JPS5936654A - Novel diamino compound, novel disazo compound and their preparation - Google Patents

Abstract

NEW MATERIAL:The compounds of formula I and formula II. EXAMPLE:9-Dicyanomethylene-2,7-diaminofluorene. USE:The compound of formula I is useful as an intermediate of the disazo compound of formula II, and the compound of formula II is useful as a photoconductive material of the photosensitive element for electrophotography, especially as a charge-generating material. An excellent laminate-type photosensitive element can be manufactured therefrom. PROCESS:The compound of formula I can be prepared by the catalytic reduction of the dinitro compound of formula III with hydrogen in an organic solvent such as dioxane in the presence of a catalyst such as Pd. The compound of formula I can be converted to the compound of formula II by dissolving the diazotized compound together with the coupler of formula IV in an organic solvent such as dimethylsulfoxide, adding a tetrazonium salt to the solution, and adding an aqueous solution of sodium acetate, etc. dropwise to the mixture.

Description

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

It has been known that certain disazo compounds are effective as charge-generating pigments used in charge-generating layers of laminated photoreceptors, which are one form of electrophotographic photoreceptors. The laminated photoreceptor referred to herein means that a charge-generating pigment having the ability to generate charge carriers by light is applied onto a conductive support by an appropriate method such as vacuum evaporation, coating of a pigment solution, or coating of a resin solution with a charge-generating pigment. A charge generation layer is formed as a thin layer by coating a dispersion liquid containing fine particles, etc.
Thereon is a charge transport layer (on which the charge carriers generated in the charge generation layer can be efficiently injected and where the charge carriers can be transferred).
Typically, this charge transport layer consists of a charge transport material and a binder resin. ) is formed on the photoreceptor.

The object of the present invention is to provide a new disazo compound that is effective in electrophotographic photoreceptors, particularly the above-mentioned laminated photoreceptor, and a new diamino compound that is an effective intermediate for producing the disazo compound. It is about providing. A laminated photoreceptor using a disazo compound derived from a diamino compound of the present invention has excellent characteristics.

Another object of the present invention is to provide the above-mentioned disazo compound and a novel method for producing a diamino compound that is effective for producing the disazo compound.

That is, one of the present invention provides formula (I) It is a diamino compound represented by

Another aspect of the present invention is the formula (II) It is a disazo compound represented by

The dinitro compound represented by is reduced to a diamino compound represented by formula (1), and this is combined with a coupler represented by shea! This is a method for producing a disazo compound represented by formula (II), which is characterized by carrying out a reaction.

The diamino compound represented by formula (I) is a useful intermediate for disazo compounds, and when combined with a suitable coupler, has a 9-dicyanomethylenefluorene skeleton, and the 2-, 5- and 7- A wide variety of disazo compounds having an azo group at this position can be synthesized. This disazo compound is expected to be used as a photoconductive material for electrophotographic photoreceptors, particularly as a charge generating material.

The disazo compound represented by formula (II) of the present invention is useful as a charge-generating substance for a laminated electrophotographic photoreceptor as described above, but it is also possible to disperse a charge-generating substance and a charge-transporting substance in the resin. It is useful as a charge-generating material in an electrophotographic photoreceptor having a single-layer type photosensitive layer, and as a photoconductive material in an electrophotographic photoreceptor having a photosensitive layer in which a photoconductive substance is dispersed in a resin.

In these manufacturing methods, 2 expressed by the above formula (1)
, 7-sinitro-9-dicyanomethylenefluorene is catalyzed by the introduction of hydrogen in a suitable organic solvent such as dioxane, acetic acid or N,N-dimethylformamide in the presence of a catalyst such as palladium on carbon or Raney nickel. It can be carried out by reduction, or it can also be carried out by reducing by reacting tin or iron in an organic acid such as acetic acid or an inorganic acid such as hydrochloric acid.

In addition, 2,7-diamitu-9- represented by the above formula (I)
Diazotization of dicyanomethylenefluorene can be carried out, for example, by adding thorium nitrite in an inorganic acid such as hydrochloric acid or sulfuric acid at a temperature of -10°C to 20°C. This diazotization reaction is completed in approximately 30 minutes to 3 hours.

The disazo compound of the formula (II) can be produced by allowing the diazotization reaction solution described above to act on the coupler of the formula (v) as it is, or by adding, for example, fluoroboric acid or an aqueous solution of sodium borofluoride. Any method may be used, including precipitating it as a tetrazonium salt, crystallizing it, and then allowing it to act. In practice, this coupling reaction is carried out by dissolving the coupler (naphthol As) in an organic solvent such as N,N-dimethylformamide or dimethyl sulfoxide (1) adding the above-mentioned tetrazonium salt, and then adding acetic acid (IJ). This can be carried out by dropping an aqueous alkaline solution such as an aqueous solution of aluminum.

This reaction is complete in approximately 5 minutes to 3 hours.

After completion of the reaction, the precipitated crystals are collected and purified by an appropriate method (for example, washing with water and/or an organic solvent, recrystallization method, etc.) to complete the production of the disazo compound.

Production examples of the diamino compound and disazo compound of the present invention produced in this manner are as follows.

Production Example 1 (Synthesis of diamino compound) 9-dicyanomethylene-2,7-cyamitsufluorene 1
5.9 gr, iron powder 27.5 gr and N,N-dimethylformamide 500 mj, 36% hydrochloric acid 7
An aqueous solution of hydrochloric acid diluted with 7 d of water was added. Next, the temperature of the above mixture was raised to 80 to 85°C over 1 hour and 30 minutes,
The mixture was further stirred at the same temperature for 2 hours. After cooling, hydroxide)
After adding a solution of 3.2g of IJum dissolved in 20+4ml of water, a small amount of diatomaceous earth was added and filtration was performed. The filtrate was concentrated and the residue was washed three times with 500 g of water to obtain 11.4 g (88.1%) of crude 9-dicyanomethylene-2,7-diamitsufluorene as a greenish brown powder. Melting point 290℃ or higher.

Next, this crude product was recrystallized from methyl cellosolve,
A pure product was obtained as black needle-shaped crystals.

Melting point 290℃ or above Elemental analysis value (as C16H1ON4) Calculated value Actual value 0% 74.40 74.55 H% 3.90 3.7O N% 21.69 21.49 Infrared absorption spectrum (KBr tablet method) νNu ( 1st
amine) 3340cIrL-'3430cII
L-” Shi Cmi N 2220m
The spectral diagram of -1 gas is shown in Figure 1.

9- Production Example 2 (Synthesis of disazo compound) To a mixture of 1.29 gr of the diamino compound synthesized in Production Example 1 and 201 d of 20% hydrochloric acid, 0% sodium nitrite was added.
．． 75 gr dissolved in 101jI/c of water.
The dropwise addition took 20 minutes at ℃. After that, 10
After stirring for a minute, sulfamic acid was added to the reaction mixture to decompose the remaining nitrous acid, and then filtered.

Separately, 2.63 g of 2-hydroxy-3-phenylcarbamoylnaphthalene (naphthol As) was dissolved in 300 d of N,N-dimethylformamide, and a diazonium salt solution was added to this solution at 10 to 15°C. Then,
A solution of 11.48 gr of IJ acetate dissolved in water at 46°C was added at 10 to 15°C for 2 minutes, and then stirred at room temperature for 2 hours to complete the reaction. The precipitated crystals were counted, 300% of N,N-dimethylformamide was added to the crystals, heated to 80°C and stirred for 2 hours, and then the crystals were counted again. After repeating this operation twice, the crystals were washed twice with 300+aJ10- of water and dried to obtain the disazo compound of the present invention as a black-purple powder.

Yield i: 2.54 gr (63.0% based on diamino form) Elemental analysis value (CS. H8°N804) Calculated value Actual value 0% 74.43 74.13 H% 3.75 3.68 N % 13.89 13.65 Infrared absorption spectrum (KBr tablet method) νNM (secondary amide) 3250cm-1νCEN
2225cm-'ν(:=Q 1
675儂-1 Further, this spectrum diagram is shown in FIG.

Application Example 76 parts by weight of the disazo compound of the present invention, 1260 parts by weight of a tetrahydrofuran solution (solid content concentration 2%) of a polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.), and 3700 parts by weight of tetrahydrofuran were pulverized and mixed in a ball mill. The resulting dispersion was applied onto the aluminum surface of a polyester base (conductive support) on which aluminum was vapor-deposited using a doctor blade, and air-dried to form a charge generation layer having a thickness of about one layer. - child, as a charge transport substance,
9-(4-diethylaminostyryl)anthracene 2
Parts by weight, polycarbonate resin (Panlite [1300
2 parts by weight (manufactured by Teijin Ltd.) and 16 parts by weight of tetrahydrofuran were mixed and dissolved to form a solution, which was applied onto the charge generation layer using a doctor blade and dried at 80°C for 2 minutes and then at 100°C for 5 minutes. A charge transfer layer having a thickness of about 20 μm was formed using the above steps, and a laminated photoreceptor was produced.

The photoconductor produced as described above was negatively charged by performing -6 kV corona discharge for 20 seconds using an electrostatic copying paper tester (manufactured by Kawaguchi Denki Co., Ltd., model 5P428). , leave it in a dark place for 20 seconds, measure the surface potential (Vpo ff) at that time, and then irradiate the surface with light using a tungsten lamp at an illumination intensity of 4.5 lux, so that the surface potential becomes % of vpo. The time (seconds) for the exposure was determined, and the exposure amount E% (lux/second) was calculated.

Result is V. -325V E% 6.3 Met.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram (KBr tablet method) of 2,7-diamitu-9-dicyanomethylene fluorene of the present invention. FIG. 2 is an infrared absorption spectrum diagram (KBr tablet method) of the disazo compound of the present invention. 13-

Claims (1)

[Claims] 1. A diamino compound represented by formula (I). 2. A disazo compound represented by formula (II). 3. Reducing the dinitro compound represented by the formula (1) to give a diaminated compound represented by the formula (1), and reacting this with a coupler represented by di.
) A method for producing a disazo compound represented by