JPH0680894A - Azo-based compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a sensitized material, 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> to R<4> are H, halogen, alkyl, etc.; (m) and (n) are 0 or 1) such as a compound of formula II. The compound, for example, is obtained by chloromethylating 1,2-bisphenylethane to give 1,2-bis(3-chloromethylphenyl) ethane, reacting the compound with NaI, then subjecting prepared 1,2-bis(3-iodomethylphenyl)ethane to ring closure by reacting with metal sodium to give (2,2)metacyclophane of formula III, reacting the compound with bromine in the presence of iron powder, successively nitrating a prepared compound of formula IV (R<1> to R<4> are Br), reducing to give a compound of formula V, further diazotizing two amino groups of the compound respectively, to give a tetrazolium salt and reacting the resulting substance with a coupler.

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, and R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group. represents a group, R ^5, R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. m and n represent 0 or 1. ] Is represented.

According to the study by the present inventors, the above general formula
The azo compound represented by (I) has high sensitivity and does not significantly reduce the 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 that 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, for example, the unique structure of 4,5,9,10-tetrahydropyrene introduced in the molecule, and is described in, for example, the above-mentioned JP-A-47.
No. -37543, the following general formula (II):

[0010]

[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:

[0012]

[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] 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).

[0014]

[Chemical 8]

[Wherein A ¹ , A ² , R ¹ , R ² , R ³ , R
⁴ , R ⁵ and R ⁶ represent the same groups as described above. ] The general formula
In the azo compound of the present invention represented by (I) and (Ia) to (Ic), the halogen atom among R ¹ , R ² , R ³ and R ⁴ is, for example, a chlorine atom, a bromine atom or an iodine atom. ,
Fluorine atom is an example. Examples of the alkyl group include lower alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group and hexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group,
Examples thereof include butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. Further, examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group and a phenanthryl group. Also R ⁵ ,
Examples of the alkyl group of R ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group and a hexyl group, and an aryl group includes a phenyl group. Group, noryl group, xylyl group, biphenyl group, naphthyl group and the like. Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and fluorine atom.

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.

[0017]

[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 heterocyclic ring 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).

[0021]

[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 condensing 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 with 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.

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

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

The azo compound of the present invention represented by the 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, 1,2-diphenylethane (1) is chloromethylated to give 1,2-diphenylethane. Bis (3-chloromethylphenyl) ethane (2) is obtained and reacted with sodium iodide (NaI) to produce 1,2-bis (3-iodomethylphenyl) ethane (3).
Then, the 1,2-bis (3-iodomethylphenyl) ethane (3) is reacted with sodium metal to ring-close,
A (2,2) metacyclophane represented by the following general formula (4) is produced.

[0037]

[Chemical 15]

Next, the above (2,2) metacyclophane
When (4) is reacted with bromine in the presence of iron powder, the general formula (5)
A 4,5,9,10-tetrahydropyrene compound in which R ¹ , R ² , R ³ and R ⁴ are bromine atoms can be obtained. To obtain a tetrahydropyrene compound in which R ¹ , R ² , R ³ and R ⁴ are substituents other than a bromine atom, the bromine atom may be substituted by a conventional method after the above reaction.

Next, the 4,5,9,10-tetrahydropyrene compound (5) is nitrated by a conventional method to give 2,7-dinitro-4,5,5 represented by the following general formula (6).
A 9,10-tetrahydropyrene compound was obtained and reduced by a conventional method to give 2,7-diamino-4,5,9,10.
-A tetrahydropyrene compound (general formula (7)) is prepared. And this 2,7-diamino-4,5,9,10-
The two amino groups of the tetrahydropyrene compound (7) are each diazotized to form a tetrazonium salt, which is coupled with a predetermined coupler in an organic solvent to give an azo compound represented by the general formula (Ia). Manufactured. The diazotization is carried out by stirring sodium nitrite or nitrous acid at a low temperature (usually-) while stirring an acidic aqueous solution of 2,7-diamino-4,5,9,10-tetrahydropyrene compound (7).
It is performed by dropping at 10 to 10 ° C.

[0040]

[Chemical 16]

[A ¹ , A ² in the above reaction process formulas,
R ¹ , R ² , R ³ and R ⁴ 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.

[0042]

EXAMPLES The present invention will be described below based on Examples and Comparative Examples. Example 1 1,2-diphenylethane represented by the above formula (1) 11.
3 g (0.062 mol) of 5.6 g paraformaldehyde, 125 ml acetic acid, 50 ml phosphoric acid and 20 g
80-9 with strong stirring with 0 ml concentrated hydrochloric acid (36%)
After reacting for about 14 hours at a temperature of 0 ° C., it was cooled to room temperature.

Next, this reaction solution was extracted with benzene, washed with water and a 10% potassium carbonate aqueous solution in this order, and then dehydrated with sodium sulfate. Then, the reaction solution was recrystallized with a small amount of hexane, the liquid component was removed using an evaporator, and 1,2-bis (3-chloromethylphenyl) ethane represented by the above formula (2) was used. 9 g (yield 63%) was obtained.

Next, 14.8 g (0.08 mol) of the above 1,2-bis (3-chloromethylphenyl) ethane was added to 1 part.
A solution was prepared by dissolving it in 00 ml of acetone, and 8.4 g of sodium iodide (NaI) was gradually added dropwise to the solution under reflux, and then the reaction was carried out for about 2 hours. Next, this reaction solution was washed with 100 ml of hot water and then dried to obtain the above formula.
20.8 g (yield 85%) of 1,2-bis (3-iodomethylphenyl) ethane represented by (3) was obtained.

Next, 9 g of metallic sodium was added to 800 ml of tetraphenylethylene and 100 ml of tetrahydrofuran.
A suspension was prepared by suspending it in a mixed solvent (ml) and maintaining the liquid temperature of the suspension at −80 ° C., while substituting nitrogen, the 1,2-bis (3-iodomethylphenyl) was prepared. ) Ethane 1
A solution prepared by dissolving 1.6 g (0.025 mol) in 500 ml of tetrahydrofuran was added dropwise, and the reaction was performed for 36 hours after the completion of the addition. After completion of the reaction, ethanol was added to the reaction solution to react unreacted metallic sodium in the solution, and then 500 ml of dichloromethane was added.

After the solid content is separated by filtration, the filtrate is washed with dilute hydrochloric acid using a separating funnel and further separated by column chromatography using a 1: 1 mixed solvent of benzene and hexane to obtain the desired product. The above formula
1.67 g of (2,2) metacyclophane represented by (4)
(Yield 32%) was obtained. Next, 8.77 g (0.042 mol) of this (2,2) metacyclophane was dissolved in 50 ml of carbon tetrachloride to prepare a solution, and 50 mg of iron powder was dispersed in this solution, and then 15 to 15 0.0 under the temperature condition of 25 ° C
10 ml of carbon tetrachloride solution containing 025 mol of bromine was added dropwise, and after completion of the addition, the mixture was stirred for about 9 hours to react, and the following formula
1,3,6,8-tetrabromo-4 represented by (5a),
7.01 g of 5,9,10-tetrahydropyrene (yield 3
2%) was obtained.

[0047]

[Chemical 17]

The above 3,6,8,11-tetrabromo-
18 g of 4,5,9,10-tetrahydropyrene was added to 200 cc of a 60% acetic anhydride solution of copper nitrate (CuNO ₃ ),
The reaction product was obtained by stirring at a temperature of 15 to 25 ° C. for 2 hours. Analysis of this reaction product revealed that the desired product was 2,7-dinitro-1,3,6,8-tetrabromo-
Since it was found to be a mixture of two kinds of compounds containing 4,5,9,10-tetrahydropyrene, it was fractionated by column chromatography to obtain 2,7-dinitro-1, represented by the following formula (6a): 3,6,8-Tetrabromo-
6.3 g (yield 29%) of 4,5,9,10-tetrahydropyrene was obtained.

[0049]

[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-mentioned 2, 2. 7-dinitro-
50 ml of 9.8 g (0.016 mol) of 1,3,6,8-tetrabromo-4,5,9,10-tetrahydropyrene
Was dissolved in tetrahydrofuran and 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,
The target compound, 2,7-diamino-, represented by the following formula (7a)
6.1 g of 1,3,6,8-tetrabromo-4,5,9,10-tetrahydropyrene was obtained.

[0052]

[Chemical 19]

The above 2,7-diamino-1,3,6,8-
Tetrabromo-4,5,9,10-tetrahydropyrene (5.52 g, 0.01 mol) and 10% hydrochloric acid (30 ml) were added to 1 part.
Into a 00 cc flask, the flask was cooled in an ice bath and the liquid temperature was maintained at -3 to 5 ° C while stirring, while stirring 1.38 g of sodium nitrite (NaNO ₃ ) in 3 ml of water to prepare a solution of 10 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,
4.2 g of a bisazo compound represented by the following formula (yield 3
8.2%) was obtained.

[0055]

[Chemical 20]

The analysis results of the obtained bisazo compound are shown below. Elemental analysis results Calculated value (%) C: 36.02 H: 1.92 N: 6.36 Measured value (%) C: 35.98 H: 1.93 N: 6.40 Mass spectrometry result m / e = 1099.98 (calculated value 1100.43) Example 2 Except that 7.15 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A2) was used.
5.03 g of a bisazo compound in the same manner as in Example 1 above.
(Yield 43%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 51.36 H: 2.586 N: 7.187 Measured value (%): C: 51.4 H: 2.61 N: 7.09 Mass spectrometry result m / e = 1170 (calculated value 1169.3) Example 3 except that 8.18 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A3) was used.
4.89 g of the bisazo compound in the same manner as in Example 1 above
(Yield 39%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 49.75 H: 2.569 N: 8.926 Measured value (%): C: 49.81 H: 2.63 N: 8.81 Mass spectrometry result m / e = 1255 (calculated value 1255.4) Example 4 Except that 7.16 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A4) was used.
5.39 g of a bisazo compound in the same manner as in Example 1 above
(Yield 46%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 49.17 H: 2.751 N: 7.167 Measured value (%): C: 49.21 H: 2.76 N: 7.21 Mass spectrometry result m / e = 1171 (calculated value 1172.6) Example 5 Except that 8.07 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A8) was used.
5.34 g of a bisazo compound in the same manner as in Example 1.
(Yield 41%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 58.83 H: 3.240 N: 8.575 Measured value (%): C: 58.81 H: 3.31 N: 8.49 Mass spectrometry result m / e = 1304 (calculated value 1306.7) Example 6 Except that 7.07 g (0.024 mol) of the coupler having the coupler residue represented by the formula (A9) was used.
5.23 g of the bisazo compound in the same manner as in Example 1
(Yield 45%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 51.62 H: 2.426 N: 9.632 Measured value (%): C: 51.58 H: 2.41 N: 9.62 Mass spectrometry result m / e = 1162 (calculated value 1163.3) 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 5.6
5 g (yield 46%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 56.70 H: 2.625 N: 6.840 Measured value (%): C: 56.01 H: 2.58 N: 6.81 Mass spectrometry result m / e = 1229 (calculated value 1228.7) 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 6.4
9 g (yield 51%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 58.51 H: 2.851 N: 11.01 Actual value (%): C: 57.99 H: 2.96 N: 11.25 Mass spectrometry result m / e = 1273 (calculated value 1272.6) 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 4.0
0 g (yield 39%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 49.06 H: 2.352 N: 8.173 Measured value (%): C: 48.95 H: 2.21 N: 8.18 Mass analysis result m / e = 1028 (calculated value 1028.3) 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. And bisazo compound 4.9
5 g (yield 43%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 54.20 H: 2.449 N: 7.292 Actual value (%): C: 54.15 H: 2.44 N: 7.31 Mass spectrometry result m / e = 1153 (calculated value 1152.4) 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 4.8
1 g (yield 42%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 54.48 H: 2.286 N: 9.774 Measured value (%): C: 54.41 H: 2.21 N: 9.79 Mass spectrometry result m / e = 1146 (calculated value 1146.4) Example 12 1-phenyl-2- (m- represented by the following formula (1b) in place of 1,2-diphenylethane represented by the above formula (1a) 2-Amino-7- (p- represented by the following formula (7b) was obtained in the same manner as in Example 1 except that 16.0 g (0.062 mol) of biphenylyl) ethane was used as a starting material.
Aminophenyl) -1,3,6,8-tetrabromo-
8.9 g of 4,5,9,10-tetrahydropyrene was obtained.

[0067]

[Chemical 21]

The 2-amino-7- (p-aminophenyl) -1,3,6,8-tetrabromo-4,
5,9,10-tetrahydropyrene 6.28 g (0.0
1 mol) and 7.15 g (0.024 mol) of a coupler having a coupler residue represented by the above formula (A2) were used in the same manner as in Example 1 to prepare 4.36 g of the bisazo compound.
(Yield 35%) was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis result Calculated value (%): C: 54.01 H: 2.752 N: 6.748 Measured value (%): C: 54.09 H: 2.78 N: 6.81 Mass spectrometry result m / e = 1246 (calculated value 1245.4) Example 13 1,2-bis (m-biphenylyl) represented by the following formula (1c) in place of 1,2-diphenylethane represented by the above formula (1a) ) 2,7-bis (p-aminophenyl) represented by the following formula (7c) in the same manner as in Example 1 except that 20.7 g (0.062 mol) of ethane was used as a starting material. -1,3,6,8-Tetrabromo-4,5,5
9.3 g of 9,10-tetrahydropyrene was obtained.

[0070]

[Chemical formula 22]

The 2,7-bis (p-aminophenyl) -1,3,6,8-tetrabromo-4,5,5
Using 7.04 g (0.01 mol) of 9,10-tetrahydropyrene and 7.15 g (0.024 mol) of a coupler having a coupler residue represented by the formula (A2),
In the same manner as in Example 1, 4.49 g (yield 34%) of a bisazo compound was synthesized.

The analysis results of the obtained bisazo compound are shown below. Elemental analysis results Calculated value (%): C: 56.35 H: 2.898 N: 6.359 Measured value (%): C: 57.42 H: 2.91 N: 6.41 Mass spectrometry result m / e = 1322 (calculated value 1321.5) Comparative Example 1 The following formula:

[0073]

[Chemical formula 23]

Chlorodian blue represented by
And Of the above-mentioned embodiments, Embodiments 1, 2, 3, 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 displacement amount (ΔV) of the voltage 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:

[0080]

[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.

(Preparation 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 was 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.

[0086]

[Table 1]

From the results shown in Table 1 above, it was found that all the bisazo compounds of the examples, which are azo compounds of the present invention, had higher charge generation efficiency and higher sensitivity than Comparative Example 1. . 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.

[0088]

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, and R ¹ , R ² , R ³ and R ⁴ represent the same or different hydrogen atom, halogen atom, alkyl group, alkoxy group or aryl group] , R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. 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 , R ² , R ³ and R ⁴ 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 , R ³ , R ⁴ and R ⁵ represent the same groups as described above. ] The azo compound of Claim 1 represented by these. 4. General formula (Ic): [Wherein A ¹ , A ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^5
6 represents the same group as above. ] The azo compound of Claim 1 represented by these.