JPS638993B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel disazo compound and a method for producing the same. BACKGROUND ART Inorganic photoreceptors using inorganic photoconductive materials such as selenium, cadmium sulfide, and zinc oxide have been widely used in electrophotography. ``Electrophotography'' generally refers to a method in which a photoconductive photoreceptor is first charged in a dark place by corona discharge, etc., and then subjected to imagewise exposure to selectively discharge the charges in the exposed areas, leaving the unexposed areas free of electrostatic charge. This is one of the image forming methods that leaves an image and further visualizes this latent image using a developing means using toner or the like to form a surface image. The basic characteristics required of the photoreceptor used in such electrophotography are (1) ability to be appropriately charged in the dark, (2) excellent charge retention in the dark, and ability to discharge the charge. (3) high photosensitivity and rapid discharge of charges upon irradiation with light; and excellent mechanical strength and flexibility. Although the conventional inorganic photoreceptors have several advantages, they also have various disadvantages. For example, the selenium photoreceptors currently widely used are (1) to
Although the condition (3) is satisfied to a considerable extent, the mechanical strength and flexibility are not satisfactory. In particular, as a variety of processes have been adopted in recent electrophotography methods, photoreceptors that are compatible with all of these processes have become required, and for example, flexible shapes are required. However, the selenium photoreceptor has low flexibility and is difficult to produce in such a shape. Similar drawbacks can also be cited for inorganic photoreceptors other than selenium photoreceptors. In recent years, in order to eliminate the drawbacks of these inorganic photoreceptors, organic electrophotographic photoreceptors using various organic photoconductive materials have been researched and developed, and have been put into practical use.
For example, a photoreceptor in which a photosensitive layer containing poly-N-vinylcarbazole and 2,4,7-trinitrofluoren-9-one is provided on a support (US Patent No.
3484237) Photoreceptor provided with a photosensitive layer containing poly-N-vinylcarbazole sensitized with a pyrylium salt dye (see Japanese Patent Publication No. 48-25658),
A photoreceptor with a photosensitive layer mainly composed of a disazo pigment (see Japanese Patent Laid-Open No. 47-37543), a photoreceptor with a photosensitive layer mainly composed of a eutectic complex consisting of a dye and a resin (See Publication No. 10735, 1972). Although these organic photoreceptors have improved the mechanical properties and flexibility of the inorganic photoreceptors to some extent, they generally have low photosensitivity and do not fully satisfy the requirements for electrophotographic photoreceptors. In general, the characteristics of an electrophotographic photoreceptor are greatly influenced by the materials used, the manufacturing method, etc., but they are particularly dependent on the photoconductive material. For this reason, research into photoconductive materials has been actively conducted, and the present invention also relates to this. An object of the present invention is to provide a novel disazo compound which is particularly useful as a photoconductive material and which solves the drawbacks of the conventional photoconductive materials for photoreceptors, and furthermore, to provide a method for producing the compound. It is to provide. That is, one of the aspects of the present invention is the general formula [In the formula, A is

[Formula] or

[Formula] (R is selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a nitro group, a dimethylamino group, a diethylamino group, and a phenyl group, and n is 1 or represents an integer of 2)], and the other one is a disazo compound represented by the formula The compound represented by and the general formula

[Formula] or

[Formula] (wherein R is selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a nitro group, a dimethylamino group, a diethylamino group, and a phenyl group, and n is An integer of 1 or 2, and X represents an anionic functional group. The disazo compound represented by the general formula 1 of the present invention is a novel compound that is colored crystal at room temperature. Specific examples are shown in Table 1 below, along with melting points, elemental analysis values, and infrared absorption spectrum data.

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[Table] To actually produce a disazo compound of the general formula according to the method of the present invention, N,N'-bis(2
-Hydroxy-3-naphthoyl)-4,4'-diaminodiphenylmethane and a naphthalenediazonium salt or benzenediazonium salt derivative of the general formula are dissolved in an organic solvent such as N,N-dimethylformamide or dimethyl sulfoxide, and Approximately −10
An alkaline aqueous solution such as a sodium acetate aqueous solution may be added dropwise at a temperature of ℃ to 20℃. Reaction is 5-30
The process is completed in minutes, and the desired novel disazo compound of the present invention can be obtained. The appropriate amount of the compound of the general formula to be used is about 2 to 5 moles per 1 mole of the compound of the formula. Also, the compound of the formula is, for example, 4,4′-
Diaminodiphenylmethane

[Formula] and 2-hydroxy-3-naphthoic acid chloride

It can be easily obtained by reaction with [Formula]. Specifically, this reaction involves dissolving the former diphenylmethane in an organic solvent such as dioxane, adding the latter naphthoic acid chloride,
It is carried out by heating in the presence of a basic catalyst such as pyridine, or by heating these diphenylmethane and 2-hydroxynaphthoic acid in an organic solvent such as toluene in the presence of phosphorus trichloride. . The disazo compound of the present invention obtained as described above is particularly useful as a photoconductive material for electrophotographic photoreceptors. Thus, for example, (1) the disazo compound is mixed with a suitable resin binder such as polyester, polyamide, polyurethane, polyketone, polycarbonate, polystyrene, polyvinyltoluene, etc. in fine particles (about 0.05 mm in diameter).
(2) In addition to the above system (1), an inorganic photoconductive material (e.g., known cadmium sulfide, cadmium sulfide-selenium, etc.) is provided on a conductive support. or a photoreceptor to which an organic photoconductive material (e.g., known poly-N-vinylcarbazole, polyvinylpyrene, etc.) is added; Examples of applications of the new disazo compound include a laminated type photoreceptor formed by a photoreceptor method and a layer of another photoconductive substance formed thereon. The photoreceptor produced in this manner is no inferior to conventional photoreceptors and can fully achieve the object of the present invention. Next, the effects of the novel disazo compound of the present invention will be explained using an example of its use in a photoreceptor. 2 parts by weight of disazo pigment of Compound No. 9 and 98 parts by weight of tetrahydrofuran are pulverized and mixed in a Pall mill, and the resulting dispersion is applied onto an aluminum-deposited polyester film with a doctor blade and air-dried to form a charge carrier with a thickness of 1μ. A generation layer was formed.
Separately, 2 parts by weight of 9-(4-diethylaminostyryl)anthracene and 2 parts by weight of polycarbonate resin [Panlite L, manufactured by Teijin Co., Ltd.] were dissolved in 16 parts by weight of tetrahydrofuran, and this was applied onto the charge carrier generation layer with a doctor blade. It was coated and dried at 120° C. for 10 minutes to form a charge transfer layer with a thickness of 16 μm, thereby obtaining a laminated photoreceptor. Next, a -6KV corona discharge was applied to the photosensitive layer surface of this photoreceptor using a commercially available electrostatic copying paper tester for 20 seconds to make it negatively charged, and then it was left in a dark place for 20 seconds, and the surface potential at that time V _pp ( volts), then irradiate the photosensitive layer with light from a tungsten lamp so that the surface potential reaches 20 lux, find the time (seconds) it takes for the surface potential to become 1/2 of _Vpp , and reduce it by half. The exposure time was set to T1/2 (seconds). the result

It was [formula]. Examples are shown below. Example 1 [N,N'-bis(2-hydroxy-
3-Naphthoyl)-4,4'-diaminodiphenylmethane 9.9gr of 4,4'-diaminodiphenylmethane was dissolved in 100ml of dioxane, while 20.7gr of 2-hydroxy-3-naphthoic acid chloride was dissolved in 150ml of dioxane. The above solution was added, and 9.5g of pyridine was added, followed by reaction at 70-95°C for 8 hours. Collect the formed pale yellow precipitate and wash with water,
Dry. This product was recrystallized from a mixed solvent of N,N-dimethylformamide and water, giving pale yellow crystals.
18.2 gr (yield 67.7%) was obtained. Melting point Elemental analysis above 290℃ C H N Calculated value (%) 78.05 4.87 5.20 Actual value (%) 77.81 4.78 5.07 Infrared absorption spectrum (KBr tablet method) is the first
As shown in the figure, absorption bands based on amide groups were observed at 1660 cm ^-1 and 1640 cm ^-1 . Example 2 (Disazo compound: Production of compound No. 1) 1.35 gr of N,N'-bis(2-hydroxy-3-naphthoyl)-4,4'-diaminodiphenylmethane obtained in Example 1 and benzenediazonium N,N cooled with 0.96g of tetrafluoroborate
-Dissolved in 300 ml of dimethylformamide, and added a solution consisting of 0.82 gr of sodium acetate and 10 ml of water dropwise at room temperature for about 5 minutes.
Stir for hours. After that, remove the formed precipitate,
Wash three times with 300 ml of water and then five times with 200 ml of N,N-dimethylformamide. Furthermore, residual N,N-dimethylformamide was washed away with acetone, and dried at 70°C under a reduced pressure of 2 mmHg to obtain 1.8 g (96%) of the disazo compound of Compound No. 1 shown in Table 1.
I got it. The infrared absorption spectrum of the obtained disazo compound is shown in FIG. Examples 3 to 17 (Disazo compound: Compound No. 2 to
16) Compounds No. 2 to 1 shown in Table 1 were prepared in the same manner as in Example 2, except that the compound shown in Table 2 below was used as the diazonium component in the production of the disazo compound of Compound No. 1 in Example 2. Sixteen disazo compounds were prepared.

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【table】 [Brief explanation of the drawing]

Figure 1 shows the N,N'-bis(2-
This is an infrared absorption spectrum of hydroxy-3-naphthoyl)-4,4'-diaminodiphenylmethane, and FIG. 2 is an infrared absorption spectrum of the novel disazo compound of the present invention obtained in Example 2.

Claims (1)

[Claims] 1. General formula [In the formula, A is [Formula] or [Formula] (R consists of a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a nitro group, a dimethylamino group, a diethylamino group, and a phenyl group) selected from the group, n represents an integer of 1 or 2)] A disazo compound represented by the following. 2 formulas A compound represented by the general formula [Formula] or [Formula] (wherein R is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a nitro group, a dimethylamino group, a diethylamino group) and a phenyl group, n is an integer of 1 or 2, and X represents an anionic functional group). [In the formula, A is [Formula] or [Formula] is as described above.] A method for producing a disazo compound represented by the following.