JP2009007523A - Azo compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an azo compound good in solubility in an organic solvent, which is a practical high-sensitive electrophotographic photoreceptor for use in a high-speed copying machine together with a laser printer, and is useful as an organic photoconductor used for a laminated-type photoreceptor, in particular; and to provide a method for producing the same. <P>SOLUTION: This azo compound is expressed by formula (I): A(E)n [wherein A is a residue of the compound and the residue A links to n of E groups through one or more heteroatoms; the heteroatoms are selected from the group consisting of N and O, forming a part of the residue A; E groups are each independently a hydrogen atom or a group: -C(=O)-O-R1 (wherein R1 is a 4-10C substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aralkyl group); and n is an integer of 1-10]. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel azo compound useful as an organic photoconductor and a method for producing the same.

Conventionally, it has been known that a certain main azo compound is useful as an organic photoconductor, particularly a charge generating pigment, used in a laminated type photoreceptor which is one form of an electrophotographic photoreceptor. As is well known, this laminated type photoconductor has a charge generation layer mainly composed of a charge generation pigment having the ability to generate charge carriers by light on a conductive support, and a charge carrier generated in the charge generation layer thereon. It is a photoreceptor provided with a charge transport layer mainly composed of a charge transport material having the ability to inject efficiently and transport it. Conventionally, as an azo compound used in such a photoreceptor, for example, benzidine described in Patent Document 1 (Japanese Patent Laid-Open No. 47-37543), Patent Document 2 (Japanese Patent Laid-Open No. 52-55643), and the like. Bisazo compounds, stilbene bisazo compounds described in JP-A-52-8832, and diphenylhexatriene-based bisazo described in JP-A-58-222152. Compounds, diphenylbutadiene bisazo compounds described in Patent Document 5 (Japanese Patent Laid-Open No. 58-222153), and the like are known.
However, a conventional multilayer type photoreceptor using an azo compound is generally unsatisfactory as a photoreceptor for high-speed copying machines because of its low sensitivity. One reason for this is that the above-mentioned azo compounds are generally very low in solubility in organic solvents, and purification is limited to washing steps with organic solvents, and it is considered that impurities are not sufficiently removed. In addition, in the production of a photoreceptor, a long dispersion process by means such as ball milling to obtain a uniform dispersion as fine particles, and a combination of a resin, a dispersion stabilizer, etc. to obtain stable dispersibility It was inevitable.
Therefore, it is desired to produce an azo compound useful as an organic photoconductor that overcomes the conventional drawbacks.

JP 47-37543 A JP 52-55643 A JP-A-52-8832 JP 58-222152 A JP 58-222153 A

  The object of the present invention is to dissolve in an organic solvent useful as an organic photoconductor used in a high-sensitivity electrophotographic photosensitive member, particularly a laminated type photosensitive member, which is practical not only for a high-speed copying machine but also for a laser printer. An azo compound having excellent properties and a method for producing the same.

  According to the present invention, an azo compound represented by the following general formula (I) is provided.

〔但し、Ａはアゾ化合物の残基でありこの残基Ａは、１つまたはそれ以上のヘテロ原子でｎ個のＥ基に結合しており、そしてこれらのヘテロ原子は、ＮおよびＯからなる群から選ばれ、残基Ａの一部を形成していて、Ｅ基はそれぞれ独立に水素または下記の基：−Ｃ（＝Ｏ）−Ｏ−Ｒ１（式中Ｒ１は、炭素数４から１０の置換または非置換のアルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、またはアラルキル基をあらわす。）ｎは、１から１０の整数である。〕

[Wherein A is a residue of an azo compound and this residue A is bonded to n E groups with one or more heteroatoms, and these heteroatoms consist of N and O Selected from the group and forming part of the residue A, each E group is independently hydrogen or the following group: —C (═O) —O—R1 (wherein R1 is from 4 to 10 carbon atoms) A substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or an aralkyl group.) N is an integer of 1 to 10. ]

  Moreover, the manufacturing method of the azo compound of general formula (I) characterized by making the compound of the following general formula (II) and the pyrocarbonic acid diester of the following formula react in presence of a base is provided.

（式中Ｒ_１は、独立に炭素数４から１０の置換または非置換のアルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、またはアラルキル基を表わす。）

(In the formula, R ₁ independently represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group having 4 to 10 carbon atoms.)

That is, according to this invention, the following azo compound and its manufacturing method are provided.
(1) An azo compound represented by the following general formula (I);

〔但し、Ａはアゾ化合物の残基でありこの残基Ａは、１つまたはそれ以上のヘテロ原子を介してｎ個のＥ基に結合しており、そしてこれらのヘテロ原子は、ＮおよびＯからなる群から選ばれ、残基Ａの一部を形成しており、Ｅ基はそれぞれ独立に水素原子または下記の基：−Ｃ（＝Ｏ）−Ｏ−Ｒ１（式中Ｒ１は、炭素数４から１０の置換または非置換のアルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、またはアラルキル基をあらわす。）を表わし、ｎは、１から１０の整数である。〕」；
（２）「前記一般式（Ｉ）のＡが、下記一般式（II）で示される化合物の残基であることを特徴とする前記（１）項に記載のアゾ化合物；

[Wherein A is a residue of an azo compound and this residue A is bonded to n E groups via one or more heteroatoms, and these heteroatoms are N and O And each of the E groups is independently a hydrogen atom or the following group: —C (═O) —O—R1 (wherein R1 is the number of carbon atoms). Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group of 4 to 10, and n is an integer of 1 to 10. ]];
(2) The azo compound according to item (1), wherein A in the general formula (I) is a residue of a compound represented by the following general formula (II);

〔但し、Ｂはアゾ化合物の主骨格を示し、Ｃｐはカップラー成分残基であり、ｍは２又は３の整数を表わす。〕」；
（３）「前記カップラー成分残基が、水酸基を有する芳香族炭化水素化合物残基および水酸基を有する複素環式化合物残基、アミノ基を有する芳香族炭化水素化合物残基およびアミノ基を有する複素環式化合物残基、水酸基およびアミノ基を有する芳香族炭化水素化合物残基および複素環式化合物残基、脂肪族もしくは芳香族のエノール性ケトン基を有する化合物残基からなる群から選ばれたものであることを特徴とする前記（２）項に記載のアゾ化合物」；
（４）「前記水酸基を有する芳香族炭化水素化合物残基が、フェノール化合物残基、ナフトール化合物残基からなる群から選ばれたものであることを特徴とする前記（３）項に記載のアゾ化合物」；
（５）「水酸基およびアミノ基を有する芳香族炭化水素化合物残基が、アミノナフトール化合物であることを特徴とする前記（３）項に記載のアゾ化合物」；
（６）「前記Ｃｐ−が下記一般式（５）乃至（１７）の少なくともいずれかで表わされるものであることを特徴とする前記（２）項に記載のアゾ化合物」；

[B represents the main skeleton of the azo compound, Cp represents a coupler component residue, and m represents an integer of 2 or 3. ]];
(3) “The coupler component residue is an aromatic hydrocarbon compound residue having a hydroxyl group, a heterocyclic compound residue having a hydroxyl group, an aromatic hydrocarbon compound residue having an amino group, and a heterocyclic ring having an amino group. Selected from the group consisting of a compound residue having a formula compound residue, an aromatic hydrocarbon compound residue having a hydroxyl group and an amino group, a heterocyclic compound residue, and an aliphatic or aromatic enol ketone group The azo compound according to item (2), which is characterized by:
(4) The azo as described in the above item (3), wherein the aromatic hydrocarbon compound residue having a hydroxyl group is selected from the group consisting of a phenol compound residue and a naphthol compound residue Compound";
(5) “Azo compound according to item (3), wherein the aromatic hydrocarbon compound residue having a hydroxyl group and an amino group is an aminonaphthol compound”;
(6) "Azo compound according to item (2), wherein the Cp- is represented by at least one of the following general formulas (5) to (17)";

上記一般式（５）〜（８）中、Ｘ、Ｙ^１、Ｚ、ｐおよびｑはそれぞれ以下のものを表わす。
Ｘ：−ＯＨ、−Ｎ（Ｒ^１）（Ｒ^２）または−ＮＨＳＯ_２−Ｒ^３。
（Ｒ^１およびＲ^２は水素原子または置換もしくは無置換のアルキル基を表わし、Ｒ^３は置換もしくは無置換のアルキル基または置換もしくは無置換のアリール基を表わす。）
Ｙ^１：水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、カルボキシ基、スルホン基、置換もしくは無置換のスルファモイル基または−ＣＯＮ（Ｒ^４）（Ｙ^２）。［Ｒ^４は水素原子、アルキル基もしくはその置換体またはフェニル基もしくはその置換体を表わし、Ｙ^２は炭化水素環基もしくはその置換体、複素環基もしくはその置換体、または−Ｎ＝Ｃ（Ｒ^５）（Ｒ^６）（但し、Ｒ^５は炭化水素環基もしくはその置換体、複素環基もしくはその置換体またはスチリル基もしくはその置換体、Ｒ^６は水素原子、アルキル基またはフェニル基もしくはその置換体を表わすか、あるいはＲ^５およびＲ^６はそれらに結合する炭素原子と共に環を形成してもよい。）を示す。］
Ｚ：炭化水素環もしくはその置換体または複素環もしくはその置換体。
ｐ：１または２の整数。
ｑ：１または２の整数。

In the general formulas (5) to (8), X, Y ¹ , Z, p and q each represent the following.
^{X: -OH, -N (R 1} ) (R 2) or -NHSO ₂ -R ^3.
(R ¹ and R ² represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)
Y ¹ : a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxy group, a sulfone group, a substituted or unsubstituted sulfamoyl group, or —CON (R ⁴ ) (Y ² ). [R ⁴ represents a hydrogen atom, an alkyl group or a substituted product thereof, or a phenyl group or a substituted product thereof, Y ² represents a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or —N═C (R ⁵ ) (R ⁶ ) (where R ⁵ is a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or a styryl group or a substituted product thereof, and R ⁶ is a hydrogen atom, an alkyl group, a phenyl group or a substituted product thereof. Or R ⁵ and R ⁶ may form a ring together with the carbon atom to which they are attached. ]
Z: A hydrocarbon ring or a substituted product thereof, or a heterocyclic ring or a substituted product thereof.
p: an integer of 1 or 2.
q: An integer of 1 or 2.

（上式中、Ｒ^７は置換もしくは無置換の炭化水素基を表わし、Ｘは前記と同じである。）

(In the above formula, R ⁷ represents a substituted or unsubstituted hydrocarbon group, and X is as defined above.)

（上式中、Ａは芳香族炭化水素の２価基または窒素原子を環内に含む複素環の２価基を表わす（これらの環は置換または無置換でもよい）。Ｘは前記と同じ。）

(In the above formula, A represents a divalent group of an aromatic hydrocarbon or a divalent group of a heterocyclic ring containing a nitrogen atom in the ring (these rings may be substituted or unsubstituted). X is the same as defined above. )

（式中、Ｒ^８はアルキル基、カルバモイル基、カルボキシ基またはそのエステルを表わし、Ａｒ^１は炭化水素環基またはその置換体を表わし、Ｘは前記と同じである。）

(Wherein R ⁸ represents an alkyl group, a carbamoyl group, a carboxy group or an ester thereof, Ar ¹ represents a hydrocarbon ring group or a substituted product thereof, and X is the same as described above.)

（上記式（１２）および（１３）中、Ｒ^９は水素原子または置換もしくは無置換の炭化水素基を表わし、Ａｒ^２は炭化水素環基またはその置換体を表わす。）

(In the above formulas (12) and (13), R ⁹ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and Ar ² represents a hydrocarbon ring group or a substituted product thereof.)

Examples of the hydrocarbon ring of Z in the general formula (6), (7) or (8) include a benzene ring and a naphthalene ring, and examples of the heterocyclic ring (which may have a substituent) include indole Examples thereof include a ring, a carbazole ring, a benzolane ring, and a dibenzofuran ring. Examples of the substituent in the ring of Z include halogen atoms such as chlorine atom and bromine atom.
Examples of the hydrocarbon ring group for Y ² or R ⁵ include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, and the like, and examples of the heterocyclic group include a pyridyl group, a thienyl group, a furyl group, an indolyl group, a benzofuranyl group, and a carbazolyl group. Group, dibenzofuranyl group, and the like. Further, examples of the ring formed by combining R ⁵ and R ⁶ include a fluorene ring. The substituent in the hydrocarbon ring group or heterocyclic group of Y ² or R ⁵ or the ring formed by R ⁵ and R ⁶ includes an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; Group, ethoxy group, propoxy group, butoxy group and the like; halogen atom such as chlorine atom and bromine atom; dialkylamino group such as dimethylamino group and diethylamino group; halomethyl group such as trifluoromethyl group; nitro group, cyano Group, a carboxy group or an ester thereof, a hydroxyl group, and a sulfonate group such as —SO ₃ Na.
Examples of the substituent of the phenyl group of R ⁴ include a halogen atom such as a chlorine atom or a bromine atom. Typical examples of the hydrocarbon group for R ⁷ or R ⁹ include an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; an aryl group such as a phenyl group, or a substituted product thereof. Examples of the substituent in the hydrocarbon group of R ⁷ or R ⁹ include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, and butoxy group; chlorine Examples thereof include halogen atoms such as atoms and bromine atoms; hydroxyl groups, nitro groups and the like.
Typical examples of the hydrocarbon ring group in Ar ¹ or Ar ² include a phenyl group and a naphthyl group, and the substituents in these groups include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group. Examples thereof include alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; halogen atoms such as nitro group, chlorine atom and bromine atom; dialkylamino groups such as cyano group, dimethylamino group and diethylamino group. In X, a hydroxyl group is particularly suitable.

  Among the above coupler residues, those represented by the above general formulas (6), (9), (10), (11), (12) and (13) are preferred, and among these, X in the above general formula is A hydroxyl group is preferred. Of these, the coupler residue represented by the general formula (14) is particularly preferable, and the coupler residue represented by the general formula (15) is more preferable.

（Ｙ^１およびＺは前記に同じ。）

(Y ¹ and Z are the same as above.)

（Ｚ、Ｙ^２およびＲ^２は前記に同じ。）

(Z, Y ² and R ² are the same as above.)

  Furthermore, among the preferable coupler residues, those represented by the general formula (16), (17) or (18) are particularly preferable.

（Ｚ、Ｒ^２、Ｒ^５およびＲ^６は前記に同じであり、またＲ^１０としては上記のＹ^２の置換基が例示できる。）

(Z, R ² , R ⁵ and R ⁶ are the same as above, and examples of R ¹⁰ include the above-described substituents for Y ^2. )

（式中、Ｒは水素原子、アルキル基、アルコキシ基またはハロゲン原子を、またｋは１〜４の整数をそれぞれ表わす。）
Ｒの具体例としては、水素原子；メチル基、エチル基、プロピル基、ブチル基などのアルキル基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などのアルコキシ基；塩素原子、臭素原子、弗素原子などのハロゲン原子が挙げられる。
前記一般式（II）におけるＢはアゾ化合物の主骨格を示し、ｍは２又は３の整数を表わす。〕
（７）「前記一般式（II）のＢが、下記一般式（III）で示されることを特徴とする前記（２）項に記載のアゾ化合物；

(In the formula, R represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and k represents an integer of 1 to 4, respectively.)
Specific examples of R include hydrogen atom; alkyl group such as methyl group, ethyl group, propyl group and butyl group; alkoxy group such as methoxy group, ethoxy group, propoxy group and butoxy group; chlorine atom, bromine atom and fluorine atom And halogen atoms such as
B in the general formula (II) represents the main skeleton of the azo compound, and m represents an integer of 2 or 3. ]
(7) The azo compound according to item (2), wherein B in the general formula (II) is represented by the following general formula (III);

（ただし、Ｒ^１１，Ｒ^１２は独立して、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、カルボキシル基及びそのエステルを表わす。）」；
（８）「前記一般式（II）のＢが、下記一般式（IＶ）で示されることを特徴とする前記（２）項に記載のアゾ化合物；

(Wherein R ¹¹ and R ¹² independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof);
(8) The azo compound according to item (2), wherein B in the general formula (II) is represented by the following general formula (IV);

（ただし、Ｒ^１３，Ｒ^１４，Ｒ^１５は独立して、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、カルボキシル基及びそのエステルを表わす。）」；
（９）「前記一般式（II）のＢが、下記一般式（Ｖ）で示されることを特徴とする前記（２）項に記載のアゾ化合物；

(Wherein R ¹³ , R ¹⁴ , and R ¹⁵ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof);
(9) The azo compound according to item (2), wherein B in the general formula (II) is represented by the following general formula (V);

（ただし、Ｒ^１６，Ｒ^１７，Ｒ^１８は独立して、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、カルボキシル基及びそのエステルを表わす。）」；
（１０）「前記一般式（II）のＢが、下記一般式（ＶI）で示されることを特徴とする前記（２）項に記載のアゾ化合物」；

(However, R ¹⁶ , R ¹⁷ , and R ¹⁸ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.);
(10) “Azo compound according to item (2), wherein B in the general formula (II) is represented by the following general formula (VI)”;

（ただし、Ｒ^１９，Ｒ^２０は独立して、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、カルボキシル基及びそのエステルを表わす。）」；
（１１）「前記一般式（II）のＢが、下記一般式（ＶII）で示されることを特徴とする前記（２）項に記載のアゾ化合物；

(Wherein R ¹⁹ and R ²⁰ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof);
(11) The azo compound according to item (2), wherein B in the general formula (II) is represented by the following general formula (VII):

（ただし、Ｒ^２１，Ｒ^２２，Ｒ^２３は独立して、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、カルボキシル基及びそのエステルを表わす。）」；
（１２）「前記一般式（II）のＢが、下記一般式（ＶIII）で示されることを特徴とする前記（２）項に記載のアゾ化合物；

(However, R ²¹ , R ²² , and R ²³ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.);
(12) The azo compound according to item (2), wherein B in the general formula (II) is represented by the following general formula (VIII):

（ただし、Ｒ^２４，Ｒ^２５，Ｒ^２６は独立して、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、カルボキシル基及びそのエステルを表わす。）」；
（１３）「前記一般式（II）のＢが、下記一般式（IＸ）で示されることを特徴とする前記（２）項に記載のアゾ化合物；

(However, R ²⁴ , R ²⁵ , and R ²⁶ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.);
(13) The azo compound according to item (2), wherein B in the general formula (II) is represented by the following general formula (IX);

（ただし、Ｒ^２７，Ｒ^２８，Ｒ^２９は独立して、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、カルボキシル基及びそのエステルを表わす。）」；
（１４）「前記一般式（II）のＢが、下記一般式（Ｘ）で示されることを特徴とする前記（２）項に記載のアゾ化合物；

(Wherein R ²⁷ , R ²⁸ , and R ²⁹ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof);
(14) The azo compound according to item (2), wherein B in the general formula (II) is represented by the following general formula (X);

（ただし、Ｒ^３０，Ｒ^３１は独立して、水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルコキシ基、カルボキシル基及びそのエステルを表わす。）」；
（１５）「前記一般式（Ｉ）のアゾ化合物の製造方法であり、前記一般式（II）の化合物と、下記式のピロ炭酸ジエステルとを、塩基の存在下で反応させることを特徴とする一般式（Ｉ）のアゾ化合物の製造方法；

(Wherein R ³⁰ and R ³¹ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof);
(15) “A method for producing an azo compound of the general formula (I), wherein the compound of the general formula (II) is reacted with a pyrocarbonate diester of the following formula in the presence of a base. A process for producing an azo compound of the general formula (I);

（式中Ｒ_１は、独立に炭素数４から１０の置換または非置換のアルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、またはアラルキル基を表わす。）」。

(Wherein R ₁ independently represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group having 4 to 10 carbon atoms).

  The azo compound of the present invention is extremely useful as an organic photoconductor used for an electrophotographic photoreceptor exhibiting high sensitivity for use in a high-speed copying machine.

Preferred compounds of the azo compound represented by the general formula (I) of the present invention include formulas (III) -1 to (III) -14 in which the main skeleton of the azo compound is the general formula (III), Formulas (IV) -1 to (IV) -5 in which the skeleton is the general formula (IV), Formulas (V) -1 to (V) -7 in which the main skeleton of the azo compound is the general formula (V), and azo compounds Formulas (VI) -1 to (VI) -5 in which the main skeleton of general formula (VI) is, Formulas (VII) -1 to (VII) -7 in which the main skeleton of the azo compound is general formula (VII), Formulas (VIII) -1 to (VIII) -5 in which the main skeleton of the azo compound is general formula (VIII), Formulas (IX) -1 to (IX)-in which the main skeleton of the azo compound is general formula (IX) 4. The main skeleton of the azo compound is the formula (X) -1 to (X) -6, which is the general formula (X).
Examples of compounds are shown below.
<Examples of compounds in which the main skeleton of the azo compound is the general formula (III)>

＜アゾ化合物の主骨格が一般式（IＶ）である化合物の例＞

<Examples of compounds in which the main skeleton of the azo compound is the general formula (IV)>

＜アゾ化合物の主骨格が一般式（Ｖ）である化合物の例＞

<Examples of compounds in which the main skeleton of the azo compound is the general formula (V)>

＜アゾ化合物の主骨格が一般式（ＶI）である化合物の例＞

<Examples of compounds in which the main skeleton of the azo compound is the general formula (VI)>

＜アゾ化合物の主骨格が一般式（ＶII）である化合物の例＞

<Examples of compounds in which the main skeleton of the azo compound is the general formula (VII)>

＜アゾ化合物の主骨格が一般式（ＶIII）である化合物の例＞

<Examples of compounds in which the main skeleton of the azo compound is the general formula (VIII)>

＜アゾ化合物の主骨格が一般式（IＸ）である化合物の例＞

<Examples of compounds in which the main skeleton of the azo compound is the general formula (IX)>

＜アゾ化合物の主骨格が一般式（Ｘ）である化合物の例＞

<Examples of compounds in which the main skeleton of the azo compound is the general formula (X)>

  The compound of the formula (I) can be synthesized as described in, for example, European Patent No. 648770 and European Patent No. 648817, or Japanese Translation of PCT International Publication No. 2001-513119, for example, in an aprotic organic solvent. In the presence of a base as a catalyst, it can be synthesized by reacting the general formula (II) with the following formula at an appropriate molar ratio at a temperature of 0 to 150 ° C., preferably 10 to 100 ° C., for 30 minutes to 20 hours. .

（Ｂ，Ｃｐ，Ｒ_１は前記に記載のとおりである）
それぞれの場合において、モル比は導入されるＥの数に左右される。好ましくはピロ炭酸ジエステルを少し過剰に用いるのが適している。

(B, Cp, R ₁ are as described above)
In each case, the molar ratio depends on the number of E introduced. Preferably, the pyrocarbonic acid diester is used in a slight excess.

  Suitable aprotic organic solvents include, for example, ether solvents such as tetrahydrofuran or dioxane, or glycol ether solvents such as ethylene glycol methyl ether and ethylene glycol ethyl ether, or acetonitrile, N, N-dimethylformamide, N, N- Examples include dimethylacetamide, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, toluene, xylene, nitrobenzene, pyridine, picoline or quinoline. Preferred solvents are pyridine, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide.

  Suitable bases as catalysts are, for example, alkali metals: sodium, potassium, etc., and their hydroxides and carbonates, or alkali metal amides, sodium amides, potassium amides, and alkali metal hydrides, such as Examples include lithium hydride. As the organic aliphatic, aromatic or heterocyclic N-bases, diazabicyclooctene, diazabicycloundecene, 4-dimethylaminopyridine, dimethylpyridine, pyridine, triethylamine and the like can be used. Preferred are organic N-bases such as 4-dimethylaminopyridine, dimethylpyridine and pyridine.

The pyrocarbonic acid diester represented by the following formula can be produced by a generally known method. It is also commercially available. R ₁ is as described above, and is preferably a branched alkyl group from the viewpoint of surprising improvement in solubility.

  The product represented by the following general formula (I) can be isolated by a usual method after completion of the reaction. In particular, since the azo compound of the present invention is excellent in solubility, it is preferable because it can be easily purified by recrystallization, column chromatogram or the like for further purity improvement.

〔但し、Ａはアゾ化合物の残基でありこの残基Ａは、１つまたはそれ以上のヘテロ原子でｎ個のＥ基に結合しており、そしてこれらのヘテロ原子は、ＮおよびＯからなる群から選ばれ、残基Ａの一部を形成していて、Ｅ基はそれぞれ独立に水素または下記の基：−Ｃ（＝Ｏ）−Ｏ−Ｒ１（式中Ｒ１は、炭素数４から１０の置換または非置換のアルキル基、アルケニル基、アルキニル基、シクロアルキル基、シクロアルケニル基、またはアラルキル基をあらわす。）ｎは、１から１０の整数である。〕

[Wherein A is a residue of an azo compound and this residue A is bonded to n E groups with one or more heteroatoms, and these heteroatoms consist of N and O Selected from the group and forming part of the residue A, each E group is independently hydrogen or the following group: —C (═O) —O—R1 (wherein R1 is from 4 to 10 carbon atoms) A substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or an aralkyl group.) N is an integer of 1 to 10. ]

The azo compound of the present invention is used as an organic photoconductor, particularly as a charge generating material in various electrophotographic photoreceptors as follows.
(1) A photoconductive layer mainly composed of the azo compound, a binder resin and, if necessary, a sensitizer is provided on a conductive support to obtain a single layer type photoreceptor.
(2) A charge transport material is further added to the system of (1) to obtain a single layer type photoconductor.
(3) A multilayer photoconductor comprising a charge generation layer comprising the azo compound as a main component on a conductive support and a charge transport layer comprising a charge transport material and a binder resin as main components provided thereon. To do.
(4) A photoconductor having a layer structure in which the charge generation layer and the charge transport layer of (3) are laminated in reverse.
In addition, since the azo compound of the present invention is excellent in solubility in an organic solvent, it can be used for other color materials such as recording medium materials and color filters.

Hereinafter, the present invention will be described with reference to examples and application examples.
<Example 1>
-Production of Compound (III-3) 0.83 grams of the precursor of Compound (III-3) (E = H) and 2.6 grams (12 moles) of pyrocarboxylic acid di-tert-butyl ester were added to 150 ml of dehydrated pyridine. After dispersing and stirring at room temperature for 15 minutes, the mixture was further heated to about 50 ° C. and reacted for 30 minutes. Gradually reddish and a homogeneous solution was obtained. After returning to room temperature, the solvent was removed, and about 50 ml of ethyl acetate was added to obtain 1.18 g (yield: 95.3%) of a red powder. This was further purified by column chromatogram (silica gel / chloroform).
Elemental analysis _{(as C 67 H 60 N 6 O 13} Cl 2) ( all _E: as _{C 5} H 9 _{O 2)}

このものの赤外線吸収スペクトル（ＫＢｒ錠剤法）は、２９８０ｃｍ^−１に飽和炭化水素による吸収、１７６０ｃｍ^−１にカルボネートのＣ＝Ｏの伸縮振動に基づく吸収が認められた。

Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2980cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1760 cm ^-1 was observed.

<Example 2>
-Production of Compound (III-4) 0.79 grams of the precursor of Compound (III-4) (E = H) and 2.6 grams (12 moles) of pyrocarboxylic acid di-tert-butyl ester were added to 150 ml of dehydrated pyridine. After dispersing and stirring at room temperature for 15 minutes, the mixture was further heated to about 50 ° C. and reacted for 30 minutes. Gradually reddish and a homogeneous solution was obtained. The temperature was returned to room temperature, the solvent was removed, and about 50 ml of ethyl acetate was added to obtain 1.02 g (yield: 85.6%) of a red powder.
Elemental analysis _{(as C 69 H 66 N 6 O 13} ) ( all _E: as _{C 5} H 9 _{O 2)}

このものの赤外線吸収スペクトル（ＫＢｒ錠剤法）は、２９８０ｃｍ^−１に飽和炭化水素による吸収、１７６０ｃｍ^−１にカルボネートのＣ＝Ｏの伸縮振動に基づく吸収が認められた。

Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2980cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1760 cm ^-1 was observed.

<Example 3>
-Preparation of compound (III-2) 1.61 grams of the precursor of compound (III-2) (E = H) and 4.3 grams (10-fold mol) of pyrocarboxylic acid di-tert-butyl ester were added to 50 ml of dehydrated pyridine, The mixture was dispersed in 200 ml of dehydrated N, N-dimethylformamide and stirred at room temperature for 15 minutes, and further heated to about 50 ° C. and reacted for 2 hours. Gradually reddish and a homogeneous solution was obtained. The temperature was returned to room temperature, the solvent was removed, and about 100 ml of ethyl acetate was added to obtain 2.24 g (yield: 93%) of a red powder.
Elemental analysis _{(as C 58 H 47 N 6 O 9} Cl) ( all _E: as _{C 5} H 9 _{O 2)}

このものの赤外線吸収スペクトル（ＫＢｒ錠剤法）は、２９８０ｃｍ^−１に飽和炭化水素による吸収、１７６５ｃｍ^−１にカルボネートのＣ＝Ｏの伸縮振動に基づく吸収が認められた。

Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2980cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1765cm ^-1 were observed.

<Example 4>
-Production of compound (III-3) 0.21 gram of precursor of compound (III-3) (E = H), 0.43 gram (6-fold mole) of pyrocarboxylic acid di-benzyl ester, 3,4-dimethylpyridine 0.54 g was dispersed in 50 ml of dehydrated N, N-dimethylformamide, stirred at room temperature for 15 minutes, further heated to about 100 ° C. and reacted for 6 hours. Gradually reddish and a homogeneous solution was obtained. The temperature was returned to room temperature, the solvent was removed, and about 50 ml of toluene was added to obtain 0.28 g (yield: 92.0%) of a red powder.
Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2980cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1760 cm ^-1 was observed.

<Example 5>
-Preparation of compound (IV-1) 2.93 grams of the precursor (E = H) of compound (IV-1) and 6.5 grams (15 times mole) of pyrocarboxylic acid di-tert-butyl ester were added to 250 ml of dehydrated pyridine. After dispersing and stirring at room temperature for 15 minutes, the mixture was further heated to about 40 ° C. and reacted for 40 minutes. A reddish purple taste was gradually obtained, and a uniform solution was obtained. The temperature was returned to room temperature, the solvent was removed, and about 100 ml of cyclohexane was added to obtain 2.91 grams (yield: 71.0%) of a red powder.
Elemental analysis (as C ₁₂₃ H ₁₁₇ N ₁₃ O ₁₈ ) (as all E: C ₅ H ₉ O ₂ )

このものの赤外線吸収スペクトル（ＫＢｒ錠剤法）は、２９８０ｃｍ^−１に飽和炭化水素による吸収、１７６５ｃｍ^−１にカルボネートのＣ＝Ｏの伸縮振動に基づく吸収が認められた。

Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2980cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1765cm ^-1 were observed.

<Example 6>
-Production of Compound (V-1) 0.92 grams of the precursor of Compound (V-1) (E = H) and 2.6 grams (12 moles) of pyrocarboxylic acid di-tert-butyl ester were added to 150 ml of dehydrated pyridine. After dispersing and stirring at room temperature for 15 minutes, the mixture was further heated to about 50 ° C. and reacted for 40 minutes. Gradually it became orange-red and a homogeneous solution was obtained. The temperature was returned to room temperature, the solvent was removed, and about 50 ml of ethyl acetate was added to obtain 1.16 g (yield: 88.0%) of a red powder.
Elemental analysis _{(as C 69 H 66 N 6 O 13} ) ( all _E: as _{C 5} H 9 _{O 2)}

このものの赤外線吸収スペクトル（ＫＢｒ錠剤法）は、２９７５ｃｍ^−１に飽和炭化水素による吸収、１７６０ｃｍ^−１にカルボネートのＣ＝Ｏの伸縮振動に基づく吸収が認められた。

Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2975cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1760 cm ^-1 was observed.

<Example 7>
-Production of compound (VI-1) 0.94 grams of the precursor (E = H) of compound (VI-1) and 2.6 grams (12 moles) of pyrocarboxylic acid di-tert-butyl ester were added to 150 ml of dehydrated pyridine. After dispersing and stirring at room temperature for 15 minutes, the mixture was further heated to about 50 ° C. and reacted for 2 hours. Gradually reddish and a homogeneous solution was obtained. The temperature was returned to room temperature, the solvent was removed, and about 50 ml of ethyl acetate was added to obtain 1.11 g (yield: 83.2%) of a red powder.
Elemental analysis _{(as C 48 H 24 N 6 O 6} Br 2) ( all _E: as _{C 5} H 9 _{O 2)}

このものの赤外線吸収スペクトル（ＫＢｒ錠剤法）は、２９８０ｃｍ^−１に飽和炭化水素による吸収、１７６０ｃｍ^−１にカルボネートのＣ＝Ｏの伸縮振動に基づく吸収が認められた。

Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2980cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1760 cm ^-1 was observed.

<Example 8>
-Preparation of compound (VII-2) 1.20 grams of the precursor of compound (VII-2) (E = H) and 1.6 grams (12 times mole) of pyrocarboxylic acid di-benzyl ester were dispersed in 150 ml of dehydrated pyridine. After stirring at room temperature for 15 minutes, the mixture was further heated to about 50 ° C. and reacted for 1 hour. A reddish purple taste was gradually obtained, and a uniform solution was obtained. The temperature was returned to room temperature, the solvent was removed, and about 50 ml of cyclohexane was added to obtain 1.60 g (yield: 79.6%) of a red powder.
Elemental analysis (as C ₁₂₂ H ₈₃ N ₉ O ₁₆ Cl ₂ ) (all as E: C ₈ H ₇ O ₂ )

このものの赤外線吸収スペクトル（ＫＢｒ錠剤法）は、２９８０ｃｍ^−１に飽和炭化水素による吸収、１７６０ｃｍ^−１にカルボネートのＣ＝Ｏの伸縮振動に基づく吸収が認められた。

Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2980cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1760 cm ^-1 was observed.

<Example 9>
-Production of Compound (VIII-5) 0.81 grams of the precursor (E = H) of Compound (VIII-5) and 2.7 grams (12 times mole) of pyrocarboxylic acid di-tert-amyl ester were added to 150 ml of dehydrated pyridine. After dispersing and stirring at room temperature for 15 minutes, the mixture was further heated to about 50 ° C. and reacted for 2 hours. Gradually reddish and a homogeneous solution was obtained. The temperature was returned to room temperature, the solvent was removed, and about 50 ml of ethyl acetate was added to obtain 1.10 grams (yield: 86.6%) of a red powder.
Elemental analysis _{(as C 75 H 72 N 6 O 13} ) ( all _E: as _{C 5} H 9 _{O 2)}

このものの赤外線吸収スペクトル（ＫＢｒ錠剤法）は、２９８０ｃｍ^−１に飽和炭化水素による吸収、１７６０ｃｍ^−１にカルボネートのＣ＝Ｏの伸縮振動に基づく吸収が認められた。

Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2980cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1760 cm ^-1 was observed.

<Example 10>
-Production of Compound (X-1) 0.16 grams of the precursor (E = H) of compound (X-1) and 0.52 grams (12 times mole) of pyrocarboxylic acid di-tert-butyl ester were added to 30 ml of dehydrated pyridine. After dispersing and stirring at room temperature for 15 minutes, the mixture was further heated to about 50 ° C. and reacted for 2 hours. Gradually reddish and a red-orange precipitate was obtained. The temperature was returned to room temperature, the solvent was removed, and about 50 ml of ethyl acetate was added to obtain 0.16 g (yield: 80%) of a red powder.
Elemental analysis _{(as C 69 H 66 N 6 O 13} ) ( all _E: as _{C 5} H 9 _{O 2)}

このものの赤外線吸収スペクトル（ＫＢｒ錠剤法）は、２９８０ｃｍ^−１に飽和炭化水素による吸収、１７６０ｃｍ^−１にカルボネートのＣ＝Ｏの伸縮振動に基づく吸収が認められた。

Infrared absorption spectrum of the (KBr tablet method) is absorbed by the saturated hydrocarbon to 2980cm ^-1, absorption based on the stretching vibration of C = O of carbonate to 1760 cm ^-1 was observed.

<Application example> (according to Example 3 of JP2007-108682)
The electrophotographic photosensitive member used in the application example was prepared as follows.
As a charge generation material, a metal-free phthalocyanine pigment (Dainippon Ink Industries Co., Ltd .: Fastogen Blue 8120B) was dispersed with a ball mill apparatus for 2 hours together with 30 parts by weight and 970 parts of cyclohexane non to obtain a charge generation material dispersion. Separately, 340 parts by weight of tetrahydrofuran, 49 parts by weight of a polycarbonate resin (Z polycarbonate, viscosity average molecular weight: 40,000, manufactured by Teijin Chemicals Ltd.), a charge transport material 20 represented by the above-mentioned azo compound (III-3) 1 part by weight, 29.5 parts by weight of a charge transport material represented by the following formula (i), and 0.1 part by weight of silicone oil (KF50-100CS, Shin-Etsu Chemical Co., Ltd.) are dissolved, and the above-described charge generation material dispersion is dissolved therein. 66.6 parts by weight of the solution was added and stirred to obtain a photosensitive layer coating solution.
On the aluminum drum having a diameter of 30 mm and a length of 340 mm (circular run-out is measured in advance and selected within 20 μm), dip coating is performed using the photosensitive layer coating solution, followed by drying. It dried at 120 degreeC for 15 minutes. The photosensitive layer was produced under the ascending / descending speed conditions such that the thickness was 25 μm.
The electrophotographic photosensitive member thus produced is mounted on a Ricoh IPSiO Color 8100 remodeling machine (with a writing LD wavelength of 780 mn and a power pack changed and the charging polarity remodeled for positive charging). Under the conditions, a continuous patch of 50,000 sheets of a full color image mixed with rectangular patches and characters with an image area ratio of 6% is printed. In this case, the dark part potential, the light part potential after printing the initial image and 50,000 sheets, The image quality was evaluated. The results are shown in Table 10.
The dark part potential, the bright part potential, and the image quality were evaluated as follows.
Dark portion potential: After the primary charging, the photosensitive member surface potential when moving to the developing portion position is adjusted, and the applied voltage of the charger is adjusted to +700 V in the initial stage. Thereafter, the constant applied voltage is maintained until the end of the test. did.
・ Bright part potential: After charging, image exposure (entire exposure), and photoreceptor surface potential when moved to the development part position ・ Image quality: Presence or absence of background contamination due to uneven charging during full color image output (white (If the part of the background is soiled, it is marked as x)

以上の説明から判るように、本発明のアゾ化合物は高速複写機用として高い感度を示す電子写真感光体に用いられる有機光導電体としてきわめて有用である。

As can be seen from the above description, the azo compound of the present invention is extremely useful as an organic photoconductor used for an electrophotographic photoreceptor exhibiting high sensitivity for use in a high-speed copying machine.

Claims (15)

An azo compound represented by the following general formula (I):

[Wherein A is a residue of an azo compound and this residue A is bonded to n E groups via one or more heteroatoms, and these heteroatoms are N and O And each of the E groups is independently a hydrogen atom or the following group: —C (═O) —O—R1 (wherein R1 is the number of carbon atoms). Represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group of 4 to 10, and n is an integer of 1 to 10. ] The azo compound according to claim 1, wherein A in the general formula (I) is a residue of a compound represented by the following general formula (II).

[B represents the main skeleton of the azo compound, Cp represents a coupler component residue, and m represents an integer of 2 or 3. ] The coupler component residue is an aromatic hydrocarbon compound residue having a hydroxyl group and a heterocyclic compound residue having a hydroxyl group, an aromatic hydrocarbon compound residue having an amino group, and a heterocyclic compound residue having an amino group , An aromatic hydrocarbon compound residue having a hydroxyl group and an amino group, a heterocyclic compound residue, and a compound residue having an aliphatic or aromatic enol ketone group, The azo compound according to claim 2. The azo compound according to claim 3, wherein the aromatic hydrocarbon compound residue having a hydroxyl group is selected from the group consisting of a phenol compound residue and a naphthol compound residue. The azo compound according to claim 3, wherein the aromatic hydrocarbon compound residue having a hydroxyl group and an amino group is an aminonaphthol compound. The azo compound according to claim 2, wherein the Cp- is represented by at least one of the following general formulas (5) to (13).

In the general formulas (5) to (8), X, Y ¹ , Z, p and q each represent the following.
^{X: -OH, -N (R 1} ) (R 2) or -NHSO ₂ -R ^3.
(R ¹ and R ² represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.)
Y ¹ : a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxy group, a sulfone group, a substituted or unsubstituted sulfamoyl group, or —CON (R ⁴ ) (Y ² ). [R ⁴ represents a hydrogen atom, an alkyl group or a substituted product thereof, or a phenyl group or a substituted product thereof, Y ² represents a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or —N═C (R ⁵ ) (R ⁶ ) (where R ⁵ is a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or a styryl group or a substituted product thereof, and R ⁶ is a hydrogen atom, an alkyl group, a phenyl group or a substituted product thereof. Or R ⁵ and R ⁶ may form a ring together with the carbon atom to which they are attached. ]
Z: A hydrocarbon ring or a substituted product thereof, or a heterocyclic ring or a substituted product thereof.
p: an integer of 1 or 2.
q: An integer of 1 or 2.

(In the above formula, R ⁷ represents a substituted or unsubstituted hydrocarbon group, and X is as defined above.)

(In the above formula, A represents a divalent group of an aromatic hydrocarbon or a divalent group of a heterocyclic ring containing a nitrogen atom in the ring (these rings may be substituted or unsubstituted). X is the same as defined above. )

(Wherein R ⁸ represents an alkyl group, a carbamoyl group, a carboxy group or an ester thereof, Ar ¹ represents a hydrocarbon ring group or a substituted product thereof, and X is the same as described above.)

(In the above formulas (12) and (13), R ⁹ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and Ar ² represents a hydrocarbon ring group or a substituted product thereof.) The azo compound according to claim 2, wherein B in the general formula (II) is represented by the following general formula (III).

(However, R ¹¹ and R ¹² independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.) The azo compound according to claim 2, wherein B in the general formula (II) is represented by the following general formula (IV).

(However, R ¹³ , R ¹⁴ , and R ¹⁵ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.) The azo compound according to claim 2, wherein B in the general formula (II) is represented by the following general formula (V).

(However, R ¹⁶ , R ¹⁷ , and R ¹⁸ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.) The azo compound according to claim 2, wherein B in the general formula (II) is represented by the following general formula (VI).

(However, R ¹⁹ and R ²⁰ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.) The azo compound according to claim 2, wherein B in the general formula (II) is represented by the following general formula (VII).

(However, R ²¹ , R ²² , and R ²³ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.) The azo compound according to claim 2, wherein B in the general formula (II) is represented by the following general formula (VIII).

(However, R ²⁴ , R ²⁵ , and R ²⁶ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.) The azo compound according to claim 2, wherein B in the general formula (II) is represented by the following general formula (IX).

^{(Wherein, R 27, R 28, R} 29 are independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group and esters thereof.) The azo compound according to claim 2, wherein B in the general formula (II) is represented by the following general formula (X).

(However, R ³⁰ and R ³¹ independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxyl group, and an ester thereof.) A method for producing an azo compound of the general formula (I), wherein the compound of the general formula (II) is reacted with a pyrocarbonic acid diester of the following formula in the presence of a base: ) For producing an azo compound.

(In the formula, R ₁ independently represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, or aralkyl group having 4 to 10 carbon atoms.)