JPS59104658A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain a photosensitive body superior in photosensitivity and characteristics of residual potential and repeated use by forming a single photosensitive layer contg. a specified bisazo compd. or a laminated photosensitive layer contg. it only in a carrier generating layer of the laminated layer on a conductive substrate. CONSTITUTION:A photosensitive layer 4 formed on a conductive substrate 1 contains in a layer 6 contg. a carrier transfer substance, further as a carrier generating substance 7, a compd. represented by the formula as shown here in which Ar1, Ar2 are each optionally subtd. aromatic carbon or hetero ring; Z is an atomic group necessary to form an optionally substd. aromatic carbon or hetero ring; and Y is optionally substd. carbamoyl. Alternatively, a carrier generating layer 2 composed essentially of said bisazo compd. and a carrier transfer layer 3 essentially composed of a carrier transfer substance may be laminated to form a photosensitive layer 4. As a result, the obtd. photosensitive body has a long life and forms a superior image.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoreceptor, and more particularly to a novel electrophotographic photoreceptor having a photosensitive layer containing a specific bisazo compound.
This relates to photoreceptors.

Conventionally, electrophotographic photoreceptors having photosensitive layers containing inorganic photoconductive compounds such as selenium, zinc oxide, and cadmium sulfide as main components have been widely used. However, these do not necessarily satisfy the properties that are considered safe for electrophotographic photoreceptors in practical use, such as sensitivity, thermal stability, moisture resistance, durability, and safety. For example, selenium-containing amorphous materials are used, and crystalline materials are significantly less sensitive to defects.

However, amorphous selenium tends to crystallize due to heat, and crystallization progresses over time, resulting in poor thermal stability and short life span. Cadmium sulfide has problems with moisture resistance and durability, and zinc oxide also has poor durability.

Furthermore, the toxicity of sulfurized domiwaum causes restrictions in manufacturing and handling.

In order to overcome these drawbacks of inorganic photoreceptors, efforts have been made in recent years to develop and refine M-organic photoreceptors having photosensitive layers containing various inorganic photoreceptors as main components.

Poly-N
-vinyl carbazole and 2.4.7-11J nitro-9
- There is a description of a southern photoreceptor having a photosensitive layer that is low in fluorenone. However, this photoreceptor does not necessarily have a high sensitivity of 1'(1'). Attempts are being made to develop more commercially viable organic photoreceptors by applying different types of photoreceptors to different materials.

For a functionally separated electrophotographic photoreceptor, each material can be selected from a wide range, and a photoreceptor with desired performance can be produced relatively easily.

Many compounds have been proposed as carrier generating substances for such functionally separated electrophotographic photoreceptors. Examples of the use of inorganic compounds as carrier-generating substances include amorphous selenium described in Japanese Patent Publication No. 4:1-16198, which is used in combination with organic photoconductive compounds; As mentioned above, the carrier generation layer made of the above-mentioned material has the drawback that it crystallizes due to heat, resulting in deterioration of the characteristics as a photoreceptor.

In addition, many electrophotographic photoreceptors have been proposed that use M-mimetic dyes or M-mechanical pigments as carrier-generating substances. For example, JP-A-54-79632 and JP-A-56-1 have been used as photoreceptors containing a bisazo compound in the photosensitive layer.
16040, Japanese Patent Publication No. 56-11945, etc. are already known. However, these bisazo compounds are not necessarily satisfactory in terms of characteristics such as sensitivity, residual wI potential, or stability during repeated use, and the selection range of carrier delivery substances is also limited. It does not fully satisfy the wide range of demands of electrophotographic processes.

An object of the present invention is to provide a photoreceptor having a photosensitive layer containing a specific bisazo compound, having high carrier generation efficiency and excellent photoconductivity.

Another object of the present invention is to reduce mischief and reduce residual potential.
Another object of the present invention is to provide an electrophotographic photoreceptor with excellent durability that can stably exhibit its good properties over a long period of time even after repeated use.

Still another object of the present invention is to exhibit an excellent carrier generation function in combination with any carrier transport substance a arbitrarily selected from a wide range of carrier transport substances. The present invention is to provide an electrophotographic photoreceptor having crushed characteristics by containing a carrier-generating substance made of a specific hisazo compound and forming a photosensitive layer made of the same.

As a result of intensive research and study to achieve the above objectives, the inventors have discovered that the bisazo compound shown in the general Nisan exhibits the mysterious photoconductivity, especially excellent carrier generation ability. The heading completes the invention.

General formula [IJ In the formula, 2 is a substituted/unsubstituted aromatic carbocyclic ring;
Represents an atomic group necessary to constitute an unsubstituted aromatic heterocycle, and represents Ar, a sister-substituted/unsubstituted aromatic carbocycle, or a substituted/unsubstituted aromatic heterocycle. Ar,
and Ar, preferred 2. Examples of the substituent include a halokene atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a trifluoromethyl group, and more preferred alkyl groups include a methyl group, Ethyl group, more preferably alkoxy group,
Contains methoxy and ethoxy groups.

Y +-j represents a substituted/unsubstituted carbamoyl group, and Y
As the substituent, aromatic carbocycle, aromatic heterocycle, and alkyl group are preferable, and these may or may not have a substituent.

That is, in the present invention, by using the bisazo compound represented by the general formula [IJ as a 90% solid material for forming the photosensitive layer of the Hiroko Yoshin photoreceptor, the excellent properties of the bisazo compound of the present invention can be obtained. By utilizing only the carrier generation ability and using it as the gear rear generation material S4 of a so-called machine n9 separation type ganko photo sensor, in which carrier generation and transport are performed using separate substances, It has excellent electrophotographic properties such as ambiguities, charge retention, sensitivity, and residual concentration, and exhibits stable characteristics with little fatigue deterioration even when used for hyp-returning. It is possible to create a photosensitive formation.

As a specific example of the bisazo compound represented by the general formula [1] that is self-effective in the present invention, there may be mentioned a compound represented by the following structural formula. This does not limit the bisazo compounds that should be used.

A (1) A (2) A (3) A (4) A (5) A (6) A (7) A (8) A (9) A (10) A (January A (IsI) A ( 13) A (14) A (16) A (17) A (,18) A (19) A (friend i] A T2]) A (22) A (2:i) A (2/I) A ( 25) A (k6) A (27) A (a) A (31) A (32) A (33) A (all) A (3!,) A (36) A (:37) A (38) A (3!Q A (4++) A (・11) A (42) A (4: () A (44) Δ (45) A (46) A (47) Δ l) A (49) A ((3 )) A (51) A (52) A (53) 8 (54) A (5ri) A (56) The bisazo compound of the present invention is obtained by converting the corresponding diamino compound into 1-tetrazotization using sodium nitrite in hydrochloric acid, After isolation as the borohydrofluoride salt, the polar and radical E'F
It can be easily synthesized by coupling it with force/ngler.

Next, a specific synthesis example of the bisazo compound of the present invention will be described.

Composite sequence 1. (Synthesis of 1+U compound A (1)) 4.4'
-Diaminotran2. (18& (11,01 mol) (n '' mb, water 20 cq7; 5''C or more) Ub, (xM tβ sodium 1.
4 (, + El ((1,02 mol')) was added dropwise to 5 ml of water.
After stirring was continued, insoluble matter was removed once, and 10 ml of bromine water '41=IM was added along f1. 14 m of 4-lamp 7y tetrazonium was deposited in an IJ and washed with sulfuric acid soap. It's 11 degrees, Tetrazonium, ml M F 100 prayers +t+*1. ．． 5′
From C1.
! i' (lJ, 02 mol) as D M F 300 m
10i was added to the water. Triethanolamine 1:l (0, (1
8 mol) was dissolved in 5 tl ml of DMF and dissolved in a bath.
, g ++, ;j 4-1y, 411i': Crystal ICd'
km L -t D M F te 2 times 2"L'/4'
L, pricked twice with acetone (4' dirty, dry-smoked and obtained the desired product!'1.9 (+9 (78%)).

Synthesis V/l12 (Synthesis of Exemplary Compound A (3)) 4.4'
- Disperse 2.08 g (0, (1 mol) of diaminotolane) in hydrochloric acid [Om2, 2 mol) of water and add 1.40.9 (1), 02 mol of sodium nitrite while maintaining the temperature at 5°C. ) was added dropwise with 5 mp of water and a bath solution heated to K. 3. At the same temperature for another 1 hour + (e, g:, p t, drained, 1 filtration, 1 insoluble matter, f'?it) Naphthol As-MX was added thereto. The precipitated crystals were collected at t4 and washed with borohydric acid. The obtained tetrazonium salt was dissolved in DMF 100 dVc, and naphthol As-MX was added while keeping the temperature below 5°C. 2
-hydroxy-3-naphthoe C1; -2', 4'
-dimethylanilide) r+ , 82 kj
t O,t)2 -T-ir・ ) Of course 1)
M
I made the melting surface which had been refined to 7 to 50 nll to 1. After that, press 1tiJ ffl for 2 hours at room temperature to remove the precipitated crystals.
i-tori - 2 times fk with CDMF, 2 times fk with Okisa, acetone
I cleaned it. 1 ill record 6.589 (1;
Jsua) is insulting 4ko.

The bisazo compound of t()1 of the present invention is a photosensitive resin 7, which is used to bond the bisazo compound of the 411' invention onto a σλ-based support tree for producing an electrophotographic sensitive element. It can be manufactured by providing nine layers of Iμ dispersed in an adhesive. Another method is to use the bisazo compound of the present invention as a carrier material that takes advantage of its particularly excellent ability to generate key drift among its photoconductive properties. By using it together with the obtained carrier-containing substance, it is also possible to form a laminated type or dispersion type so-called function 5+ release photosensitive element.The bisazo compound used in the present invention has the general formula ( Among the bisazo compounds represented by IJ, it can be used alone or in combination of two or more.
In addition, the mechanical structure of Ichiko Yoshin Kangen Body, which can be used in combination with other bisazo compounds, has the shape of the gods.''
The photographic photosensitive material 14 of the present invention can take any of the forms shown in FIGS. 1 to 6.
It is in the form of a diagram. In FIG. 1 and FIG. A photosensitive layer 4 made of heather is provided. As shown in FIGS. 2 and 4, this photosensitive layer 4 is
The intermediate layer 5 provided on the conductive support may be provided as a valve. In this way, when the photosensitive layer 4 has a two-layer structure, a Shimoshisha J4 photosensitive film having excellent electrophotographic A% properties can be obtained.

Further, in the + invention, as shown in Figures @5 and 6, the photosensitive layer 4 comprising the carrier-generating substance 7 dispersed in I@6 containing a carrier-transporting substance as a main component is coated on a conductive support. 1 may be provided directly or via an intermediate J@5.

When the bisazo compound of the present invention is used as a carrier-generating substance, carrier-transporting substances that can be used in combination with it include trinitrofluorenone, tetranitrofluorenone, and the like. In addition, heterocyclic compounds such as po-17 N-vinylcarbazole are used as lft! Polymers possessed in the L chain, triazole-spun spindles, oxadienol monopolymers,
Imitazole conductor, bilazo-11 fatty acid conductor, polyaryl alkane derivative, phenylene diamine derivative, hydrazone derivative, amino-substituted chalcone conductor, to1-noa-1-furamine conductor, carnoxole derivative, stilbene derivative, etc. The electron-donating material force that easily transports holes (can be mentioned, or the electron-donating material used in the present invention is
It is not limited to these.

When forming a two-layer photosensitive layer with a number of stripes, the second carrier generation layer, which is removed, can be formed by the following method.

B(1) A method of applying a solution of the above-mentioned bisazo compound in a suitable solvent, or a bath liquid in which a binder is added and mixed and dissolved.

B(2) A method in which the above-mentioned bisazo compound 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 added as necessary is applied.

The bath medium or dispersion medium used for forming the carrier generation layer includes n-butylamine, diethylamine, ethylenediamine, isobronoquinolamine, triethanolamine, triethylenecyamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, and cyclohexanone. , benzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, inglobanol, ethyl acetate, butyl acetate, dimethyl sulfoxide and the like.

When using a carrier generation layer or a carrier transport layer with a binding agent, any binding material can be used. It is preferable to use

As such a stomach molecule/car script, the following can be used as an analogy. Of course, it is not limited to these.

C (1) Polycarbonate C (2) Polyester C (3) Methacrylic resin C (4) Acrylate resin C (5) Polyvinyl chloride C (6) Polyvinylidene chloride C (7) Polystyrene C (8) Polyvinyl acetate C (9) Styrene-butanene copolymer C (10
) Vinyritine m-acrylonitrile copolymer C (31) Vinyl chloride-vinyl acetate copolymer C (1
2) Vinyl thickened-vinyl acetate-hydrothermal maleic acid copolymer C (13) Silicone resin C (1.1) Polycone-alkyd Jugetsu Hyaku C (15)
Phenol formaldehyde resin C (16) Styrene-alkylene resin C (17) Bo 17 N
- Vinylcarbazole C (li8) Forivinyl butyral These binding agents can be used alone or as a mixture of 1d2N or more.

The thickness of the carrier generation layer 2 formed in this way is 0.
．． It is preferably 0.01 μm % 2fJ am, and more preferably 0.05 μm to 577 m. Also,
When the carrier generating layer or the photosensitive layer is a dispersed thread, the particle size of the bisazo compound is preferably 577 m or less, more preferably 111 m or less.

The electroconductive nh used in the electrophotographic photoreceptor of the present invention includes metal plates such as aluminum and stainless steel, and conductive polymers, as well as tetraelectric compounds such as indium oxide and tin oxide, and aluminum on the surface of paper and plastic films. Examples include those coated with a thin layer of metal such as baladicum, threaded or laminated.

As an intermediate layer such as a masochistic layer or a barrier layer, in addition to the molecular bonding agent used as a binder for the photosensitive layer,
casein, polyvinyl alcohol, methylcellulose,
Organic molecules such as carboxymethyl cellulose or aluminum oxide are used.

The electrophotographic photoreceptor position of the present invention has the above-mentioned composition, and as is clear from the examples described later, it has excellent sensitivity characteristics, charging characteristics, and residual potential characteristics, and has little fatigue deterioration even when used repeatedly. It has poor durability.

Hereinafter, embodiments of the present invention will be specifically explained, but the embodiments of the present invention are not limited thereby.

Example 1 A monolithic support formed by laminating aluminum depressions on a polyester film was coated with vinyl chloride, vinyl acetate, and maleic anhydride. An intermediate layer with a thickness of 0.05 μm is provided,
On top of that, Exemplary Compound A (1) 2, & was mixed with 1°2-dichloroethane 1001rLt K and dispersed in a hole mill for 10 hours. After drying the dispersion, the film 1)' or 0.6z! mK and coated to form a carrier generation layer. Next, 6 g of 1-phenyl-3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline represented by the following structural formula and polycarbonate resin dried kneepirone S-1 were added.
000J (manufactured by Yoshikasu Chemical Co., Ltd.) 10 & 1. ．． The electrophotographic photoreceptor of the present invention was prepared by dissolving 2 dichloroethane in 70M and applying this bath solution on the carrier generation layer so that the film thickness after drying was 12 μm to form a carrier transport layer. did.

The photoreceptor obtained as described above was subjected to the following characteristic evaluation using an electrostatic paper tester manufactured by Kawaguchi Electric Seisakusho Co., Ltd. SP-428. The surface potential vA when charged for 5 seconds at a charging voltage of -6KV, then the illuminance on the photoreceptor surface is 35
The exposure amount (half-exposure amount') required to attenuate the surface potential VA by half by irradiating the surface potential VA with 7 liters of light so as to obtain 1 ux was determined. Also 301ux-5e
His surface potential (residual potential) after exposure with an exposure amount of C VR
I asked for After that, the surface of the photoreceptor was defrosted by irradiating light of 20 (+0 lux) for 1 second.

In addition, he repeated the same position 100 times and got 1 go.

The results are shown in Table 1.

Comparison) For 11u using the F bisazo compound as a carrier generating substance, a comparison photoreceptor was prepared by combining it with Example 1 and using a Hiei raJ photosensitive chamber with 7 and 0. How many measurements were carried out, and the results shown in Table 2 were obtained7.
'l.

Table 2 Comparative Example 2 A comparative photoreceptor was prepared in the same manner as in Example 1 except that Ffer bisazo compound was used as the carrier generating substance.

Regarding this comparative photoreceptor, measurements were carried out in the same manner as in Example 1, and the results shown in Table 3 were obtained.

As is clear from the results in Table 3 onwards, the electron 4 photoreceptor t4- of the present invention was different from the comparative photoreceptor in terms of τ, sensitivity, residual potential, and repetition stability. It is.

Examples 2 to 6 As a carrier photobiotic, Compound A (4) i
Af8), A (10), A (26),
An uninvented electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that A (39) was stiffened, and the same measurements were performed.The results shown in Table 4 were obtained.

Table 4 From the results, it is clear that the electrophotographic photoreceptor of the present invention exhibits excellent characteristics.

Practical II + 0 7 Aluminum is vapor-deposited on a polyester film, and the intermediate layer used in Example 1 is provided on the support, and then exemplified compound A (372 g and polycarbonate resin [Panlite L -1250J (manufactured by Teijin Chemicals) 2
g and 1,2-chloroethane were added to 100 mm of 1,2-chloroethane and dispersed in a hole mill for 10 hours.The film thickness after drying was 0.5 mm.
A carrier-generating layer was formed by coating the sample to a thickness of m. Next, N,N-diethylaminobenzaldehyde 1,1-diphenylhydrazone 69 represented by the structural formula -F and polycarbonate tallow ['Panlite L-1
250J 109 and 1,2-dichloroethane 110m
The electrophotographic photoreceptor of the present invention was prepared by applying a solution of yam in A to form a carrier transport layer so as to have a dry film thickness of 12 pm.

Measurements were carried out on this electron regeneration photoreceptor in the same manner as in Example 1, and the results shown in Table 5 were obtained.

Table 5 Example Exemplary compound A (Fl) as a carrier generating substance.

An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 7 except that A (9) and A (31) were used, and the same measurements were performed. Ta.

Actual image jl 11 Exemplary compound A (2) 2.9% was mixed with 100% of 1,2-dichloroethane on the support with an intermediate layer provided with the intermediate layer used in step 1, and mixed with a ball mill. A dispersion solution dispersed for 10 hours was applied so that the film thickness after drying was 0.5 pm K to form a carrier generation layer. Next, 6 g of 3-(p-methoxyphenyl)-6-medoxy 9-(p-methoxyphenyl)carbazole represented by the following structural formula.
and polyester resin [Vylon 200J (manufactured by Toyobo Co., Ltd.) [Og] were dissolved in 70 ml of 1,2-dichloroethane. An electrophotographic photoreceptor of the present invention was prepared.

When this electrophotographic photoreceptor was measured in the same manner as in Example 1, the results shown in Table 7 were obtained.

Table 7 Example j2 On the conductive support provided with the intermediate layer used in [Example 11], 29 was mixed with 5 mb of ethylenediamine and 95 ml of trihydrofuran. V, who was completely relieved, was formed by Kenta I (my friend's 1-Do J'-n (transferred to become 1, fi 71m and career fanged) \,....Kirani On top of that, [record +,・
6 g of 4-methoxy-4'-di(r)-t1)aminostilbene and 10.9 g of methacrylic resin (Mitsubishi Rayon Co., Ltd. N) were added to 70 g of 1,2-dichloroethane. The thickness of the film after drying is 17 μm.
m to form a carrier transport layer,
An electrophotographic photoreceptor of the present invention was prepared.

Is this electrophotographic photoreceptor treated in the same manner as in Example 1? )
As a result, the results shown in Table 81 were obtained.

8th table IIl! j Shio iJ 13 Fi on the tetraelectric support layer provided with the intermediate layer used in Example 1
ll 7J<Compound A (5) 3, li' and polycarbonate resin 1 Euhiron S-1000J 10
& and 4-(N-(p)methoxyphenyl-N-phenylamino)penmertecht- represented by the following structural formula
The present invention was prepared by mixing 6 g of 1,1-dynenylhydrazone and 1,009 g of i,-1,2-dichloroethane, dispersing in a ball mill for 12 hours, and coating the main specimen with K to a film thickness of 18 μm. 't11. Child photographic photosensitive photoreceptor.

Regarding this electronic copying paper tester rs
Electrophotography A:% m11j was determined using the Tynaminoku method using "Model P-428" (manufactured by Kawaguchi Electric Co., Ltd.).

Wipe the surface of the photosensitive layer at +6 KV for 5 seconds and apply the light of a tungsten rung until the illuminance on the surface of the photosensitive layer is 3Jlux K72, then reduce the exposure by half (E-shib).
), we found that E s2 = 4. ! '11ux-s
ec, and furthermore, the surface potential when giving an exposure trade of 3 (Jlux"Sec) (Gosarutun IM 11 is VR=
It was +18 V.

Example 14 The electrophotographic photoreceptor of the present invention obtained in Example 01 was mounted on a photographic device R U -Bix 200034 J (manufactured by Konishiroku Photo Industry Co., Ltd.) to form a copied image. However, the contrast was good and the gradation was excellent, and a clear image that was faithful to the pattern was obtained.
Even after reversing the edges 1,000 times, a clear image that remained exactly the same as the initial image was obtained, demonstrating stable characteristics.

As is clear from the above examples, the electrophotographic photoreceptor according to the present invention is significantly improved in sensitivity, residual potential, and repeatability.

[Brief explanation of the drawing]

1 to 6 are cross-sectional views showing examples of the mechanical configuration of the electrophotographic photoreceptor of the present invention, respectively. ■... Electrostatic support 2... Carrier generation layer: 3... Carrier transporting layer 4... Photosensitive) Zeng 5... Intermediate J Zeng 6... Layer 7 containing a carrier transporting substance ...Carrier-generating substance agent Yoshimi Kuwahara 61 Komo 5 Ko 6 Z diagram 4 diagram

Claims (2)

[Claims] (1) A photoreceptor comprising a photosensitive layer containing a bisazo compound represented by the following general formula [IJ] on a conductive support. General formula 10 represents a substituted or unsubstituted aromatic heterocycle, and 2 represents a 1-substituted or
Represents a group of atoms necessary to constitute an unsubstituted aromatic heterocycle or a substituted/unsubstituted aromatic heterocycle. YilL represents an unsubstituted carbamoyl group. (2) The photosensitive layer contains a carrier-transporting substance and a carrier-generating substance, and the carrier-generating substance has the following formula:
The photoreceptor according to claim 1, which is a bisazo compound represented by Ij.