JPH0680895A - Azo-based compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a sensitized material, pigment, solar cell, etc., having high sensitivity and excellent light stability free from extreme reduction in surface potential caused by repeated use. CONSTITUTION:A compound of formula I (A<1> and A<2> are coupler residue; R<1> and R<2> are H, alkyl, etc.; R<3> and R<4> are H, halogen, etc.; (m) and (n) are 0 or 1) such as a compound of formula II. The compound, for example, is obtained by reacting a bis(chloromethyl)benzene-based compound of formula III with a bis(mercaptomethyl)benzene-based compound of formula IV in the presence of a base such as KOH to give a dithio(3,3)metacyclophane-based compound of formula V, successively nitrating the compound, reducing and then diazotizing two amino groups of a prepared diaminodithio(3,3)metacyclophane-based compound with sodium nitrite, respectively, to give a tetrazolium salt and finally coupling the salt with a coupler in an organic solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various photosensitive materials such as charge generating materials for electrophotographic photoreceptors, azo compounds which are preferably used as pigments, solar cells and the like. .

[0002]

2. Description of the Related Art As charge generating materials for electrophotographic photoreceptors, photosensitive materials used for pigments, solar cells, etc.,
Conventionally, inorganic photoconductors such as selenium and cadmium sulfide have been known, but these are toxic and are not desirable because of high production cost. Therefore, in place of these inorganic substances, various organic substances having excellent workability and being advantageous in terms of manufacturing cost and having a high degree of freedom in functional design,
Proposed as a photosensitive material.

As the organic photosensitive material, many compounds such as phthalocyanine compounds, perylene compounds, quinacridone compounds, anthanthrone compounds and azo compounds have been proposed. For example, as azo compounds, there are JP-A-47-37543 and JP-A-57-1957.
The one disclosed in Japanese Patent Publication No. 67 is known.

[0004]

However, the above-mentioned conventional photosensitive materials have problems that the photosensitive wavelength region is narrow and the sensitivity is low. Further, the conventional light-sensitive materials also have insufficient light stability. The present invention solves the above problems and has high sensitivity as a photosensitive material,
Another object of the present invention is to provide a novel azo compound having excellent light stability.

[0005]

Means and Actions for Solving the Problems To solve the above problems, the azo compound of the present invention has the general formula (I):

[0006]

[Chemical 5]

[Wherein A ¹ and A ² represent the same or different coupler residues, R ¹ and R ² represent the same or different hydrogen atom, an alkyl group or an alkoxy group, and R ³ and
R ⁴ is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. m and n are 0 or 1
Indicates. ] Is represented. According to the studies by the present inventors, the azo compound represented by the general formula (I) has high sensitivity and does not cause a significant decrease in surface potential due to repeated use. In addition, it is possible to stably maintain high sensitivity for long-time exposure or exposure at high temperature, and it is excellent in light stability.

The present inventors presume the reason why the azo compound of the present invention has such high sensitivity and photostability as follows. That is, the azo compound of the present invention is caused by the peculiar structure of dithio (3,3) metacyclophane introduced into the molecule.
No. -37543, the following general formula (II):

[0009]

[Chemical 6]

[Wherein A ¹ and A ² represent the same coupler residue as described above, Y represents a hydrogen atom, a methyl group, a methoxy group,
Indicates an ethoxy group, hydroxyl group, chlorine atom or bromine atom]
Alternatively, the following general formula (III) exemplified in JP-A-54-46558:

[0011]

[Chemical 7]

A conventional bisazo compound represented by the formula [wherein A ¹ and A ² represent the same coupler residue as described above and R represents a hydrogen atom, an ethyl group, a chloroethyl group or a hydroxyethyl group] and the like. It is presumed that this is because the carrier generation ability during light irradiation is superior. The above general formula
The azo compound of the present invention represented by (I) basically contains an azo compound represented by the following general formulas (Ia) to (Ic).

[0013]

[Chemical 8]

[Wherein A ¹ , A ² , R ¹ , R ² , R ³ , R
⁴ represents the same group as described above. ] The above general formulas (I) and (Ia)
~ In the azo compound of the present invention represented by (Ic),
Examples of the alkoxy group of R ¹ and R ² include a methoxy group and an ethoxy group, and examples of the alkyl group include a methyl group and an ethyl group. The alkyl group of R ³ and R ⁴ includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and the like. Are, for example, a phenyl group, a noryl group, a xylyl group, a biphenyl group, a naphthyl group, and the like, and examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, a fluorine atom and the like.

Examples of the coupler residues A ¹ and A ² include groups represented by the following general formulas (a) to (g). The coupler residues A ¹ and A ² may be the same or different from each other.

[0016]

[Chemical 9]

In each formula, R ³⁰ represents a carbamoyl group, a sulfamoyl group, an allofanoyl group, an oxamoyl group, an anthraniloyl group, a carbazoyl group, a glycyl group, a hydantoyl group, a phthalamoyl group, and a succinamoyl group. These groups include a halogen atom, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a nitro group, a cyano group, an alkyl group, an alkenyl group, a carbonyl group, a carboxyl group and the like. It may have a substituent.

R ³¹ represents an atomic group necessary for forming an aromatic ring, a polycyclic hydrocarbon or a heterocycle by condensing with R ³⁰ and the benzene ring having a hydroxyl group, and these rings are as described above. You may have the same substituent. R ³² represents an oxygen atom, a sulfur atom or an imino group. R ³³ represents a divalent chain hydrocarbon or aromatic hydrocarbon, and these groups may have the same substituents as described above.

R ³⁴ represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, and these groups may have the same substituents as described above. R ³⁵ is a divalent chain hydrocarbon, an aromatic hydrocarbon, or the following formula (h) in the above general formulas (e) and (f).

[0020]

[Chemical 10]

It represents an atomic group necessary for forming a heterocycle with the moiety represented by, and these rings may have the same substituents as described above. R ³⁶ is a hydrogen atom, an alkyl group,
It represents an amino group, a carbamoyl group, a sulfamoyl group, an allofanoyl group, a carboxyl group, an ester of a carboxyl group, an aryl group, or a cyano group, and groups other than a hydrogen atom may have the same substituents as described above.

R ³⁷ represents an alkyl group or an aryl group, and these groups may have the same substituents as described above.
As the alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,
Examples thereof include lower alkyl groups having 1 to 6 carbon atoms such as tert-butyl group, pentyl group and hexyl group.

Examples of the aryl group include phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthryl group and phenanthryl group. Examples of the alkenyl group include lower alkenyl groups having 2 to 6 carbon atoms such as vinyl group, allyl group, 2-butenyl group, 3-butenyl group, 1-methylallyl group, 2-pentenyl group and 2-hexenyl group. To be

Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and fluorine atom. In R ³¹ , the atomic group necessary for forming an aromatic ring by condensing with R ³⁰ and a benzene ring having a hydroxyl group includes, for example, an alkylene group such as a methylene group, an ethylene group, a propylene group and a butylene group. To be

The aromatic ring formed by the condensation of R ³¹ with R ³⁰ and a benzene ring having a hydroxyl group is
Examples thereof include naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring and naphthacene ring. In R ³¹ , the atomic group necessary for condensing with R ³⁰ and a benzene ring having a hydroxyl group to form a polycyclic hydrocarbon is, for example, a methylene group, an ethylene group, a propylene group, a butylene group, or a carbon atom. Examples include alkylene groups of the numbers 1 to 4.

Examples of the polycyclic hydrocarbon formed by the condensation of R ³¹ with R ³⁰ and a benzene ring having a hydroxyl group include a carbazole ring, a benzocarbazole ring and a dibenzofuran ring. Further, in R ³¹ , an atomic group necessary for forming a heterocycle by condensing with R ³⁰ and a benzene ring having a hydroxyl group is, for example, a benzofuranyl group, a benzothiophenyl group, an indolyl group, a 1H-indolyl group, bezoxazolyl. Group, benzothiazolyl group, 1H-indaryl group, benzimidazolyl group, chromenyl group, chromanyl group, isochromanyl group, quinolinyl group, isoquinolinyl group, cinnolinyl group, phthalazinyl group, quinazonilyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, xanthenyl group , Acridinyl group, phenanthridinyl group, phenazinyl group, phenoxazinyl group, thianthrenyl group and the like.

Examples of the aromatic heterocyclic group formed by condensation of R ³¹ and R ³⁰ and a benzene ring having a hydroxyl group include, for example, thienyl group, furyl group, pyrrolyl group,
Oxazolyl group, isoxazolyl group, thiazolyl group,
Examples thereof include isothiazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group and thiazolyl group. Further, it may be a heterocyclic group condensed with another aromatic ring (for example, a benzofuranyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinolyl group, etc.).

In R ³³ and R ³⁵ , examples of the divalent chain hydrocarbon include ethylene group, propylene group and butylene group, and examples of the divalent aromatic hydrocarbon include phenylene group, naphthylene group, Examples thereof include phenanthrylene group. Examples of the heterocyclic group represented by R ³⁴ include a pyridyl group, a pyrazyl group, a thienyl group, a pyranyl group and an indolyl group.

In R ³⁵ , the atomic group necessary for forming a heterocycle with the moiety represented by the formula (h) is, for example, phenylene group, naphthylene group, phenanthrylene group, ethylene group, propylene group or butylene. Examples include groups. Examples of the aromatic heterocyclic group formed by R ³⁵ and the moiety represented by the formula (h) include, for example, benzimidazole group, benzo [f] benzimidazole group, dibenzo [e, g] benzimidazole group. Group, benzopyrimidine group and the like. These groups may have the same substituents as described above.

In the above R ³⁶ , examples of the carboxyl group ester include methyl ester, ethyl ester, propyl ester, butyl ester and the like. Specific examples of the coupler residue A represented by the general formulas (a) to (g) include the following groups.

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

The azo compound of the present invention represented by the above general formula (I) can be synthesized by various methods. For example, taking the azo compound represented by the general formula (Ia) as an example, first, as shown in the following reaction process formula, bis (chloromethyl) benzene compound (1) and bis (mercaptomethyl) By reacting the benzene compound (2) with a base such as potassium hydroxide, a dithio (3,3) metacyclophane compound represented by the general formula (3) is produced.

[0036]

[Chemical 15]

Next, the above compound is nitrated by a conventional method to obtain a dinitro-dithio (3,3) metacyclophane compound represented by the following general formula (4), which is reduced by a conventional method. A diamino-dithio (3,3) metacyclophane compound (general formula (5)) is prepared. And this diamino-dithio (3,3) metacyclophane compound
The two amino groups of (5) are each diazotized to form a tetrazonium salt, which is coupled with a predetermined coupler in an organic solvent to produce an azo compound represented by the general formula (Ia). The diazotization is carried out by adding sodium nitrite or nitrous acid dropwise at a low temperature (usually -10 to 10 ° C) while stirring an acidic aqueous solution of diamino-dithio (3,3) metacyclophane compound (5). Done.

[0038]

[Chemical 16]

[A ¹ , A ² in the above reaction process formulas,
R ¹ and R ² represent the same groups as described above. The above-described azo compound of the present invention can be used in various fields such as various light-sensitive materials and pigments, solar cells, and the like in addition to the charge generating material in the electrophotographic photoreceptor described above.

[0040]

EXAMPLES The present invention will be described below based on Examples and Comparative Examples. Example 1 22.7 g (0.21 mol) of methoxybenzene and 50 ml of concentrated sulfuric acid were added to 150 ml of chlorodimethyl ether, and the mixture was reacted under reflux for about 40 minutes and then cooled with ice water for about 30 minutes to obtain the following formula (1a). 12.06 g (yield 28%) of 2,6-bis (chloromethyl) methoxybenzene represented by

Further, the above 2,6-bis (chloromethyl)
0.6 g (0.05 mol) of methoxybenzene and 8.37 g (0.11 mol) of thiourea were reacted in 75 ml of dimethylsulfoxide (DMSO) at a temperature of 15 to 25 ° C. And 2,6-bis (mercaptomethyl) represented by the following formula (2a) as a colorless oily compound
8.41 g (yield 84%) of methoxybenzene was obtained.

Next, 4.2 g of potassium hydroxide and 20
Put 00cc of dry ethanol into a 3-neck flask,
After substituting the inside of the flask with nitrogen, 4.72 g of the above 2,6-bis (chloromethyl) methoxybenzene (0.
7023) and 2,6-bis (mercaptomethyl) methoxybenzene 4.61 g (0.023 mol).
A solution dissolved in 0 ml of benzene was slowly added dropwise using a dropping funnel. Then, after stirring and reacting at room temperature for about 48 hours, the reaction solution was concentrated by an evaporator and extracted with 700 ml of dichloromethane to obtain a reaction product.

Next, the reaction product is fractionated by column chromatography using a 1: 1 mixed solvent of benzene and hexane to obtain the desired product, which is represented by the following formula (3a): 8,16- There were obtained 4.82 g (yield 65%) of dimethoxy-dithio (3,3) metacyclophane. The above reaction formula is described below.

[0044]

[Chemical 17]

The above 8,16-dimethoxy-dithio (3,3)
3) 15 g of metacyclophane was added to 200 cc of a 60% acetic anhydride solution of copper nitrate (CuNO ₃ ) and stirred at a temperature of 15 to 25 ° C. for 2 hours to obtain a reaction product. Analysis of this reaction product revealed that it was the desired product, 5,13-dinitro-
Since it was found to be a mixture of two compounds containing 8,16-dimethoxy-dithio (3,3) metacyclophane, it was separated by column chromatography to obtain 5,13 represented by the following formula (4a). -Dinitro-8,16-dimethoxy-dithio (3,3) metacyclophane 4.82 g
(Yield 65%) was obtained.

[0046]

[Chemical 18]

Next, a solution prepared by dissolving 0.49 g (0.013 mol) of lithium aluminum hydride (Li Al H ₄ ) in 60 ml of tetrahydrofuran was placed in a 2000 cc flask, and this solution was charged with the above 5, 5. A solution of 6.76 g (0.016 mol) of 13-dinitro-8,16-dimethoxy-dithio (3,3) metacyclophane in 50 ml of tetrahydrofuran was added dropwise under reflux.

After completion of the dropping, while cooling the flask with ice water, a sufficient amount of water was added to decompose excess lithium aluminum hydride, and 20% of potassium sodium tartrate was added.
After adding the aqueous solution, the aqueous layer was extracted several times with 30 cc of ether. Then, add sodium sulfate and dry,
As a result, 4.16 g of 5,13-diamino-8,16-dimethoxy-dithio (3,3) metacyclophane represented by the following formula (5a) was obtained.

[0049]

[Chemical 19]

3.63 g of the above 5,13-diamino-8,16-dimethoxy-dithio (3,3) metacyclophane
(0.01 mol) and 10% hydrochloric acid (30 ml) were put in a 100 cc flask, and the flask was cooled in an ice bath to a liquid temperature of -3.
A solution prepared by dissolving 1.16 g of sodium nitrite (NaNO ₃ ) in ₃ ml of water was stirred while maintaining the temperature at -5 ° C.
The solution was added dropwise over a period of 30 minutes and then stirred for 30 minutes to carry out a tetrazotization reaction. Then, activated carbon was added to this reaction solution to remove excess components, and then the activated carbon was filtered off.

Next, 150 ml of a 6% aqueous sodium hydroxide solution was placed in a 500 ml beaker, and the above-mentioned formula was added to this solution.
5. A coupler having a coupler residue represented by (A1).
After dissolving 3 g (0.024 mol), the liquid temperature was adjusted to 5 to 15
The above reaction solution was added dropwise over 20 minutes while maintaining the temperature at 0 ° C., and then the mixture was stirred at room temperature for another 5 hours. Then, after leaving this reaction solution for a whole day and night, the solid content is filtered off, washed with water and dimethylformamide in this order, and dried,
4.37 g of the bisazo compound represented by the following formula (yield 4
8%).

[0052]

[Chemical 20]

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%) C: 68.55 H: 4.65 N: 9.22 Measured value (%) C: 68.83 H: 4.43 N: 9.92 Mass spectrometry result m / e = 911 (calculated value 911.03) Example 2 Except that 7.15 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A2) was used.
4.12 g of a bisazo compound in the same manner as in Example 1 above.
(Yield 42%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis results Calculated value (%): C: 63.74 H: 4.114 N: 8.5576 Actual value (%): C: 63.78 H: 4.59 N: 8.63 Mass spectrometry result m / e = 980 (calculated value 979.95) Example 3 except that 8.18 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A3) was used.
5.23 g of the bisazo compound in the same manner as in Example 1 above.
(Yield 49%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 60.84 H: 3.971 N: 10.51 Actual value (%): C: 60.69 H: 3.87 N: 10.21 Mass spectrometry result m / e = 1067 (calculated value 1066.0) Example 4 Except that 7.16 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A4) was used.
3.73 g of a bisazo compound in the same manner as in Example 1 above.
(Yield 38%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 61.08 H: 4.306 N: 8.548 Measured value (%): C: 61.81 H: 4.29 N: 8.55 Mass spectrometry result m / e = 983 (calculated value 983.15) Example 5 Except that 8.07 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A8) was used.
In the same manner as in Example 1, 4.36 g of bisazo compound
(Yield 39%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis results Calculated value (%): C: 70.95 H: 4.691 N: 10.03 Actual value (%): C: 71.13 H: 4.59 N: 10.21 Mass spectrometry result m / e = 1118 (calculated value 1117.3) Example 6 Except that 7.07 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A9) was used.
In the same manner as in Example 1, 4.09 g of bisazo compound
(Yield 42%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 64.13 H: 3.932 N: 11.51 Actual value (%): C: 63.81 H: 4.01 N: 11.51 Mass spectrometry result m / e = 974 (calculated value 973.95) Example 7 Same as Example 1 except that 7.86 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A11) was used. Bisazo compound 4.6
7 g (yield 45%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 69.34 H: 4.073 N: 8.086 Measured value (%): C: 69.21 H: 4.05 N: 8.01 Mass spectrometry result m / e = 1038 (calculated value 1039.3) Example 8 Same as Example 1 except that 8.39 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A12) was used. Bisazo compound 4.2
2 g (yield 39%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 70.96 H: 4.280 N: 12.93 Measured value (%): C: 70.58 H: 4.29 N: 13.05 Mass spectrometry result m / e = 1084 (calculated value 1083.3) Example 9 Same as Example 1 except that 5.45 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A13) was used. And bisazo compound 3.0
9 g (yield 37%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 63.00 H: 4.085 N: 10.02 Measured value (%): C: 62.99 H: 4.13 N: 9.98 Mass spectrometry result m / e = 837 (calculated value 838.90) Example 10 Same as Example 1 except that 6.94 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A14) was used. Bisazo compound 3.9
5 g (41% yield) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 67.35 H: 3.977 N: 8.726 Measured value (%): C: 67.48 H: 4.01 N: 8.63 Mass spectrometry result m / e = 964 (calculated value 963.05) Example 11 Same as Example 1 except that 6.87 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A19) was used. And bisazo compound 4.5
9 g (yield 48%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 67.77 H: 3.791 N: 11.71 Actual value (%): C: 67.89 H: 3.75 N: 11.59 Mass spectrometry result m / e = 957 (calculated value 957.05) Example 12 In place of the 2,6-bis (chloromethyl) methoxybenzene represented by the above formula (1a), 2,6 represented by the following formula (1b)
-Bis (chloromethyl) methoxybiphenyl 6.47 g
5-Amino-13- (p-aminophenyl) -8,16 represented by the following formula (5b) was prepared in the same manner as in Example 1 except that (0.023 mol) was used as the starting material.
-Dimethoxy-dithio (3,3) metacyclophane 5.
23 g was obtained.

[0064]

[Chemical 21]

Then, the 5-amino-13- (p-aminophenyl) -8,16-dimethoxy-dithio (3,3
3) 4.39 g (0.01 mol) of metacyclophane,
Using a coupler having a coupler residue represented by the above formula (A2) 7.15 g (0.024 mol), Example 1
5.49 g of bisazo compound (yield 52
%) Was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 65.97 H: 4.199 N: 7.958 Measured value (%): C: 65.01 H: 4.09 N: 7.99 Mass spectrometry result m / e = 1056 (calculated value 1056.0) Example 13 In place of the 2,6-bis (chloromethyl) methoxybenzene represented by the above formula (1a), 2,6 represented by the above formula (1b).
-Bis (chloromethyl) methoxybiphenyl 6.47 g
(0.023 mol) and used in place of 2,6-bis (mercaptomethyl) methoxybenzene represented by the formula (2a), 2,6-bis (mercapto) represented by the following formula (2b). Methyl) methoxybiphenyl 4.73 g (0.0
23 mol) was used, and in the same manner as in Example 1, 5,13-bis (p-aminophenyl) -8,16-dimethoxy-dithio (3,3 represented by the following formula (5c).
3) 5.38 g of metacyclophane was obtained.

[0067]

[Chemical formula 22]

The 5,13-bis (p-aminophenyl) -8,16-dimethoxy-dithio (3,3)
In the same manner as in Example 1 except that 5.15 g (0.01 mol) of metacyclophane and 7.15 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A2) were used. 5.99 g of bisazo compound (yield 53%)
Was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis results Calculated value (%): C: 67.90 H: 4.273 N: 7.423 Measured value (%): C: 66.09 H: 4.29 N: 7.39 Mass spectrometry result m / e = 1131 (calculated value 1132.1) Comparative Example 1 The following formula:

[0070]

[Chemical formula 23]

Chlorodian blue represented by
And Of the above-mentioned embodiments, Embodiments 1, 2, 8, 10,
The following tests were carried out on 11, 12, 13 and the bisazo compound of Comparative Example 1 to evaluate the characteristics. Measurement of Charge Generation Efficiency The bisazo compound of each Example and Comparative Example and the polyester resin as the binder resin were mixed in a suitable solvent so that the amount ratio of the bisazo compound was 10% by weight, A coating liquid was prepared by uniformly dispersing. Then, as shown in FIG. 1, this coating solution is applied to the ITO electrode layer 102 of the transparent sheet 101 having the ITO electrode layer 102 formed on one surface thereof.
Apply to the surface of the side where the
The resin dispersion layer 103 was formed. Then, a gold electrode layer 104 was laminated on the back surface of the pigment / resin dispersion layer 103 to prepare a sample.

Next, the ITO electrode layer 10 of the above sample was prepared.
2 and the gold electrode layer 104 were connected to the measurement circuit as shown in the figure. As shown in FIG. 2, the measurement circuit considers the sample equivalently as one capacitor, and forms a bridge circuit with the sample CS, one variable capacitor C1, and two fixed capacitors C2 and C3. Is.

Next, the power supply device 1 is connected to the bridge circuit.
While the voltage is applied from 06, the sample pigment / resin dispersion layer 103 is irradiated with laser pulse light as excitation light from the transparent sheet 101 side to obtain the sample CS from the equilibrium state (light non-irradiation state). The amount of voltage displacement (voltage drop ΔV, unit mV) was measured by the storage scope 107 connected to the bridge circuit. As the light source for irradiating the sample CS with the laser pulse light, the nitrogen gas laser NL connected to the power supply device 106 via the switch SW and the laser light from the nitrogen gas laser NL are irradiated. , Sample CS
A dye laser DL for irradiating the laser pulse light to the laser beam, and a monitor device 108 for monitoring the light energy of the laser pulse light emitted from the dye laser DL via a half mirror HM provided in the optical path of the laser pulse light. Was used.

Then, the charge generation efficiency (η) was obtained from the measured voltage displacement amount (ΔV) of the sample CS by the following formula. Charge generation efficiency η = (C · ΔV / eNφ) · [1 / fv ·
f (ε1, ε2)] where each symbol in the above formula is as follows. C: capacitance of sample (= 4.8 × 10 ⁻¹⁰ , dielectric constant of sample = 2.71) e: elementary charge Nφ: number of absorbed photons (= 5 × 10 ⁻¹⁰ , monitor device) Fv: volume fraction of pigment (= 7.25, volume fraction when the amount ratio of bisazo compound is 10% by weight) ε1: Dielectric of bisazo compound Ratios (all have been set to 4.45 because there are few structural differences) ε2: Dielectric constant of polyester resin (= 2.60) f (ε1, ε2): Correction function, calculated by the following formula.

F (ε1, ε2) = ε2 / [ε1 + 2ε2-fv · (ε1-ε2)] The electric field strength between both electrodes was 3 × 10 ⁷ V / m. Table 1 shows the charge generation efficiency (η) calculated by the above formula in the samples using the bisazo compounds of Examples and Comparative Examples. Light Stability Test Using the bisazo compounds of the above Examples and Comparative Examples as charge generating materials, single-layer type and multi-layer type photoconductors were prepared by the following procedure.

(Production of Single Layer Type Photoreceptor) 8 weight of bisazo compound as a charge generating material and the following formula as a charge transporting material:

[0077]

[Chemical formula 24]

N, N, N ', N'-tetrakis (3-methylphenyl) -m-phenylenediamine 1 represented by
00 parts by weight and polycarbonate 10 as a binder resin
0 parts by weight together with a predetermined amount of tetrahydrofuran,
A single layer type photosensitive layer coating liquid was prepared by mixing and dispersing using a ball mill. Apply this coating liquid to a diameter of 80 mm x length of 350 mm
Drum type positive charging type electrophotographic photoconductor having a single-layer type photosensitive layer having a film thickness of 24 μm after being coated on the surface of the aluminum base tube by a dipping method and then dried by heating at 100 ° C. for 30 minutes in a dark place. The body was made.

(Production of Laminated Photoreceptor) 100 parts by weight of polyvinyl butyral as a binder resin, 100 parts by weight of a bisazo compound as a charge generating material, and a predetermined amount of tetrahydrofuran were charged in a ball mill and mixed with stirring for 24 hours. Then, a charge generation layer coating liquid was prepared. This coating solution is applied to the surface of an aluminum tube having a diameter of 80 mm and a length of 350 mm by a dipping method, and then, in a dark place, 11
Dry with hot air for 30 minutes at 0 ° C and cure to a film thickness of 0.5μ
m charge generating layer was formed.

Next, 100 parts by weight of polycarbonate as a binder resin and N, N, and N as a charge transport material are used.
N ', N'-tetrakis (3-methylphenyl) -m-
100 parts by weight of phenylenediamine and a predetermined amount of toluene were mixed by stirring with a homomixer to prepare a charge transport layer coating solution. This coating solution is applied onto the charge generation layer previously formed on the surface of the raw tube by a dipping method, and dried by hot air at 90 ° C. for 30 minutes to form a charge transport layer having a thickness of about 20 μm, and laminated. A drum type negative charging type electrophotographic photosensitive member having a mold photosensitive layer was produced.

(Measurement of Light Stability) The single-layer type and laminated type photoconductors prepared as described above were first placed in an electrostatic copying tester (Gentec Cynthia 30M, trade name, manufactured by Gentech). After charging and positively or negatively charging the surface, the charged electrophotographic photosensitive member is exposed under a condition of an exposure intensity of 10 lux by using a halogen lamp which is an exposure light source of an electrostatic copying tester. Then, after starting the exposure,
The surface potential at the time when 0.15 seconds had elapsed was measured and defined as the residual potential V1r.p. (V).

Next, the above photoconductor is loaded into an electrostatic copying machine (model number DC-1657, manufactured by Mita Kogyo Co., Ltd.), and 1000
After continuous copying of the sheets, the residual potential V2r.p. (V) after repeated exposure was measured in the same manner as above. And
Difference ΔVr.p. (V) between the residual potentials V1r.p. and V2r.p.
I asked. The results are shown in Table 1.

[0083]

[Table 1]

From the results shown in Table 1 above, all of the bisazo compounds of the examples, which are the azo compounds of the present invention,
It was found that the charge generation efficiency was higher than that of Comparative Example 1 and the sensitivity was high. In addition, the photoconductor using the bisazo compound of each of the above Examples has a smaller residual potential change amount due to repeated exposure than the photoconductor using Comparative Example 1, and therefore, the bisazo compound of each of the above Examples is obtained. It was found that the compounds of the type also have excellent light stability.

[0085]

INDUSTRIAL APPLICABILITY As described above, the azo compound of the present invention has high sensitivity and excellent light stability. Therefore, various photosensitive materials such as charge generating materials in electrophotographic photoreceptors and pigments are used. It can be suitably used for solar cells and the like.
Further, the diazonium salt of the present invention is an intermediate suitable for producing the azo compound.

[Brief description of drawings]

FIG. 1 is a block diagram showing an outline of an apparatus used for measuring charge generation efficiency in Examples.

FIG. 2 is a circuit diagram showing more detailed contents of the device.

Claims (4)

[Claims] 1. General formula (I): [Wherein A ¹ and A ² represent the same or different coupler residues, R ¹ and R ² represent the same or different hydrogen atom, alkyl group or alkoxy group, and R ³ and R ⁴ represent the same or different hydrogen. An atom, a halogen atom, an alkyl group or an aryl group is shown. m and n represent 0 or 1. ] The azo compound represented by. 2. General formula (Ia): [In the formula, A ¹ , A ² , R ¹ and R ² represent the same groups as described above. ] The azo compound of Claim 1 represented by these. 3. General formula (Ib): [Wherein A ¹ , A ² , R ¹ , R ² and R ³ represent the same groups as described above. ] The azo compound of Claim 1 represented by these. 4. General formula (Ic): [In the formula, A ¹ , A ² , R ¹ , R ² , R ³ and R ⁴ represent the same groups as described above. ] The azo compound of Claim 1 represented by these.