JPS58144358A - Novel bisazo compound and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formulaI{A is group of formula II[Z is (substituted) aromatic carbon ring, etc.; R1 is (substituted) aromatic carbon ring residue or (substituted) aromatic heterocyclic residue; R2 is H, alkyl or (substituted) aromatic carbon ring residue]or formula III[R3 is (substituted) alkyl, (substituted) aralkyl, or (substituted) aryl]}. EXAMPLE:The compound of formula IV. USE:A photoconductive compound useful as a main component of a photosensitive material for electrophotography. PROCESS:The compound of formulaIcan be prepared by reacting the tetrazonium salt of formula V (X is anion) with the compound of formula VI, etc. An exact and clear copy having high contrast can be obtained by using the photosensitive material composed of said compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel bisazo compound and a method for producing the same.

Conventionally, inorganic photoreceptors having a photosensitive layer containing an inorganic photoconductive compound such as selenium, zinc oxide, or cadmium sulfide as a main component have been widely used as electrophotographic photoreceptors. but,
These are characterized by sensitivity, thermal stability, moisture resistance, durability, etc.
It is not always satisfactory, and there are restrictions in production and handling of selenium and cadmium sulfide due to their toxicity.

In order to overcome these drawbacks of inorganic photoreceptors, research and development have been actively conducted in recent years on organic photoreceptors having photosensitive layers containing various organic photoconductive compounds as main components. For example, Japanese Patent Publication No. 50-10496 describes an organic photoreceptor having a photosensitive layer containing poly-N-vinylcarbazole 2:,2,4.7-)linysilo-9-fluorenone. However, this photoreceptor is not necessarily satisfactory in terms of sensitivity and durability. In order to further improve these drawbacks, the carrier generation function and carrier transport function are shared by different substances, and a more sensitive organic photoreceptor has been developed. Attempts are being made to develop. In a function-separated type electrophotographic photoreceptor, each material can be selected from a wide range of materials, and a photoreceptor with arbitrary performance can be produced relatively easily. A large number of compounds have been proposed as IJ7 generating substances for photoreceptors. An example of using an inorganic compound as a carrier generating substance is amorphous selenium described in Japanese Patent Publication No. 43-16198, which is used in combination with an organic photoconductive compound. This carrier generation layer has a disadvantage in that it crystallizes due to heat and deteriorates the characteristics as a photoreceptor.

Furthermore, many electrophotographic photoreceptors using organic dyes or organic pigments as carrier-generating substances have been proposed. For example, as an electrophotographic photoreceptor containing a bisazo compound in the photosensitive layer, JP-A-47-37543, JP-A-53-133,
445, JP-A-55-117151, JP-A-56-116040, etc. are already known. However, these bisfuji compounds are not necessarily satisfactory in terms of characteristics such as sensitivity, residual potential, and stability during repeated use, and the selection range of carrier transport substances is also limited, making it difficult for electrophotographic processes. It does not fully satisfy a wide range of demands.

An object of the present invention is to provide novel bisfuji compounds that are particularly useful as organic photoconductive compounds that solve the various drawbacks of conventional organic photoconductive compounds, and methods for producing these compounds. The bisfuji compound is a compound represented by the following general formula.

[In the formula, z: tt-substituted/unsubstituted aromatic carbocycle or substituted/unsubstituted aromatic ring 11! ! A group of atoms necessary to form a ring.

R1: Substituted or unsubstituted aromatic carbon group R1: Hydrogen atom, alkyl group, or R3: Substituted or unsubstituted alkyl group, substituted or unsubstituted 7-ralkyl group, or substituted or unsubstituted 7-aryl group. ] This bisfuji compound is [wherein represents a XeGet anion. ] and the tetrazonium salt represented by the general formula (J8) (19) (21) (22) (23)
2.7-'/Nitro-9-fluorenone tomalonic acid nitrile by a known method, for example, J, Org, Ch
A diamino compound can be obtained as described in EWK1 Vol. 1, page 644 (1965), and a tetrazonium salt can also be obtained by using sodium nitrite. The counter ion of this tetrazonium salt is appropriately selected depending on the solubility of the coupling component in the next coupling reaction. For example, anions include C7e and H804θ.

Illustrated for So, Nae, BF4θ+ PF@e, etc.
! ? , : jJ [It may also be a double salt with a polyvalent metal salt such as Kabensen. Further, the solvent for the force tabling reaction is appropriately selected depending on the solubility of the tetrazonium salt and the coupling component, and water, N,N-dimethylformamide, etc. are preferable.

As a catalyst for the coupling reaction, a base catalyst is generally used, such as an inorganic base such as sodium acetate or aqueous sodium, or an organic base such as jetanolamine or tri-T-tanolamine.

The bisazo compound of the present invention produced as described above is particularly useful as a photoconductive compound, and the effects of the novel bisazo compound of the present invention will be explained below using an example of its use in an electroharp IIl sensor.

Exemplary compound (1) 2 jl and polycarbonate resin [
2 g of Panlite L-1250J (manufactured by Konjin Kasei Co., Ltd.) was added to 100 aJ of 1°2-dichloroethane, and dispersed in a ball mill for 12 hours. A 0.05 μm thick layer of vinyl chloride-vinyl acetate-maleic anhydride copolymer [Eslec MF-10J (manufactured by Tanezu Kagaku Co., Ltd.)] was formed as an intermediate layer on a polyester film laminated with aluminum using this dispersion. On top of that, there is one membrane when drying.

A Vctlt cloth was applied so that the voltage was 05 μmrLK, and a carrier generation layer was formed. On top of that, 3-(
.

-methoxystyryl) -9-(p-methoxyphenyl)carbazole (6 g) to polycarbonate) 4! t Mb
"Pan 5 I) With L-1250J 109 [1,
A carrier transport layer was formed by coating a solution dissolved in 2-dichloroethane 10011!7 so that the dry film thickness was 12 μmK, and an electrophotographic photoreceptor was prepared.

The body of W35Jll created in this way was attached to an electrophotographic copying machine r U-Bix 2000RJ (manufactured by Konishiroku Photo Industry Co., Ltd.), and the image was copied. I got a picture book.

Even after repeating this 12,000 times, there was no change.

An electrophotographic photoreceptor was prepared in the same manner as in Reference Example except that the following bisazo compound was used in place of Exemplified Compound (1).

Furthermore, when an image was similarly copied using this photoreceptor, only an image with a lot of fog was obtained.

In addition, as copying is repeated, the contrast of the copy image decreases, and after 2000 repetitions, the copy Wi
I can no longer get the image.

As described above, the bisfuji compound of the present invention is suitable as a photoconductive compound and is mainly used for this purpose.
It is not limited to this.

EXAMPLES Next, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.

Example 1 (Production example of exemplified compound (1)) 10.81 # (0.04 mol) of 2.7-sinitrofluorenone and 2.91 jl (0,044 mol) of malonic acid nitrile were mixed with a thermometer and a moisture separator. benzene in a mirofask with
'200111j and reflux. Vinegar W while refluxing! 17'ILt and 4d of piperidine were added and the mixture was refluxed for 2 hours, then cooled and the resulting crystals were collected by filtration.

This yellow crystal Jl was recrystallized from a mixed solvent of acetonitrile and N,N-dimethylformamide and yellow needle crystals 8.2
711 (yield 65.0%) was obtained. Melting point 184-188
°C (decomposition). 2.7-sinitrofluorene cy=174
Infrared absorption of 0cWt-'(C=O) disappears・C=224
0cIL-' (C=N)K The appearance of new infrared absorption confirms that 2,7-sinitro-9-fluorenylidene-propanedinitrile has been obtained.

The thus obtained 2,7-di=)0-9-fluorenylidene-propanzini) IJ Le 4.771 (
0,015 mol) was dispersed in 40ml of hydrochloric acid, and 14.41i of soot powder was slowly added to the dispersion while stirring. After addition, reflux for 1 hour, and after repulsion, add ice water at 300 W.
Lt was added, and the precipitate was collected by filtration and dried. yellow solid 4
．． 7511 (yield 95.8%) was obtained. In the infrared absorption spectrum (Fig. 1), this product shows that ν = 15 of the starting material.
205711-' (No,) and y=1342cr
The absorption of lL-1(Not) disappears and new ν=2
800CI! Since a broad absorption near L-" (NH,+) is observed, it is found that it is 2,7-di7minor-9-fluorenylidene-propanedinitrile dihydrochloride. Melting point: 137-140℃ ( decomposition).

Thus obtained 2,7-diami2-9-fluorenylidene-propanzini) 13-dihydrochloride 3.3
11 (0,01-v-ru) [i! ! ! This dispersion was cooled to 5° C. with stirring, and an aqueous solution of 1.41 dK of sodium nitrite dissolved in 20111j of water was added dropwise. After the dropwise addition was completed, the mixture was stirred for an additional hour, filtered, and the filtrate was mixed with 10I! Add ammonium hexafluorophosphate and collect the resulting crystals by filtration to obtain tetrazonium hexa7A.
The O phosphate salt was obtained. This crystal was dissolved in N,N-dimethylform 7amide zooW1i.

2-Hydroxy-3-su7toic acid anilide 5.2711
(0.02 mol) of N,N-dimethylformamide 20
0j&'CW%L, plus triethanolamine 5.5
The solution was cooled to 5° C., and the previous tetrazonium salt solution was added dropwise while stirring vigorously.

After the dropwise addition was completed, the mixture was stirred for 1 hour while being cooled, and further stirred for 2 hours at room temperature, and the resulting crystals were collected by filtration.

I want this crystal! The mixture was washed twice with N,N-dimethylform 7mide (7) and twice with a7tone (11), and then dried to obtain 6.7ON (yield: 83.0%) of a blue compound. # Infrared absorption spectrum of this blue compound! Shown in Figure 2. ν” 1
6805711-' (C=O) has absorption and elemental analysis (as CuHwrNsO4) HN Theoretical value (%) 74.43 3.74 13.89 Actual value (%) 74.61 3.70 13.67 and FD −
M/e, which is a molecular ion in mass spectrum, = 806
was observed, confirming that the target exemplary compound (1) was synthesized. The melting point is 300"C or higher. This bisfudi compound was mixed with 0.1% of 1.8-diazabicyclo(5,4,O]-7-undecene.

FIG. 3 shows the visible absorption spectrum when dissolved in N,N-dimethylformamide solution.

Examples 2 to 5 Various bis-1zo compounds were produced in the same manner as in Example 1, except that the coupling component in Example 1 was replaced with the compound in question. The results are shown in IIK.

Further, the infrared absorption spectra of these bisazo compounds are shown in FIGS. 4 to 7, respectively. Furthermore, electrophotographic photoreceptors were prepared using these bisfuji compounds in the same manner as in the above-mentioned application examples, and a photocopying test was conducted in the same manner, and good photocopied images were obtained in all cases.

Any of the bisfuji compounds shown in the exemplified compounds other than Examples can be coupled in the same manner using a 7-tall AS or 7-talic acid imide coupler to produce the bisazo compound of the present invention. I can do it.

Below, Muhaku

[Brief explanation of the drawing]

The first gJ is the 2,7-di7minonitril and 9-sashishioreeJ in Example IK? This is an infrared absorption spectrum (KBr method) of chloride hydrochloride. FIG. 2 and FIG. 3 are the infrared absorption spectrum (KBr method) and visible absorption spectrum of exemplary compound (1) in Example IK, respectively. Figures 4 to 7 are infrared absorption spectra (KBr method) of the bisazo compounds obtained in Examples 2 to 5, respectively.0 Agent: Yoshimi Kuwabara Patent'') Haruki Shimada, Director General 2 Name of the invention: Novel bisazo compounds Compound and its manufacturing method 3 Relationship with the person making the amendment +'l Patent applicant address 1-chome Nishi-Shinjuku, Shinjuku-ku, Tokyo
Name (127) Roku Konishi Photography - L Gyo Co., Ltd. 4 Agent 191 J, G Address 1 Sakura-cho, Hino-shi, Tokyo Application form 7 Contents of amendment (1) To the right of "Patent layer""(Patent Law No. (patent application pursuant to the provisions of the proviso to Article 38)" is inserted. (2) Insert [1,'number of inventions stated in the scope of claims 2] between the "title of the invention" and the "inventor."

Claims (1)

[Claims] (1) General formula [wherein A is 2: A group of atoms necessary to constitute a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic heterocycle. R1: hydrogen atom, alkyl group, and Rs: substituted/unsubstituted alkyl group, substituted-unsubstituted 7-ralkyl group, or substituted/unsubstituted 1-aryl group. ] A bisfuji compound represented by General formula [In the formula, xo represents an anion. ] and the general formula [where z: is a substituted/unsubstituted aromatic carbocyclic ring or a substituted/unsubstituted aromatic heterocyclic ring: a substituted/unsubstituted full cow group, a substituted □ - Represents an unsubstituted 7ralkyl group or a substituted/unsubstituted 7aryl group. ] A general formula characterized by reacting with a compound represented by [where A is the same as above]. ] A method for producing a novel bisfuji compound represented by