JPH0228660A - Photosensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity and repetition characteristics, to enable a photosensitive material to match a high speed copying process, and to enhance reproducibility of a red copied picture by forming a layer containing a specified azo compound and a specified perylene compound as a carrier generating material. CONSTITUTION:The layer contains the compound represented by formula I and the compound represented by formula III as the carrier generating material. In these formulae, each of X<1> and X<2> is halogen, optionally substituted alkyl, or the like, and at least one of them is halogen; each of p and q is 0, 1, or 2; A is a group represented by formula II; Ar is an aromatic carbon ring group or the like having at least one fluorinated hydrocarbon group; Z is a nonmetallic atomic group necessary to form an optionally substituted aromatic carbon group or the like; and Q is -O- or the like, thus permitting the obtained photosensitive body sensitive enough to match the speed up of a copying process, to be superior in repetition characteristics and reproducibility of a red picture.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a photoreceptor, particularly an electrophotographic photoreceptor.

Conventional technology Conventionally, inorganic photoconductive materials such as selenium, zinc oxide, titanium oxide, and cadmium sulfide have been mainly used as photosensitive materials for electrophotographic photoreceptors. Research and development is also actively underway.

On the other hand, photosensitive materials using organic photoconductive substances (OPC) are generally less toxic than inorganic photoconductive substances, and are advantageous in terms of flexibility, lightness, film formability, cost, etc. Since then, it has been attracting attention recently.

In any electrophotographic photoreceptor, the functions of charge generation and transport are separated into each layer, and each function can be set independently. This is advantageous in terms of photoreceptor design because it provides a wider range of options.

In addition, the functionally separated type photoreceptor can improve the electrophotographic characteristics and is excellent in terms of sensitivity, repeatability, mechanical strength, etc.5 Such electrophotographic photoreceptors are generally used in electrophotographic copying machines, printers, etc. Although it is widely used, recently, as electrophotographic copying machines and printers have become faster, the time required for the copying process has been significantly shortened, and the number of copies has also increased.
There is a growing demand for higher sensitivity and higher durability of photoreceptors.

Typical examples of highly sensitive carrier-generating substances conventionally used in electrophotographic photoreceptors include polycyclic quinone compounds and azo pigments.

However, electrophotographic copying machines usually use white light from an A light source, a fluorescent lamp, or the like, and the photoreceptor is simultaneously irradiated with light having wavelengths over the entire visible light range. In this respect, although polycyclic quinone compounds have an extremely excellent ability to generate light carriers, they have a spectral sensitivity of 400 to 570 ns+, and are sensitive to light with longer wavelengths. Therefore, it can be said that there is a limit to increasing the sensitivity. On the other hand, photoreceptors using ab-based pigments, such as disazo pigments, have a spectral sensitivity that extends to around 700no+, but on the other hand, the photosensitivity at short wavelengths decreases, and there is still a certain limit to achieving high sensitivity. It can be said that it has.

Furthermore, an important issue is that electrophotographic copying machines are
Since it is used as a necessity in government offices, offices, public institutions, etc., it is necessary to faithfully reproduce the original manuscript, and in particular, the reproducibility of red stamps and underlines (red lines) in various documents is required. Ru.

To do this, copy and reproduce the red image with 600nI1
It must have spectral sensitivity characteristics that either there is no sensitivity in one or more wavelength ranges, or the sensitivity in these wavelength ranges is lower than the sensitivity in other wavelength ranges. However, each carrier-generating substance has its own spectral sensitivity characteristics, and it is difficult to find a carrier-generating substance that satisfies the electrophotographic characteristics and can reproduce red originals to a degree suitable for the purpose of copying. Have difficulty.

In order to improve the reproducibility of red color, there is a method of installing a red cant filter (cyan filter) in the optical path of white light, but for example, when using the above-mentioned disazo pigment,
When light with wavelengths longer than 00 nm is cut off, the photosensitivity decreases significantly.

As mentioned above, conventional photoreceptors are not necessarily sufficient in terms of photosensitivity and red reproducibility, especially for high-speed electrophotographic copying machines and small-sized copying machines (although high-sensitivity photoreceptors that can support these The appearance of the body is expected.

Object of the invention The object of the invention is to have a high degree of spectral sensitivity over a wide range of wavelengths, high sensitivity, and excellent repeatability.
It is an object of the present invention to provide a photoreceptor that can cope with high-speed copying processes and has excellent copying reproducibility of red images.

D6 Structure of the invention and its effects The present invention provides a photoreceptor having a layer containing a compound represented by the following general formula [1] and a compound represented by the following general formula (III) as carrier-generating substances. This is related.

General formula (1) (X' and Xt each represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a nitro group, a cyano group, a hydroxy group, or a substituted or unsubstituted amino group) and at least one of XI and X2 is a halogen atom.

p and q each represent an integer of O1 or 2, p and q cannot be O at the same time, and when p is 2, XI may be the same or different groups, and when q is 2 In the case, X2 may be the same or different groups.

A represents a group represented by the following general formula (If).

General formula (II) 1,. 1 (wherein, Ar represents an aromatic carbocyclic group or an aromatic heterocyclic group having a small number of fluorinated hydrocarbon groups.

Z represents a group of nonmetallic atoms necessary to form a substituted or unsubstituted aromatic carbocycle or a substituted or unsubstituted aromatic heterocycle. ) m and n each represent Oll or an integer of 2.

However, m and n do not become O at the same time. [General design ■]: [In the general formula CI [[], Q represents -〇- or ゝND.

/ D is hydrogen, or a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group,
represents an aryl group or a heterocyclic group] The present invention includes a layer containing a specific Ab compound represented by the general formula CI) and a perylene compound represented by the general formula (I[I) as carrier-generating substances. It has a remarkable feature in that it is provided.

That is, the above perylene compound has, for example, a spectral sensitivity spectrum as shown in FIG.
-7), its photosensitive wavelength range extends from 400 to 5 BQ nm.

Although such perylene compounds have good photosensitivity among various materials, as mentioned above, their
However, it lacks sensitivity on the long wavelength side, has a limit in terms of improving photosensitivity, and is not necessarily compatible with high-speed copying machines.

As a countermeasure to this, it may be possible to sensitize the long wavelength side by using other carrier-generating substances in combination, but the problem lies in the selection of carrier-generating substances to be combined, and depending on this selection, the above perylene compound may be sensitized. There is also a possibility that the original photosensitivity on the short wavelength side may be impaired. Furthermore, it is not necessarily the case that there is a uniform selection method for such selection, and the actual situation is that the selection is made from among a large number of compounds through repeated experiments. Furthermore 600na
If the photosensitivity to long wavelengths of + or more becomes too large, the reproducibility of red color will not be sufficient.

Here, the present inventors have discovered that satisfactory results can be obtained by using the above perylene compound and the compound represented by general formula [I] in combination.

That is, the compound represented by the general formula (I) exhibits a spectral sensitivity spectrum as shown in FIG.
By using the below-mentioned example azo compound 11h71) in combination with the above perylene compound, as shown in Figure 1, the light sensitivity inherent to the above perylene compound is maintained while significantly sensitizing the long wavelength side of 580 nm or more. In addition, it has become possible to suppress the photosensitivity of red light to a level that does not interfere with red image reproduction. This made it possible to realize a practical photoreceptor that could sufficiently cope with the speeding up of the copying process, had excellent repeatability, and was capable of reproducing red images.

Further, in the present invention, even if a relatively thick "layer containing the perylene compound or the like as a carrier generating substance" is formed, the characteristics as a photoreceptor are good, and therefore, the unevenness of the step,
It is advantageous in terms of production since coating defects such as dripping and agglomeration are less likely to occur during production.

The specific configuration will be described below.

The content ratio of the perylene compound and the compound represented by the general formula (I) in the layer is (100: 100) by weight (compound represented by the perylene compound knee design [I]).
) is preferably within the following range, (100: 1
) to (100:20) is more preferable. In this range, red color reproducibility is even better and photosensitivity can also be increased.

The maximum value of spectral sensitivity at wavelength λ≦600 nm is Q, 1
(λ≦600nm), and the maximum value of spectral sensitivity at wavelength λ≧600no+ is Q□X (λ≧600na+)
Then, the ratio of both is Q, (λ≦600na
+) / Q @ax (λ≧600nm) = 1
00/50 or less is more preferable in terms of red color reproducibility.

Next, the compound represented by -1%i formula [I] will be described.

-a Examples of the halogen atom represented by Xl and X2 in formula (1) include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

In the bisazo compound of the present invention, at least one of xl and X2 has a halogen atom.

As the alkyl group represented by XI and , 1so-propyl group, trifluoromethyl group, t-butyl group, and the like.

The alkoxy groups represented by XI and X2 are preferably substituted or unsubstituted alkoxy groups having 1 to 4 carbon atoms, and examples of such alkoxy groups include:
Methoxy group, ethoxy group, β-chloroethoxy group, 5ec
-butoxy group and the like.

Furthermore, the substituted or unsubstituted amino group represented by XI and , N, N-dimethylamino group, N.

N-diethylamino group, N-phenylamino group, N, N
-diphenylamino group, an acetylamino group substituted with an acyl group, p-chlorobenzoylamino group, and the like.

-Design CI), p and q are each 0.
represents 1 or 2, but p and q are never 0 at the same time, preferably p=1. This is the case when q=0 or p=1 and q=1.

Furthermore, when p or q is 2, XI or X2 can be the same or different groups, respectively.

In addition, in the above -design (1), A is the following -design (I
f).

General formula [II] -Z/ In the formula, Ar represents an aromatic carbocyclic group or an aromatic heterocyclic group having one fluorinated hydrocarbon group, but the number of carbon atoms in the fluorinated hydrocarbon group 1 to 4 fluorinated hydrocarbon groups are preferred, such as trifluoromethyl group, pentafluoroethyl group, tetrafluoroethyl group,
Examples include heptafluoropropyl group. Among these, a more preferred fluorinated hydrocarbon group is a trifluoromethyl group. Further, examples of the aromatic carbocyclic group include a phenyl group, a naphthyl group, an anthryl group, etc., and a phenyl group is preferable. Further, examples of the aromatic heterocyclic group include a carbazolyl group and a dibenzofuryl group. Furthermore, substituents other than the fluorinated hydrocarbon group in the aromatic carbocyclic group and the aromatic heterocyclic group include, for example, substituted and unsubstituted alkyl groups having 1 to 4 carbon atoms, such as a methyl group. , ethyl group, isopropyl group, t-butyl group, trifluoromethyl group, etc.; substituted and unsubstituted aralkyl groups, such as benzyl group,
Phenethyl group ring; halogen atom, such as chlorine atom, bromine atom, fluorine atom, iodine atom; substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, such as methoxy group,
Ethoxy group, isopropoxy group, t-butoxy group, 2-
Chlorethoxy group, etc.; Hydroxy group; Substituted or unsubstituted aryloxy group, such as p-chlorophenoxy group, 1-naphthoxy group ring; Acyloxy group, such as acetyloxy group, p-cyanobenzoyloxy group ring; Carboxyl group, etc. Ester groups, such as ethoxycarbonyl group, m-bromophenoxycarbonyl group; Carbamoyl group, such as aminocarbonyl group, t-butylaminocarbonyl group, anilinocarbonyl group ring; Acyl group, such as acetyl group, O-nitrobenzoyl group ring: Sulfo group, sulfamoyl group, such as aminosulfonyl group, t-butylaminosulfonyl group, p-1-lylaminosulfonyl group, etc.; amino group, acylamino group, such as acetylamino group, benzoylamino ring; sulfonamide group, such as methane Examples include sulfonamide group, p-)luenesulfonamide group, and the like; cyano group, dinitro group, and the like. Among these substituents, preferred are substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, trifluoromethyl rings; halogen atoms, such as Chlorine atom, bromine atom, fluorine atom, iodine atom; substituted or unsubstituted alkoxy groups having 1 to 4 carbon atoms, such as methoxy group, ethoxy group,
These include t-butoxy group, dichlorotoxy group, etc.; nitro group; cyano group, etc.

In the above design (n), Z is an atomic group necessary to form a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic heterocycle, and specifically, for example, a substituted/unsubstituted aromatic heterocycle. Substituted benzene ring, substituted/unsubstituted naphthalene ring, substituted/unsubstituted naphthalene ring,
Represents an atomic group necessary to form an unsubstituted indole ring, a substituted/unsubstituted carbazole ring, etc.

As substituents for the atomic group necessary to form these rings, a series of substituents such as those listed as substituents for Ar are listed, but halogen atoms (chlorine atoms, bromine atoms, fluorine atoms) are preferred. atom, iodine atom), a sulfo group, and a sulfamoyl group (for example, an aminosulfonyl group, a p-tolylaminosulfonyl group, etc.).

The bisazo compound represented by the above-mentioned design [I] of the present invention is preferably the following design [III), (IV) and (V).
, (Vl).

(Leaving space below) Design (III) General formula [Seki general formula (V) General formula (VII Toru-Q)NH-Ar' In the formula, X"% X"% X" and x" are hydrogen atoms , represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a nitro group, a cyano group, a hydroxy group, or a substituted or unsubstituted amino group, and At least one of them is a halogen atom. X" and Xlb, and X" and X2b may be the same or different groups.

Ar' has the same meaning as Ar in Design (1) above.

Y has the same meaning as the substituent Zl17) in -Design (1) above.

Specific examples of the bisazo compound shown in the above-mentioned design [I] of the present invention will be described below, but the bisazo compound of the present invention is not limited thereto.

(Hereinafter, blank space) The bisazo compound represented by the above-mentioned design [I] can be easily synthesized by a known method.

Synthesis Example 1 (Synthesis of Exemplified Compound No. 71) 2.7-Diami2-4-bromo-9-fluorenone 2-
89 g (0.01 mol) of hydrochloric acid IQmN, water 20
Sodium nitrite is dispersed in 1 m of sodium nitrite while keeping it below 5℃.
．． A solution of 40 g (0.02 mol) dissolved in 5 ml of water was added dropwise. After continuing stirring at the same temperature for an additional hour, insoluble materials were removed by filtration, and a solution of 4.6 g of ammonium hexafluorophosphate dissolved in 50 ml of water was added to the filtrate.

The precipitated tetrazonium salt was collected by filtration and treated with N,N-dimethylformamide (DMF) at 100 mj! dissolved in.

While keeping the temperature below 5℃, add 6.62 g of 2-hydroxy-3-naphthoic acid-3'-trifluoromethylanilide (
A solution of 0.02 mol) dissolved in 200 rrl of DMF was added dropwise.

While continuing to maintain the temperature below 5°C, add 6 g (0.04 mol) of triethanolamine to 30 mj of DMF! After 4 reactions, the precipitated crystals were collected by filtration, washed with DMF, washed with water, and dried to obtain 8.71 g of the desired product. Theoretical value C = 60.5%, H = 2.77%, N = 8.63% Actual value C = 60.1%, H = 2.95%, N = 8.72% Synthesis example 2 (exemplary compound Synthesis of 11kL219) 2.89g (0
,01 mol) in 10 ml of hydrochloric acid and 2 Qmj of water! distributed in
Sodium nitrite 1.40g (0
, 02 mol) in 5 ml of water was added dropwise. After continuing stirring at the same temperature for another hour, insoluble matter was removed by filtration, and 4.6 g of ammonium hexafluorophosphate was added to the filtrate with 5Q of water.
A solution dissolved in mffi was added.

The precipitated tetrazonium salt was collected by filtration and dissolved in 100 ml of N,N-dimethylformamide (DMF).

2-hydroxy-3-(3'-
trifluoromethylphenylcarbamoyl)benzo(a
) carbazole 8.40g <0.02) mol in DMF
A solution dissolved in 200 mjl was added dropwise.

Subsequently, 6 g (0.04 mol) of triethanolamine dissolved in 30 ml of DMF was added dropwise while keeping the temperature below 5°C, and after stirring for 1 hour at below 5°C and 4 hours at room temperature, crystals precipitated. was collected by filtration, washed with DMF, washed with water, and dried to obtain 5.2 g of the desired product.

Theoretical value C = 63J%, H = 2.87%, N = 9.73% Actual value C = 63.4%, H = 2.97%, N = 10.01
% For other compounds of the present invention, diazonium salts were prepared using the corresponding amino compounds in the same manner as in Synthesis Example 1, and
Then 2-hydroxy-3-naphthoic acid-substituted anilide or 2-hydroxy-3-(substituted phenylcarbamoyl)benzo(a)-i! It can be produced by reacting with substituted or unsubstituted carbazole.

Next, a perylene compound represented by -Design (III) will be described.

In the general formula (nl), D represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a ring group, or a heterocyclic group, including both substituted and unsubstituted groups, When a substituent is present, preferred examples of the substituent include a hydroxy group, an alkoxy group, an amino group, a nitro group, and a halogen atom.

The "W-substituted alkyl group" includes an araltole group.

Preferred specific examples are listed below, but of course the invention is not limited to these.

■-1: Perylene-3.4,9.10-tetracarboxylic acid anhydride, ■-2: Perylene-3.4,9.10-tetracarboxylic acid diimide, m-3: N,N'-dimethyl-perylene- 3,4゜9.
10-tetracarboxylic acid diimide, m-4: N, N'-
Di-n-butyl-perylene-3゜4.9. lO-tetracarboxylic acid diimide, II[-5:N,N'-di-β-
Hydroxyethyl-perylene-3,4,9,10-tetracarboxylic acid diimide, lll-6:N,N-diphenyl-perylene-3,4°9.10-tetracarboxylic acid diimide, 111-7:N
, N'-di(4-methoxyphenyl)perylene-3,
4,9,10-tetracarboxylic acid diimide, lll-8:N,N'-di(3-methoxyphenyl)
Perylene-3,4,9,10-tetracarboxylic acid diimide, m-9:N,N'-di(2-methoxyphenyl)-perylene-3,4.9.10-tetracarboxylic acid diimide, 111-10: N,N'-di(4-ethoxyphenyl)-perylene-3,4,9,10-tetracarboxylic acid diimide, lll-11:N,N'-di(3,5-dimethylphenyl)-perylene-3 , 4,9,10-tetracarboxylic acid diimide, l-12:N,N'-di(4-chlorophenyl)-perylene-3,4,9,10-tetracarboxylic acid diimide, 111-13:N,N '-G(3-chlorophenyl)
perylene-3,4,9,10-tetracarboxylic acid diimide, m-14:N,N-di-3-pyrenyl-perylene-3,
4,9,10-tetracarboxylic acid diimide, lll-15:N,N-di(2-pyridyl)-perylene-3,4,9,10-tetracarboxylic acid diimide, lll-16:N,N'- dibenzyl-perylene-3,
4゜9.10-tetracarboxylic acid diimide, 11-17
:N,N'-di(4-nitrophenyl)-perylene-3.4.9.10-tetracarboxylic acid diimide, I[[-18:N,N'-di(4-dimethylaminophenyl)-perylene- 3,4,9,10-tetracarboxylic acid diimide, I[[-19:N-N'-di(4-benzeneazophenyl)-perylene-3,4,9,10-tetracarboxylic acid diimide, Such perylene compounds can be synthesized by known methods, but can also be obtained as commercial products.

Various configurations of electrophotographic photoreceptors are known, but
The electrophotographic photoreceptor can take any of these forms.

Usually, the configuration is as shown in FIGS. 2 to 7. Figures 2 and 3
In the figure, a carrier generation layer 2 containing the above-mentioned perylene compound and a compound represented by -Design 7Ps〆[I] and a carrier transport substance as necessary is formed on a conductive support 1, and a carrier transport substance to be described later is formed on the conductive support 1. Photosensitive layers 4A and 4B are provided as a laminate with a carrier transport layer 3 contained as a main component, and the stacking order of the carrier generation layer 2 and the carrier transport layer 3 is different between FIGS. 2 and 3. As shown in FIGS. 4 and 5, these photosensitive layers 4A and 4B are coated on a conductive support.
A photoreceptor having the best electrophotographic properties can be obtained when the photosensitive layer has a two-layer structure, which may be provided through an intermediate layer 5 such as an adhesive layer or a barrier layer. Further, as shown in FIGS. 6 and 7, a photosensitive layer 4D formed by dispersing the perylene compound and the compound represented by design [I] in a layer 6 containing a carrier transport substance is attached to a conductive support. 1
A protective layer may be provided thereon directly or via the intermediate layer 5, or may be provided as the outermost layer.

In the configuration of the present invention, "a layer containing a compound represented by design [I] and a compound represented by general formula (III) as a carrier generating substance" is a carrier-generating substance in FIGS. 2 to 7. This corresponds to the generation layer 2 and the photosensitive layer 40.

The carrier generation layer 2 and the photosensitive layer 40 can be formed directly on the conductive support 1 or the carrier transport layer 3, or by providing an intermediate layer 5 such as an adhesive layer or a barrier layer as necessary, for example, by the following method. can be formed.

M-1) Apply a solution in which the above perylene compound and the azo compound represented by design [I] are dissolved together or separately in an appropriate solvent, or a solution in which a binder resin is added and mixed as necessary. Method.

M-2) The above perylene compound and the azo compound represented by design [I] are mixed together or separately into fine particles (preferably particle size 5) in a dispersion medium using a ball mill, homomixer, etc.
μm or less, more preferably 1 μm or less), and if necessary, a binder resin is added and mixed and dispersed, and a dispersion is applied.

Examples of the solvent or dispersion medium used for forming the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methylethylketone, cyclohexanone, Benzene, toluene, xylene, chloroform, l,2-dichloroethane, 1.2-dichloropropane, 1.1.2-trichloroethane, 1.1.1-)dichloroethane, trichloroethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol , ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve, and the like.

Further, the carrier transport layer can be formed in the same manner as the carrier generation layer described above.

Any binder resin can be used to form the carrier generation layer or the carrier transport layer, but it is preferable to use a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating. Preferred examples of such high molecular weight polymers include, but are not limited to, the following.

P-1) Polycarbonate P-2) Polyester P-3) Methacrylic acid P-4) Acrylic resin P-5) Polyvinyl chloride P-6) Polyvinylidene chloride P-7) Polystyrene P-8) Polyvinyl acetate P-9 ) Styrene-butadiene copolymer P-10) Vinylidene chloride-acrylonitrile copolymer P-11> Vinyl chloride-vinyl acetate copolymer P-12)
Vinyl chloride-vinyl acetate-maleic anhydride copolymer P-13) Silicone resin P-14) Silicone-alkyd resin P-15) Phenol formaldehyde resin P-16>
Styrene-alkyd resin P-17) Poly-N-vinylcarbazole P-18) Polyvinyl butyral P-19) Polyvinyl formal These binder resins can be used alone or as a mixture of two or more.

In the carrier generation layer, the weight ratio of the carrier generation substance to the binder is preferably 100:0 to 1000.
If the content of the carrier generating substance is less than this, the photosensitivity will be low and the residual potential will increase, and if it is more than this, the dark decay and acceptance potential will decrease.

The thickness of the carrier generation layer to be formed is preferably o, o
i~10 μm.

Further, in the carrier transport layer formed as described above, the amount of the carrier transport substance is preferably 20 to 200 parts by weight, particularly preferably 30 to 150 parts by weight, per 100 parts by weight of the binder resin in the carrier transport layer.

Moreover, the thickness of the carrier transport layer formed is preferably 5 to 50 μm, particularly preferably 5 to 30 μm.

The carrier transport substance is not particularly limited, but includes, for example, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole m8, triazole derivatives, imidazole derivatives, imidasilone derivatives, imidazolidine derivatives, bisimidapridine derivatives, styryl compounds, hydrazine compounds, pyrazoline derivatives, amine derivatives, oxacilone derivatives, benzothiazole derivatives, benzimidazole m4, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, Examples include one or more selected from poly-9-vinylanthracene and the like.

As the carrier transporting substance, it is preferable to use a substance that not only has an excellent ability to transport carriers generated during light irradiation to the support side but also is suitable for combination with the perylene compound and the azo compound represented by -Design [I]. The preferred carrier transport materials are the following - Designs (A) and (B).
and (C).

General formula (A) However, Ar', Ar2% Ar' each represents a substituted or unsubstituted aryl group, Ar3 represents a substituted or unsubstituted arylene group, and R''' is a hydrogen atom, substituted or unsubstituted Represents a substituted alkyl group or a substituted or unsubstituted aryl group.

Specific examples of such compounds are described in detail on pages 3 to 4 of JP-A-58-65440 and pages 3-6 of JP-A-58-198043.

General formula (B) However, R7 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and R11 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. JP-A-58-134642 and JP-A No. 58-166354.
It is stated in the publication of the issue.

-Design (C) However, R9 is a substituted/unsubstituted aryl group, and RIo
is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amino group, or a hydroxy group, and R'' is a substituted or unsubstituted aryl group, a substituted or unsubstituted Synthesis methods and examples of these compounds representing a substituted heterocyclic group are described in detail in Japanese Patent Publication No. 148750/1982, which can be incorporated into the present invention.

Other preferred carrier transport materials of the present invention include:
Examples include hydrazone compounds described in JP-A-57-67940, JP-A-59-15252, and JP-A-57-101844, respectively.

The conductive support used for the photoreceptor may be a metal plate containing an alloy, a metal drum, or a conductive polymer, coated with a thin layer of metal such as aluminum, palladium, or gold containing a conductive compound or alloy such as indium oxide. Examples include paper, plastic film, etc., made conductive by vapor deposition or lamination.

As an intermediate layer such as an adhesive layer or a barrier layer, in addition to the polymer used as the binder resin, an organic polymer material such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminum oxide is used.

Organic amines can be added to the photosensitive layer of the present invention, and it is particularly preferable to add a secondary amine.

Examples of such secondary amines include dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, and di-isobutylamine.4. Di-n amylamine, di-isoamylamine, di-
n-hexylamine, di-isohexylamine, di-n-pentylamine, di-isopentylamine, di-n-octylamine, di-isooctylamine, di-n-nonylamine, di-isononylamine, di-n-decylamine, G
Examples include isodecylamine, di-n-monodecylamine, di-isomonodecylamine, di-n-dodecylamine, and di-isododecylamine.

The amount of organic amines to be added is preferably 1 times or less, preferably 0.2 to 0.005 times the amount of the carrier generating substance.

An antioxidant can be added to the photosensitive layer for the purpose of preventing ozone deterioration.

Typical examples of such antioxidants are shown below, but are not limited thereto.

Group (I): Hindered phenols dibutylhydroxytoluene, 2,2'-methylenebis(6-t-butyl-4-methylphenol) 4.4'
~Butylidenebis(6-t-butyl-3-methylphenol), 4,4'-thiobis(6-butyl-3-methylphenol), 2,2-butylidenebis(6-t-
butyl-4-methylphenol), α-tocopherol, β-tocopherol, 2,2.4-1-dimethyl-6
-Hydroxy-7-t-7'yl chroman, pentaerythyltetrakis (3-(3,5-di-t-butyl-4
hydroxyphenyl)propionate), 2,2'-thiodiethylenebis(3-(3,5-di-t-butyl-4
-hydroxyphenyl)propionate), 1.6-
Hexanediol bis(3-(3゜5-di-tert-butyl-4-hydroxyphenyl)propionate), butylhydroxyanisole, dibutylhydroxyanisole, 1-[2((3,5-di-tert-butyl-4-hydroxy) phenyl)propionyloxy)ethyl]-4
-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)-2,2°6.
6-titramethylpiperidyl, etc.

Group (n): paraphenylenediamines N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-5ec-butyl-p7 phenylenediamine, N-phenyl-N-5ec-butyl-
p-phenylenediamine, N,N-diisopropyl-p
-phenylenediamine, N, N'-dimethyl-N, N
-di-t-butyl-p-phenylenediamine, etc.

(Group I [[): Hydroquinones 2.5-di-t-octylhydroquinone,
Cydodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chloronohehydroquinone, 2-
t-octyl-5-methylhydroquinone, 2-(2.
-octadecenyl)-5-methylhydroquinone, etc.

(TV) group: organic sulfur compounds dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate, etc.

Group (V): Organic phosphorus compounds such as triphenylphosphine, tri(nonylphenyl)phosphine, tri(dinonylphenyl)phosphine, tricresylphosphine, tri(2,4-dibutylphenoxy)phosphine, and the like.

These compounds are known as antioxidants for rubber, plastics, oils and fats, and are easily available commercially.

These antioxidants may be added to the carrier transport layer.

In that case, the amount of antioxidant added is 10 parts of the carrier transport substance.
0.1-100 parts by weight, preferably 1 part by weight
~50 parts by weight, particularly preferably 1 to 25 parts by weight.

The carrier generation layer may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential or fatigue during repeated use, etc.

Examples of electron-accepting substances that can be used here include succinic anhydride, maleic anhydride, dibromaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride,
Tetrabromo phthalic anhydride, 3-nitro phthalic anhydride,
4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1.3.5-trinitrobenzene, varanitrobenzonitrile, Vicryl chloride, quinone chlorimide,
Chloranil, brumanil, dichlorodicyanobarabenzoquinone, anthraquinone, dinitroanthraquinone, 2
, 7-sinitrofluorenone, 2.4.7-1-linitrofluorenone, 2゜4.5.7-titranitrofluorenone, 9-fluorenylidene [dicyanomethylene malonodinitrile], polynitro-9-fluorenylidene [dicyanomethylenemalonodinitrile], picric acid,
0-nitrobenzoic acid, p-nitrobenzoic acid, 3.5-dinitrobenzoic acid, pentafluorobenzoic 6.5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid,
Examples include mellitic acid and other compounds with high electron affinity.

The amount of the electron-accepting substance added is determined by the weight ratio of carrier-generating substance:electron-accepting substance=10Q: (0,01 to 20
0), preferably 100: (0,1-100)
It is.

The electron-accepting substance may be added to the carrier transport layer. The amount of electron-accepting substance added to this layer is carrier transporting substance:electron-accepting substance=100:(0,01~
100), preferably 100: (0,1-50
).

In addition, the photoreceptor of the present invention may also contain, if necessary, an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, and may also contain a dye for color sensitivity correction.

E. Examples The present invention will be described in detail below, but the embodiments of the present invention are not limited thereby.

Example-1 5 g of polycarbonate resin (Panlite L -1250° manufactured by Kijin Kasei) was heated with 1,2-dichloroethane at 200 mA.
After dissolving in the mixture, 10 g of Exemplary Perylene Compound (III-7) was mixed as a carrier generating substance CGM2 and dispersed with a sand grinder for 10 hours. This is called liquid A.

Next, after dissolving 1 g of the above polycarbonate resin in 120 mA' of 1,2-dichloroethane, the carrier generating substance C
Mix 171.2 g of exemplified azo compound N as GMI,
Dispersion was performed using a sand grinder for 10 hours. This is called liquid B.

200 ml of the above liquid A and 20 mA of liquid B were stirred and mixed to obtain a coating liquid for forming a carrier generation layer. This was coated with a wire bar on a polyester base coated with A1 vapor deposition, and after drying, the film had a carrier of 0.3 μm in diameter. A generation layer was formed.

Next, using a carrier transport layer forming coating liquid having the following composition,
A carrier transport layer having a thickness of 20 μm after drying was coated on the carrier generation layer using a blade to obtain a photoreceptor.

1.2-dichloroethane Polycarbonate resin (same as above) 00mJ 5 g H,C 2g This obtained photoreceptor was designated as sample number 1.

Next, sample holes 2 to 8 were prepared in the same manner as sample hole 1 except that the carrier-generating substance used or the content ratio thereof was changed as shown in Table 1.

A characteristic evaluation test of the photoreceptor sample NtLt~8 thus obtained was conducted as follows.

[Sensitivity test]

Electrostatic charging test device EPA-8100 (Kawaguchi Electric ■
7. Exposure amount E required to reduce the surface potential of the photoconductor by half from the initial potential using (j!ux-sec) was measured.

[Repeated characteristic test]

Using the electrostatic charging test device EP A-8100,
1st time and 1st time when charging-exposure-removal is repeated 100 times
00th charge potential change ΔV0 → 100 (v)
was measured.

[Red color reproducibility test]

Using an improved electrophotographic copying machine r U-Bix 1550J (manufactured by Konica ■) and equipped with a surface potential needle,
When copying a control patch as a document, setting the black paper potential to -600V and the white paper potential to -too V, the surface potential of the photoreceptor corresponding to the red patch V□, (■ ) was measured. The lower the value of V r *4, the worse the reproducibility of the red image.

The obtained results are summarized in Table-1.

Incidentally, the spectral sensitivity spectrum of the comparative sample 6%7 is shown in FIG.

(Left below) *Comparative Azo Compounds From the results in Table 1, the photoreceptors of the examples showed superior performance in all aspects of sensitivity, reproduction reproducibility of red images, and repeatability compared to the comparative photoreceptors. It is clear that

Example-2 The combination of carrier-generating substances used was changed as shown in Table-2, and the polycarbonate resin used in the coating solution for forming the carrier transport layer was replaced with Kneepilon Z-200 (manufactured by Mitsubishi Gas Chemical ■). Samples 9 to 12 were prepared in the same manner as in Example-1, and the same characteristic evaluation tests as in Example-1 were conducted on these samples, and the obtained results are shown in Table-1.
Shown in 2.

(The following is a blank space) From the results in Table 2, it can be seen that the photoreceptors of Examples exhibit excellent performance in all respects of sensitivity, copying reproducibility of red images, and repeatability.

Example-3 The combination of carrier-generating substances used was changed as shown in Table-3, and the polycarbonate resin used in the coating liquid for forming the carrier-transporting layer was replaced with Niepiron Z-200 (mentioned above). Example except for replacing .
Samples 13 to 15 were prepared in the same manner as in Example 1, and the same characteristic evaluation tests as in Example 1 were conducted on these samples, and the obtained results are shown in Table 3.

(The following is a blank space) From the results in Table 3, it can be seen that the photoreceptors of Examples exhibit excellent performance in all aspects of sensitivity, red image copying reproducibility, and repeatability.

Example-4 The same procedure as Example-1 was carried out except that the combination of carrier-generating substances used was changed as shown in Table-4, and the polycarbonate resin used in the coating liquid for forming the carrier transport layer was replaced with UBICH3. Sample m16-1
8 was prepared, and the same characteristic evaluation test as in Example 1 was conducted on these samples, and the obtained results are shown in Table 4.

(The following is a blank space) From the results in Table 4, it can be seen that the photoreceptors of Examples exhibit excellent performance in all respects of sensitivity to white light, sensitivity to semiconductor laser light, and repeatability.

Example 5 A polyethylene terephthalate sheet-like conductive substrate on which aluminum is vapor-deposited is coated with vinyl chloride-vinyl acetate-maleic anhydride copolymer (S-LEC MF-10: manufactured by Sekisui Chemical Co., Ltd.) with a thickness of about 0.1 μm. An intermediate layer was formed.

Next, a coating solution for forming a carrier transport layer having the following composition was applied onto the intermediate layer and dried to form a carrier transport layer having a thickness of 15 μm.

1.2-Dichloroethane 100ml Polycarbonate resin (Panlite L1300 manufactured by Teijin Chemicals) 15g H,C 2g Next, polycarbonate resin (Panlite L1250,
(manufactured by Kijin Kasei ■) 5g to 200m of 1,2-dichloroethane
! ! After dissolving in the mixture, 10 g of Exemplary Perylene Compound (III-7) was mixed as a carrier generating substance CGM2 and dispersed with a sand grinder for 10 hours. This is called liquid A.

Next, after dissolving 1 g of the above polycarbonate resin in 120 ml of 1.2 dichloromethane, the carrier generating substance CGM
As I, 2 g of the exemplified azo compound Na (71) was mixed and dispersed with a sand grinder for 10 hours. This is called liquid B.

The above A liquid is 200 mj! 4 g of the following carrier transport substance was added to a dispersion obtained by stirring and mixing 20 mj2 of liquid B,
Furthermore, 2Qml of monochlorobenzene was added to prepare a coating solution for forming a carrier generation layer. This coating solution was spray coated onto the carrier transport layer to form a carrier generation layer having a thickness of 5 μm.

The photoreceptor thus obtained is referred to as sample light 19.

Next, in sample light 19, the carrier-generating substance used or its content was changed as shown in Table 5, and in other respects, samples 20 to 23 were prepared in the same manner as sample 19, and each of these samples was prepared. The characteristics were evaluated in the same manner as in Example 1, and the obtained results are shown in Table 5.

(The following is a blank space) From the results in Table 5, it can be seen that the photoreceptors of Examples exhibit excellent performance in all aspects of sensitivity, red image copying reproducibility, and repeatability.

[Brief explanation of the drawing]

FIG. 1 is a graph showing quantum efficiency spectra for each carrier generating substance. FIG. 2, FIG. 3, FIG. 4, FIG. 5, FIG. 6, and FIG. 7 are sectional views showing examples of the structure of the photoreceptor, respectively. In addition, in the symbols shown in the drawings, l・------・=---m-conductive support 2-1--
−・−−−−1−Carrier generation layer 3−・−・−−−−
---Carrier transport layer 4A, 4B, 4D ---
---Photosensitive layer 5-----Intermediate layer 6----------This is a layer containing a charge transporting substance. Agent Patent Attorney Hiroto Aisaka Number/nm Figure 3 Figure 5 Figure 7

Claims (1)

[Claims] 1. A photoreceptor having a layer containing a compound represented by the following general formula [I] and a compound represented by the following general formula [III] as carrier-generating substances. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. group, hydroxy group, or substituted or unsubstituted amino group, X^1 and X^2
At least one of them is a halogen atom. p and q each represent an integer of 0, 1 or 2, p and q cannot be 0 at the same time, and when p is 2, X^1 may be the same or different groups, When q is 2, X^2 may be the same or different groups. A represents a group represented by the following general formula [II]. General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aromatic carbocyclic group or an aromatic heterocyclic group having at least a fluorinated hydrocarbon group. Represents a group of nonmetallic atoms necessary to form an aromatic carbocycle or a substituted or unsubstituted aromatic heterocycle.) m and n each represent an integer of 0, 1, or 2. However, m and n never become 0 at the same time. [General formula [III]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In [General formula [III], Q represents -O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. D is hydrogen, or a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group,
Represents an aryl group or a heterocyclic group. ]