JPS5933254A - Novel tetrazonium salt compound, new disazo compound and method for producing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a novel tetrazonium salt compound.

This invention relates to 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. Here, the laminated photoreceptor is a conductive support.
Charge-generating pigments, which have the ability to generate charge carriers by light, can be prepared by suitable methods such as empty vapor deposition, coating of a pigment solution (dispersion of fine particles of pigment dispersed in a resin solution), etc. A charge generation layer is formed by forming a thin layer by coating, and the charge carriers generated in the charge generation layer are placed on top of the charge generation layer.
This is a photoreceptor in which a charge transport layer is formed which is not injected at a high rate but is ejected and moves (the charge transport layer normally consists of a charge transport substance and a binder resin).

Conventionally, as disazo compounds used in this type of photoreceptor, for example, benzidine-based disazo compounds or Japanese Unexamined Patent Publication 1988-52-88
Stilbene-based disazo compounds described in Publication No. 32 are known. However, the photoreceptor of the conventional product type 1-type using a disazo compound has a photosensitive wavelength range in the visible range of approximately 450 to 700 nmK, and based on this photosensitive wavelength characteristic, the image reproducibility of red originals is poor. Therefore, when this photoreceptor is mounted, there is a disadvantage in the design of the copying machine because it is necessary to use a filter that cuts red light.

The object of the present invention is to obtain a novel tetrazonyl A, which can produce a wide range of disazo compounds that are effective in electrophotographic photoreceptors, particularly in the above-mentioned laminated type photoreceptors.
The purpose of the present invention is to provide a W compound.

Another object of the present invention is to provide effective
In particular, we would like to provide a novel disazo compound that is effective in the above-mentioned laminated photoreceptor.1 The laminated photoreceptor using the disazo compound of the present invention is compared to the conventional photoreceptor using a disazo compound. Since the photosensitive wavelength range is on the short wavelength side of the visible range (approximately 450 to 6001 m), the reproducibility of copied images of red originals is excellent.

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

That is, one aspect of the present invention is a novel tetrazonium salt compound represented by the following general formula (1) (wherein, Y represents an anionic functional group); This is a novel disazo compound represented by (11).

(In the formula, X represents a substituted or unsubstituted aromatic ring or heterocycle, and Ar represents an ff-substituted or unsubstituted aromatic ring or heterocycle.) Specific examples of the aromatic ring in X in general formula (n) Examples include benzene rings and naphthalene rings.

Specific examples of the heterocycle include an indole ring, a carbazole ring, and a benzofuran ring.

Further, specific examples of the aromatic ring in ArK include a benzene ring and a naphthalene ring, and specific examples of the hetero ring include a dibenzofuran ring and a carbazole ring.

Specific examples of the substituents on the above rings include lower alkyl groups having 1 to 4 carbon atoms such as methyl groups, and 1-carbon atoms such as methoxy groups.
-4 alkoxy groups, ---logenes such as chlorine, nitro groups, etc. can be exemplified.

In general formula (1), when X: and Ar are benzene rings, a more specific example of the compound is a compound represented by the following general formula (g). n In this general formula, n is An integer from 0 to 4, where n is 2
In the above cases, R may be the same or different. Further, specific examples of R include a lower alkyl group having 1 to 4 carbon atoms such as a methyl group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, a halogen such as chlorine, and a nitro group.

Furthermore, another one of the present invention is 1 represented by Narita).
, 5-diaminoanthraquinone is diazotized to form the general formula (
1) A tetrazonium salt represented by (wherein, Y represents an anionic functional group), and then this tetrazonium salt and the general formula (wherein Ar represents a substituted or unsubstituted aromatic ring or heterocycle). General formula (11) % formula % ((In the formula, X represents a substituted or unsubstituted aromatic ring or a hetero salt, and Ar represents an unsubstituted or unsubstituted aromatic ring or hetero ring.) This is a method for producing a disazo compound represented by

Specific examples of substituents for X, Ar, and C in the general formula (l) are the same as in the case of the general formula (b).

The tetrazonium salt compound represented by formula (1) is a useful intermediate for disazo compounds, and by combining with a suitable coupler, it can be used to form a wide range of disazo compounds having an anthraquino/skeleton and diazo groups at the 1st and 5th positions. Compounds can be synthesized. This disazo compound is expected to be used as a photoconductive material for electrophotographic photoreceptors, particularly as a charge generating substance.

θ in the tetrazonium salt compound of general formula (I)
Typical examples of θ e anion functional groups are CL, Br, I
It is IBF4.

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

4 in the method for producing the tetrazonium salt of general formula (1),
Diazotization of 1,5-diaminoanthraquino/ is carried out using, for example, #A acid or sulfuric acid. It is carried out by adding sodium nitrite in iodic acid at -10°C to 10°C.

This diazotization reaction is completed in about 30 minutes to 3 hours. Further, the diazotization reaction solution K, such as hydroborofluoric acid or an aqueous solution of sodium borofluoride, is added to obtain a tetrazonium salt.

The production of the disazo compound of the above general formula (Kawa) can also be carried out by directly allowing the δ liquid at the above diazotization degree to act on the coupler of the above general formula #■,
Also for diazotization reaction solution.

For example, it can also be obtained by adding fluoroboric acid or an aqueous solution of sodium borofluoride to precipitate the tetrazonium salt of general formula (11), isolating the tetrazonium salt, and then reacting the tetrazonium salt with a coupler of general formula (2). In reality, this reaction is carried out using N,N-dimethylformamide (DMF),
Mix and dissolve the tetrazonium salt and coupler in an organic solvent such as dimethyl nulphoxide, and knead the mixture until approximately -1
This is carried out by dropping an alkaline aqueous solution such as an aqueous sodium acetate solution at 0°C to 40°C. This reaction is complete in approximately 5 minutes to 3 hours. After the reaction is complete, the precipitated crystals are counted and purified by an appropriate method (
For example, cleaning with water and/or organic solvents.

Recrystallization method, etc.) completes the production of the disazo compound.

An example of the production of the tetrazonium salt and disazo compound of the present invention produced in this manner is as follows. .

Production Example 1.5-cyanoanthraquinone [commercially available as a reagent from Tokyo Kakogyo Co., Ltd.] 24.6 g (0,
103 mol) and 175 ml of 36% hydrochloric acid.
A solution prepared by dissolving 7% sodium nitrite/lium 154Ir in 50 me of water was added dropwise at 3 to 8° C. over 1120 minutes. After the dropwise addition was completed, the mixture was stirred for an additional 1 hour and 30 minutes at approximately θ°C.
Add 10 ml of cold water, and perform V filtration to remove a small amount of impurities.
0 ml was added. About 10 crystals precipitated
Anthraquinone-1,5-bisdiazonium histetrafluoroborate 42.8 #r (95,
3%).

Infrared absorption spectrum (KBr tablet method) νNS
2300 r:tnyc01695ttn Elemental analysis value C14H, N4 o2E2 p, actual measured value Total 11' value 8% 13.10 13.22 In addition, an infrared absorption spectrum diagram is shown in FIG.

Then, the tetrazonium salt 2.18 thus obtained
1r (0,005 mol) and a coupler represented by the general formula eV) is dissolved in 0.0 l-E-le of MF300 m/, and in this is added 6 parts of vinegar and 1.64 t of sodium, 14 parts of water.
A solution dissolved in rnl was added dropwise at room temperature of 1/C over about 15 minutes. After the addition was completed, the mixture was further stirred at the same temperature for 2 hours, and the precipitated crystals were collected at θi. D hx f1'300 n1tt, r dispersion (5°8
After stirring at 0°C for 2 hours, the crystals were collected.

Furthermore, this operation was repeated twice. Thereafter, the crystals were washed with water and dried to obtain the disazo compound of the present invention. Tables 1 and 2 show the disazo 1 h anastomoses of the present invention synthesized by the above-mentioned "A[1) ji to f-)".

Below are the margins.
It is a reddish-purple powder. Figures 2 to 24 show infrared absorption spectra (KB) of typical disazo compounds of the present invention.
r tablet method).

218th! ! Kl... Compound NL l Fig. 3... Compound N2 Fig. 4... Kashumonon 3 Fig. 5... Compound 4 Fig. 6... Compound N5 Fig. 7... Compound Part 6 Figure 8...Combination Part 7 Figure 9...Compound 1 Ilu8 Figure 10...Compound-9 Part 1
Figure 1... Compound 1410 Figure 12... Compound tooth 11
Figure 13... Compound 1'412 Figure 14...
・Compound 1'%13 Figure 15... Compound 1'
h14 Figure 16... Compound tooth 15 Figure 17.
... Compound ~, 16 Figure 18... Compound 1 Hiroshi] 7
Figure 19: Compound N2 Figure 4: Compound 1 Aim 19 Figure 21: Compound rs 20 Figure 22: Compound N121 Figure 23: Compound N
22 Figure 24... Compound tooth 23 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 photoreceptors, and this point will be clarified. For this purpose, specific usage examples are shown below.

Application example 76iJ1' parts of the disazo compound 7412 of the present invention,
Tetrahydrofuran solution (solid content concentration 2%) of polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) 126
0i parts by weight, and 3700 parts by weight of tetrahydrofuran to yl? -Polyester base (conductive support) that is pulverized and mixed in Lumir and the resulting dispersion is aluminum-deposited.
It was applied onto Al<m> using a doctor blade and air-dried to form a charge generation layer with a thickness of about 1 μm. On the other hand, 2 parts by weight of 9-ethylcarbazole-3-aldehyde 1-methyl-1-phenylhydrazine, Polycar No.? 1300 for Nate resin (). After mixing and dissolving 2 parts by weight (manufactured by Teijin Kasei Ltd.) and 16 parts by weight of tetrahydrofuran to form a solution, this was applied onto the charge generation layer using a doctor blade and heated at 80°C for 2 minutes and then at 100°C.
The mixture was dried for 5 minutes to form a charge transport layer with a thickness of about 20 μm, thereby producing a laminated photoreceptor shown in Fig. 25.

The photoconductor thus prepared was tested using a commercially available electrostatic copying paper tester [(newly manufactured by Kawaguchi Electric Co., Ltd.)].

5P-428 type) to measure its electrostatic properties.

That is, first, a corona discharge of 16 KV was applied to the photoreceptor for 20 seconds to make it negatively charged, the surface potential at that time was measured, Vdo (tk?lt) was determined, and the photoreceptor was left in the dark for 20 seconds to allow it to decay in the dark. .

The surface potential at that time was measured and defined as vpo (Nruto).

Next, the surface of the tungsten lamp has an illuminance of 2o.
The layer was irradiated with light at a temperature of -yt' so as to obtain a lux, and the time (seconds) until the surface potential reached % of Vpo was determined, and the amount of light EM (lux seconds) was determined. Similarly,
Find the time (seconds) until it reaches 115 and 1/1° of Vpo, and calculate the exposure amount E115 (lux seconds) and E1/IQ (
looks/seconds).

The results were as follows.

[Brief Description of the Drawings] Figure 1 is an infrared absorption spectrum diagram (KBr tablet method) of tetrazonium J, iii of the present invention, and Figures 2 to 24 are infrared absorption spectra of typical disazo compounds of the present invention. Figure (KBr tablet method). FIG. 25 is an enlarged sectional view of an electrophotographic photoreceptor according to the present invention, and 11 is a polyester paste. 22 is an aluminum vapor deposited film, and 33 is a charge generation layer. 44 represents a charge transport layer. Procedural amendment September 1982 r! Kazuo Wakasugi, Commissioner of the Japan Patent Office1, 41 indications, Patent Application No. 142620, filed in 1982, 2, title of the invention, 3, person making the amendment, relationship to the case, applicant, 1-chome Nakamagome, Ota-ku, Tokyo. 3 Examiner No. 6 (674) Ricoh Co., Ltd. - Representative Dai et al. Samurai 4, Agent 5, "Invention Q) Detailed information uAJ 6, Amendment θ) Contents (1) of the specification subject to amendment Specification 8, page 20, lines 13-14 I amend "phenylhydrazine" to "phenylhydrazone."that's all

Claims (1)

[Claims] 1. A tetrazonium salt compound represented by the general formula (I) θ (wherein Y represents an anionic functional group). 2. A disazo compound represented by the general formula 〇〇 (wherein, X represents a substituted or unsubstituted aromatic ring or heterocycle, and Ar represents a substituted or unsubstituted aromatic ring or heterocycle). 3. 1,5-diaminoanthraquinone represented by formula a is diazotized to form a tetrazonium salt represented by the general formula +1) (wherein Y represents an anionic functional group), and then this tetrazonium salt and the general formula tv+ (wherein, X represents tW, a substituted or unsubstituted aromatic ring or heterocycle, and %Ar represents a substituted or unsubstituted aromatic ring or heterocycle). with the general formula (TI) Ar -HNoCOH (where x& represents a substituted or unsubstituted aromatic ring or heterocycle, and Ar represents a substituted or unsubstituted aromatic ring or het='W); A method for producing the represented disazo compound.