JPS59197465A - Novel tetrazonium salt compound, novel disazo compound and production thereof - Google Patents

Abstract

NEW MATERIAL:Disazo compounds of formula I wherein A is a group of formula II, III, IV or V (wherein R is alkyl, alkoxy, nitro, halogen, cyano, halomethyl; n is 0, 1, 2, 3; when n is 2 or 3, R's may be the same or different groups). USE:Disazo compds. effective in electrophotographic materials, particularly, laminated photosensitive materials. Laminated photosensitive materials using the compd. of formula I is highly sensitive and has excellent image reproducibility of a red copy since the sensitive wavelength range lies only in a short wavelength side (450-600nm) of visible light. PREPARATION:A diamino compd. of formula VI is diazotized to form a tetrazonium salt which is then reacted with a compd. of formula VIII, IX, X or X I to produce the desired compd.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a novel tetrazonium salt compound, a novel disazo compound, and a method for producing soybean paste.

BACKGROUND OF THE INVENTION It has been known that certain types of disazo compounds are effective as charge-generating pigments used in charge-generating layers of laminated photoreceptors, which are one form of electrophotographic photoreceptors. Here, f, Im photoreceptor refers to a conductive support in which a charge-generating pigment having the ability to generate charge carriers by light is applied to a conductive support by an appropriate method such as wall evaporation, coating of a pigment solution, or A v-charge generation layer is formed as a single layer of N in a dispersion chamber containing fine particles of pigment dispersed in a resin solution, and the charge carriers generated in the charge generation layer can be efficiently injected onto the layer, and the charge carriers can be moved easily. charge transport layer (usually this charge transport layer comprises a charge transport material and
It consists of a binder resin. ) is formed on the photoreceptor.

Conventionally, as the disazo compound used in this yuzu photoreceptor, for example, benzidine-based disazo compounds described in JP-A No. 47-37543 and JP-A No. 52-55643, or special Kaisho 52-
Stilbene-based disazo compounds described in Japanese Patent No. 8832 are known. However, conventional photoreceptors using disazo compounds generally have low sensitivity;
00 nm, and judging from this light wavelength characteristic, the image re-fA property of the red source 4 was poor. Therefore, when this photoreceptor is installed, it is necessary to use a filter that cuts out red light, which is disadvantageous in terms of copying machine equipment.

OBJECTIVE The object of the present invention is to provide effective
In particular, it is another object of the present invention to provide a novel tetrazonium salt compound from which a wide range of disazo compounds can be obtained which are effective in the above-mentioned at]-type h photoreceptors. In particular, the purpose is to provide a novel disazo compound that is effective in the above-mentioned laminated photoreceptor, and the laminated photoreceptor using the disazo compound of the present invention is more effective than the conventional photoreceptor using a disazo compound. Since its sensitivity is high and its sensitive wavelength range is limited to the short wavelength fill (approximately 450 to 600 nm) in the visible range, it also has excellent reproduction of red original images.

Still another object of the present invention is to provide a method for producing the above-mentioned disazo compound.

Specifically, one aspect of the present invention is a novel tetrazonium salt compound represented by the following general formula (1).

(In the formula, X represents an anionic functional group.) Another aspect of the present invention is a novel disazo compound represented by the general formula (n).

where R is an alkyl group such as methyl, ethyl, propyl, butyl, an alkoxy group, a nitro group, a halogen, a cyano group, or a cyano group. represents a rometeru group, n is an integer of 0, 1, 2 or 3, and when n is an integer of 2 or 3, R may be the same or different groups. ) to cause thorns. ] Furthermore, another aspect of the present invention is to diazotize a diamino compound represented by formula (ffi) to obtain tetrazonium compound represented by formula (1) (wherein, X represents an anionic functional group). salt, then this tetrazonium salt, and the bifurcated formula (IV), (V), (VD or (■
) A novel disazo compound represented by the general formula (R and n are as described above) is reacted with a compound represented by This is a manufacturing method.

The tetrazonium salt compound represented by formula (1) is a useful intermediate for disazo compounds, and when combined with an appropriate cassillary, it has a xanthone skeleton and its 2
A simple disazo compound having an azo group at the 7-position and the 7-position can be synthesized. This disazo compound is expected to be used as a photoconductive material for electrophotographic photoreceptors, particularly as a charge-reducing material.

e in the tetrazonium salt compound of general formula (1)
Representative examples of e e anionic functional groups include CI, Br, and I.

AsF6, SbF? Preferably,
BF? It is.

As mentioned above, the disazo compound of the present invention is useful as a charge-generating substance for electrophotographic photoreceptors of the product Ifim. Useful as a charge-generating material in an electrophotographic photoreceptor having a dispersed single-layer 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. It is.

The tetrazonium salt represented by the general formula (I) of the present invention can be obtained, for example, by reducing 2,7-cinitroxanthone and then diazotizing it. 2,
The preparation of 7-sinitroxanthone and 2,7-diamitoxanthone has been described, for example, by A.
and H*A, Walker.

Journal of Chemical 5ocie
ty, 1953, 1348 (1953), the xanthone was nitrated in fuming nitric acid to give 2,
7-sinitroxanthone, which was dichlorinated in hydrochloric acid.
By reducing the 2,7-
Diamitsukisanthone is obtained. This reduction reaction is 95~
The process is completed in about 3 hours at a temperature of 100°C.

Diazotization of the 2.7-diaminoanthraquinone is carried out by adding sodium 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. Furthermore, a tetrazonium salt can be obtained by adding, for example, a borofluoride aqueous solution or a 7-color sodium borofluoride water bath to this diazotization reaction solution.

The disazo compound of the general formula (II) can be produced by directly allowing the diazotization reaction solution to act on a coupler, or by adding, for example, hydrogen borofluoride or borofluoride to the diazotization reaction solution. It can also be obtained by isolating the tetrazonium salt by adding an aqueous sodium solution or the like to precipitate it as a tetrazonium salt of general formula (I), and then reacting the tetrazonium salt with Cassirer. In practice, this reaction is carried out by dissolving a tetrazonium salt and cassiller in a supernatant solvent such as N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO), and then dissolving the tetrazonium salt and cassillary in a mixed bath at about -10°C to 40°C. This is carried out by dropping an alkaline aqueous solution such as an acetic acid aqueous solution at °C. This reaction is complete in approximately 5 minutes to 3 hours.

After the reaction is completed, 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.

The novel disazo compound of the present invention is a colored crystal at room temperature, and specific examples thereof are shown in Table 1 below along with melting points, cumulative analysis values, and infrared absorption spectrum data.

(Leaving space below) Example 1 (Preparation of tetrazonium fence) 29.1 fl of 2,7-diamituxanthone was added to hydrochloric acid consisting of 224 liters of water and 1 liter of salt, and heated to about 60'Q. After heating for 1 hour, it was cooled to -3°C, and then 18.7 liters of nitrite and 9011 liters of water were added to it.
The bath liquid dissolved in the solution was lowered at a temperature of -3°C to 0°C for 50 minutes. Thereafter, after stirring at the same temperature for 30 minutes, 150 ml of 42% borohydrogen fluoride was added to the reaction solution, and the precipitated crystals were separated, washed with water, and heated to 47.13,1 it (
Pale yellow crystals of tetrazonium difluoroporate were obtained with a yield of sax%). The decomposition point is 145°C or higher, and the infrared absorption spectrum (KBr tablet method) is as shown in the -1e 1st case, with an absorption band based on N2 at 228 O, and an absorption band based on N2 at 1685 crn-', and an absorption band based on >C=O ( Absorption bands were observed.

Example 2 (Production of disazo compound A1) Tetrazonium salt obtained in Example 15. Q l/ and 2-hydroxy-3-7toenyl anilide 6 as a coupling component,
25 & (02 moles of tetrazonium salt) were dissolved in 700 ml of cooled N,N-dimethylformamide, and a bath solution consisting of 4.0.9 ml of sodium acetate and 35 ml of water was added to the mixture at 5 to 10°C. for 20 minutes at temperature'C
After both were removed and cooling was discontinued, the mixture was further stirred at room temperature for 3 hours. Thereafter, the formed precipitate was collected and washed three times with 700 ml of N,N-dimethylformamide heated to 80°C, then washed twice with 700 ml of water, and then washed at 80°C with 2 Wj!
After drying under reduced pressure of nHg, ml of the disazo compound 8.2.9 (yield 90.0%) of the compound shown in Table 1 was obtained. This disazo compound appeared as a red powder, and its infrared absorption spectrum (KBr tablet method) was shown in FIG.

Examples 3 to 40 (Production of disazo compound points 2 to 39)
In the production of the disazo compound of compound Al in Example 2, compounds A2 to 39 shown in Coating 1 were prepared in the same manner as in Example 1, except that the compounds in Table 2 below were used as coupling components.
disazo compound was prepared.

Further, infrared absorption spectra of five representative disazo compounds of the present invention are shown in Figures 3 to 9.

Figure 3: Compound A13 Figure 4: Compound A
16 Figure 5... Compound A31 Figure 6... Compound point 32 Figure 7... Compound A 33 Figure 8... Compound A 34 Figure 9... Compound A35 (blank below) Table 2 Effects As mentioned above, the disazo compound of the present invention is effective as a photosensitive material for electrophotographic photoreceptors, particularly as a charge-generating material for laminated thermal photoreceptors. An example of usage is shown. Furthermore, in order to clarify the inventive step of the present invention, a comparison with conventional disazo compounds is also shown.

Application example: 76 parts by weight of the disazo compound &13 of the present invention, 1260 parts by weight of a tetrahydrofuran solution (solid content 6%, 2L%) of polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.), and 3700:fit parts of tetrahydrofuran were ground in a sol mill. The resulting dispersion was applied using a doctor blade onto the aluminum surface of an aluminum-vaporized polyester base (conductive support), and air-dried to form a charge generation layer with a thickness of approximately 1 μm. . On the other hand, 9-
Ethylcarbasol-3-aldehyde 1-methyl-1
- 2 parts by weight of phenylhydrazof, 2 parts by weight of polycarbonate resin (Gunlite 1300, manufactured by Teijin Kasei Ltd.) and 16 parts by weight of tetrahydrofuran were mixed and dissolved to form a solution, and this was applied to the charge generating layer. with a doctor blade and dried at 80°C for 2 minutes and at 100°C for 5 minutes to form a cargo transporting layer with a thickness of about 20 μm,
A laminated photoreceptor (A) shown in No. 10 was prepared.

For comparison, following the procedure for producing the photoreceptor described above, instead of the disazo compound of the present invention,
4,4'-bis(2-hydroxy-3-phenylcarbamoyl-1-naphthylazo)-3,3, which is a benzidine-based disazo compound shown in J-37543 and JP-A-52-55643; '-dichlorodiphenyl and ■ 4,4'-bis(2-hydroxy-3-phenylcarbamoyl-1-naphthylazo)stilbene, which is a stilbene-based disazo compound described in JP-A No. 52-8832. A photoreceptor (B) and a photoreceptor (C) were respectively produced in exactly the same manner except for the following.

The electrostatic properties of the photoreceptors (A), (B), and (C) thus prepared were measured using a commercially available electrostatic copying paper tester (Kawaguchi Electric Co., Ltd., 5P-428 model). did. That is, first, a corona discharge of 16 KV is applied to the photoreceptor for 20 seconds to negatively charge the photoreceptor, and the surface potential at that time is measured to be Vd.

(volt) was determined, the sample was allowed to decay in the dark for 20 seconds, and the surface potential at that time was measured and determined as Vpo (volt). Next, the photosensitive layer is irradiated with light from a tungsten lamp so that the surface has an illuminance of 20 lux, and the time (seconds) until the surface potential reaches % of Vpo is determined, and the exposure amount E3A (lux/second) is determined. ). Similarly, Vp
Find the time (seconds) until o becomes 115 and 1/lO,
The exposure amount E115 (lux 0 seconds) and El/10 (lux seconds) were determined. I showed this result to 3.

Further, in order to investigate the sensitive wavelength range of the photoreceptor (A) according to the present invention, spectral sensitivity was measured using the following measurement procedure.

First, the photoreceptor is charged to a surface potential of -800 volts or more by electric discharge in a dark place, and the surface potential is -800 volts or more.
Dark decay until the surface potential becomes 180071 volts.
? When the photoreceptor was turned to its default state, the photoreceptor was irradiated with monochromatic light of 1 μW/d, which was separated using a monochromator. Then, the time (seconds) until the surface potential attenuated to -400V was determined, and the half-reduced exposure amount (μW-sec/di) was calculated.

On the other hand, the apparent potential difference obtained by exposure is calculated by subtracting the potential attenuation due to dark decay from the above potential difference of 400 volts, and then calculating the potential difference actually obtained by exposure. (Vo 1 t-ad
*aW-'e5ec-') was calculated and used as the sensitivity. This spectral sensitivity curve is shown in FIG.

As is clear from the results of Example 3, photoreceptor (A) using the disazo compound of the present invention has extremely high sensitivity compared to photoreceptors (B) and (C) using conventional disazo compounds. I understand.

Moreover, from FIG. 11, the photoreceptor (A) using the disazo compound χ of the present invention has a photosensitive wavelength range of about 450 to 60
0 nm, and from this it can be understood that the image reproducibility of the red original is good.

[Brief explanation of drawings]

FIG. 1 is an external ray absorption spectrum diagram (KBr51ii method) of the tetrazonium salt compound of Example. FIG. 2 to FIG. 9 are infrared absorption spectra (KBr tablet method) of the alternative disazo compound of the present invention. FIG. 10 is an enlarged cutaway diagram of a 115-element element related to the present invention, in which 11 is a polyester paste, 22 is an aluminum heat-deposited film, 33 is a charge generation layer, and 44 is a charge transport layer. represents. The gxt diagram is a spectral sensitivity curve of the electrophotographic photoreceptor according to the present invention. Drawing j →→υu 5ririυ zauu zusu (J
16su υ lb υ 0 conflict (no change in content) Figure %2 Kazuo Wakasugi, Commissioner of the Patent Office 1. Display of the case 1981 Patent Application No. 73177 Relationship with the case Patent applicant 1-3 Homare 6, Nakamagome, Ota-ku, Tokyo (674) Ricoh Co., Ltd. - Representative Hama 1) Hiro 4, Agent 5 , in the "Detailed Description of the Invention" of the specification to be amended...]\6, Contents of the amendment (1) On page 14, line 11 of the specification, "1953J" is amended to j1953J. (2) In the third line from the bottom of the same page, "2,7-diamithuanthraquinone" is replaced by "2,7-diamituxanthone."
Correct to. (3) On page 36, line 6, replace “100℃” with “1
Corrected to 05°C. (4) In the third line from the bottom of page 37, the phrase "time until..." is corrected to "time until...". That's all 6゜Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 7゜1
, Indication of the case 8゜New tetrazonium salt compound, new disazo compound and its manufacturing method 3, Relationship with the amended person case Patent applicant 1-3-6 Nakamagome, Ota-ku, Tokyo (674) Stock Ricoh Company Representative Hama 1) Hiro 4, Agent 5, Submit appropriate drawings 2 to 9 from which the text explaining the content of the amendment has been deleted from the figures 2 to 9 of the drawings subject to the date correction of the amendment order as attached. do. List of attached documents

Claims (1)

[Claims] 1. A tetrazonium salt compound represented by the general formula (I) (wherein X represents an anionic functional group). 2 general formula (If), where R represents an alkyl group, an alkoxy group, a nitro group, a halogen, a cyano group or a halomethyl group,
n is a differential number of 0, 1, 2 or 3, and when n is an integer of 2 or 3, R may be the same or different groups. ). ] A novel disazo compound represented by & The diamino compound represented by the general formula (Ill) is diazotized to form the general formula (1
) (wherein, X represents the anion m 7712 M), and this tetrazonium salt and the general formula ([V) , (V) , (Vll or <S'fl) (formula In the formula, R represents an alkyl group, an alkoxy group, a nitro group, a halogen, a cyano group, or a halomethyl group, and n is O.
, 1, 2 or 3, and when n is an integer of 2 or 3, R may be the same or different groups. ) (wherein R and n are as described above). ] A method for producing a novel disazo compound represented by