JPS5933253A - Novel tetrazonium salt, novel disazo compound and its preparation - Google Patents

Abstract

NEW MATERIAL:A tetrazonium salt compound shown by the formula I (Y is anionic functional group) and a disazo compound shown by the formula II (X is aromatic ring, or hetero ring; Ar is aromatic ring, or hetero ring). USE:A tetrazonium salt compound is useful as a intermediate for disazo compounds. The disazo compounds are useful as photoelectric materials for sensitized materials for electrophotography, especially as charge-generating materials. Since a laminate type sensitized material has a photosensitive wavelength band in about 450-600nm at short wave side of visible light range, it has improved reproducibility of reprography image of red manuscript. PROCESS:2,7-Diaminoanthraquinone shown by the formula III is diazotized with sodium nitrite in an inorganic acid to give a tetrazonium salt shown by the formula I . This compound is reacted with a coupler shown by the formula IV at -10-40 deg.C to give a disazo compound shown by the formula II.

Description

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

Conventionally, a certain yuzu disazo compound has been used for charge generation/(j
It is known to be effective as a charge-generating pigment used in This ξ-di layered photoreceptor is produced by applying a charge-generating pigment, which has the ability to generate charge carriers by light, onto the 4'lR support IJ body by an appropriate method, such as vacuum vaporization. A charge generation layer is formed as a thin layer by spraying a liquid or applying a dispersion in which particles of a material are dispersed in a resin solution, and then a charge generation layer is formed on top of the thin layer.
(4) J3: (61 transport layer (usually this transport layer 1, charge transport material) The photoreceptor is made of a mixture of lees, fat, and fat.

Conventionally, as a disazo compound used for this sleeve photoreceptor, for example, Japanese Patent Publication No. 47-37543+j, and
゛Zinzidine-based disazo compounds listed in ml in JP-A No. 52-55643, etc. or JP-A No. 52-55643 etc.
Stilbene thread disazo compounds listed in I[i] in Japanese Patent No. 2-8832 are known. However, conventional laminated photoreceptors using disazo compounds generally have low sensitivity;
0 to 700nmFC, this photosensitive wavelength is approximately the same as the original red color! II image reproducibility was poor. Therefore, when this photoreceptor is mounted, it is necessary to use a filter that cuts off the red light 8, which is disadvantageous in terms of single-shot shooting.

It is an object of the present invention to provide a versatile tetrazonium salt compound from which a wide range of disazo compounds can be obtained which are effective in electrophotographic photoreceptors, particularly in photoreceptors of the RIi type mentioned above. purpose.

Another object of the present invention is to provide a film that is effective in photoreceptors, particularly the laminated type photoreceptor mentioned above.
In order to provide a disazo compound of the r group, a laminated type photoreceptor using the disazo compound of the present invention CJ1 using a conventional disazo compound has a sensitivity of 8 <
,'E fc%The short length whose photosensitive wavelength range is in the visible range81
Since the wavelength is limited to Il (approximately 450 to 600 nm), the reproducibility of copied images of red originals is also poor.

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

That is, the favorite ψJ is the novel tetrazonium geochemical compound genote 2 represented by the following general formula (1).

(In the formula, Y is an anionic functional group.) There is also another novel disazo compound of the present invention represented by the general formula (n).

(In the formula,
No 14 aromatic ring 1ktJ, heterogeneous <'i-represents n
Specific examples of the aromatic ring in X of general formula (II) include benzene ring and naphthalene ring, and specific examples of heterogeneous ring ψ11 include indole nucleus, carpazole ring, benzofuran ring, and the like.

Specific examples of aromatic rings that can be used for Ar include benzene rings and naphthalene rings, and specific examples of hetero rings include dibenzofuran and carnozole.

Specific examples of the above-mentioned monkey groups include lower alkyl groups with 1 to 4 carbon atoms such as methyl groups, alkoxy groups with 1 to 4 carbon atoms such as methoxy groups, fluorine, chlorine, -! Examples include A group, halogen such as iodine, trifluoromethyl group, nitro group, and cyan group.

In the case where X and Ar are benzene rings in the general formula (11) ((2l, -), a compound represented by the following general formula (■) can be further exemplified as a compound with th constant.

In this general formula, n is an integer of 0 to 4, and n is 2
In the above case, R may be the same or different. Further, specific examples of R include tl, lower alkyl groups such as methyl group and ethyl group, lower alkoxy groups such as methoxy group and ethoxy group, halokenes such as fluorine, monochlorine, chloride, and iodine;
Thorinolmenalp, nitro group, and cyano group can be clearly seen.

1, one of my brother Akira's Ilc songs is diazotized 2,7-diamithanthraquinone represented by the formula (kawa) to form a compound with the general formula (shi (where Y represents an anionic functional group). ), and then combine this tetrazonium salt with the general formula (1v) HOCON■-Ar ゛・X・′ (wherein, f: represents a substituted or unsulfurized aromatic ring or -hetero group. * and Ar are the same as above).

Specific examples of the X, Ar, and Vi groups in general formula (IV) are the same as those in the previous general formula (■).

The tetrazonium salt compound shown in formula (1) is a useful intermediate for disazo compounds, and when combined with an appropriate cassillary compound, it has an anthraquinone skeleton and has an anthraquinone skeleton at the 2-position and the 7-position. A wide variety of disazo compounds can be synthesized that break down the azo group. Then, this disazo compound Q'<j & J Hiroko photoreceptor's T;
In particular, it is expected that it will be used as a 4-story building.

To the tetrazonium tower compound of general formula (1), 1.・Representative column of anion function Ji and 12 are CI, B
r.

○ ■ e Q Q 2Q” BF4
r PF6, B(-@enter, CIO,,80,.

e e 0 1(3C-@-80,, AsF6, SbF', ,
is excluded, preferably Bli"?.

The disazo compound of the present invention represented by the formula (11) V1.
As mentioned above, it is useful as a charge generator for a laminated electrophotographic photoreceptor. [Collection] A photoreceptor with a single-layer type photosensitive layer in which the vapor is called tq and dispersed;
It is also useful as a photoconductive material 4J to be applied to a rectangular photosensitive material having a photosensitive layer in which a photosensitive material is dispersed in ltf.

In the method for producing the tetrazonium salt of general formula (1),
2. Diazotization of 7-cyamitsuanthraquinone is
(11-For example, by adding sodium nitrite in salt N or an inorganic acid such as marrow acid at -lO°0 to 20°C.

This diazotization reaction is completed in approximately 30 minutes to 3 hours. Furthermore, by adding, for example, borofluoride acid, sodium borofluoride solution, etc. to the diazotization reaction mixture, a tetrazonium salt can be prepared.

The production of the disazo compound of the general formula (1) is performed by l H+
The diazotization reaction 6 solution of 2 is converted into 11 of the above general formula (IV)
Alternatively, the tetrazonium salt of general formula (1) can be obtained by adding, for example, fluoroboric acid or a fluoroboric acid (IJ) water bath solution to the diazotization reaction solution. It can also be obtained by isolating the tetrazonium salt by precipitation and then reacting it with a coupler of general formula (IV). Actually, this reaction is carried out by mixing a tetrazonium salt and Cassilar in an inorganic bath medium such as N,N-dimethylformamide (DMF) or dimethyl sulfoxide, and then heating the mixture to about -1O
This is carried out by dropping an alkaline water bath solution such as an aqueous sodium acetate solution at a temperature of 40°C to 40°C. This reaction &4i is completed in approximately 5 minutes to 3 hours. Reaction Sashiko 1・, -1 Analysis 11:l #L! Remove the i-crystal from the vi [7] by an appropriate method (e.g.
j/andme4t:: ftjha1meC'.

Ru? 5s: Preparation of the above-mentioned disazo compound from (-) (e.g., purification, recrystallization method, etc.) tJ: Photon production.

An example of the production of the tetrazonium salt and disazo compound of the present invention produced in this manner by νL is shown in the following 9.

Production Example 2. 4.76 gr of 7-diamithanthraquinone was added to 100 ml of cold water under ice-cooling. Sodium 3. Ogr in water 10 m
e &C melt'I? (Bath liquid f!: Approximately 2 at 0~5゛0
Peng was defeated after a little over 0 minutes. This reaction mixture was stirred for an additional 40 minutes at about 0°0, poured into 400 ml of cold water, and then a small amount of non-acetate was removed, and 42T was added to liquid V.
oltBF, 50! +tt power increased by 11. The resulting precipitate was collected, washed with 100 mt (1) h of water, further washed with 100 methanol (100 mt), and 4 T of methanol. Tetrafluoro 712 rate 7,1
69 (82,1%) obtained.

Infrared green absorption spectrum (KBr tablet method) 1/M,”
2280 cm-'νCo 1680cr
n-' Elemental analysis IlinoC,,H,N40. As B2F, actually measured snoring value N% 13.03 13.22 Figure 1 shows an infrared absorption spectrum.

Then, in this way, a) the tetrazonium salt 2.
18 gr (0,005 mol) and 0.01 mol of the coupler represented by general formula (IV) were added to DMF 300 at
A bath solution of 1.64 gr of sodium acetate dissolved in 14 d of water was added to the bath at room temperature for about 15 minutes. +II
i got it down. After 1rIiJ, the mixture was further stirred for 2 hours at the same temperature, and then the precipitated crystals were thickened. (If the coarse crystal cake was dispersed in 300 ml of DMF,
After stirring for 2 hours, the crystals were collected at P17, and this operation was repeated 21 times. After that, the crystals were washed with water and dried, and the disazotized 8.9 kume of Honura Akira was added (47k).

The above production example is shown in 6-1 and 6-2 (temporarily synthesized fc
Examples of the disazo compound of the present invention are shown.

(Left below) These new disazo compounds are red to reddish-purple powders at room temperature. FIGS. 2 to 19 show infrared absorption spectra (KBr tablet method) of typical disazo compounds of the present invention.

Figure 2: Compound Nn 1 Figure 3: Compound 12 Figure 4: Compound pile 3 Figure 5:
...Compound M44 No. 6...INu 5 after combination
Figure 7... Compound R 6 Figure 8... Compound 11 boiled J
a 7 Mud Figure 9... Compound Ni18 Figure 10.
...Compound Nn 9 Stripe 11 Figure...Compound shade 10-Figure 12...Compound 1↓111 13th
Figure...Compound N111231414Figure...Compound N
n14 Figure 15...Compound 1゛4α16@i
Figure 416...Compound jne17 Figure 17...
Compound direction 18 Figure 18... Compound Nn19 Figure 19... Compound 1.1 120 As mentioned above, the disazo compound of the present invention can be used as a photosensitive material for electrophotographic photoreceptors, especially for charge reduction in laminated photoreceptors. Effective as a generating material υ,
In order to clarify this point, below are specific application examples.
shows. Furthermore, in order to clarify the inventive step of the present invention,
A comparison with conventional disazo compounds is also shown.

Application example Disazo compound 1iCL12 of the present invention (76 f5)
ij"F>li, polyester resin (manufactured by Byron 200 Co., Ltd., Raijinbo), tetrahydrone oran soluble oil (solid content 2%) 1260 summer, hjre 1ki, and tetrahydrofusin 3700 parts. The resulting dispersion was ground and mixed in a ball mill, and the resulting dispersion was coated on a polyester-based aluminum plate made of aluminum x 677J using a doctor blade, air-dried, and made into an aluminum plate with a thickness of approximately 1 μm. A charge generation layer composite of L was formed. On the other hand, 2N volume of 9-ethelcarno9zole-3-altehyde 1-methyl-1-phenylhydrazine, polycarbonate resin' (
1300 for pan light. After making a solution by mixing 1 part of Keijin Kasei Co., Ltd. and 16 parts by weight of tetrahydrofuran, this was applied to the above-mentioned tumbler with a doctor blade and heated to 80°0. 100°
0 for 5 minutes to form a charge transport layer with a thickness of approximately 20 μm, as shown in FIG.
It was created.

For comparison, in place of the disazo compound of the present invention, (1) the above-mentioned JP-A-45-37543 and JP-A-52-55 were
4゜4'-His(2-hydroxy-3-phenylcarbamoyl, -1-naphthylazo)-3,3'- which is a benzidine thread disazo compound disclosed in Publication No. 643
dichlorodiphenyl and (g) 4°4'-bis(
In exactly the same manner except that 2-hydroxy-3-phenylcarbamoyl-1-naphthylazo)stilbene was used,
A photoreceptor (B) and a photoreceptor (C) were respectively produced.

The photoreceptors (A), (B), and (C) thus prepared were tested using an electrostatic copying paper tester u manufactured by IJ.
(Kawaguchi's machine manufactured by r, 5P-428 type) using
Its electrostatic properties were measured. That is, first, apply 16 to the photoreceptor.
Perform a KV corona discharge for 20 seconds to make it negatively charged, measure the surface potential at that time, determine Vdo (N), leave it in the dark for 20 seconds to decay in the dark, and measure the surface potential at that time. It was set as Vpo (volt). Then,
The photosensitive layer is irradiated with light from a tungsten lamp so that the illuminance on the surface is 20 lux, and 2<1IIi
'uL (The time (seconds) until i becomes % of Vpo was determined and defined as exposure @E% (lux seconds).Similarly, vp.

14 and 1/1o of 9 hours (sho) were found, and Rikojo i: E 15 (looks/sho) and E/1o (look 16 seconds) were found. This polished rice e: is shown in #-3.

(Hereinafter, blank space) In addition, the photosensitive wavelength range of the photoreceptor (A) related to the present invention is -
8, the spectral sensitivity was measured using the following measurement procedure.

First, the photoreceptor is charged to a surface potential of -800 or more by corona discharge in a dark place, and the surface potential is -800 or more.
The surface potential was reduced to -800yl when the temperature reached 1.
When the photoreceptor reaches υ, use a monochromator to perform spectroscopy and irradiate the photoreceptor with a 4L color source of lpw/all.

Then, find the time ($) at which the surface potential decays to 1400V, and calculate the time ($) for the surface potential to decay to 1400V,
rl ) was calculated.

On the other hand, the apparent potential obtained by exposure is determined by subtracting the potential attenuation due to dark decay from the potential difference 400 above to find the potential difference actually obtained by exposure. from the light decay rate (Volt 11al
-pW*aec) was calculated and defined as pestilence. This spectral sensitivity curve is shown in FIG.

As is clear from the rice polishing of coating-3, the photoreceptor (A) using the disazo compound of the present invention has a significantly higher le
It can be seen that the t degree is high.

From FIG. 21, it can be seen that the photoreceptor (A) using the disazo compound of the present invention has a photosensitive wavelength range of approximately 450 nm.
It can be seen that it can be detected at ~600 nm, which makes it clear that this is a good thing for the red manuscript.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram (KBr 1' agent method) of a tetrazonium salt compound of a production example. 217j to 19 show infrared 6! of the alternative disazo compounds of the present invention. It is a spectral diagram (KLlriij pruning method). Figure 20 is similar to the present invention: Tomoko Waru: tfJc impression 11
Enlarged section irI+ figure of the body, 11←j polyester pace, 22Q1 aluminum fish m Jk'! , 331J,
``tri gr'jG live fetus, 44 is '113: All loading layers are loaded. Figure 21 t; I: Electrophotographic sensor according to the present invention;
This is the spectral sensitivity curve of the body. Procedural amendment (September 168, 168 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office!) 1 display 1982 Special Patent Application No. 1426218゜2, related to the title of invention case Patent applicant U1 Ward, Tokyo Nakamagome 1-chome, No. 3, No. 6 (674) Ricoh Co., Ltd. - Representative Takeshi Oten 4, Agent 5, Subject of amendment A4F r Detailed description of the invention J's ball; 0M Masa no Yamatani (1 ) In the 4th negative line 3-4 of specification 1u, amend it as ``Pigment liquid J saarunoso ``Shunka Lingxin''.
A certain σ) is corrected as ``phenylhydrazone''. that's all

Claims (1)

[Claims] 1. A tetrazonium salt compound represented by the general formula (I) (wherein Y represents an anionic functional group). 2. General formula (II) (wherein, X represents a substituted or unsubstituted aromatic ring or heterocycle, and Ar represents [M or an unsubstituted aromatic ring or heterocycle)] disazo compound. 3゜Formula (Ill) (J is used to diazotize 2,7-diamithanthraquinone to obtain a tetrazonium salt represented by the general formula (1) (wherein, Y represents an anionic functional group sound) Then, this tetrazonium group and the general formula (IV) (wherein, of general formula (II) (wherein, A method for producing a disazo compound represented by 6, and Ar represents an aromatic ring or a hetero-like group.