JPH01315753A - Photosensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity and reproducibility of a red copy image by incorporating a specified compound as a carrier generating material. CONSTITUTION:The excellent sensitivity and reproducibility of a red copy image can be obtained by incorporating in one of the layers of the photosensitive body as the carrier generating material the compound represented by formula I and the compound represented by formula III, and in formulae I and III, each of X<1> and X<2> is halogen, optionally substituted alkyl or alkoxy, nitro, cyano, hydroxy, or optionally substituted amino; each of p and q is 0, 1, or 2; A is a group of formula II; Ar is an aromatic hydrocarbon group or such a heterocyclic group having a fluorinated hydrocarbon group; Z is a nonmetallic atomic group necessary to form an optionally substituted aromatic hydrocarbon group or heterocyclic group; each of m and n is 0, 1, or 2; Q is a coupler residue; and each of r and s is 0, 1, or 2.

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 materials (OPC) are generally less toxic than inorganic photoconductive materials, and are advantageous in terms of flexibility, lightness, film formability, cost, etc. For this reason, 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 function-separated type photoreceptor can improve the electrophotographic photoreceptor and is excellent in sensitivity, repeatability, mechanical strength, and the like.

Such electrophotographic photoreceptors are generally widely used in electrophotographic copying machines, printers, etc., but recently, with the speeding up of electrophotographic copying machines and printers, the time required for the copying process has been significantly shortened. As the number of photoreceptors increases, there is a demand for higher sensitivity and higher durability of photoreceptors.

Typical examples of high frequency 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 r+n+, 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 azo pigments, such as disazo pigments, have a spectral sensitivity that extends to around 700 nm, 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, especially the reproducibility of red stamps and underlines (red lines) in various documents. required. For this purpose, in order to copy and reproduce red images, it is necessary to use a material that has no sensitivity in the wavelength range of 60Qna+ or higher, or has spectral sensitivity characteristics in which the sensitivity in these wavelength ranges is lower than the sensitivity in other wavelength ranges. must not. However, each carrier-generating substance has its own spectral sensitivity characteristics, and satisfies the electrophotographic characteristics.
Moreover, it is difficult to find a carrier-generating substance that can reproduce red originals to a degree suitable for the purpose of copying.

In order to improve the reproducibility of red color, there is a method of providing a red cut filter (cyan filter) in the optical path of white light, but for example, when using the above-mentioned disazo pigment, 6
When light with wavelengths longer than 00 nm is used, 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. is expected to appear.

C6 Purpose of the Invention The purpose of the present invention is to have a highly sensitive spectral sensitivity characteristic over a wide range of wavelengths, a high frequency range, excellent repeatability, be able to cope with high-speed copying processes, and a red An object of the present invention is to provide a photoreceptor with excellent image reproduction reproducibility.

20 Structure of the invention and its effects The present invention comprises a compound represented by the following general formula [I] and the following -
The present invention relates to a photoreceptor having a layer containing a compound represented by the formula (I[l) as a carrier generating substance.

General formula [1] [XI and Xz 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 , Xl and X2 is a halogen atom.

p and q each represent Oll or an integer of 2, p and q cannot be 0 at the same time, and when p is 2, Xl 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 maximum (II).

- Maximum (U) (wherein Ar represents an aromatic carbocyclic group or an aromatic heterocyclic group having at least a fluorinated hydrocarbon group.

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 never become 0 at the same time. ] General formula If) ○ [Q represents a coupler residue.

r and S each represent an integer of 0, 1 or 2.

However, r and S do not become O at the same time. ] The present invention provides a method for combining a specific azo compound represented by maximum (1) and a specific azo compound represented by the general formula (I [[) (hereinafter sometimes referred to as an anthraquinone compound) into a carrier. It has a remarkable feature in that it has a layer containing the generated substance.

That is, the compound represented by -maximum (III) has, for example, a spectral sensitivity spectrum as shown in FIG.
~570 nm.

The compound represented by -maximum (I [ It had its limitations and was not necessarily compatible with high-speed copying machines and the like.

As a countermeasure to this problem, it may be possible to sensitize the medium wavelength and short 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, -m There is also a possibility that the inherent photosensitivity of the compound represented by formula (I[I) 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, if the photosensitivity at long wavelengths of 600 ns+ or more becomes too large, the reproducibility of red color will not be sufficient.

Here, the present inventor has discovered that satisfactory results can be obtained by using a specific azo compound represented by -maximum (III) in combination with a compound represented by general formula CI).

That is, the compound represented by the -i formula (1) exhibits a spectral sensitivity spectrum as shown in FIG. 1, but (
Exemplary azo compound N171) described below, and -maximum (I
By using the compound represented by II) in combination, the first
As shown in the figure, while significantly sensitizing the long wavelength side of 570 nm or more, the original photosensitivity of the compound expressed as -maximum (I [I) can be maintained, and the photosensitivity of red light can be improved to reproduce red images. It has now become possible to suppress it to an acceptable level.

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.

The specific configuration will be described below.

- The content ratio in the layer of the anthraquinone compound represented by the formula CI [] and the compound represented by the general formula CI) is the weight ratio (the above anthraquinone compound to the compound represented by the formula [1]), It is preferably within the range of (100:O) to (100:10Q), and (100:1) to (100
It is more preferably within the range of: 20). In this range, red color reproducibility is even better and photosensitivity can also be increased.

Q is the maximum value of spectral sensitivity at wavelength λ≦600 nm or less. ,
Let X (λ≦600 nm) be the maximum value of spectral sensitivity at wavelengths λ≧600 nm or more. ax (λ≧600nm
), the ratio of both is Q, , (λ≦600n
m)/Q,,X(λ≧60OnI11) = 1
00150 or less is more preferable in terms of red color reproducibility.

Next, the compound represented by formula CI) will be described.

Examples of the halogen atom represented by Xl and Xi in general 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 XI and X2 has a halogen atom.

The alkyl groups represented by XI and X2 are preferably substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms, and examples of such alkyl groups include methyl group, ethyl group, β-cyanoethyl group, etc. , 1so-propyl group, trifluoromethyl group, t-butyl group, and the like.

The alkoxy groups represented by XI and XI 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, 5e
Examples include c-butoxy group.

Furthermore, the substituted or unsubstituted amino group represented by Xl and Ethylamino group, 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.

In formula CI), p and q are 0, respectively.
1 or 2, but p and q are never 0 at the same time, preferably p=1, q=0 or p=1, q=1.

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

In addition, in the above formula (1), A is the following formula (n
).

General formula (n) In the formula, Ar represents an aromatic carbocyclic group or an aromatic heterocyclic group having at least one fluorinated hydrocarbon group, and fluorine having 1 to 4 carbon atoms in the fluorinated hydrocarbon group Hydrocarbon groups are preferred, such as trifluoromethyl, pentafluoroethyl, tetrafluoroethyl,
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 ring; 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, etc.; Carboxyl group , its ester groups such as ethoxycarbonyl group, m-bromophenoxycarbonyl group; carbamoyl group such as aminocarbonyl group, t-butylaminocarbonyl group, anilinocarbonyl ring; acyl group such as acetyl group, 0-nitrobenzoyl group Ring; Sulfo group, sulfamoyl group, e.g. aminosulfonyl group, t-butylaminosulfonyl group, p-tolylaminosulfonyl group Ring; Amino group, acylamino group, e.g. acetylamino group, benzoylamino group Ring; Sulfonamide group, e.g. methane Examples include sulfonamide group, p-toluenesulfonamide group, etc.; cyano group; nitro group, etc. 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,
t-butoxy group, 2-chloroethoxy group ring; nitro group;
Such as cyano group.

In formula (II) above, 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. Represents the atomic group necessary to form a substituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted indole ring, a substituted or 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 formula (I) of the present invention is preferably the following formula (Il/), (V), [■]
, is represented by [■].

(Leaving space below) General 2〇η - (2) I-Ar' General formula ry) 7 General formula [■ General formula [In the formula, X ``s Atom, substituted or unsubstituted alkyl group, substituted or unsubstituted flukoxy group, nitro group,
Represents a cyano group, a hydroxy group, or a substituted or unsubstituted amino group;
Among them, a small number (both one is a halogen atom.X11
and XIk, and X! a and Xo may be the same or different groups.

A and I have the same meaning as A in formula (1) above.

Y has the same meaning as the substituent of Z in formula [1] above.

Specific examples of the bisazo compound of the present invention represented by the general formula [I] will be described below, but the bisazo compound of the present invention is not limited thereto.

(Blank below) -NH-Ar Similar to bottom blank) The bisazo compound represented by formula (I) above can be easily synthesized by a known method.

Synthesis Example 1 (Synthesis of Exemplified Compound Magnetodynamic 71) 2.89 g of 2.7-diamitu-4-bromo-9-fluorenone (0,
01 mol) was dispersed in IQml of hydrochloric acid and 20ml of water,
Sodium nitrite 1.40g (0
, 02 mol) dissolved in 5 ml of water was added dropwise. After stirring for another hour at the same temperature, insoluble matter was removed by filtration, and 4.6 g of ammonium hexafluorophosphate was added to the filtrate in 5 Qm of water.
I! A solution dissolved in was added.

The precipitated tetrazonium salt was collected by filtration and dissolved in 100 ml of N,N-dimethylformamide (DMF). 5℃
2-Hydroxy-3-naphthoic acid-
3'-trifluoromethylanilide 6.62g (0,
02mol) to DMF200rrl? The solution was added dropwise.

Subsequently, a solution of 6 g (0.04 mol) of triethanolamine dissolved in 39 ml of DMF was added dropwise while keeping the temperature below 5°C, and the mixture was stirred at below 5°C for 1 hour and at room temperature for 4 hours. After the reaction, the precipitate was collected by filtration, washed with DMF, washed with water, and dried to obtain 8.71 g of the target product. Theoretical values C = 60.5%, H = 2.77%, N = 8.63% Actual measurement Values C=60.1%, H=2.95%, N-8,72% Synthesis Example 2 (Synthesis of Exemplified Compound NIL219) 2.89 g of 2.7-diamitu-4-bromo-9-fluorenone (0,
01 mol) in 10 ml of hydrochloric acid and 20 ml of water, and heated to 5°C.
Sodium nitrite 1.40g (0,0
A solution of 2 mol) dissolved in 5 mff1 of water was added dropwise. After stirring for another hour at the same temperature, insoluble matter was removed by filtration, and 4.6 g of ammonium hexafluorophosphate was added to the filtrate in 50 mL of water.
A solution dissolved in 1 was added.

The precipitated tetrazonium salt was collected by filtration and dissolved in 100 ml of N,N-dimethylformamide (DMF). 5℃
8.40 g (0,02) moles of 2-hydroxy-3-(3'-)lifluoromethylphenylcarbamoyl)benzo(a)carbazole in DMF2
QOrtj! A solution dissolved in was added dropwise.

6 g (0.04 mol) of triethanolamine was added to D M F 30 m j! while keeping the temperature below 5°C.
Add the solution dissolved in
Stir for hours. After the reaction, the precipitated crystals were collected by filtration, washed with DMF, washed with water, and dried to obtain 5.2 g of the desired product.

Theoretical value C = 63.6%, H = 2.87%, N = 9.73% Actual value C = 63.4%, H = 2.91%, N = IQ, 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
It can then be produced by reacting with 2-hydroxy-3-naphthoic acid-substituted anilide or 2-hydroxy-3-(substituted phenylcarbamoyl)benzo(a)-substituted or unsubstituted carbazole.

Next, an anthraquinone compound represented by the formula (I[[) will be described.

-i Among the compounds represented by the formula (I[[), the following are exemplified as preferred. Of course, it is not limited to these.

General formula (III-A) General formula (III-B) General formula (III-C) General formula (I[ID) In addition, as the coupler residue Q, the following are exemplified as preferable ones. , but not limited to these.

Here, U is 1 or 2, t is 0.1 or 2, E is an amino group or hydroxy group, G is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carunic acid group, a sulfonic acid group, substituted or unsubstituted. and substituted or unsubstituted sulfonamide groups; Cyclic aromatic rings and substituted products thereof,
R6 is a hydrogen atom, substituted or unsubstituted amino group, alkyl group, carbamoyl, or carboxylic acid group or its ester group -1 is a substituted or unsubstituted aryl group, R
7 and 3 each represent a substituted or unsubstituted alkyl group, ralkyl group or aryl group.

R9 is preferably a hydrogen atom, a mele group, an alkyl group having 1 to 4 carbon atoms such as an ethyl group, or an aryl group which may have a substituent. Also, Ar
2 is preferably a substituted or unsubstituted carbocyclic aromatic ring, and specific examples include a benzene ring and a naphthalene ring. Substituents bonded to these rings include nitro group, cyano group, carboxylic acid group, sulfonic acid group, chlorine atom,
A halogen atom such as a bromine atom, an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a dimethylamino group is selected. R6 is a hydrogen atom, a methyl group, an alkyl group having 1 to 4 carbon atoms such as an ethyl group, an amino group, a dialkylamino group such as a dimethylamino group, or a substituted group such as an aryamino group such as a phenylamino group. Preferred are amino groups, carbamoyl groups, carboxylic acid groups, and methyl ester and ethyl ester groups thereof. Ar' represents a substituted or unsubstituted aryl group, and examples of the substituent include a nitro group, a cyano group, a carboxylic acid group, a sulfonic acid group, a halogen atom, an alkyl group such as a methyl group or an ethyl group, and a methoxy group. , an alkoxy group such as an ethoxy group, or a dimethylamino group. R? , R1+
each represents a substituted or unsubstituted alkyl group, aralkyl group, or aryl group, and specifically, unsubstituted alkyl groups such as a methyl group, an ethyl group, a linear or branched propyl group, and a butyl group. group, hydroxyalkyl group, alkoxyalkyl group, acyloxyalkyl group,
Alkyl groups having substituents such as alkylaminoalkyl groups, aralkyl groups such as benzyl groups and phenethyl groups,
5- to 7-membered cycloalkyl groups such as cyclopentyl group and cyclohexyl group, 5- to 7-membered cycloalkenyl groups such as cyclohexenyl group, unsubstituted aryl groups such as phenyl group, chlorphenyl group, methoxyphenyl group , a tolyl group having a substituent such as a tolyl group.

Next, specific examples of the compound represented by the general formula (III) will be shown, but the invention is not limited thereto.

(Margins below) Represented by the general formula (I[[-A): I[[-A-2
6CF:l It Hl (bottom margin) Magnetic Q I-A-Father I[-A-8 L nl-A-Ki1hQ 111-A-ω III -A -61 1-A-Father 111-A-田Ntl QII[-
A-Seki 111-A-Ta I [[-A-Ta HC C31+.

■-869 111-A-70 -A-n Represented by general formula (I[I-B): 1[1-B-1 -B-2 111-I3-3 111-B-4 111-B-5 rs-n-4 1l-B-7 11[-I3-8 -B-9 111-B-10 I[[-B-11 However, - formula (II[-A] All couplers can be used.

Space below) Represented by the general formula CDI-C): 11[-C-4 Box-C-5 111-C-6 m-C-I I[1-C-8 111-C-9 -C -10 -C-14 111-C-15 11[-C-16 un -C-11 Jn However, all the couplers exemplified in formula [II[-A] can be employed.

(lower margin) represented by the general formula [II[-D]: I[[-D-1 1[1-D-2 I[r-D-3 111-D-4 Ill-D-5 1111D -6 111-D-7 1[[-D-8 111-D-9 111-D-10 I[[-D-11 -D-12 111-D-13 1[[-D-14 111-D -15 11I-D-16 I[-D(7 I[[-D-18 111-D-19 I[r-D-K III -D -21 II[-D-22 I[[-D-Edict I[[-D-24 I[ID-A111-D-3 I[[-D-27 ■〜D-田I[-D-4I[-D-KADI -D -31 1[ 1-D-32 111-D-O1-D-Su I [1-D-A5o3I (SO:lH D-O [[-D -40 II[-D-41 m-D-Ko III-D-8 -D-44 However, all the couplers exemplified in formula (m-A) can be employed.

The above anthraquinone compounds can be synthesized by known methods.

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 anthraquinone compound and a compound represented by formula CI) and a carrier transporting substance as necessary is formed on a conductive support 1, and a carrier transporting substance which will be described later is the main component. The photosensitive layers 4A and 4B are provided as a laminate with a carrier transporting layer 3 containing a carrier as shown in FIG. As shown in FIGS. 4 and 5, these photosensitive layers 4A and 4B are coated on a conductive support.
It may be provided via an intermediate layer 5 such as an adhesive layer or a barrier layer. When the photosensitive layer has a two-layer structure as described above, a photoreceptor having the most excellent electrophotographic properties can be obtained. Further, as shown in FIGS. 6 and 7, a photosensitive layer 4D formed by dispersing the anthraquinone compound and the compound represented by the general formula [I] in a layer 6 containing a carrier transport substance is conductively supported. It may be provided directly on the body 1 or via an intermediate layer 5. Further, a protective layer may be provided as the outermost surface layer.

In the structure of the present invention, "a layer containing a compound represented by general formula [I] and a compound represented by general formula (III) as carrier-generating substances" is shown in FIGS. 2 to 7 as follows: This corresponds to the carrier generation layer 2 and the photosensitive layer 4D.

The carrier generation layer 2 and the photosensitive layer 4D can be formed directly on the conductive support 1 or the carrier transport layer 3, or if necessary, with an intermediate layer 5 such as an adhesive layer or a barrier layer provided thereon, for example, in the following manner. can be formed by

M-1) The above anthraquinone compound and - Formula C1)
A method of applying a solution in which the azo compounds represented by the following are dissolved together or separately in a suitable solvent, or a solution in which a binder resin is added and mixed as necessary.

M-2) The above anthraquinone compound and general formula [I]
The azo compounds represented by are made into fine particles (preferably particle size 5 μm or less, more preferably 1 μm or less) in a dispersion medium by a ball mill, homomixer, etc., together or separately,
A method in which a binder resin is added as necessary and a mixed and dispersed dispersion is applied.

Solvents or dispersion media used to form the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methylethylketone, cyclohexanone, and benzene. , toluene, xylene, chloroform, 1.2-dichloroethane, 1,2-dichloropropane, 1.1.2-)lichloroethane, 1.1.1-trichloroethane, trichloroethylene, tetrachloroethane, dichloromethane, tetrahydrofuran, dioxane,
Examples include 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. preferable. 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 0.0
It is 1 to 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 derivatives, triazole derivatives, imidazole derivatives, imidasilone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, and hydrazone compounds. , pyrazoline FANE derivative, amine derivative, oxacilone derivative, benzothiazole derivative, benzimidazole derivative, quinazoline derivative,
Examples include one or more selected from benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, and the like.

As the carrier transport substance, in addition to having an excellent ability to transport carriers generated during light irradiation to the support side, there are materials suitable for combination with the anthraquinone compound and the 'ti azo compound represented by formula (I). is preferably used, and a preferable charge transport material is represented by the following formula (A
), (B) and (C).

- Formula (A) However, Ar' and Ar'SAr' each represent a substituted or unsubstituted aryl group, A and 3 represent a substituted or unsubstituted arylene group, and R6 represents a hydrogen atom, a substituted or unsubstituted Represents an alkyl group or a substituted or unsubstituted aryl group.

Specific examples of such compounds are given in pages 3 to 4 of JP-A No. 58-65440 and pages 3 to 6 of JP-A No. 5B-198043.
It is described in detail on the page.

However, R7 is a substituted or unsubstituted oryl group or a substituted or unsubstituted heterocyclic group, and R11 is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted oryl group. For details, see JP-A-58-134642 and JP-A-58-1663.
It is described in Publication No. 54.

- Formula (C) However, R9 is a substituted/unsubstituted aryl group, and R10
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 RI' is a substituted or unsubstituted aryl group, a substituted or unsubstituted Synthesis methods and illustrations of these compounds representing substituted heterocyclic groups are disclosed in Japanese Patent Publication No. 57-148750.
It is described in detail in the Japanese Patent Application Publication No. 2003-100000, and can be incorporated into the present invention.

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

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.

Such secondary amines include, for example, dimethylamine, diethylamine, di-n propylamine, di-isopropylamine, di-n butylamine, di-isobutylamine, 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, di- -isodecylamine, di-n-monodecylamine, di-isomonodecylamine, di-n-dodecylamine, di-isododecylamine, and the like.

The amount of organic amines to be added is preferably 1 times or less, preferably 0.62 times 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 the invention is not limited thereto.

Group (1): 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-3-methylphenol),
-butyl-4-methylphenol), α-tocopherol, β-tocopherol, 2,2.4-)tumethyl-6
-Hydroxy-7-t-7'yl chroman, pentaerythyltetrakis (3-(3,5-di-t-butyl-4
-Hydroxyphenyl)propionate 1.2.2'-
Thiodiethylenebis(3-(3,5-di-butyl-4-hydroxyphenyl)propione)), 1.6-
Hexanethiorbi(3-(3゜5-di-tert-butyl-4-hydroxyphenyl)propionate), Butylhydroxyanisole, Dibutylhydroxyanisole, L-(2-((3,5-di-tert-butyl-4) −
Hydroxyphenyl)propionyloxy)ethyl]-
4-(3-(3,5-di-tar t-butyl-4-hydroxyphenyl)propionyloxy)-2,2゜6
．． 6-titramethylpiperidyl, etc.

(I [) group: paraphenylenediamines N-phenyl-
N'-isopropyl-p-7 22-diamine, N,N
'-5ec-butyl-p-phenylenediamine, N
-Phenyl-N-5ec -Butyl-p-phenylenediamine, N,N'-diisopropyl-p-phenylenediamine, N,N'-dimethyl-N,N'-di-t
-butyl-p-phenylenediamine, etc.

(II [) group; Hydroquinones 2.5-di-t-octylhydroquinone, 2゜6-sidedecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-
Octyl-5-methylhydroquinone, 2-(2-octadecenyl)-5-methylhydroquinone, etc.

Group (IV): 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 to 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, 0-dinitrobenzene, m-dinitrobenzene, 1.3.5-) dinitrobenzene, varanitrobenzonitrile , picryl chloride, quinone chlorimide,
Chloranil, pullmanil, dichlorodicyanobarabenzoquinone, anthraquinone, dinitroanthraquinone, 2
．． 7-cynitrofluorenone, 2,4.7-)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 acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds with high electron affinity. can be mentioned.

The amount of electron-accepting substance added is based on the weight ratio of carrier generation f
: Electron-accepting substance=100 : (0,01-200
), preferably 100:(0,1-100).

The electron-accepting substance may be added to the carrier transport layer, and the amount of the electron-accepting substance added to the layer is carrier transport 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 5g of polycarbonate resin (Panlite L-1250゜manufactured by Kijin Kasei) in 200mm of 1,2-dichloroethane
1, an exemplified anthraquinone compound (I[[-A-14) LOg
were mixed and dispersed using 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-dichloroethane, the carrier generating substance CG
As ML, 71.2 g of an exemplary azo compound dynamic magnet was mixed and dispersed with a sand grinder for 10 hours.

This is called liquid B.

The above A liquid 200ml and B liquid 20mj! A coating solution for forming a carrier generation layer was obtained by stirring and mixing, and this was coated on a polyester base coated with Al vapor deposition using a wire bar, and after drying, a carrier generation layer of 13 μm in thickness was formed.

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

1,2-dichloroethane 100 ml Polycarbonate resin (same as above) 15 g 2 g The obtained photoreceptor is designated as sample N1L1.

Next, in Sample No. 1, Samples Il&L2 to L8 were prepared in the same manner as Sample N11l, except that the carrier generating substances used or their content ratios were changed as shown in Table 1.

Characteristic evaluation tests of photoreceptor samples 1 to 8 thus obtained were conducted as follows.

[Sensitivity test]

Using an electrostatic charging tester EPA-8100 (manufactured by Kawaguchi Denki ■), the exposure amount El/□ (lux-sec) required to reduce the photoreceptor surface potential by half from the initial potential was measured.

[Repetition characteristic test]

Using the above electrostatic charging test device EPA-8100, the amount of change in charging potential between the 1st and 100th times when charging-exposure → static-elimination is repeated 100 times ΔyO-y100 (
V) was measured.

[Red color reproducibility test]

Using an improved electrophotographic copying machine r'U-Btx 1550J (manufactured by Konica ■) equipped with a surface electrometer, a Kodak Power Control Punch was used as the document, and the potential of the black paper was -600V, and the potential of the white paper was set to -600V. The surface potential V, d (V) of the photoreceptor corresponding to the red batch was measured when copying was performed with the potential set to -100V.

The lower the value of V red, the worse the reproducibility of the red image.

The obtained results are summarized in Table-1.

Note that the spectral sensitivity spectrum of comparative sample N11ll is
It is shown in the figure.

*Comparative Azo Compounds From the results shown in Table 1, the photoreceptors of the examples showed superior performance in all aspects of sensitivity, copying reproducibility of red images, and repeatability compared to the comparative photoreceptors. it is obvious.

Example 2 The combination of carrier generating substances used was changed as shown in Table 2, and the polycarbonate resin used in the coating liquid for forming the carrier transport layer was replaced with Kneepilon Z-200 (Mitsubishi Gas Chemical side type). Samples 9 to 12 were prepared in the same manner as in Example-1, and characteristic evaluation tests were conducted on these samples in the same manner as in Example-1.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 aspects of sensitivity, red image copying reproducibility, 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 .
Sample fish 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 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 changed to UPIP0CI (.

Sample N1116 was prepared in the same manner as in Example-1 except that
-18 were prepared, and the same characteristic evaluation tests as in Example-1 were 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 On a polyethylene terephthalate sheet-like conductive substrate on which aluminum has been vapor-deposited, a layer of about 0 thickness made of vinyl chloride-vinyl acetate-maleic anhydride copolymer (Esle MF-10: manufactured by Block Chemical Industry Co., Ltd.) is placed. An intermediate layer of .1 μm 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 100mj! 15 g of polycarbonate resin (Panlite K-1300 manufactured by Teijin Chemicals) Next, polycarbonate resin (Panlite L-1250)
, manufactured by Kijin Kasei ■) 5g to 200g of 1,2-dichloroethane
mj! Exemplary anthraquinone compound (I[I-A-14) 10
g were mixed and dispersed using a sand grinder for 10 hours.

This is called liquid A.

Next, 1 g of the above polycarbonate resin was mixed with 120 mj of 1,2-dichloroethane! After dissolving in the carrier generated product [C
Exemplary azo compound NN11(71)2 was mixed as GMl and dispersed with a sand grinder for 10 hours. This is B
Make it into a liquid.

To a dispersion obtained by stirring and mixing 200 ml of the above liquid A and 20 mf of liquid B, 4 g of the following carrier transport material was added, and 20 mj2 of monochlorobenzene was further added to obtain a coating liquid for forming a carrier generation layer. This coating liquid was spray coated onto the carrier transport layer to form a carrier generation layer with a thickness of 5 m.

The photoreceptor obtained in this way is designated as sample column 19.

Next, Samples N120 to N23 were prepared in the same manner as Sample N119 except that the carrier generating substance used in Sample IVh19 or its content was changed as shown in Table 5. Characteristic evaluations similar to those in Example 1 were performed for each of these samples, 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.

Figures 2, 3, 4, 5, 6, and 7 are
FIG. 3 is a cross-sectional view showing a configuration example of each photoreceptor.

In addition, in the reference numerals shown in the drawings, 1-・-----・Electroconductive support 2...--・--Carrier generation layer 3--------・=・-・Carrier transport layer 4A, 4th,
4 D-------------Photosensitive layer 5-----One intermediate layer 6-------------A layer containing a charge transport substance.

Agent: Patent Attorney Hiroshi Aisaka Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 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] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [Q represents coupler residue. r and s each represent an integer of 0, 1 or 2. However, r and s never become 0 at the same time. ]