charge transport substances. A solution containing the above components was mixed and dissolved using a doctor blade, and dried at 80°C for 2 minutes and then at 105°C for 5 minutes to form a charge transport layer with a thickness of about 20 μm. A photoconductor Nα1 was prepared.

Examples 2 to 25 The following table was substituted for the bisazo pigment NQl used in Example 1.
Photoreceptors Nα2 to Nα25 were prepared in the same manner as in Example 1, except that the bisazo pigment shown in Example 1 was used.

Examples 26 to 40 Example 1 except that 1-phenyl-3-(4-diethylaminostyryl)-5-(4-diethylaminophenyl)pyrazoline was used as the charge transport substance and the bisazo pigment shown in Table 2 below was used. In the same manner as above, the photoconductor Nα26-4
0 was created.

Examples 41 to 55 Photoconductor N was prepared in the same manner as in Example 1, except that α-phenyl-4'-N,N-diphenylaminostilbene was used as the charge transport substance and the bisazo pigment shown in Table 3 below was used.
α41-55 were created.

Examples 56 to 65 Photoconductor N
α56-65 were created.

These photoreceptors Na 1 to 65 were negatively charged by -6KV corona discharge for 20 seconds using an electrostatic copying paper tester (Kawaguchi Denki Seisakusho, model 5P428), and then charged for 20 seconds. Leave it in a dark place, and the surface potential V at that time
po (V), then irradiate the surface with light using a tungsten lamp at an illuminance of 4.5 lux, find the time (seconds) until the surface potential reaches 172 of Vpo, and calculate the exposure amount. El/2 (lux seconds)
was calculated. The results are shown in Tables 1 to 4.

Table-1 Table-1 (continued) Table-2 Table-3 Table-4 As is clear from the results in Tables-1 to Table-4 above, the photoreceptor of the present invention has excellent sensitivity in the visible range. I know that there is. Further, in producing a photoreceptor, there is no need to perform vapor deposition or use an organic amine, which is advantageous in terms of production.

Furthermore, the photoreceptor NQ12 of the present invention was installed in a copying machine manufactured by Ricoh Co., Ltd., model FT-4700, and the image output was 10.0.
The copying process was repeated 00 times, but as a result, neither photoreceptor changed due to repeated copying processes, and clear images were obtained. From this, it can be understood that the photoreceptor of the present invention is also excellent in durability.

[Brief explanation of the drawing]

FIGS. 1 and 2 are enlarged sectional views showing an example of the structure of the photoreceptor of the present invention. FIG. 3 is an infrared absorption spectrum (KBrBr method) of the bisazo pigment Nα1 used in the present invention. 11... Conductive support 13... Bisazo pigment 1
5... Charge generation layer 17... Charge transport layer 191
, 192...photosensitive layer

Claims (1)

[Claims] 1. On a conductive support, represented by the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, Ar represents a coupler residue) A photoreceptor for electrophotography, characterized in that a layer containing a bisazo pigment as an active ingredient is formed.