JPS58122967A - Novel trisazo compound and production thereof - Google Patents

Abstract

NEW MATERIAL:Trisazo compounds of formulaI, wherein R is a group of formula V. USE:Materials for electrophotographic photosensitive substances. In a lamination type photosensitive substance, the compound is effective in the wave range of semiconductor laser. PREPARATION:4,4',4''-Triaminotriphenylamine of formula II is diazotized to form a hexazonium salt of formula III (wherein X is an anionic functional group) which is then reacted with 2-hydroxy-3-phenylcarbamoylbenzo[a]carbazole derivative of formula IV to obtain the desired trisazo compound of formulaI.

Description

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

Traditionally, trisazo compounds or disazo compounds have been used in the layering of Ei-no-so-type Kangen-ko, which is one of the photoconductor shapes commonly used in the Amashi Shaboku method. It is said that the price is high. Here, the Oshiru-type Kankōsho means a cruel method for Mitsuo Kokumukai Mjt family, which generates a Kame Isshu-sei on top of the Fz salary, such as JK Sora Mubi, The microscopic particles of the IT family are made into a thin layer in the stone bath or in the resin solution, and are formed into a thin layer by a layer of cloth, and the origin of the material is increased.
On top of that, the 1L load generated by Kame σI Brother No can be efficiently stocked and the charge transfer layer where the transfer is performed (through the IL load transfer warehouse UI Zong is closed, moving! 1
It is a photoreceptor with the shape of I17I and BosentsuNtan (consisting of h and h). (tel rice, this yuzu photoreceptor V
As a disazo compound that has been used for a long time, the world's
1! l+Is 47-37543 publication, or ilj
'Unexamined Japanese Patent Publication No. 52-55643, etc. I/(disclosed benzidine-based disazo pigments, etc.)
Examples include the triphenylamine thread trisazo M family disclosed in No. 11 Sho 53-132547M.

However, conventional photoreceptors using trisazo oils and disazo oils, for example,
se3) 9+ using base metal! +; Compared to the photoreceptor of Isogotsu, it suffers from drawbacks such as low sensitivity and not being suitable as a photoreceptor for Kountara Photographer.

- There is also a need for photoreceptors for use in near-chilling laser printers, and there is an urgent need to develop photoreceptors that are still sensitive to the wavelength range of VC lasers.

Fuji's objective is to provide a new trisazo compound that is effective even in the range of laser beams used in the photoreceptor type photoreceptor.

Another object of the present invention is to provide a method for displaying the above-mentioned trisazotized resin.

Book)! 64 lights are highly sensitive and can be used for general purposes and half 2J!
With the aim of developing a charge-generating pigment that has a flat sensitivity in the wavelength range of the I-ray laser, we conducted extensive research on a large number of disazo and trisazo compounds, and as a result, we developed the following general formula: The tris azo compound represented by IF-1] differs greatly depending on the type or position of the substituent in Rvc, and the tris azo compound represented by However, I have discovered that it has excellent characteristics. That is, the present invention has the following general formula [1] = 5-. It is a trisazo compound coated with This illegal trisazo compound is a black crystalline substance at room temperature.

The kiln 7N photoreceptor using the trisazo compound of the present invention is comparable in sensitivity to inorganic thread photoreceptors, and has an extremely fast response to light with a wavelength of 8 fJOnm.

For illustrative purposes, the trisazo compounds of the present invention are shown.

6-Next-1 Figures 1-1 to 1-4 show the infrared absorption spectra (KBr drinking method) of the trisazo compounds of 1-1 to I-4 above, and VC in Figures 2-1 to 24 shows the thermal Analysis diagram (TG-DSC)
, and XI eclipse diffraction patterns are shown in Figures 3-1 to 3-4. In Fig. 2, curve A indicates the heat-temperature curve Am, and curve B indicates the differential heat curve. The above trisazo compound of the present invention can be produced by the following method.

That is, 4, 4', 47', -) riaminotriphenylamine represented by the other formula [11] of the present invention is diazotized and coated with the general formula [oil]. Hexazonium salt, N.

(where, This is a method for preparing a trisazo compound using the general formula C1), which involves reacting with .

In this preparation method, 4,4',4''-triaminotriphenylamine is diazotized by diazotizing it in a dilute inorganic gas such as dilute hydrochloric acid or dilute sulfuric acid in a sodium nitrite bath solution at -10°C. The diazotization reaction is carried out by addition at 10°C for approximately 30 minutes to 30 minutes.
It concludes with "Time 1". Furthermore, it is preferable to precipitate the tetrazonium salt by adding, for example, hydrofluoric acid or sodium fluoroboric acid (MW) to the reaction mixture, and use the crystals in the next reaction after forming the crystals. Next, the coupling reaction is carried out by reacting the tetrazonium salt with the 2-hydroxy-3-phenylcarbamoylbenz[a]carbazole derivative of the general formula [IV]. In reality, this reaction is called N,N-dimethylformamide (DMF)-? Tetrazonium salt and Cassirar are mixed and dissolved in a Takeiso bath medium such as dimethyl sulfoxide, and an alkaline water bath solution such as sodium acetate bath medium is added dropwise to this at a temperature of about -1°9-40'C ( (The reaction is carried out by the following steps. This reaction takes about 5 minutes to 3 hours to complete the crystallization process. After the reaction is complete, the precipitated crystals are deposited on B-+, and then the crystals are prepared by a bloody method (e.g. with water or/and ), washing with a bath agent, recrystallization method, etc. to produce the above-mentioned trisazo compound. Wow.

Production example 1 4.4',4''-triaminotriphenylamine 8.7
g to 150 ml of diluted salt and 13 ml of water (Diluted Salt Co., Ltd.) and stirred well at room temperature for about 30 minutes.Then, the mixture was cooled to about 0'C and diluted with sodium nitrite. M component-3 obtained by dissolving 7.7 g of rum in 30 ml of water in a VC bath
°~2°'G (1) At temperature for about 20 minutes? I did the painting. Thereafter, the mixture was stirred at the same temperature for about 1 hour, and the insoluble matter was separated, and the precipitate was dissolved in c*vc 42% borofluoride-based fermented water and treated with LiO for 7 nights. After adding water and drying, 15.3% hexazonium trifluoroborate (yield 87%) was dissolved in yellow viscous madder (decomposition point: approx. 129°C).
) was obtained.

Next, hexazonium salt 1.2 obtained as above. j
9 and 2-hydroxy-3-(2-methyl-5-chlorophenylcarbamoyl 9benzo(, 1) 29 g of Rubazole was dissolved in 210 ffl of DMF, and 29 g of sodium acetate was added to this in 30 ml of water, and the fc bath liquid was heated to The mixture was added dropwise over a period of about 5 minutes.After the addition was completed, the mixture was stirred at the same temperature for an additional 3 hours, and one crystal that had precipitated was collected.

Disperse the neglected coarse crystal cake in 3 ooml of DMF.

After stirring at room temperature for 1 hour, one pile of crystals was added, and this operation was repeated four times. The trisazo compound (1-1) of the present invention is obtained by washing the sacrificial crystals with water and drying them.
/ (7s %,) iV*.

Black crystal decomposition point 300℃ or higher 7c thread + JT1 direct measurement value Calculated value 0%? 0.50 70.84 H article 3,76 3.96 H% 11.92 11.93 Infrared symmetrical absorption spectrum (KBr tablet method) 'e=0 (second
7mid) 16so,;'Manufacturing? 1''2 Production Example 1 2-Hydroxy/-3-(2-methyl-5-chlorophenyl) Lupamoylnobenzo[a]carbazole 2.91/K 7111 Ethe, 2-Hydro
#'/-3-(2-ethoh?diphenylcarbamoyl)
Benzo[a)carbazole 2.9. Trisazo metal of the present invention (1-2) with the same substance except for reZn 2.3
1 (76%) attended.

Black crystal decomposition point 300℃ or above Elemental analysis value Actual value Calculation 1 direct C force 73.59 73.84 H% 4.56 4.6O N% 11.79 12.04 Foreign powder absorption spectrum (KBr tablet Oki) law c=0 (secondary amide)
1670cIn' equipped shield? lJ3 Tai Sumire? 2-Hydroxy-3-(2-methyl-5-chlorophenyl force in 1)
Instead of 2.9 g of carbazole, 2-hydroxy-3-
(2,5-dimethylphenylcarbamoylnopenzo [a
] Trisazo metal of the present invention (1-3) 1.9 g (65
%) within 1.゛Black crystal decomposition point Elemental analysis above 300℃ 111 Actual measurement Total II-value 0% 76.09 76.26 Hφ 4b1 4.75 N≠ 11.93 12.43 Infrared absorption spectrum (KBri criminal law) νc= 0(g2
Amide) 1680cWL'13- Manufacture? l14 Fitting? 2.9.9 l of 2-hydroquine-3-(2-methyl-5-chlorophenylcarbamoyllumpenzoCa)carbazole (on the contrary, 2-hydroquine-3-(2-methyl-5-chlorophenyl)
3-(2,4-dimenalphenylcarpamoyl)hen[a]carpasol 2.7.9 were used, and the trisazo compound of the present invention (1-4) 2,0,
Lit (68%).

Black crystal decomposition point 300℃ or higher Element system analysis value Actual value Calculated value Cchi 76.41 76.26 N% 4.46 4.75 N% 11.93 12.43 Extra? IN absorption spectrum (KBr Shunsho method) 1/c=
0 (Second amide) 1680cm' Akira Honto's trisazo compound! As shown in the 1111th series, the proboscis is valid as a 'turtle-like occurrence' of the cylindrical type, and in order to clarify this point, below VC we will show examples of the 14-exceptions. In order to clarify the inventive step of the present invention, a comparison with conventional azo compounds and a comparison with a photoreceptor made of unfiltered thread will also be made.

For nine? sJ%q node IJ, <-f SO&vIJ (1-176
CtTif part, polyester resin (Pylon 20u, manufactured by Gyuyo Boseki Co., Ltd.) in a tetrahydrofuran bath solution (solid content 2% acupuncture), 1260 parts of tetrahydrofuran, and 3700 parts of tetrahydrofuran were pulverized and mixed in a ball mill. Then, the liquid was applied to aluminum using a doctor blade on a polyester base (24 cage-like supports), and air-dried to form a polyester base with a speed of about 1 μm. Form a hole. - Force, 9-14-diethylaminophenyl) anthracene l n jfE i1 ~, polycarbonate resin board (130 (1, model made by Teijin) l mouth (shaping part and tetrahydrofuran 8-ridge plate part) ← After dissolving the 8' bath and adding the +'e liquid, add this to 6j1
1. Heat a raw pigeon with a doctor blade and bend it at 80℃ for 2 minutes, then at 10℃ for 5 minutes to form a 20μm thick layer. I created a laminated photoreceptor (A) using the same layer as in "Tsumyo", except for the following clothes. IIv, C7θ-sensitivity samples (B) to (D) were prepared.

Clothes -2 Next, the following photoreceptor was created for comparison.

Comparative Example 1 Instead of the trisazo compound of the present invention, a triphenylamine thread trisazo tA, which is disclosed in JP-A-53-132547 mentioned PI'+1, was used.
-Tris(2-hydroxy-3-phenylcarbamoyl-1-naphthylazonotriphenylamine) was used, except that 9-(4-diethylaminophenyl)anthracene was used as the 'unloading' member. A comparison photoreceptor (E) was prepared using a method that was completely similar to the application example.

Hi 1 Akin v + 12 Hi Soft? 1-phenyl-3-(4-diethylaminostyryl)-5-(4-
A comparative photoreceptor (F) was prepared using the same method as in Comparative Example 1 except for the exit hole.

Comparative Example 3 Polynisteria (Liao 10 Shengdu, 2,4.7-trinitro-9-fluorenone 10 East Button, General formula of the present invention (
A trisazo compound in which R is 2-methyl-4-methoxyphenyl group in 1)? ! I (% Kaisho 53-1323
47, 8) Z Turtle W and 198 weight parts of tetrahydrofuran were pulverized and mixed in a ball mill, and the resulting dispersion was doctored onto a polynisglue film prepared by boiling aluminum ura. Comparative photoreceptor (G) having a photosensitive layer coated with a blade and dried at 100° C. for 10 minutes to a thickness of 10μ17 f: Not produced.

Comparison v: + 4 Pll'', female Japanese Unexamined Patent Publication No. 47-37543 1 or tt! 4,4'-His(2-
1.083 parts of hydrochloride (3-phenylcarbamoyl-l-naphthylaso)-3,3'-dichlorodiphenyl is commonly understood as 2446 parts of ethylenecyamine, and when added to this bath liquid, -butylamine 20.08 i
The power of the capital [1, history of tetrahydrofuran 54.36
Added Sumire-Gan part force 1 and created Jun&. Next, this coating was applied onto a polyester film that had been vaporized with aluminum using a doctor blade, and heated to 80°C for 50 minutes.
A charge generation layer having a thickness of about 0.5 μm was formed by drying for a minute. A++ 1-phenyl-3-(4-
Diethylaminostyryl J-5-(4-diethylaminophenyllivirazoline 1.iiLm), polycarboy - 1300 (Teijin Kasei Co., Ltd.) 1 plate weight, and tetrahydrofuran 18-lan The solution consisting of the 8'34< sandwich portion was applied with a doctor blade, and dried at 80°C for 2 minutes and then at vctoo°C for 5 minutes to form a charge transfer layer with a thickness of about 20 μm.
Ratio 17X) + photoreceptor (H) made by a woman.

Comparative Example 5 A mixture of Se-As (4U wt) was steamed on 4 aluminum machines using fish scraps as a raw material at a substrate fabrication temperature of 200°C and a steaming source temperature of 410 to 415°C under a true temperature of 10 Torr.
L, A s2s e3 with a photosensitive layer of about 60 μm
A hole that creates a sensing body. This photosensitive layer for comparison of inorganic yarn is designated as (I).

Next, I created 9&! like the one above! Regarding the photoreceptor, a commercially available electrostatic copying paper testing device (5P manufactured by Kametetsu Manufacturing Co., Ltd.
-428 type) was used to test its accuracy.

In other words, 16KV (or +6KV) is applied to the trenchless photoreceptor.
After carrying out 1M1 of corona manta'ton for 20 seconds to make negative (or stop) VC, let it go dark for 20 seconds and measure the surface level Vpo (V) at that time. Then, the cloth UFJ1 was irradiated with light using a tungsten lamp at an illuminance of 20 lux, and the surface '1 was exposed to V.
1/2 of po, 1/I Time until O + 14I
(Calculate 40, path light a E I /2 + h l /
IO (looks 4+) was calculated. Wear the results.
Shown in 3.

Clothes-3 In addition, in order to clarify that the photoreceptor of the invention has an extremely high sensitivity due to the length of the thorn V length,
The following measurements were performed.

The photoconductor (A) to (11) is exposed to light by corona discharge in the dark H1, and the photoconductor (Il
Then, using a monochromator, the photoreceptor was irradiated with monochromatic light of 11+w/cyt. Then, we lengthen the time (sho) until the first story of the clothes is attenuated by hvr, and (at this time, the loss of clothes due to dark side) is corrected, jiL (Itw-sec/crd)
The polished rice is shown in Cloth-4.

(The following is a blank space) 21-Table-4 As is clear from the results of In-3 and Table-4, the photoconductor (A+) related to the present invention is softer than other photoconductors. It can be seen that the sensitivity is comparable in terms of sensitivity, and the sensitivity is several tens of times lower in the wavelength range (8 (1 nm)) of a semi-dedicated laser.

As mentioned above, the trisazo compound of the present invention is an extremely useful detergent for both electron-donating and A-sensing materials, and because it is an important material, It can be clearly understood that the trisazo compound of this invention is an extremely excellent compound, as it has many of the first points such as low cost.

[Brief explanation of drawings]

Figures 1-1 to 1-4 show (1-1)2 to (1-4) of the present invention.
) Extra absorption spectrum of trisazo compound of formula, 2nd-
Figures 1 to 2-4 show thermal distribution diagrams, and Figures 3-1 to 3-4 show X-ray diffraction diagrams. FIG. 4 shows an example of the structure of a photoreceptor, which is an example of the trisazotized adduct of the present invention. 1... Electrophilic support 2..., +5 realester base 3... Atsubenium #kame 4...
・'Turtle brotherization layer 5...' Leisure plan f movement j so song f14
A...Differential heat balance formalism B...Differential heat distortion procedure amendment document March 311, 1980 Commissioner of the Japan Patent Office Shima 1) Haruki Tono 111.1, Indication of the case 1982 Patent Application No. 5682 No. 2, Title of the invention: Novel trisazo compound and method for producing the same Ricoh Co., Ltd., No. 6, 1-3, Nakamagome, Ota-ku, Tokyo (674) - Representative: Dai et al., Takeshi 4, Agent: 6 Contents of amendment (1) Amend the claims as shown in the attached sheet. (2) Correct "in addition to" in the 12th line of the 10th line of Ming MI to ``instead of J''.
Correct the month to "polyester". (4) “Photoconductor cA” in 4-story 11-tatami room No. 24 Tei Nigyogetsu
"is" is corrected to "photoreceptor (Al-(D) is"). 7 I"l record of the sealed document Paper 1 General rules Paper special l?T-scope of refinement 1, expressed by the general formula [1] Trisazo compound 1-2 4,4',4'-triaminotriphenylamine represented by the formula [ll] is diazotized to form a hexazonium salt represented by the general formula [111], and ■N. (However, X is an anion. Representing a functional group) is reacted with a 2-hydroxy-3-phenylbenz[a]carbazole visiting body 2- represented by the general formula [&] (wherein R is the same as above). A method for producing a trisazo compound represented by the general formula [!], characterized by: 3-

Claims (1)

[Claims] 1 Represents a trisazo compound represented by the general formula [■]. ) 2. Diazotize 4,4',4'-triaminophenylamine expressed by formula [l) to form a hexazonium salt represented by general formula [111), (il!L, X are anionic functional groups) ) and 2-hydroxy-3-phenylcarbamoylbenz[a]carbazole represented by the general formula [1v] (where l (is the same as Fiil)) and the opposite [d. A method for producing a trisazo compound, which is processed by formula 121, where the distance is 0 m. (However, R is the same as +411.)