JPS6177055A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to stabilize characteristics at the time of repeated uses by forming a photosensitive layer contg. cyclic diphenylamine deriv. represented by a specified general formula on a conductive substrate to form an electrophotographic sensitive body. CONSTITUTION:The electrophotographic sensitive body is obtained by forming on the conductive substrate 1 of a metallic plate, paper, plastic film, or the like, the photosensitive layer 4 composed of the laminate of a carrier generating layer 2 composed essentially of a carrier generating material, and a carrier transfer layer 3 contg. as the carrier transfer material the cyclic diphenylamine deriv. represented by the formula shown here in which A is an atomic group necessary for combining C and N atoms located at the ends of the broken lines with said atomic group to form an optionally unsubstd. 5- or 6-membered hetero ring; Y1, Y2 are each R3 or -CR4=CR5Ar; Ar is an aromatic or heterocyclic residue; R1-R3 are each H, halogen, alkyl, or the like; R4, R5 are each H or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an electrophotographic photoreceptor, and more particularly to a novel electrophotographic photoreceptor having a photosensitive layer containing an organic photoconductive compound as a main component.

(Prior Art) Conventionally, electrophotographic photoreceptors (hereinafter sometimes simply referred to as photoreceptors) have been made of selenium, zinc oxide, cadmium sulfide,
Kuta photoreceptors having a photosensitive layer containing a Kuroiso photoconductive compound such as silicon as a main component have been widely used. but,
These materials are not necessarily satisfactory in terms of sensitivity, thermal stability, moisture resistance, durability, etc. For example, when selenium crystallizes, its properties as a photoreceptor deteriorate, making it difficult to manufacture, and Fingerprints, etc. cause crystallization,
The performance as a photoreceptor deteriorates. In addition, cadmium sulfide has problems in moisture resistance and durability, and zinc oxide has problems in durability, etc.

In order to overcome these drawbacks of uncircumcised photoreceptors, the development and research of photoreceptors with photosensitive layers mainly composed of various organic photoconductive compounds has been actively conducted in recent years6. No. 50-10496 describes an organic photoreceptor having a photosensitive layer containing nihapoly N-vinylcarbazole and 2,4,7-dolinitro-9-fluorenone 6
However, this photoreceptor is not always satisfactory in terms of sensitivity and durability.In order to improve the shortcomings, the carrier generation function and the carrier transport function are shared by different substances, and a higher performance organic photoreceptor has been developed. Attempts are being made to develop the body. Many studies have been conducted on such so-called functionally separated photoreceptors because each material can be selected from a wide range and photoreceptors with arbitrary performance can be produced relatively easily. .

As a result, various 7zo compounds have been developed and put into practical use as carrier-generating substances. On the other hand, regarding carrier transport substances, for example, JP-A-51-94829, JP-A-5
No. 2-72231, $1Jli No. 53-27033,! Kaimei No. 55-52063, JP 58-65440
A wide variety of substances have been proposed, as disclosed in Japanese Patent Publications and the like.

[Problem that the invention seeks to solve]

Although some electrophotographic photoreceptors made using carrier transport materials such as those described above exhibit relatively excellent electrophotographic performance, their durability against light or electrical loads is weak, and their durability during repeated use is poor. It does not fully satisfy practical requirements because it causes instability and deterioration of performance.
It has been desired to develop a carrier transport material that has even better carrier transport function and exhibits stable performance over long periods of use.

Furthermore, in recent years, Ar laser, He
Gas lasers such as Ne lasers and semiconductor lasers are beginning to be used. These lasers can be turned on and off in chronological order as a Vf characteristic, and are considered particularly promising as a light source for printers with image processing functions such as Intelligent Printers and computer output printers. ing. Among these, semiconductor lasers are attracting attention because their nature does not require electrical signal/optical signal conversion elements such as acousto-optic elements, and because they can be made smaller and more flexible. However, this semiconductor laser has a low output compared to a gas laser, and the oscillation wavelength is also long (approximately 780 nm or more), so the spectral sensitivity of conventional photoreceptors is too high on the short wavelength side. It is difficult to apply this method to devices that use lasers as light sources, and new improvements have been required for carrier transport materials.

The present invention has been carried out in order to solve these problems and provide an electrophotographic photoreceptor with extremely high durability.

[Means to solve the problem]

The above problem has been solved by an electrophotographic photoreceptor characterized by having a photosensitive layer containing a cyclized diphenylamine derivative represented by the following general formula CI on a conductive support.

Examples of the core of the compound represented by the above general formula [I], which represents the atomic group forming the multi-ring of the general formula (1) and in which W is completed, include the following.

In the general formula (1), the heterocycle represented by W′c is an alkyl group, an aryl group, an alkoxy group, a noaryl group, a noaryl group, a noaralkyl group, a cyano group,
It may have a substituent such as a halogen atom, and the substituted group may form a ring, for example, as shown below.

In general formula (T), Y,,Y, are R1 or -CR,=
CR5Ar is represented, but there are no words in which both Y, Y and 2 are R3. 11. , R2i represents a hydrogen atom, a halogen atom (e.g. bromine atom, chlorine atom, fluorine atom, etc.), an alkoxy group (e.g. nodoxy group, nidoxy group, propioxy group, etc.), a hydroxy group, an alkyl group (e.g. methyl group,
ethyl group, propyl group, thi-butyl group, inpropyl group, etc.), noalkyl 7mino group (e.g. trimethylamine 7 group,
7 diarylamine groups (e.g., 7 diphenylamine groups, etc.), noaralkyl 7-mino groups (e.g., 7 nobennorami groups, etc.), 7-cya group*, or a nitro group, and R,, R, are hydrogen atoms. , cya7 group, halogen atom, phenyl group, or heterocyclic group (e.g., bilinol group, furyl group, chenyl group, pyrrolyl group, etc.) These phenyl groups and heterocyclic groups are alkoxy groups, alkyl groups, sia/groups,
It may have a substituent such as a halogen atom. Ar represents an aromatic carbocyclic or heterocyclic group, and examples include the following groups.These aromatic carbocyclic and heterocyclic residues may have the substituents listed in R11R21R).

That is, in the present invention, by using the cyclized diphenylamine derivative represented by the general formula [I] as a photoconductive substance of an electrophotographic photoreceptor, only the excellent carrier transport ability of the cyclized diphenylamine derivative of the present invention can be utilized. By using this as a carrier transport material in a so-called function-separated electrophotographic photoreceptor in which carrier generation and transport are performed using separate materials, the coating has excellent physical properties.
Excellent electrophotographic properties such as charge retention, sensitivity, and residual potential.
In addition, it is possible to produce an electrophotographic photoreceptor that exhibits less fatigue deterioration even after repeated use and exhibits stable characteristics even when exposed to heat or light. Further, the cyclized diphenylamine derivative used in the present invention has the general formula [I
] The cyclized diphenylamine derivatives shown can be used alone or in combination of two or more,
It may also be used in combination with other photoconductive materials.
．． 1.

Said general formula (1)'? Specific examples of the cyclized diphenylamine derivatives that are effective in the present invention include those having the following structural formula, but this does not limit the cyclized diphenylamine derivatives according to the present invention. .

Example compound B-(5) B-(8) B-(9) l B-(13) B-Q6) B-(21) B-(Z3) a-(24)
0B (35 - (88)) Those having the +14 structure of the general formula [ra].

General formula [1a1 B-(89)-(142) Those having the structure of general formula [Ib].

General formula [Ib] B-(+43)~(196) Those having the structure of general formula [IC].

General formula [:I 61 B-(+97)~(250) Those having the structure of general formula [Id].

-Formula (Id) These compounds can be easily synthesized, for example, by the following method or other known methods.

Synthesis Example 1 Synthesis of Exemplified Compound B-(15) Tetrahydroquinoline was condensed with p-yokudo 7-nisole in the presence of potassium carbonate and copper powder to obtain N-(p-methoxyphenyl)tetrahydroquinoline.

This was then treated with 7 methylformamide and phosphorus oxychloride to obtain an intermediate.

The resulting intermediate, N-(p-/)xyphenyl)-6
- formyltitrahydroquinoline 2.68g (0,Ol
Benz Jk noethyl phosphonate derived from mol and benol 117mide 2.30 g (0, Olmol)
was dissolved in 30 mH of N,N-dimethylformamide, and 2
4 liters of 8% sodium methylate methanol solution was added dropwise.

After stirring at room temperature for 6 hours, set aside overnight and add 30ml of water.
added. The precipitated crystals were collected by filtration and recrystallized from etaryl to give pale yellow needle crystals 2.72. I got it. Yield 79% Elemental analysis CHN Theoretical value (C,, 11,, NO) 84.18 7.
06 4.09 Actual value 84.01 7
．． 10 4.13 The elemental analysis values were in good agreement with the theoretical values, and it was confirmed that the obtained compound was exemplified compound B-(151).

The compounds of the present invention as described above have almost no photosensitivity to visible light by themselves, but by applying a certain sensitization method, they can be imparted with photoconductivity to visible light and can be used alone to form a photoreceptor. You can force it. The first method is to add an organic dye and perform spectral sensitization (dye sensitization).

The second method is to form a charge-transferring lead body and sensitize it. Dyes that can be used for spectral sensitization include the following.

(1) Methyl violet, crystal violet,
Triphenylmethane dyes such as malachite green (Z); Xanthine dyes such as erythrosine and rose bengal; (3) Methylbruzin dyes; cyanine dyes such as (6) styryl dyes such as p-methylamino/styrylquinoline (7) biryllium base dyes such as pyrylium salts, thiapyrylium salts, and benzobyrylium salts (8) 3.3'-norbazolylmethane dyes Further, examples of electron-accepting substances that can be formed with the compound of the present invention and a charge transfer complex include 2,4.7-)linitrofluorenone, 2
, 4,5,7-titrani), Lewis acids such as fluorene, chloranil, and tetracyan/quinomethane.

However, when the compound of the present invention is combined with a carrier-generating substance having a carrier-generating ability such as another organic dye, pigment, or non-optical conductor by utilizing only its carrier-transporting ability, a functionally separated photoreceptor is produced. The most favorable effect is obtained.

The dyes listed in (1) to (8) above are also useful as carrier-generating substances, but other substances such as humans are also useful.

(1) Azo dyes such as monoazo dyes, nos-7zo dyes, and trisazo dyes (2) Perylene dyes such as perylenic anhydride and perylenic acid imide (3) Indigo dyes (4-7 Polycyclic quinones (5) quinacridone dyes (6) bisbenzimiguzole dyes (7) ingesuron dyes (8) squarelylium dyes (9) ) 7thalosy7ine pigments such as metal 7lyronanine and metal-free phthalocyanine (10) Selenium, selenium alloys (11) Inorganic photoconductors such as C dS , C dse , amorphous silicon, etc. (12) Beryllium salt pigments , a eutectic compound formed from a thiapyrylium salt dye and a polycarbonate Among these various carrier-generating substances, the following general formulas (III) to particularly preferable carrier-generating substances are particularly preferable in consideration of their properties as photoreceptors for semiconductor laser printers. Examples include azo compounds as shown in (XV[).However, the general formula (I[[)
In (XVI) to (XVI), A represents a group of the general formula [■].

General formula ([1) In the formula, Z represents Rs+i iz+Rsz+Rs++Rss+R
s++Rs2+Rs++ Rs++ Rss and Ra
6 represents a hydrogen atom/halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a nitro group, a cya/group, a noalkylamino group, a diphenylamine group, an amide group, an acyl group, a carboxyl group, or an alkoxycarbonyl group.

General formula (III) Qt Qt [wherein Q and Q2 are a hydrogen atom, a halogen atom,
[General formula] representing an alkyl group or an alkoxyl group
■] IQ4Qs [In the formula, Q 3. Q and Q represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxyl group,
] General formula [V] [In the formula, Q6 and Q7 are hydrogen atoms, ha:I General formula (Vl) General formula [■] General formula [■] General formula (IX) υ General formula (X) [In the formula, Q is a hydrogen atom, a halogen atom,
represents an alkyl group, a hydroxyl group, or an alfxyl group] General formula (XI) [wherein, Ql. and Q I+ is a hydrogen atom, a halogen atom, or a hydrogen atom. represents a hydrogen atom, an alkyl group, a hydroxyl group, or a furfuxyl group; ] General formula (Xllll) [In the formula, Ql and Q15 are hydrogen atoms, )) represent a rodene atom, an alkyl group, a hydroxyl group, or an alkoxyl group, X and x2 are halogen atoms (F, C(L, Br General formula [x■] [wherein Ql6 and Ql7 represent a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group or an alkoxyl group, and Q represents a hydrogen atom, a Schiff group, an alkyl group or a phenyl group, Q1 to Q2. are a hydrogen atom, a halogen atom, a 7-cya group, an alkyl group, an alkoxyl group, a hydroxyl group, a 7-amino group, a 7-nofurkylamy group, and a nophenylamy-7 general formula (XV) [wherein, Q21 and Q2. represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, or an alkoxyl group; represents a pheasant carbonyl group, a halogen atom or an ano group.] General Formula (XVI) [In the formula, Q26 and Q2. represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxyl group;

1 represents a hydrogen atom, a Schiff group, a halogen atom, an alkyl group, or a phenyl group. Specific examples of the above carrier-generating substances are as follows.

Those having the structure of the general formula [■].

Those having the structure of the general formula [■].

1. No. 9 Those having the structure of general formula [v].

11 years Showa 61-77055 (14) Those having the structure of the general formula Cvt).

The structure has the general formula CX'll''l.

Structure of general formula [1■]? What you have.

N==N-^ Those having the structure of the general formula CIX'].

Those having the structure of general formula [X].

Those having the structure of the general formula [~1].

Those having the structure of the general formula [■].

Among those having the structure of the general formula (Xlll), those having the structure of the following general formula IXHfa).

General formula (XUIal) The following general formula (
Those having the structure xrva'H.

General formula [XIVa] ′　　　　　　　　　　　　　-・ Those having the structure of general formula [Xv].

A structure of general formula (XVI).

In addition, photoreceptors for visible light may be used as light sources such as halogen lamps, xenon lamps, tungsten lamps, and LEDs.
, He-Ne laser, Matkohasonoike visible laser, etc.), particularly preferred carrier generating substances are those of the following general formulas [X■] to [XXχ]. Examples include azo compounds. However, in the following general formulas [X■] to (XXX), A' represents the general formula [■'].

General formula [u'] In formula C, Z' represents, and R21 to R75 and R,, +R,, are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, hydroxyl groups, nitro groups, sia7 groups, dialkyl ami/group, no 7 enyl ami 7
group, amido group, acyl group, carporsyl group, or alkoxycarbonyl group.

General formula [X■] Q32 Q33 [In the formula, Q 32 and Q represent a hydrogen atom, )) a rogene atom, an alkyl group, a hydroxyl group, or an alkoxyl group. ] General formula [X
XIX) [In the formula, Q,! and Q3? represents a hydrogen atom,)) a rodene atom, a furkyl group, or an alkoxy group,] General formula (XX) General formula (XXT) General formula [χ■] NL; LAN General formula (XX [[l) [In the formula, Q and @ represent )10 dene atoms, alkyllkoxyl groups, dialkylami/groups, hydroxyl groups, or cyano groups, and p represents an integer of O to 5. ] General formula (XXIV) [wherein, Q, and Q,. is a hydrogen atom, /% el
1 phenyl general formula (XXV) having an anchor, a furkyl group, a cinnamyl group, an acyl group, an ester group, or a substituent; A44 [wherein, Q +1 and Q +2 are hydrogen atoms, halogen atoms, represents a furkyl group, an alkoxy group or a hydroxyl group] General formula [XX ■] General formula [XX■] A1 [In the formula, Q +s and Q□ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a hydroxyl group,
] General formula (XXIX) [wherein, Q ty and Q,. represents a hydrogen atom, a halogen atom, a furkyl group, an alkoxy group, or a hydroxyl group] General formula (XXX) [wherein Ql and Q, represents a hydrogen atom, a halogen atom, a furkyl group, an alkoxy group or a hydroxyl group,
] Specific examples of compounds represented by these general formulas are as follows: [
Those who have a debt of [Jun].

0,.

・÷ Something with the structure of type 17 [expletive].

0, + 0C-a in the general formula (XTX) that nurtures Nakasuzo
Fish having the structure [Fish-a] Fish having the structure of (xg-b) among those having the structure of the general formula [I].

Among those having the structure of the general formula [sei], those having the structure of 0C-c).

6 Uri white Those having the structure of general formula (XX).

Those having the structure of general formula [X'A].

Something that has the structure of a general formula [sei].

Those having the structure of the general formula (XX!

Those having a compound of general formula (XXIV).

Q8・Q40 - Those having the structure of snoring formula (XXV).

Those having the structure of the general formula 1'X)fvl).

Those having the structure of general formula (XXi).

·tsu Those with general formula [■] lily construction.

Q□.

Something that has the structure of the general formula.

Q- Those having the structure of the general formula CXXX).

Q.

Since the cyclized diphenylamine derivative used in the present invention does not have the ability to form a coating by itself, a photosensitive layer is formed by combining various binders.

Although any binder can be used here, it is preferable to use a hydrophobic, high dielectric constant, electrically insulating film-forming polymer. Examples of such high molecular weight polymers include, but are not limited to, the following.

(1) Polycarbonate (2) Polyester (3) Methacrylic resin (4) Acrylic resin (5) Polyvinyl chloride (6) Polyvinylidene chloride (7) Polystyrene (8) Polyvinyl acetate (9) Styrenic copolymer resin (e.g. styrene -butanoene copolymer, styrene methyl phthacrylate copolymer) (10) Acrylonitrile copolymer (fat (e.g. vinylidene chloride-acrylonitrile copolymer 44?) (11) Vinyl chloride-vinyl acetate copolymer (12) )
tJK vinyl bivinylate-maleic anhydride copolymer (13) Silicone resin (14) Silicone-fluid resin (15) 7
E7-L A1 fat (e.g. 71-nol-formaldehyde resin, ugly-cresol-formaldehyde resin, etc.) (16) Styrene-alkyd fat (17) Poly-N-vinylcarbazole (18) Polyvinyl butyral (19) Polyvinyl 7t Lumal These binders can be used alone or as a mixture of two or more.

As shown in FIGS. 1 and 2, the photoreceptor of the present invention comprises a carrier-generating layer 2 containing a carrier-generating substance as a main component and a cyclized diphenylamine derivative of the present invention as a carrier-transporting material on a conductive support 1. A photosensitive layer 4 consisting of a laminate with a carrier transport layer 3 containing as a main component is provided. fjS3
As shown in the figure and FIG. 4, this photosensitive layer 4 may be provided via an intermediate layer 5 provided on the conductive support 1. When it has a two-layer structure, an electrophotographic photoreceptor having the most excellent electrophotographic properties can be obtained. Further, in the present invention, as shown in FIG. 5 and (I+16), a photosensitive layer 4 formed by dispersing all particulate carrier generating substances 7 in a layer 6 mainly composed of the carrier transporting substance is provided with conductive support. 5 and 6 by adding a sensitizing dye or a Lewis acid to a carrier transporting material without using a carrier-generating material, which may be provided directly on the body 1 or via an intermediate layer 5. Similarly, preferable results can also be obtained by providing a single-layer photosensitive layer 4.

Here, add photosensitive layer 4! Which of the carrier generation layer 2 and carrier transport 7!3 should be the upper layer in the configuration depends on the following:
band? It is determined by whether the polarity is positive or negative. That is, when forming a negatively charged photosensitive layer, it is advantageous to use the carrier transport layer 3 as the upper layer, because the cyclized nophenyl 7mine derivative in the carrier transport layer 3 has a high transport rate for holes. This is because it is a substance that has the ability.

Again two/! ! Carrier generation N constituting the photosensitive M4 of the configuration
2 can be formed by the following method either directly on the conductive support 1 or the carrier transport layer 3 or after providing an intermediate layer such as an adhesive layer or a barrier layer if necessary.

(1) Vacuum evaporation method (2) Method of applying a solution prepared by dissolving a carrier-generating substance in a suitable solvent.

(3) A method in which a carrier-generating substance is made into fine particles in a dispersion medium using a ball mill, a homomixer, etc., and a dispersion obtained by mixing and dispersing with a binder as necessary is applied.

The thickness of the carrier-generated N2 formed in this way is:
The thickness is preferably 0.01 to 5 microns, more preferably 0.05 to 3 microns.

Further, the thickness of the carrier transport layer 3 can be changed as necessary, but it is usually preferably 5 to 30 microns. This carrier transport/l! ! The composition ratio in No. 3 is preferably 0.8 to 10 parts by weight of the binder to 1 part by weight of the carrier transport material containing the cyclized diphenylamine derivative of the present invention as a main component. When forming the photosensitive layer 4 in which a substance is dispersed, it is preferable to use the binder in an amount of 5 parts by weight or less based on 1 part of the carrier-generating substance.

Further, when the carrier generation M2 is configured as a dispersion type using a binder, it is preferable to use the binder in an amount of 5 parts by weight or less per 1 part by weight of the carrier generation substance.

As the conductive support 1 used in the construction of the electrophotographic photoreceptor of the present invention, the following are mainly used, but the invention is not limited to these: l) aluminum plate;
Metal plates such as stainless steel plates.

2) A thin layer of metal such as aluminum, paranoum, or gold is provided on a support such as paper or plastic film by lamination or vapor deposition.

3) A layer of a conductive compound such as a conductive polymer, indium oxide or tin oxide is provided on a support such as paper or a plastic film by coating or 'fIk deposition.

As an intermediate I@5 such as an adhesive layer or a barrier layer,
In addition to the polymer used as the binder, organic polymer substances such as gelatin, casein, starch, polyvinyl alcohol, vinyl acetate, ethyl cellulose, and carboxymethyl cellulose, or aluminum oxide may be used.

The photoreceptor of the present invention has the above-mentioned structure, and has excellent charging characteristics, sensitivity characteristics, and image forming characteristics, as is clear from the examples described below.

EXAMPLES The present invention will be specifically explained below using Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Selenium was evaporated onto a conductive support consisting of a polyester film laminated with aluminum foil to a thickness of 0.
．． A carrier generation layer of 5 microns was formed. On top of that, 6 parts by weight of Exemplified Compound B-(6) and polycarbonate [
Panrai) L-1250J (Teijin Chemicals*) 1
01 ffin is dissolved in 90 parts by weight of 1,2-nochloroethane, and this solution is coated so that the film thickness after drying is 11 microns to form a carrier transport layer. A photoreceptor was created.

Regarding this electrophotographic photoreceptor, electrostatic copying paper test ￥c+F
trSP-428 type” (Kawaguchi?f Co., Ltd. [Seisakusho 91])
The electrophotographic characteristics were measured using the dynamic force method.

That is, the surface potential when the surface of the photosensitive layer of the photoreceptor is charged with a charging voltage of -6 KV for 5 seconds, and then the light from a tungsten lamp is irradiated so that the illumination intensity on the photoreceptor surface is 35 lux, and the surface potential is Exposure amount required to reduce the potential vA by half (half-reduction exposure fth) E
The surface potential (residual potential) after irradiation with an exposure dose of ux.5ea) and 301ux-see was determined. *The same measurement was repeated 100 times.

The results are shown in the 1st ft.

The photoreceptor in Table 1 has sufficient charge retention power, high sensitivity, low residual potential, and maintains good characteristics even after repeated use (1), and has excellent characteristics as an electrophotographic photoreceptor. .

Comparative Example 1 Measurements were carried out in the same manner as in Example 1 on the photoreceptor of Example 11 and rHI, except that Compound T-1 below was used instead of Exemplified Compound B-(6) as a carrier transport substance. As a result, the results of the tR2 table were obtained.

As is clear from the results in Table 12 and above, the comparative photoreceptor was significantly inferior to the photoreceptor of the present invention of Example 1 in terms of stability during repeated use.

Examples 2 to 4 Exemplified compound B-(7)l B-(10), B instead of exemplary compound B-(6) as a carrier generating substance
An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 1 using -(19). The initial characteristics of these photoreceptors were measured in the same manner as in Example 1, and the results shown in Table 3 were obtained.

Third Example 5 A polyester film made of a vinyl chloride-vinyl acetate-maleic anhydride copolymer [S-LEFUKU MF-1 (1) (manufactured by Block Chemical Co., Ltd.) was coated on a conductive support with aluminum vapor-deposited on a polyester film. A medium r, ll scrap with a thickness of 0.05 microns is provided, and on top of that, Nobromo 7s 7thron ['e/Lightread 7d 2 Y J (C11, No.
1 part by weight of 1 company M) was added to 30 parts by weight of 1,2-dichloroethane and dispersed in a ball mill, and 11.5 parts by weight of polycarbonate "Panlite L-+250J (Teijin Kasei Co., Ltd.) was dissolved in the resulting dispersion. A well-mixed coating solution was applied so that the i thickness after drying was 2 microns to form carrier generation) 4.

On top of that, 6 parts of exemplified compound B-(26) and polyester [Vylon 200J (Toyobo Co., Ltd. *) 10iIl
The electrophotographic photoreceptor of the present invention is formed by coating a solution prepared by dissolving fi part in 90 parts by weight of 1,2-nochloroethane so that the film thickness after drying is 11 microns. Created. Measurements were carried out on this photoreceptor in the same manner as in Example 1, and the fourth result was obtained.

Table 4 Comparative Example 2 Exemplified compound B-(2B) as carrier'WR sending substance
A comparative photoreceptor was prepared in the same manner as in Example 5 except that the following compound T-2 was used instead of .

When this comparative photoreceptor was measured in the same manner as in Example 1, the results shown in Table 5 were obtained.

As is clear from the results shown in Table 5, the comparative photoreceptor was significantly inferior in sensitivity and repeated stability compared to the compound of the present invention.

Example 6 Polyester [Nosilon 200
A 0.1 micron thick intermediate layer made of J (manufactured by Toyobo Co., Ltd.) was provided.

On top of that, the structural formula below is used as a carrier-generating substance! 2. A carrier-generating layer was formed by dispersing 1 part by weight of the azo pigment in 60 parts by weight of 1,2-dichloroethane and applying the mixture to a dry film thickness of 0.3 microns. Furthermore, 6 parts by weight of Exemplified Compound B-(20) and 1 part of polycarbonate "Panlite L-1250j (manufactured by Teijin Chemicals)"
The electrophotographic photoreceptor of the present invention was prepared by forming a carrier transport layer by coating a solution obtained by dissolving 0 heavy wind part in 90 parts by weight of 1,2-dichloroethane so that the film thickness after drying was 15 microns. did. The initial characteristics of this photoreceptor were measured in the same manner as in Example 1, and V A = -990v.
, E% = 2.81ux・sea and VR=O
It was V.

This photoreceptor was also used in an electrophotographic copying machine [U-Bix2000].
When I attached it to RJ (Konishi Roku Photo Industry Co., Ltd. 91) and performed a photocopy test, I obtained a copy image that was faithful to the original, had high contrast (excellent gradation, and was clear).

Even after this was repeated 1000 times, a good copy image was obtained that was as good as the initial one.

Example 7 An electrophotographic photoreceptor of the present invention was produced in the same manner as in Example 6 except that the following compound was used as a carrier generating substance.

The initial characteristics of this photoreceptor are VA = -1060v, E8 =
2.7 lux·see, Vp=Ov. This was transferred to an electrophotographic copying machine rU-Bix 2000 RJ (
(manufactured by Konishiroku Photo Industry Co., Ltd.) and conducted a live-action test.10
Even after repeating this process 00 times, a copy image as good as the initial one was obtained.

Example 8 The cyclized nophenyl7mine derivative of this patent can also be used as a carrier transport material for photoreceptors for semiconductor laser printers.
It has particularly excellent performance. Actually, a photoreceptor for a semiconductor laser was produced as described below, and good results were obtained.

A vinyl chloride-vinyl acetate-maleic anhydride copolymer was placed on an aluminum drum with an outer diameter of 10c+e as a conductive support.
A 0.05 μm thick intermediate layer made of S-LEC M F-10J (manufactured by Tanezu Kagaku Co., Ltd.) was provided, and 2 g of the compound G-151 was added to 110 μm of 1.2-nochloroethane on the intermediate layer.
A carrier generation layer was formed by mixing the dispersion liquid with a ball mill and applying the dispersion liquid so that the thickness after drying was 0.1 μm. On this carrier generation layer, 6 g of Exemplified Compound B-(11) and 10 methacrylic resin "Acrybet" (manufactured by Mitsubishi Raymin Co., Ltd.) were added 1.
A carrier transport layer was formed by applying a solution dissolved in 70 ml of 2-nochloroethane so that the film thickness after drying was 10 μm, thereby producing an electrophotographic photoreceptor of the present invention.

The sensitivity of this photoconductor to 790ni semiconductor laser light is 400 votl ・c+*' ・11 W-'
・A live-action test was conducted using an experimental machine equipped with a semiconductor laser (790n) that produced a laser beam intensity of 0.85 watts on the surface of the photoreceptor of the present invention, which had an intensity of 5ee-' (light range fIM degree). Ta.

After the surface of the photoreceptor was charged to -6 KV, it was exposed to laser light and reversely developed at a bias voltage of -250 V. A good image without capri was obtained.

Comparative Example 3 A comparative photoreceptor was obtained in the same manner as in Example 8, except that Compound T-3 below was used instead of Exemplified Compound B-(11).

The sensitivity of this photoreceptor to 790n+a semiconductor laser light is 90voH-cII2・μw−+・5ee−+
(light extinction speed). Using this comparative photoreceptor, an actual photographic test using a semiconductor laser was conducted in the same manner as in Example 8, but there was a lot of fog and good images could not be obtained.

Examples 9 to 32 Photoreceptors were prepared by combining the carrier-generating substances shown in Table 6 and the carrier-transporting substances of the present invention.

The conditions for producing the photoreceptor were all the same as in Example 8, except for the types of the two materials mentioned above. The sensitivity of each sample to 79 On+s laser light was good as shown in the table.

As is clear from the results of the above Examples and Comparative Examples, the photoreceptor of the present invention has better stability, sensitivity, durability, and combination with a wide range of carrier transport materials than the comparative photoreceptor.Table 6 [Example 33] ~56] A photoreceptor was prepared by replacing the carrier-generating substance and carrier-transporting substance n-(zo) of Example 6 with the carrier-generating substance and carrier-transporting substance shown in Table 7, respectively.
The photosensitivity Ei to visible light was measured by the same method as above, and the results shown in Table 7 were obtained. As shown in the table, all photoreceptors using the carrier transporting material according to the present invention exhibit high photosensitivity.

Table 7 [Effects of the Invention] According to the present invention, it is possible to obtain an excellent photoreceptor that has high sensitivity, extremely stable characteristics upon repeated use, and has no toxicity problem.

[Brief explanation of drawings]

1 to 61 are sectional views showing examples of the mechanical structure of the electrophotographic photoreceptor of the present invention, respectively. 1... Conductive support 2... Carrier generation layer 3... Carrier transport layer 4... Photosensitive layer 5... Intermediate layer 6 ...Layer 7 containing a carrier transport substance...
... Carrier generating substance agent Patent attorney No 1) Parent-in-law Figure 2 Figure 4

Claims (3)

[Claims] (1) An electrophotographic photoreceptor comprising a photosensitive layer containing a cyclized diphenylamine derivative represented by the following general formula [I] on a conductive support. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Y_1 and Y_2 represent R_3 or -
CR_4=CR_5Ar, where Y_1, Y_2
are never both R_3. Ar represents an aromatic carbocyclic or heterocyclic residue, R_1, R_2, R_3 are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a dialkylamino group, a sialylamino group, a dialkylamino group, a cyano group or represents a nitro group,
R_4 and R_5 are hydrogen atoms, halogen atoms, cyano groups,
Represents a phenyl group or a heterocyclic residue. ] (2) The photosensitive layer contains a carrier-generating substance and a carrier-transporting substance, and the carrier-transporting substance has the general formula [I
] The electrophotographic photoreceptor according to claim 1, which is a compound represented by the following. (3) The electronic device according to claim 1 or 2, wherein the photosensitive layer is constituted by a laminate of a carrier-generating layer containing a carrier-generating substance and a carrier-transporting layer containing a carrier-transporting substance. Photographic photoreceptor.