JPH0239542B2 - SHINKINABISUAZOKAGOBUTSUOYOBISONOSEIZOHO - Google Patents

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. However, these have limited sensitivity, thermal stability,
Moisture resistance, durability, etc., are not always satisfactory, and selenium and cadmium sulfide have limitations in production and handling 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, in Japanese Patent Publication No. 50-10496, poly-N-vinylcarbazole and 2,4,7
There is a description of an organic photoreceptor having a photosensitive layer containing -trinitro-9-fluorenone. However, this photoreceptor is not necessarily satisfactory in sensitivity and durability. In order to further improve these drawbacks, attempts have been made to develop organic photoreceptors with higher sensitivity by assigning the carrier generation function and the carrier transport function to different substances. For a functionally separated electrophotographic photoreceptor, each material can be selected from a wide range, and a photoreceptor having arbitrary performance can be produced relatively easily. Many compounds have been proposed as carrier generating substances for such functionally separated electrophotographic photoreceptors. As an example of using an inorganic compound as a carrier generating substance, for example,
-There is amorphous selenium described in Publication No. 16198,
Although this is used in combination with an organic photoconductive compound, it has the disadvantage that the carrier generation layer made of amorphous selenium crystallizes due to heat, deteriorating its properties 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, Japanese Patent Application Laid-open No. 47-37543,
JP-A-53-133445, JP-A-55-117151, JP-A-56-116040, etc. are already known. However, these bisazo compounds are not necessarily satisfactory in terms of characteristics such as sensitivity, residual potential, and stability during repeated use.
Furthermore, the selection range of carrier transport substances is also limited, and the wide range of requirements of electrophotographic processes cannot be fully satisfied. An object of the present invention is to provide novel bisazo 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 bisazo compound of the present invention is a compound represented by the following general formula. [In the formula, A is

【formula】 or

A bisazo compound represented by the formula: where R ₁ is a phenyl group or a phenyl group substituted with a methyl group or a naphthyl group]. This bisazo compound is [In the formula, X represents an anion. ] and the general formula

【formula】 or

[In the formula, R ₁ represents a phenyl group or a phenyl group or a naphthyl group substituted with a methyl group. ]

It is produced by reacting with the compound represented by. The bisazo compounds of the present invention thus obtained are illustrated below, but the present invention is not limited only to these exemplified compounds. The tetrazonium salt, which is a raw material compound of the present invention, can be prepared by, for example, 2,7-dinitro-9-fluorenone and malonic acid nitrile by a known method, for example, by J.Org.
Chem., Vol. 30, p. 644 (1965), 2,7-dinitro-9-fluorenylidene-propanedinitrile obtained by dehydration condensation is reduced to obtain a diamino compound, and further nitrite is added. Tetrazonium salts can be obtained with sodium. The counter ion of the tetrazonium salt here is appropriately selected depending on the solubility of the coupling component in the next coupling reaction. For example, anions include Cl , HSO ₄ , SO ₃ Na , BF ₄ , PF ₆
etc., and may also be used as a double salt with a polyvalent metal salt such as zinc chloride. Further, the solvent for the coupling reaction is appropriately selected depending on the solubility of the tetrazonium salt and the coupling component, and water, N,N-dimethylformamide, etc. are preferable. A base catalyst is generally used as a catalyst for the coupling reaction, such as an inorganic base such as sodium acetate or sodium hydroxide, or an organic base such as diethanolamine or triethanolamine. The bisazo compound of the present invention produced as described above is particularly useful as a photoconductive compound,
The effects of the novel bisazo compound of the present invention will be explained below using an example of its use in an electrophotographic photoreceptor. 2 g of exemplified compound (1) and 2 g of polycarbonate resin "Panlite L-1250" (manufactured by Teijin Chemicals)
Add to 100ml of 2-dichloroethane and use a ball mill to
Dispersed for 12 hours. This dispersion was applied as an intermediate layer on a polyester film laminated with aluminum, and vinyl chloride-vinyl acetate-maleic anhydride copolymer "Eslec MF-10" (manufactured by Sekisui Chemical Co., Ltd.)
A layer of 0.05 μm thick was provided, and the layer was coated to a dry film thickness of 0.5 μm to form a carrier generation layer. Moreover, as a carrier transport material, 3
-(p-methoxystyryl)-9-(p-methoxyphenyl)carbazole 6g with 10g of polycarbonate resin "Panlite L-1250" 1,
A carrier transport layer was formed by applying a solution dissolved in 100 ml of 2-dichloroethane to a dry film thickness of 12 μm, and an electrophotographic photoreceptor was prepared. When the photoreceptor thus created was attached to an electrophotographic copying machine "U-Bix2000R" (manufactured by Konishiroku Photo Industry Co., Ltd.) and the image was copied, the resulting copied image was high in contrast, faithful to the original, and clear. Obtained.
This did not change even after repeating this 2000 times. 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. Furthermore, as copying was repeated, the contrast of the copied image decreased, and after 2000 repetitions, it was no longer possible to obtain a satisfactory copied image. As described above, the bisazo compound of the present invention is suitable as a photoconductive compound and is mainly used for this purpose, but it is not limited thereto. 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)) 2,7-dinitrofluorenone 10.81 g (0.04
mol) and malonic acid nitrile 2.91g (0.044 mol)
is mixed with 200 ml of benzene and refluxed in a three-necked flask equipped with a thermometer and a water separator. While refluxing, 7 ml of acetic acid and 4 ml of piperidine are added, and after refluxing for a further 2 hours, it is cooled and the resulting result is filtered off. The yellow crystals were recrystallized from a mixed solvent of acetonitrile and N,N-dimethylformamide to obtain 8.27 g of yellow needle crystals (yield: 65.0%). Melting point 184-188
°C (decomposition). ν= of 2,7-dinitrofluorene
Infrared absorption of 1740cm ^-1 (C=O) disappears, ν=2240
The appearance of new infrared absorption at cm ^-1 (C≡N) confirms that 2,7-dinitro-9-forolenylidene-propanedinitrile was obtained. 2,7-dinitro-9 thus obtained
-Fluorenylidene-propanedinitrile 4.77g
(0.015 mol) was dispersed in 40 ml of hydrochloric acid, and 14.4 g of tin powder was slowly added to this dispersion while stirring. After addition, reflux for 1 hour, and then add ice water after reaction.
300 ml was added, and the precipitate was collected by filtration and dried. 4.75 g (yield 95.8%) of a yellow solid was obtained. In the infrared absorption spectrum ( ^Fig . ₁ ) ^, this _product shows
The absorption disappears and a new broad absorption near ν = 2800 cm ^-1 (NH ₃ +) is observed, indicating that it is 2,7-diamino-9-fluorenylidene-propanedinitrile dihydrochloride. Melting point 137-140
℃ (decomposition). 2,7-diamino-9 thus obtained
-Disperse 3.31 g (0.01 mol) of fluorenylidene-propanedinitrile dihydrochloride in 100 ml of hydrochloric acid,
This dispersion was cooled to 5° C. while stirring, and an aqueous solution of 1.4 g of sodium nitrite dissolved in 20 ml of water was added dropwise. After the addition was completed and stirred for an additional hour,
After filtration, 10 g of ammonium hexafluorophosphate was added to the filtrate, and the resulting crystals were collected by filtration to obtain tetrazonium hexafluorophosphate salt. The crystals were dissolved in 200 ml of N,N-dimethylformamide. 2-Hydroxy-3-naphthoic acid anilide 5.27
g (0.02 mol) of N,N-dimethylformamide
Dissolve in 200ml and additionally triethanolamine 5.5
g was added, the solution was cooled to 5° C., and the previous tetrazonium salt solution was added dropwise with vigorous stirring.
After the dropwise addition was completed, the mixture was stirred for 1 hour while cooling, and further stirred at room temperature for 2 hours, and the resulting crystals were collected by filtration. The crystals were washed twice with N,N-dimethylformamide (1) and twice with acetone (1), and then dried to obtain 6.70 g (yield: 83.0%) of a blue compound. The infrared absorption spectrum of this blue compound is shown in FIG. It has absorption at ν=1680cm ^-1 (C=O) and elemental analysis (as C ₅₀ H ₃₀ N ₈ O ₄ ) C H N Theoretical value (%) 74.43 3.74 13.89 Actual value (%) 74.61 3.70 13.67 and FD− M/ which is a molecular ion in mass spectrum
Since e=806 was observed, the target example compound (1)
was confirmed to have been synthesized. Melting point is over 300℃. In addition, this bisazo compound was added to 0.1% of 1,
FIG. 3 shows the visible absorption spectrum of 8-diazabicyclo[5,4,0]-7-undecene dissolved in N,N-dimethylformamide solution. Examples 2 to 5 Various bisazo compounds were produced in the same manner as in Example 1, except that the coupling components in Example 1 were replaced with the compounds listed in the table. The results are shown in Table 1. Further, the infrared absorption spectra of these bisazo compounds are shown in FIGS. 4 to 7, respectively. Further, electrophotographic photoreceptors were prepared using these bisazo compounds in the same manner as in the above-mentioned application examples, and a photocopying test was conducted in the same manner, and good copy images were obtained in all cases. Any of the bisazo compounds shown in the exemplified compounds other than Examples can be coupled in the same manner using a naphthol AS-based or naphthalic acid imide-based coupler to produce the bisazo compound of the present invention.

【table】

【table】 [Brief explanation of drawings]

Figure 1 shows the 2,7-diamino-
This is an infrared absorption spectrum (KBr method) of 9-fluorenylidene-propanedinitrile dihydrochloride.
Figures 2 and 3 are infrared absorption spectra (KBr method) of exemplary compound (1) in Example 1, respectively.
and visible absorption spectrum. 4 to 7 are infrared absorption spectra (KBr method) of the bisazo compounds obtained in Examples 2 to 5, respectively.

Claims (1)

[Claims] 1. General formula [Wherein A is [Formula] or [Formula], and R ₁ is a phenyl group or a phenyl group or a naphthyl group substituted with a methyl group.] A bisazo compound represented by the following formula. 2 General formula [In the formula, X represents an anion. ] and the general formula [Formula] or [Formula] R ₁ represents a phenyl group or a phenyl group or a naphthyl group substituted with a phenyl group or a methyl group. ] General formula characterized by reacting with a compound represented by [In the formula, A is the same as above. ] A method for producing a novel bisazo compound represented by