JPS59104655A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain always a good copied image with high sensitivity without any accumulation of potential even during repeated uses by incorporating a specified bisazo compd. in a carrier generating layer and a specified hydrazone compd. in a carrier transfer layer. CONSTITUTION:A carrier generating layer incorporates a compd. represented by formula I or II in which Ar1, Ar2, Ar3 are optionally substd. aromatic carbon rings; R1, R2 are electron acceptor groups, such as CN; A is one or groups represented by formulae III-V, or the like; X is OH, optionally substd. amino, or -NHSO2-R6; R6 is optionally substd. alkyl or aryl; Y is H, halogen, optionally substd. alkyl, or the like; Z is an atomic group constituting an optionally substd. aromatic carbon or hetero ring; R3 is H, optionally substd. amino, or the like; A' is optionally substd. aryl; n is 1 or 2; and m is 0-4. A carrier transfer layer incorporates a compd. represented by formula VI in which R7, R8 are each H or halogen; R9, R10 are each optionally substd. arylene; and Ar4 is optionally substd. arylene. Thus, a long-lived photosensitive body is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor in which a photosensitive layer comprising a combination of a carrier generation phase and a carrier transport layer is provided on a conductive support.

Until now, carrier generators that absorb OL light and generate charge carriers (hereinafter simply referred to as "carriers") have been developed.
] (hereinafter referred to as jcGMJ) (hereinafter referred to as jCGLJ), and a carrier transport material (hereinafter referred to as [CTMJ) that transports one or both of positive and negative carrier collapses generated in this CGL. .

) (hereinafter referred to as 1c'I'LJ)
That's what it means. ) to form a photosensitive layer of an electrophotographic photoreceptor. In this way, by assigning the two basic functions necessary for the photosensitive layer, ie, generation of carriers and transport thereof, to separate layers, the range of materials that can be used in the composition of the photosensitive layer can be selected from a wide range. In addition, it becomes easy to independently select materials or material systems that optimally perform each function, and by doing so, it becomes possible to independently select materials or material systems that optimally perform each function, and by doing so, it becomes possible to improve the appearance of various objects dispersed in the Kameko photographic process, such as the surface appearance when charged. It becomes possible to construct an electrophotographic photoreceptor having excellent properties such as a high electric potential, high charge retention ability, high photosensitivity, and high stability during repeated use.

Conventionally, the following examples of such photosensitive layers are known.

(1) C consisting of amorphous selenium or cadmium sulfide
C consisting of GL and bol) -N-vinylcarbazole
A structure in which TL and TL are laminated.

(2) Apodic selenium or sulfide (CUL)
and C'1'L containing 2,4.7-)dinitro-9-fluorenone are laminated.

(3) A structure in which CGL composed of a perylene derivative and C'l'L' containing an oxadiazole derivative are laminated (see the specification of U.S. Pat. No. 1, No. 3,871,882).
.

(4) CT containing CGL composed of chlordiayan blue or methylskarylium and pyrazoline derivative
A structure in which L is laminated (see % JP-A-51-90827).

(5) CGL composed of amorphous selenium or its alloy and C containing a polyarylalkane aromatic amino compound
Structure in which TL and TL are laminated (% Gansho 52-147251
Honorary title).

(6) CGL containing a perylene derivative and CTL containing a polyarylalkane aromatic amino compound
(Japanese Patent Application No. 19907-1983).

As described above, many photosensitive layers of this type are known, but in conventional electrophotographic photoreceptors having such photosensitive layers, the electricity of the photosensitive layer when repeatedly subjected to electrophotographic processing is low. It has the disadvantage of severe mechanical fatigue and a very short service life.

For example, when subjected to an electrophotographic process repeatedly,
Jlj! of the electric potential of the electrophotographic photoreceptor! It is not possible to maintain stable image forming characteristics because the image is not maintained in a stable state.

Further, the use of specific bisazo compounds as CGM is disclosed in, for example, JP-A-55-117151 and JP-A-54.
Although it is disclosed in Publication No.-145142, etc.
Even in combination with CTM, which is said to be able to be combined with M, the above-mentioned drawbacks are still considerable.

As can be understood from this, a carrier transporting substance that is effective against a specific carrier-generating substance is not always effective against other carrier-generating substances, and An effective carrier-generating substance is
Nor can it be said that it is effective against other carrier transport substances.

If the combination of both substances is inappropriate, the electrophotographic sensitivity will not only decrease, but also the discharge efficiency at low electric fields will be degraded, resulting in a large amount of residual material. Each time it is used repeatedly, a potential accumulates, making it practically unusable for electrophotographic purposes.

In this way, there is no lawful selection method for suitable combinations of the constituent substances of the carrier generation phase and the constituent substances of the carrier transport phase, and it is practical to select a suitable combination from among the many substances 9IA, M'+. Need to decide.

The present invention comprises a photosensitive layer consisting of a combination of a carrier generation phase and a carrier transport phase, and has high sensitivity, and also maintains a stable potential history state even when repeatedly subjected to an electrophotographic process. An object of the present invention is to provide an electrophotographic photoreceptor that can consistently form good visible images.

The above object is to provide an electrophotographic photoreceptor in which a photosensitive layer comprising a combination of a carrier generation phase and a carrier transport phase is provided on a conductive support, wherein the carrier generation phase has the following general formula [
1] or a bisazo compound represented by the general formula [1'], and the carrier transport phase contains a hydrazone compound represented by the following general formula [1].

It is composed of

General formula [port t1 A-IN=N-Ar1-C1+=C-Ar2-CH=C
H'-Ar3-N-N-AA-4N=IN Ar1
-(JR=U-Ar2-U=L:H-Ar5-N=N
A [wherein, Ar1, Ar2 and Ar3: each substituted or unsubstituted carbocyclic aromatic ring group, R1 or lt2: each electron-withdrawing group, A:X BeY: hydrogen atom, halogen atom, substituted or unsubstituted Substituted alkyl group, flukoxy group, carboxyl group, sulfo group, substituted or unsubstituted carbamoyl group, or substituted or unsubstituted sulfamoyl group (However, when m is 2 or more, mutually different groups ) Z: Atom group necessary to constitute a substituted or unsubstituted carbocyclic aromatic ring or a substituted or unsubstituted heterocyclic aromatic ring, R6: Hydrogen atom, substituted or unsubstituted 7-mino group, substituted or unsubstituted carbamoyl group, carboxyl group or ester group thereof, A': substituted or unsubstituted aryl group, n: integer of 1 or 2, m20-4. represents an integer. ] Formula [...] [In the formula, ■Moa and 几82 each have a hydrogen atom or no rogen atom, i (9 and 10' each have a substituted or unsubstituted aryl group, Ar 4 : a substituted or unsubstituted arylene group Among the bisazo compounds represented by the general formula [1)-i or [1'], the following general formula (Ia) is preferred.
Or it is represented by the general formula Ll'a, :].

-General formula Ia) N A-N=N-Ar1-CH=C-Ar2-CH=CH-
Ar5-N=N-A General formula 1'a] In the formula, Ar1, Ar2, Ar3 and A are the same as defined in General formula [1] or General formula 1']. ] Those that are historically unfavorable are especially the following general formula Llb) or [
1'b).

General formula 1m1b) N Summer A N=N Ar3-CH=CAr6-CH=CH-A
r7-N*N-A [wherein, Ar5, Ar6 and Ar7: ffi, which is the same as defined in general formula [1] or general formula [l'], represents an unsubstituted phenyl group; As the substituent group, those selected from alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, nitrogen atoms such as chlorine atom and bromine atom, water 11M and cyan group are preferable. . That is, in the present invention, the bisazo compound represented by the general formula [1] or the general formula 1'] is used as the CUM, and the hydrazone compound represented by the general formula [...] is used as the CTM, and these are combined. Especially,
This constitutes a photosensitive layer of a so-called functionally separated type photoreceptor in which carrier generation and carrier transport are performed using separate materials. As a result, it is possible to provide an electrophotographic photoreceptor that has high sensitivity, maintains a stable potential history state even when subjected to repeated electrophotographic processes, and can therefore always form good visible images. can.

In addition, in our electrophotographic photoreceptor, the wavelength 60
A large spectral sensitivity can be obtained even in the long wavelength range of 0 to 7QQ11In. Therefore, for example, a helium-neon laser with a wavelength of 6328A can be used as a light source for forming a latent image, and in addition to the so-called potential cutoff that occurs when the electric field is low. Since the potential of the non-image area becomes zero or close to zero when a good boundary image is formed, good development can be achieved even with a one-component developer consisting only of toner, which cannot obtain a large expiry bias.

Specific examples of the hisazo compound represented by general formula [1] in Mtl include those having the following structural formula, but are not limited thereto.

Exemplary Compounds Specific examples of the bisazo compound represented by the above general formula [1'] include those having the following structural formula, but are not limited thereto.

Exemplary compound engineering
Engineering + +1 +) + B
.

Examples of the hydrazone compound represented by the general formula (1) in II include, for example, those having the following structural formula, but are not limited thereto.

Compound II-1) ■-2) Item-3) (II-=1) (n-5) (n-6) (II-7) (n-8) (n-9) (II-10 ) (11-H) (■-12) (1-13) (n-14) Next, the mechanical structure of the electrophotographic photoreceptor of the present invention will be explained.

In one example of the present invention, as shown in FIG. C containing a hydrazone compound as the main component
'1' L 3 are stacked and formed, and these C(Jl,
2 and C'1' L3 constitute the photosensitive layer 4.

Here, as the material of the conductive support f4-1, for example, aluminum, nickel, copper, zinc, Zladium, silver,
Metallic metals such as indium, tin, platinum, gold, stainless steel, and brass can be used. However, the invention is not limited to these, and for example, as shown in FIG.
It is also possible to configure the 2-substrate I.
A may be made of a flexible material such as paper or paper, and has sufficient strength to withstand stress such as bending or tension. Gold @ 7
-Siminate the metal plate or vacuum vaporize the metal plate N-FL-(,
It can be provided by attaching or by other methods.

The above C (jL2 is the above-mentioned bisazo compound alone,
Or by adding a suitable binder resin to this,
Alternatively, it can be formed by adding a substance having high mobility for carriers of specific or non-specific polarity, that is, CTM.

As a specific method, a method can be easily used in which the above-mentioned bisazo compound is dissolved or dispersed in an appropriate solvent or dissolved or dispersed together with an appropriate binder resin and then applied onto the support and dried. .

In this method, examples of the solvent or dispersion medium include +1-butylamine, diethylamine, ethylenediamine, inpropaturamine, monoethanolamine,
Triethanolamine, triethylenediamine, N, N
-dimethylform 7mide, acetone, methyl ether ketone, cyclohexanone, benzene, toluene, xylene, chloroform, l,2-dichloroethane, dichloromethane, ketone hydrofuran, dioxane, methanol,
Ethanol, improper tool, ethyl acetate, butyl acetate 1 dimethyl sulfoxide, and others can be used.

In addition, as the binder resin, for example, polyenalene,
Polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate 4] f'' knife, silicone tHh, melamine shaft J-cut 1, etc. Addition polymerization type tree; "a,
One-phrase addition type Kirizushi, K-type Kijji fat, Banhini Co-monomeric resin containing two or more of the repeating units of these resins, for example, vinyl chloride-acetic acid 1:' = A Co-i Union [1
In addition to insulating paulownia 11iq such as fat, vinyl chloride-vinyl vinegar rice-maleic anhydride copolymer side fat, it is possible to use semiconductors such as polyvinylcarbazole.

The ratio of the binder resin to the bisazo compound is in the range of 0 to 100 iN, particularly 0 to ioN.

mJ Ha C(jL 2 K t;k,g viscera f(L
Applicable iOC'll'M1 [5 may be added.

The thickness of the CGI 2 formed as described above is preferably 0.005 to 20 microns, particularly preferably 0.05 to 5 microns. If it is less than 0.0005 microns, sufficient photosensitivity cannot be obtained, and if it exceeds 20 microns, sufficient %LM retention cannot be obtained.

Further, MjJ CTL3 can be formed using the hydrazone compound described above in the same manner as C()L2 described in p1, that is, alone or together with a binder resin.

The thickness of the CT L 3 may be 2 to 100 microns, preferably 5 to 30 microns.

The electrophotographic photoreceptor of the present invention may have other mechanical configurations. For example, as shown in FIG. 3, the conductive support 1
A suitable intermediate N1 layer 5 may be provided thereon, the CGI 2 may be formed through this, and the C'l'L, 3 may be formed on this CGI, 2. This intermediate layer 5 has a function to prevent free carriers from being injected into the photosensitive layer 4 from the conductive support 1 during charging of the photosensitive layer 4, or to prevent the photosensitive layer 4 from being injected into the photosensitive layer 4. It is possible to provide a wall layer as an adhesive layer that is integrally attached to the wall. The turbidity of intermediate Jso 5 including Ru1 is aluminum oxide, aluminum oxide,
Gold jiI4 oxide such as indium oxide, acrylic side fat,
Methacrylic #J resin, vinyl chloride 1U6, vinyl resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, Melagan 11 fat, vinyl chloride-vinyl acetate conjugate resin, vinyl chloride-
A monomolecular compound such as a vinyl acetate-maleic anhydride co-based resin can be used.

Further, as shown in FIG.
, 3 may be formed, and CUI and 2 layers may be formed on this C'l' L 3 to form a photosensitive layer 4fL.

In history, it has also been possible to form a single-layer photosensitive layer by dispersing the bisphun compound as described above into a phase containing a hydrazone compound or a carrier placed on a table to form a carrier-generating layer. If necessary, secret additives can be added to the formation of the ltS layer.

Hereinafter, embodiments of the present invention will be described, but the invention is not limited thereto.

Example 1 A conductive support made of 100 micron polyethylene terephthalate coated with aluminum was coated with a thin film of a copolymer of hinyl chloride-vinyl acetate-maleic anhydride (Eslec MP-104 <manufactured by Block Chemical Industry Co., Ltd.). An intermediate layer with a thickness of about 0.05 microns was provided, and the exemplified compound (1-9
1.5f of the bisazo compound shown in ) was dispersed with 100-1,2-dichloroethane in a ball mill for 8 hours,
The resulting dispersion was applied onto the intermediate layer using a doctor blade and sufficiently dried to form a CGL with a thickness of about 0.5 microns.

On the other hand, hydrazone compound 11.25f shown in exemplified compound (1-10) and 42 recarbonate resin "No?/Light L-1250J (manufactured by Kijin Kasei Co., Ltd.)
-Dichloroethane 100-, the dissolved solution was spread on the CGL using a doctor blade, and sufficiently dried to form a cTL with a thickness of 12 microns, thereby forming an uninvented electrophotographic image. Step 7 is to make the photoreceptor. This will be referred to as "Sample 1".

Examples 2 to 8 Seven types of uninvented electrophotographic photoreceptors were manufactured in the same manner as in Example 1, except that in the formation of Cub and CTL, the combinations shown in Table 1 below were used as exemplary compounds. . These will be referred to as "Sample 2" to "Sample 8", respectively.

1st Printing Example 9 An intermediate layer was prepared on a conductive support in the same manner as in Example 1, and 1.5 g of the bisazo compound shown as Exemplary Compound (I-9) and polycarbinate resin "Puffly" L were added. -1
250J O15g and 1,2-dichloroethaneloo
In addition to mt, perform polydispersion in a Zeel mill for 12 hours,
The resulting dispersion was applied onto the intermediate layer using a doctor blade and thoroughly dried to form a CGL having a thickness of about 1 micron.

On this CGL, CTL was added in the same manner as in Example 1.
was formed, thereby producing an electrophotographic photoreceptor of the present invention. This will be referred to as "Sample 9."

Example 10 In the formation of CGL, Exemplified Compound (1'-43) was used as the bisazo compound, and in the formation of CTL, Exemplified Compound (11-4) was used as the hydrazone compound.
) An electrophotographic photoreceptor of the present invention was produced in exactly the same manner as in Example 9 except that the material shown in Example 9 was used. This is rKI40
Let it be J.

Comparative Example 1 A comparative electrophotographic photoreceptor was produced in the same manner as in Example 3, except that a pyrazoline derivative having the following structural formula was used in place of the hydrazone compound in the formation of CTL in Example 3. This will be referred to as "comparative sample 1."

Comparison Example 2 A comparative electrophotographic photoreceptor was produced in the same manner as in Example 3, except that in the formation of CTI in Example 3, a mexadiazole derivative having the following structural formula was used in place of the hydrazone compound. . This will be referred to as "comparative sample 2."

The electrophotographic photoreceptors obtained as described above, Samples 1 to 10, as well as Comparative Sample 1 and Comparative Sample 2, were examined using an electrometer SP-428mJ (manufactured by Kawaguchi Electric Seisakusho). The photographic characteristics were investigated. Namely, the acceptance potential VA (V) when the narrow surface of the photoreceptor was exposed to 7PH voltage -6KV for 5 seconds, and the potential Vl (V) after being left in the dark for 5 seconds... Exposure amount E 1/2 (Lux・sec) required to sensitize to (initial potential) t-1//2, dark sensitivity decay rate (VA-νr)/VA X 100 (%),! :
I got M.

The results are shown in Table 2.

Table 2 From the results in Table 2, it is clear that the electrophotographic photoreceptor of the present invention has a large sensitivity. Dry type electronic copying machine [LJ-Hix 2000RJ (
The black paper potential vb (v) and the white paper potential Vw (V) at an exposure aperture value of 1.0 were measured using an "electrostatic voltmeter 144D-ID type" by attaching it to a camera (manufactured by Konishiroku Photo Industry Co., Ltd.) and performing continuous shooting. (manufactured by Monshi Electronics Inc.) and was measured immediately before development. The results are shown in Table 3.

The black paper potential referred to here refers to the surface potential of the photoreceptor when a black paper with a reflection density of 1.3 is used as an original and the above-mentioned one cycle of copying is carried out, and the white paper potential refers to the surface potential when a blank paper is used as an original. represents the surface potential of the photoreceptor.

Table 3 (However, in the table, Δvb (shin) and ΔVw (V) indicate the amount of variation in the hot paper level νb (v) and blank paper potential VW (V), respectively, and + in variation i indicates an increase, and - indicates a decrease. represent.

As is clear from the conclusion of the third section in C, the electrophotographic photoreceptor of the present invention maintains the potential history state stably even when subjected to repeated electrophotographic processes, and can produce visible images of good image quality. can be stably formed in large numbers.

[Brief explanation of the drawing]

FIG. 1 is an explanatory cross-sectional view showing an example of the structure of the photoreceptor of the present invention, FIG. 2 is an explanatory cross-sectional view showing another example of the structure of the photographic photoreceptor of the present invention; FIG. 4 is an explanatory sectional view showing another example of the structure of the electrophotographic photoreceptor of the present invention. 1... Conductive support 2... Carrier generation layer (C()L) 3... Carrier transport layer (CTI) 4... Photosensitive layer 5... Intermediate layer IA...
Insulating base IB... conductor ii L/I drawing's side
l' (No change in content) Figure 1 #2 Figures 3 to 4 Procedural amendments, Kae. April 26, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi 1. Indication of the case 1988 Patent Application No. 214036 2. Title of the invention Electrophotographic photoreceptor 3. Person making the amendment Relationship to the case Patent applicant (I - :1 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo
No. Box v” Sheep 1 (Masterpiece) (127) Roku Konishi Photography Shiba Co., Ltd. 4, Agent 5 Date of amendment order March 29, 1981 6 Number of inventions increased by amendment 2) Purification of drawings 11 ( No change in content) Procedural amendment (voluntary) March 8, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1, Indication of the case: Patent Application No. 214036, filed in 1982, 2, Title of the invention: Electrophotographic photoreceptor 3, Relationship with the case of the person making the amendment Patent applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 5, Invention of the specification subject to amendment Detailed Description Column 6, Contents of Amendment 1) The structural formula in Comparative Example 1 on page 83 of the specification is corrected as follows. [

Claims (1)

[Scope of Claims] 1) An electrophotographic photoreceptor comprising a photosensitive layer formed of a combination of a carrier generation phase and carrier transport holes provided on a conductive support, wherein the carrier generation phase has the following general formula [1] or An electrophotographic photoreceptor comprising a bisazo compound represented by the general formula (l'), and wherein the carrier transport hole contains a hydrazone compound represented by the following general formula (n).General formula [1) % Formula % General formula u'] In the C formula, Ar1, Ar2 and Ar3: each substituted or unsubstituted carbocyclic aromatic ring group, 1t1i or H2: each electron-withdrawing group, A Ni-Ni-1802-几6, Y: hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, carboxyl group to alkoxy group, sulfo group, substituted or unsubstituted carbamoyl group, or substituted or unsubstituted sulfamoyl group, (provided that m is 2 In the above cases, mutually different groups may be used.) Z: An atomic group that is the key to forming a substituted or unsubstituted carbocyclic aromatic ring or a substituted or unsubstituted heterocyclic aromatic ring. , A: a hydrogen atom, a substituted or unsubstituted amine group, a substituted or unsubstituted carbamoyl group, a carboxyl group or an ester group thereof, A: an unsubstituted aryl group, n: an integer of 1 or 2, m: Represents an integer from 0 to 4. '' General formula (n) [wherein R7 and R8: each a hydrogen atom or ).rogen atom, 几9 and R10' each represent a substituted or unsubstituted aryl group, Ar4: a substituted or unsubstituted arylene group. ]