JPS62267363A - Novel bisazo compound and its production - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (Z is benzene ring, naphthalene ring, or carbazole ring; R is H, halogen, lower alkyl, lower alkoxyl or nitro; n is 1-3). EXAMPLE:1, 8-bis[4-(2-hydroxy-3-phenylcarbamoylnaphthyl-1-aze)phe-nyl]-1,3,5,7- octatetraene. USE:Organic photoconductors. Useful for highly sensitive electrophotographic photosensitizers (especially laminate type ones) for use in high-speed copying machines and laser printers. PREPARATION:A coupling reaction is made between a tetrazonium salt of formula II (X is anionic functional group) and a coupler of formula III.

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to novel bisazo compounds useful as organic photoconductors and methods for producing the same. Prior Art Conventionally, certain azo compounds have been used in organic photoconductors used in laminated photoconductors, which are one form of electrophotographic photoconductors.
It is known to be particularly useful as a charge-generating pigment (hereinafter referred to as "margin"). As is well known, this laminated photoreceptor is coated with 'ttV' on a conductive support by light.
Charge generating material 1~ mainly composed of a heavy-duty generating pigment having the ability to generate fT carriers, and a charge transporting material having the ability to efficiently inject charge carriers generated in a charge generating layer thereon and further transport the charge carriers. This photoreceptor is provided with a charge transport layer containing as a main component. Conventionally, azo compounds used in such photoreceptors include, for example, benzidine-based bisazo compounds described in JP-A-47-37543 and JP-A-52-55643, and those described in JP-A-52-8832. Stilbene-based bisazo compounds described, JP-A-58-22
Diphenylhexatriene-based bisazo compounds described in JP-A No. 2152, diphenylbutadiene-based bisazo compounds listed in JP-A-58-222153, and the like are known. However, since conventional stirred layer m IB light materials using azo compounds generally have low sensitivity, ultra-high speed? It is unsatisfactory as a photoconductor for photographic machines. On the other hand, in recent years, there has been a demand for the development of a photoconductor for laser printers, which is particularly sensitive to the wavelength range of semiconductor lasers. The reality is that it is not possible to meet these objectives. Purpose What is the purpose of this invention? A high-sensitivity electrophotographic photoreceptor that is practical not only for photo cameras but also for laser printers.
Particularly, the object of the present invention is to provide a bisazo compound useful as a photorestrictor used in a laminated photoreceptor, and a method for producing the same. One of the structures of the present invention is the general formula ■ ′・Z・PaZ′ (ffl l, Z represents a habenzene, naphthalene ring, or cartumazole ring, R may be the same or different, and R is a hydrogen atom, a halogen atom, a lower represents an alkyl group, a lower alkoxyl group, or a nitro group, and n represents an integer of 1, 2, or 3. ) A coupling reaction is carried out between a tetrazonium salt represented by N2. , the general formula written in Ail! This is a method for producing bisazo compound v/1 shown in Here, in the general formula ■, the second official clause i,! ; Typical examples of X are C40, Br
0. Io, BFP, PF6e. B(0685)4, 0t04, SO Tomoe H
3C+SO3, AsF6. 5bF7 etc., preferably BP? It is. The bisazo compound represented by the general formula I of the present invention is produced as follows. First, the above general formula ■ as a raw material
The tetrazonium salt of is prepared by reducing 1,8-bis(4-nitrophenyl)-1,3゜5.7-octatetraene (hereinafter referred to as dinitro compound) to form 1,8-bis(4-aminophenyl)-1. , 3,5,7-octatetraene (hereinafter referred to as "diamino compound"), and diazotization of this results in I). Both the dinitro compound and diamino compound used here are new. Note that dinitro compounds include, for example, 4-nitrosinnamyltriphenylphosphonium puromy)',! =5-(4-nitrophenyl)-2,4-pentadienal-1 in the presence of a basic catalyst, which is the so-called Witteig reaction. The dinitro compound produced by this reaction contains a portion of the 3-monocysate, but this is because the crude reaction product cannot be directly used.
Alternatively, after Japanese preparation, it can be converted into an all-trans form by heat treatment in an aromatic hydrocarbon solvent such as toluene or xylene together with a catalytic amount of iodine. Reduction of the dinitro compound is usually carried out by heating to a temperature of 70 to 120° C. using iron-hydrochloric acid, tin-chloride monohydrochloric acid, etc. as a reducing agent, and the reaction is completed in about 0.5 to 3 hours. When a hydrochloric acid reducing agent is used, diazotization of the diamino compound should be carried out in an organic solvent such as N, N-dimethylform or amide. After being dispersed in M acid, this
The reaction is carried out by adding sodium nitrite at a temperature of -10 to 20 DEG C., and the reaction takes about 0.5 to 3 hours to complete the process. This reaction yields the tetrazonium salt of the general formula (1), but the diazotization reaction solution is further added with, for example, borohydrogen fluoride.
By adding an aqueous solution such as sodium difluoride and converting it into a salt, a tetrazonium base of the general formula] can be obtained. To prepare the bisazo compound of the present invention using the tetrazonium salt obtained in this way, firstly, the tetrazonium salt is separated from the reaction solution, and then the tetrazonium salt is mixed with the general formula shown above.

It is dissolved in an organic heating medium such as N, N-dimethylformamide or dimethyl sulfoxide together with a coupler of
The coupling reaction may be carried out by dropping an alkaline aqueous solution such as a sodium acetate aqueous solution at a temperature of 0°C. This reaction is completed in about 5 minutes to 3 hours. After the reaction is completed, the precipitated crystals are collected and purified by a suitable method such as washing with water and/or a mortar, recrystallization, etc. 1) to obtain the desired bisazo compound. Incidentally, the production of bisazo compounds is also possible by allowing a coupler to act on the diazotization reaction mixture. Do as above! Specific examples of the bisazo compound of the present invention manufactured by A are shown in Table 1 along with melting points (decomposition points), elemental analysis results, and infrared absorption spectrum data. (Hereinafter, blank spaces) The bisazo compound of the present invention is used as an organic photoconductor, particularly as a charge-generating substance, in various electrophotographic photoreceptors, for example, in the following manner. 1) A photoconductive layer containing the bisazo compound, a binder resin, and, if necessary, a sensitizer as main components is provided on a conductive support to obtain a single-layer photoreceptor. 2) A heavy-duty transport substance is further added to the system 1) to produce a single-layer type photoreceptor. 3) A charge-generating layer containing the bisazo compound as a main component is provided on a conductive support, and a charge-transporting layer containing a heavy-duty transport substance and a binder resin as a main component is further provided on top of the charge-generating layer to obtain a laminated photoreceptor. . The present invention will be explained below using examples and application examples. Example 1 4-Nitrocinnamyltriphenylphosphonium proma()'31.5f and U5-(4-nitrophenyl)
) - 2,4-Pentashener "Rue 1:12.79 in dry methanol 510 - to dry dimethylformamide (
DMF) 64-1 m [l] in mixed solvent, under N2 stream, 28% methanol solution of sodium methoxide 15.6
t was added dropwise over 2 hours to react. Next, the reaction solution was stirred at room temperature for 6 hours, and then added to 50% methanol water bath solution 3Q.
Add Q-, filter the precipitate, wash with water, and dry to obtain 1,8-bis(4-nitrophenyl)-1 containing the 3-monocysate.
, 3,5,7-octatetraene crude product 19.9 F
I got it. Next, this was heated and refluxed in 500 mm of xylene with iodine of catalyst ν, and then recrystallized with DMF to form 1.8-bis(4-nitrophenyl)-1 with an all-trans structure.
Dark red needle crystals of 3,5,7-octatetraene 14.
9f (yield 69%) was obtained. 7Flp, 238.5-240.5°C. Elemental analysis (as Ozo Hta NtO): OHN Actual value (supper) 68,77 4.63 7.91 Calculated value (
%) 68.95 4.64 8.04 Visible spectrum (in DMF): λmax×, 439 nm The infrared absorption spectrum (KBr tablet method) of this product is shown in FIG. As you can see from this figure, 1510cvr-'
Absorption based on the stretching vibration of the nitro group was observed at and 1335cPn-', and absorption based on the out-of-plane bending vibration of the trans olefin was observed at 0]0 and 950m''. 8-bis(4-nitrophenyl)-1,3,5,7-octatetraene 11.2
11 to DMF 250-, and iron powder 22.5F to this.
After the addition, dilute hydrochloric acid consisting of 5.6 parts of concentrated hydrochloric acid and 19 parts of water was added while stirring, and stirring was continued at 80 to 88°C for an additional 5 hours. After cooling to 50° C., a 10% caustic soda water bath solution was added to make it alkaline, and the insoluble portion was filtered hot with Celite. The P solution was diluted with water, and the precipitated crystals were filtered, washed with water, and dried to obtain a diamino compound of 7.99 (yield: 85%). This was recrystallized from a DMF-water mixed solvent, and 1.8-
Dark red plate-like crystals of bis(4-aminophenyl)-1,3,5,7-octatetraene were obtained. mp, 262.
5-264.5°C. Elemental analysis (as 02oH2oNt): OHN Actual value (correspondence) 83,01 7.02 9.75 Calculated value (correspondence) 83,28 7,00 9.71 The infrared absorption spectrum of this product is shown in Figure 2 (= shows this. As you can see from the figure, the first
The absorption based on the stretching vibration of class amine is also l OI Q
cm-' and 955 cm-'' absorption based on out-of-plane bending vibration of transolefin was observed. Production of tetrazonium salt 1,8-bis(4-aminophenyl)-1 obtained as described above ,3,5,two-octatetraene6.1
The mixture was added to dilute hydrochloric acid consisting of Salt Schiff, 2d and water Loom, and stirred at 60°C for 2 hours. After rapidly cooling to -2℃,
A solution prepared by dissolving 3.23 f of sodium nitrate in 10 - of water was added dropwise at -5 to -2°C over 50 minutes. Then, press for 20 minutes at the same temperature and rinse with 4oC of cold water. -, a trace amount of insoluble matter was removed by filtration, and a 42% aqueous solution of hydroboric acid was added to the furnace solution to precipitate a crystalline compound, which was dried to give a dark red tetrazonium salt of 8.4 f (yield 82 regrets). The infrared absorption spectrum of this product is shown in FIG. As can be seen from this figure, absorption based on the stretching vibration of the diazonium salt was observed at -1 of 2230. 0.55f of 3-hydroxy-2-naphthoic acid anilide was dissolved in DMF200-, and the tetrazonium salt 0492 obtained as described above was added thereto, followed by acetic acid solution (I).
A solution of 0.34 f of Jum dissolved in 4 g of water was heated at room temperature for 2
The reaction was carried out dropwise over a period of 0.09 hours. Next, the mixture was stirred at the same temperature for 3 hours, and the generated bisazo pigment was placed in front of a furnace, and DMF25
It was washed 5 times with 0 m/m, followed by 2 washes with 250 m/m of water. This was further dried under reduced pressure to obtain a bisazo pigment of compound A 12: ], 8-bis[4-(2-hydroxy-
0.729 (yield: 82%) of 3-phenylcarnomoylnaphthyl-1-azo)pheni/l/]-1,3,5,7-octatetraene was obtained as a blue-black powder. Decomposition point: 276°C. Elemental analysis (as C,, H4°N, O): 0
-HN Actual value (%”) 77.44 4.72
9.87 total 111 [i11 "(%) 77
．． 48 4.83 10.04 Visible spectrum [ethylenediamine/DMF (1/9
:'vot)] :λmax, 596 nm Infrared absorption spectrum of this product (KB r tablet method)
is shown in Figure 4. As you can see from this diagram, 1675 cm
Absorption based on the stretching vibration of C=O in Mata 995
Out-of-plane bending vibration of trans olefin in cm-'! Absorption capacity based on /l was suppressed. Example 2 0.665' of 3-hydroxy-2-phenylcarnomoylanthracene was dissolved in DMF200-, and 0.49 f of the tetrazonium salt obtained in Example 1 was loaded onto the ship, followed by 0.665' of 3-hydroxy-2-phenylcarnomoylanthracene. A solution of 342 dissolved in water was added dropwise at room temperature over 20 minutes. Next, at the same temperature,
After stirring for an hour, the formed pigment was filtered and DMF 25
0Il! It was washed 4 times with t and then twice with 250ml of water. This was heated and dried under reduced pressure to obtain a bisazo compound of Compound 29: 1.8-bis[4-(2-hydroxy-3-
Phenylcarnomoylanthryl-1-azo)phenyl)-1,3゜5.7-octatetraene as a blue-black powder with 0.81? (yield 86%). Decomposition point 28
7℃. Elemental analysis (as 011!H44N604): CHN Actual value (CH) 79.20 4.48 8.74 Calculated value (CH) 79.46 4,74 8.97 Visible spectrum [ethylenediamine/DMF (]/9: v
ol, )) :λmax, fi34nm The infrared absorption rate (KBr tablet method) of this product is shown in FIG. As can be seen from this figure, there is absorption based on the stretching vibration of C=O at 5680 cm-', and also at 1010a'''
Absorption based on out-of-plane bending vibration of the trans-olefin was observed directly at the 1 and 960 rows. Example 3 2-hydroxy-3-phenylcarbamoyl-11H-
Benzo[a]carnozole 1.11f in DMF 20
After adding 0.73 f of the tetrazonium salt obtained in Example 1 to this, acetic acid solution was added.
A solution of 52f dissolved in water was added dropwise at room temperature over 30 minutes. Next, after stirring at the same temperature for 3 hours, the generated bisazo pigment was filtered, and the residue was diluted with DMF 300-
It was washed twice and then twice with 300 g of water. This was heated and dried under reduced pressure to obtain a bisazo compound of Compound 13: l,8-bis[4-(2-hydroxy-3-7enylcarnomoyl-1IH-benzo[a)carbazolyl-1-azo)phe'] 2/m)-1,3,5,7-octatetraene as a blue-black powder (yield: 90
h) Obtained. Decomposition point: 305°C. Elemental analysis (as Ce1l H2S N@o): C
HN Actual value (%) 77.77 4.4510.78 Calculated value (%) 78,08 4.58 11.04 Visible spectrum [ethylenediamine λmax, 620 nm Infrared absorption spectrum of this product (KB r @ agent method)
is shown in Figure 6. As you can see from this diagram, 3450 cm
-', the absorption based on the stretching vibration of carbazole N)l is
In addition, absorption based on out-of-plane bending vibration of trans-olefin was observed in 1000(7)-1. Examples 4 to 29 The bisazo compounds of Compounds f1 to ]1 and 14 to 28 were prepared in the same manner as the method for producing bisazo compound 12 of Example 1 using couplers corresponding to Compounds A I'' 11 and 14 to 28, respectively. The decomposition points, elemental analysis results, and I-temperature spectrum data of these compounds are shown in Table 1.The infrared absorption spectrum (KBr method) of the bisazo compound A22 is also shown in Figure 7. Application example Compound A 22 bisazo compound 7 as a charge generating substance
, 5 parts and 500 parts of a 0.5% tetrahydrofuran solution of polyester resin [■ Toyobo Co., Ltd., Niiron 200] were ground and mixed in a mail mill, and the resulting dispersion was coated on an aluminum-deposited polyester film using a Dr. Pund. Then, air dry it to a thickness of about 1 μm. ! A f charge generation layer was formed. Next, as a charge transport substance, 2 parts of 9-nityllupazole-3-aldehylazone-1-methyl-1-phenylhydrazone was added to 10% tetrahydrofuran of a polycarbonate resin (K-1300 manufactured by Ondai). The solution was dissolved in a bath, and this bath solution was applied onto the charge generation layer using a doctor blade, and heated at 80°C for 2 minutes and then at 120°C for 5 minutes.
The charge transport layer was dried for minutes to form a charge transport layer approximately 20 pfi thick. Next, in order to examine the sensitivity in the visible range of the laminated electrophotographic photoreceptor obtained in this way, this photoreceptor was heated to 16 KV in a dark place using an electrostatic copying paper tester [Type 5P428 manufactured by Kawaguchi Electric Manufacturing Co., Ltd.]. After charging by performing corona discharge for 20 seconds, dark decay was performed for 20 seconds, and the surface potential V at this time. (2 lt), and then the illuminance on the photoconductor surface is 4.5.
The time (sec
) is calculated, and the half-reduced exposure amount E1/2 is calculated as the sensitivity in the visible range.
(tux·sec) was calculated. As a result, VO is 533 Zelt, and E1/! is 0, 4
It was 9 lux @sec. Further, the following measurements were performed to examine the sensitivity of this photoreceptor to long wavelength light. First, the photoreceptor is charged by corona discharge in a dark place, and then
When the surface potential reaches 800 volts due to dark decay,
Spectroscopy was performed at 780 nm using a monochromator]μ
W/i monochromatic light was irradiated. Next, the surface potential is ”/2
The time (S) required for the light to attenuate to (400, f volts) was determined, and the exposure fij' (pW*s-cfjI-) was determined to calculate the light attenuation rate 5 (volt-aJ·μJ''). The result was S"580V-7-/JJ-1. As described above, the photoreceptor using the bisazo compound of the present invention has extremely high sensitivity not only in the visible range but also in semiconductor laser f-mode. Effect As can be seen from the above explanation, the bisazo compound of the present invention can be used in electrophotographic photoreceptors that exhibit high sensitivity both for high-speed copying machines and laser printers, especially for organic photoreceptors used in laminated photoreceptors. It is extremely useful as an isoelectric material.

[Brief explanation of the drawing]

Figures 1 to 3 are infrared absorption spectra of dinitro compounds, diamino compounds, and tetrazonium salts, which are intermediates for producing the bisazo compound of the present invention;
The figure shows the infrared absorption spectra of bisazo compounds of the invention A I 2.29.13 and 22, respectively. Patent Applicant Ricoh Co., Ltd. - Procedural Amendment July 10, 1985 Michibe Uga, Commissioner of the Patent Office1, Indication of Case Patent Application No. 111288 of 19852, Title of Invention Novel bisazo compounds and their Manufacturing method 3, relationship with the case of the person making the amendment Patent applicant: 1-3-6 Nakamagome, Ota-ku, Tokyo (674) Rico Co., Ltd. - Representative: Hama 1) Hiro 4, Agent: Kojimachi, Chiyoda-ku, Tokyo 4-chome 5 (〒102) (651
3) One patent attorney: Shigeru Tsukimura Telephone: Tokyo (263)
3861-35, Column 6, "Detailed Description of the Invention" in the Specification Subject to Amendment, Contents of the Amendment

Claims (1)

[Claims] 1. General formula I ▲ Numerical formulas, chemical formulas, tables, etc.▼ (However, Z represents a benzene ring, a naphthalene ring, or a carbazole ring, and R may be the same or different, and a hydrogen atom,
It represents a halogen atom, a lower alkyl group, a lower alkoxyl group or a nitro group, and n represents an integer of 1, 2 or 3. ) A bisazo compound represented by 2. General formula II ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X represents an anionic functional group.) Tetrazonium salt represented by General formula III ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, Z, R , n is the same as general formula I below) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, Z is a benzene ring, naphthalene ring, or carbazole ring) , R may be the same or different, and represent a hydrogen atom,
It represents a halogen atom, a lower alkyl group, a lower alkoxyl group or a nitro group, and n represents an integer of 1, 2 or 3. ) A method for producing a bisazo compound shown in