JPS5944052A - Electrophotographic receptor - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic receptor having high photosensitivity and capable of maintaining its potential at each cycle of repeated use stable, and forming always good visible images, by incorporating a specified bisazo compd. in a carrier generating phase and a styryl compd. in a carrier transferring phase. CONSTITUTION:An electrophotographic receptor is obtained by forming a photosensitive layer made of a combination of a carrier generating phase having formula I (Ar1, Ar2 are each optionally substd. phenylene; A is one of formulae III, IV, and V; R1 is optionally substd. alkyl or aryl; and R2 is optionally substd. aryl or heterocyclic), and a carrier transferring phase having formula II in which R3, R4 are each optionally substd. alkyl or aryl; R6 is optionally substd. aryl or heterocyclic; and R6-R9 are each H, halogen, alkyl, alkoxy, or alkylamino.

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 phase is provided on a 2J4 qualitative support.

Until now, the charge carriers (
A carrier generating layer (hereinafter referred to as rcGLJ) containing a carrier-generating substance (hereinafter referred to as rcGMJ) '4i that generates a carrier-generating substance (hereinafter referred to as rcGMJ);
A carrier transport substance (hereinafter referred to as
-It is called cTMJ. ) carrier transport J-
(hereinafter referred to as "CTL").
It has been proposed to constitute a photosensitive layer of an electrophotographic photoreceptor. In this way, by assigning the two basic functions necessary for photosensitive printing, namely carrier generation and carrier transport, to separate layers, the range of materials that can be used in the composition of the photosensitive layer is widened, and It has become possible to select a material or material system that optimally performs each function, and by doing so, it has become possible to select a material or a material system that optimally performs each function, and by doing so, it is possible to improve the properties of the various nodes required in the electrophotographic process, for example, when the surface ￥α position is It becomes possible to produce an electrophotographic photoreceptor which has excellent static characteristics such as high stability retention, high photosensitivity, and high stability in repeated use.

Conventionally, the following types of photosensitive layers are known.

(1) C consisting of amorphous hyaline or cadmium sulfide
GL, CTL composed of poly-N-vinylcarbazole
[7th configuration]

(2) A structure in which a CGL made of amorphous selenium or (nicked cadmium J) and a CTL having 2,4,7-1-linitro-9-fluorenone fFr are laminated.

(3) CGI consisting of a perylene derivative and oxadiazole fil! A structure in which CTL containing a conductor is laminated (see U.S. Special Agreement No. 3,871,882).

(4) CTL containing CGt consisting of chlordiayan blue or methylscalyllium and a pyrazoline derivative
A 41° four-layered structure (Japanese Patent Application Laid-open No. 51-90827
No. Publication Examination).

(5) A structure in which CGL made of amorphous selenium or its alloy and CTL containing a polyarylalkane-based aromatic amine compound are laminated (filed application 11f152
-147251 Specification Co.).

(6) CGL containing perylene derivative and 7Jζ
A structure in which a CTL containing a monoarylalkane-based aromatic amino compound is laminated (Patent application I1153-199)
No. 07 specification) O As described above, there are many known photosensitive layers of this type, but in conventional IL electrophotographic photoreceptors based on such photosensitive layers, 'Seiko' is repeatedly used. Electrical fatigue of the photosensitive layer when subjected to photographic processes d! It has intense flashing and has a very short service life.

For example, when subjected to repeated electrophotographic processes,
The history of the electrophotographic photoreceptor is not maintained stably on its own, making it impossible to obtain stable image forming properties.In addition, it is known that a specific bisazo compound is used as a CGM in J44, for example, in JP-A-55-1989. (6) In combination with C The drawbacks are quite large. (
11 for certain carrier-generating substances. Carrier-generating substances that are effective against other gear-generating substances are not always effective against other gear-generating substances, and carrier-generating substances that are effective against specific carrier-transporting substances are not always effective against other gear-generating substances. It cannot be said that it is effective. If the combination of both substances is inappropriate, not only will the electronic sensitivity become low, but especially low I
Due to the poor efficiency of waste electricity in the v field, the residual current at t41m becomes large, and in the worst case, the potential accumulates each time it is used repeatedly. The supply [7] will be lost.

In this way, there is no lawful selection method for suitable combinations of carrier generation phase (4) constituents and carrier transport phase constituents, but rather an advantageous combination is determined practically from among many substance groups. The present invention has a photosensitive layer consisting of a carrier generation phase, a carrier transport phase, and f:m, has high sensitivity, and has been repeatedly subjected to an electron four-phase process. It is an object of the present invention to provide an electrophotographic photoreceptor that can maintain a stable potential history state and always 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 Φfit phase is provided on a 4'* support, in which the carrier generation phase is represented by the following general formula σ]. This is achieved by an electrophotographic photoreceptor containing the bisazo compound shown below, and wherein the carrier transport phase contains a styryl compound shown by the following general formula 00.

General formula [Ar1 and Ar2 in the DC formula: each substituted, un-1d substituted phenylene group, n+: bit 4g4, un-1d-substituted alkyl group,
Arrival 29, 112: 1tffi conversion, not 11th' Hou (/') -f
Reel M, 0 representing a compound JM group] General formula 1) 0 [In the formula, R3 and R4: substituted and unsubstituted alkyl groups, respectively;
Aryl group, Rs: Ii & substituted, unsubstituted aryl group, double-bed ring group, R6-R9: each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an argylamino group. That is, in the present invention, a bisazo compound represented by t; 1 and the general formula σ] is used as CGM, and a styryl compound fcTM represented by the general formula 0 (1) is used in combination. occurrence and 4
This constitutes a photosensitive layer of a so-called functionally separated photoreceptor in which 111 and 111 are each made of separate materials.

And due to this, the sensitivity is large and moreover, the L
'i! 1. The potential history state is maintained stably even when subjected to the negative process, thus always forming a good visible 17II7 bed. It is possible to provide a JL photoreceptor.

Specific examples of the bisazo compound represented by the general formula (Ill) include those having the following structural formula (1), but are not limited to these (I-2 ) (I-3) (■-4) (I-5) (I-6) CI-7) (I-8) (I-9) (1-10) (1-12) (I-13) (I-15) (I-22) (I-23) (I-24) 345- (I-25) Specific examples of styryl compounds represented by the general formula symbol include those having the following structural formula: Examples include, but are not limited to.

Exemplary compound (n-1) (II-2) (1'[-3) (n-4) (I[-5) (II-6) (II-7) (I-8) (TI-9) (II-11) (i-12) (II-13) (I[-15) (II-16) (l[-17) (I[-18) (II-19) (II-20) (■ ~21) (II-22) (II-23) (M-24) (II-25) (IF-26) (II-27) (If-28) 2ub (II-29) li3 (II-30) (II-31) Next, the 4'A4JA structure of the electrophotographic photoreceptor of the present invention will be explained.

In the second embodiment of the present invention, as shown in FIG. A CTL 3 containing a compound as a main component is formed in a form, and a photosensitive layer 4 is constituted by these CCl 2 and CTL 3.

Here, as the conductive support 10I, for example, a sheet of metal such as aluminum, nickel, copper, zinc, radium, sea bream, indium, tin, platinum, gold, stainless steel, or brass may be used. I can do it. However, the invention is not limited thereto, and for example, as shown in FIG. Suitable materials include paper, plastic sheets, and other materials that are flexible and have sufficient strength against stress such as bending and tension. The conductor can also be provided by laminating metal sheets, vacuum depositing metal, or by other methods.

The above-mentioned CGL2 can be prepared by using the above-mentioned bisazotized compound alone, by adding an appropriate binder resin J resin, or by adding a substance having a high mobility to carriers of specific or non-specific polarity, that is, CTM. It can be formed by adding something.

Specific method and 1. Then, a method is conveniently used in which the aforementioned bisazo compound is dissolved or dispersed in a suitable m-agent alone or together with a suitable binder resin and then applied and dried. As the binder sebum, for example, polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin,
Addition polymerization type 4σ1 resins, polyaddition type resins, polycondensation type resins such as vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, and these resins. Copolymers containing two or more of the repeating units, such as vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, etc. , polymeric organic semiconductors such as BoIJ-N-vinylcarbazole. The ratio of this binder resin to the bisazo compound is θ~100% by weight, especially 0~10%.
The weight range is -.

Appropriate 01'M may be added to the CGL2 as necessary.

The thickness of the CGL 2 formed as described above is preferably 0.005 to 20 microns, particularly preferably 0.005 to 20 microns, particularly preferably 0.
．． 05-5 microns. If it is less than 0.005 microns, sufficient photosensitivity cannot be obtained, and if it exceeds 20 microns, sufficient load retention cannot be achieved.

Further, the Ci'' L 3 can be formed using the styryl compound described above in the same manner as the CCl 2 described above, ie, alone or together with a binder resin.

Then, the CTM of the box may be implied. This C'r
The thickness of L3 is 2-100 microns, preferably 5-100 microns
It is 30 microns.

The electrophotographic photoreceptor of the present invention may have other mechanical configurations. For example, as shown in FIG. 3, a suitable intermediate layer 5f may be provided on the conductive support 1, CCl2 may be formed through this, and CTL3 may be formed on the CGI, 2. At this intermediate tH5, free carriers are transferred from the conductive support 1 to the photosensitive layer 4 when the photosensitive layer 4 is charged.
It can have a function of preventing the photosensitive layer 4 from being touched or a function of an adhesive layer that integrally adheres the photosensitive layer 4 to the conductive support. Materials for the intermediate layer 5 include aluminum oxide, fully open oxide such as indium oxide, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin. , polycarbonate resin, silicone resin, melamine resin, vinyl-vinyl acetate copolymerization
A polymeric material such as vinyl-maleic anhydride copolymer resin can be used.

Further, as shown in FIG. 4, a CTL 3f is formed on the conductive support 1 with or without the intermediate layer 5, and a CGL 2 is formed on this CTL 3 to constitute a photosensitive layer 4. Good too.

Furthermore, it is also possible to form a single-layer photosensitive layer by dispersing the bisazo compound described above in a 7Lfc carrier transport phase containing the styryl compound described above to form a carrier generation phase.

In addition, various additives can be added to the compound forming the photosensitive material (J) according to the present invention, if necessary.

Examples of the present invention will be explained below, but the present invention is not limited thereto.

Example 1 On a conductive support made of polyethylene terephthalate with a thickness of 100 microns made of aluminum,
An intermediate layer with a thickness of approximately 0.1 micron made of vinyl acetate-maleic anhydride copolymer "Eslec MF-10J (manufactured by Block Chemical Industry Co., Ltd.) was provided on vinyl chloride, and the exemplified compound (I-1
) and the polyester resin [Pylon 200J (manufactured by Toyobo Co., Ltd.) II] were added to tetrahydrofuran 909 and dispersed in a ball mill for 12 hours, and the resulting dispersion was added to the intermediate layer in item 11 above. Apply with a doctor blade and dry thoroughly to a thickness of approximately 0.
A 5 micron CGL was formed.

On the other hand, the styryl compound 11.25.9 shown as the exemplified compound (l[-18) and the polycarbonate resin "Panritem-1250j (manufactured by Kasei Kasei Co., Ltd.) 159" were dissolved in 100 ml of 1°2-dichloroethane. The solution was coated onto the CGL using a doctor blade and sufficiently dried to form a CTL with a thickness of 12 microns, thereby producing c books of α-child photosensitive materials of the present invention.

This is also referred to as −[Sample 11.

Example 2 - 11 are actual examples in which each of the exemplified compounds (I-2), (i-3) and (i-2x) was used as a bisazo compound in the formation of muCGL. EXAMPLE 1 An EIIJ electrophotographic photoreceptor of the present invention was manufactured in exactly the same manner as in Example 1.

These are "Sample 2", "Sample 3" and "Sample 4" respectively.
”.

Example 5 An electronic photoreceptor of the present invention was produced in the same manner as in Example 1, except that the exemplified compound (If-22) was used as the styryl compound in the formation of CTL. This is called “Sample 5”
shall be.

Comparative Example 1 Formation of CT L in Example 1 In 1/C, a hydrazone visiting conductor having the following structural formula was used in place of the styryl compound, but the procedure was the same as in Example 1. A photoreceptor was produced. This was used as "Comparative Sample 1" Comparative Example 2 The same procedure as in Example 1 was used except that in the formation of the CTL of Example Sieve 1, a pyrazoline derivative having the following structural formula was used instead of the styryl compound. A comparative electrophotographic photoreceptor was manufactured using the same method.This is referred to as "Comparative Sample 2."

Electrophotographic photoreceptors processed as described above, Samples 1 to 1
U electrometer? -8P-428 Cut 1 (manufactured by Kawaguchi Denki) was used to investigate its electrophotographic properties. In other words, the received charge rffV^M when the surface of the photoreceptor is charged with a charging voltage of -6 KV for 5 seconds, and the exposure amount that is necessary for dark decaying for 5 seconds to attenuate the potential (initial potential) of lc to ki. E g (, sec) was investigated.

Results are required according to the results shown in Table 1.

Table 1 From the results shown in Table 1, it is clear that the electrophotographic photoreceptor of the present invention has high sensitivity〇゛Also, Samples 1 to 5, #5 Cane Sample 1, and Comparative Samples 2 each using a dry electronic copying machine [U-Bix 2000R
J (manufactured by Konishiroku Photo Industry Co., Ltd.) for continuous copying, and the black paper potential vb (v) and white paper potential Vw (V) at an exposure print value of 2.5 were measured using an "electrostatic voltmeter 144D-ID". The measurement was made using a mold (manufactured by Monroe Electronics Inc.) immediately before printing. The results are shown in Table 2.

The black paper potential here refers to the surface 'tJi of the photoreceptor when the above-mentioned copying cycle is performed using a black paper with a reflection ld degree of 1.3 as the original, and the white paper potential refers to the surface of the photoreceptor when the copy cycle described above is performed. Represents the surface potential of the photoreceptor when it is used as an original.

Table 2 (However, in the table, ΔV11 (v) and ΔVw (V) are black paper potential% (V) and white paper '+Pt, 1■Vw, respectively.
(v) indicates a variation (■), and (g) in the variation (■) indicates an increase, and - indicates a decrease. As is clear from the results in Table 2, the electrophotographic material of the present invention maintains the stable state of the electrophotographic material even when subjected to repeated electronic processes. It is possible to stably form a large number of visible images with good image quality.

[Brief explanation of the drawing]

Fig. 1 is an explanatory sectional view showing an example of the 411I configuration of the electrophotographic photoreceptor of the present invention, Fig. 2 is an explanatory sectional view showing another configuration V/I of the electrophotographic photoreceptor of the invention, and Fig. 3 FIG. 4 and FIG. 4 respectively show ifi2 Meigetsu #1I)rifilshi1 showing still other structural examples of the electrophotographic photoreceptor of the present invention. 1... Conductive support t4 2... Carrier generation jt
l(CGL)3...Gearia transport layer (C1'l
-i...photosensitive) device 5...intermediate layer IA...insulating,! l (Body IBoo...Hirom 1 Ejaculate I Figure #2 Figure 3

Claims (1)

[Scope of Claims] 1) An electrophotographic photoreceptor in which a photosensitive layer consisting of a combination of a carrier generation phase and a carrier transport phase -C is provided on a 2J4 electrostatic support -L, wherein the carrier generation phase has the following general formula [ I
1.) An electrophotographic photoreceptor, characterized in that the carrier phase contains a styryl compound represented by the following general formula (J). General formula [1] [In the formula, Ars and Arm: substituted or unsubstituted phenylene or RI: substituted or unsubstituted alkyl group, aryl A~, R2: substituted or unsubstituted aryl group, heterocyclic group, represent. ] General formula []FI [In the formula, 11i and R: each substituted or unsubstituted alkyl group, oryl group, r<s: If-substituted, unsubstituted aryl group, polycyclic ring group, R6 to R #: 0 each representing a hydrogen atom, halogen atom, alkyl group, alkoxy group, or alkylamine group]