JP4566585B2 - Azo compound, method for producing the same, and material for photosensitive layer - Google Patents

Description

  The present invention relates to a novel azo compound, a method for producing the azo compound, and a material for a photosensitive layer.

  Conventionally, azo compounds have been widely used as dyes or pigments in various industrial fields for a long time. For example, they are used for dyeing fibers, coloring materials for color photographic materials, and more recently for photochromic applications. This is an extremely important group of compounds. This azo compound is generally synthesized by coupling a “diazonium compound” and a “coupler compound”. With regard to the diazonium compound and coupler compound, compounds having various structures are used depending on the intended use of the azo dye or pigment, and the azo dye or azo pigment obtained by selecting the diazonium compound and coupler compound. Absorption wavelength and intensity, solubility in water, fastness to light, dispersion characteristics in resin, and the like are determined.

  In particular, in the field of electrophotographic photoreceptors, certain azo compounds are useful as organic photoconductors, particularly charge generating pigments, used in laminated photoreceptors that are one form of electrophotographic photoreceptors. Are known. As is well known, this multi-layer type photoreceptor 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. Is a photosensitive member provided with a charge transporting layer mainly composed of a charge transporting material having the ability to efficiently inject and transport this. Examples of the azo compound used in such a photoreceptor include a benzidine-based bisazo compound (see Patent Document 1 and Patent Document 2), a stilbene-based bisazo compound (see Patent Document 3), a diphenylhexatriene-based bisazo compound ( Patent Document 4), diphenylbutadiene bisazo compounds (see Patent Document 5), and the like are known.

  On the other hand, as a coupler compound used for such an azo pigment, for example, a naphthol coupler (see Patent Document 6), a benzcarbazole coupler (see Patent Document 7), a naphthalimide coupler (see Patent Document 8), Perinone couplers (see Patent Document 9), azulene couplers (see Patent Document 10), anthracene couplers (see Patent Document 11), and the like are already known.

  However, a conventional multilayer type photoreceptor using an azo compound generally has low sensitivity and durability, so that it is not always sufficient for practical use, and it satisfies various requirements required for an electrophotographic process. However, the present situation is that further improvement in sensitivity and durability is desired.

JP 47-37543 A JP 52-55643 A JP-A-52-8832 JP 58-222152 A JP 58-222153 A JP 47-37543 A JP 58-122967 A JP 54-79632 A Japanese Patent Laid-Open No. 57-176055 Japanese Patent Application Laid-Open No. 60-10256 Japanese Patent Laid-Open No. 61-257993

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, an object of the present invention is to provide a novel azo compound suitably used for a practical high-sensitivity electrophotographic photoreceptor, an efficient production method of the azo compound, and a material for a photosensitive layer. .

  As a result of intensive studies to solve the above problems, the present inventors have been able to easily produce a novel azo compound using a specific coupler, and in particular, it is practical when used for an electrophotographic photoreceptor. It was found that it has excellent sensitivity and durability.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> An azo compound represented by the following general formula (1).
However, the general formula (1), r ₁ and r ₂ represent each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a nitro group. Two Cp represent a coupler residue, one of the two Cp is a coupler residue represented by the following general formula (2), the other one of Cp is the following general formula (2), following general formula (8) and lower SL is a coupler residue represented by any one of formulas (24).
However, in said general formula (2), R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group each independently. However, R ₁ and R ₂ may be bonded to each other to form a substituted or unsubstituted alkylene ring, a substituted or unsubstituted unsaturated aliphatic ring, or a substituted or unsubstituted aromatic ring. X represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyclic unsaturated aliphatic group, an aromatic group, a heterocyclic group, or an amino group, which may be further substituted with a substituent .
However, in the general formula (8), Z ₁ is condensed with a divalent organic residue that forms a substituted or unsubstituted hydrocarbon ring by condensation with a benzene ring in the formula, or a benzene ring in the formula. Represents a divalent organic residue that forms a substituted or unsubstituted heterocyclic ring. R ₁₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group. Y ₂ represents a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group.
However , in the general formula (24), y ₂ represents an aromatic hydrocarbon divalent group or a heterocyclic divalent group containing a nitrogen atom in the ring. These rings may be further substituted with a substituent.
<2> In the general formula (1), one of the two Cp is a coupler residue represented by the following general formula (5), and the other one of Cp is the following general formula (5), formula (2), an azo compound according to <1> is a coupler residue represented by any of the following general formula (8) and lower following general formula (24).
In the general formula (5), A ₁ represents an aromatic group, or a heterocyclic group, which may be further substituted by substituents. m shows the integer of 1-6.
However, in said general formula (2), R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group each independently. However, R ₁ and R ₂ may be bonded to each other to form a substituted or unsubstituted alkylene ring, a substituted or unsubstituted unsaturated aliphatic ring, or a substituted or unsubstituted aromatic ring. X represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyclic unsaturated aliphatic group, an aromatic group, a heterocyclic group, or an amino group, which may be further substituted with a substituent .
However, in the general formula (8), Z ₁ is condensed with a divalent organic residue that forms a substituted or unsubstituted hydrocarbon ring by condensation with a benzene ring in the formula, or a benzene ring in the formula. Represents a divalent organic residue that forms a substituted or unsubstituted heterocyclic ring. R ₁₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group. Y ₂ represents a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group.
However , in the general formula (24), y ₂ represents an aromatic hydrocarbon divalent group or a heterocyclic divalent group containing a nitrogen atom in the ring. These rings may be further substituted with a substituent.
<3> In the general formula (1), one of two Cp is a coupler residue represented by the following general formula (2), and the other one of Cp is represented by the following general formula (8). The azo compound according to <1>, which is a coupler residue.
However, in said general formula (2), R < ₁ > , R < ₂ > , R < ₃ > and R < ₄ > represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group each independently. However, R ₁ and R ₂ may be bonded to each other to form a substituted or unsubstituted alkylene ring, a substituted or unsubstituted unsaturated aliphatic ring, or a substituted or unsubstituted aromatic ring. X represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyclic unsaturated aliphatic group, an aromatic group, a heterocyclic group, or an amino group, which may be further substituted with a substituent.
However, in the general formula (8), Z ₁ is condensed with a divalent organic residue that forms a substituted or unsubstituted hydrocarbon ring by condensation with a benzene ring in the formula, or a benzene ring in the formula. Represents a divalent organic residue that forms a substituted or unsubstituted heterocyclic ring. R ₁₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group. Y ₂ represents a substituted or unsubstituted hydrocarbon ring group or a substituted or unsubstituted heterocyclic group.
<4> In the general formula (1), one of the two Cp is a coupler residue represented by the following general formula (2), and the other Cp is represented by the following general formula (24). The azo compound according to <1>, which is a coupler residue.
However, in said general formula (2), R < ₁ > , R < ₂ > , R < ₃ > and R < ₄ > represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group each independently. However, R ₁ and R ₂ may be bonded to each other to form a substituted or unsubstituted alkylene ring, a substituted or unsubstituted unsaturated aliphatic ring, or a substituted or unsubstituted aromatic ring. X represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyclic unsaturated aliphatic group, an aromatic group, a heterocyclic group, or an amino group, which may be further substituted with a substituent.
However, in the general formula (24), y ₂ represents an aromatic hydrocarbon divalent group or a heterocyclic divalent group containing a nitrogen atom in the ring. These rings may be further substituted with a substituent.
<5> The method for producing an azo compound according to any one of <1> to <4>, wherein the diazonium salt compound represented by the following general formula (9) and the coupler represented by the following general formula (10) A method for producing an azo compound, comprising reacting a compound.
However, in the general formula (9), r ₁ and r ₂ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a nitro group. Z ⁻ represents an anionic group,
HCp Formula (10)
However, in said general formula (10), Cp represents a coupler residue.
<6> A photosensitive layer material comprising the azo compound according to any one of <1> to <4>.

  According to the present invention, a novel azo compound that can solve various problems in the prior art and that is easier to manufacture than conventional ones, and that can produce a highly sensitive electrophotographic photosensitive member, particularly when used as a charge generating material. Can be provided.

(Azo compound and production method thereof)
The azo compound of the present invention is represented by the following general formula (1).
However, the general formula (1), r ₁ and r ₂ represent each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a nitro group. Two Cp represent a coupler residue, and at least one of the two Cp is a coupler residue represented by any one of the following general formula (2), the following general formula (3), and the following general formula (4). is there.
However, in said general formula (2), general formula (3), and general formula (4), R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > are respectively independently a hydrogen atom, a halogen atom, an alkyl group, or Represents an alkoxy group. However, R ₁ and R ₂ may be bonded to each other to form a substituted or unsubstituted alkylene ring, a substituted or unsubstituted unsaturated aliphatic ring, or a substituted or unsubstituted aromatic ring. X represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyclic unsaturated aliphatic group, an aromatic group, a heterocyclic group, or an amino group, which may be further substituted with a substituent. Y is a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted aralkylene group, a substituted or unsubstituted aromatic divalent organic residue, substituted or unsubstituted A divalent organic residue having heteroaromaticity or a divalent carbonyl group-containing organic residue represented by CO-Z- (wherein Z is an alkylene group, a cycloalkylene group, an aromaticity divalent) And a divalent organic residue having heteroaromaticity, which may be further substituted with a substituent.
In the method for producing an azo compound of the present invention, a diazonium salt compound represented by the following general formula (9) is reacted with a coupler compound represented by the following general formula (10).
However, in said general formula (9), r < ₁ >, r < ₂ > represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a nitro group each independently, Z < ^- > represents an anion group,
HCp Formula (10)
However, in said general formula (10), Cp represents a coupler residue.
Hereinafter, the details of the azo compound of the present invention will be clarified through the description of the production method of the azo compound of the present invention.

The azo compound of the present invention and the raw material for producing the azo compound can be produced by the following method.
That is, a styrene compound represented by the following general formula (11) and an acetylenedicarboxylic acid ester compound represented by the following general formula (12) are reacted as follows (Diels-Alder reaction) to produce the following general formula ( A naphthalene compound represented by 13) is obtained.

However, the reaction is a Diels-Alder reaction accompanied by an oxidation reaction, and Liebigs Ann. Chem. , 595, 1 (1955), the reaction with hydroquinones and iodine is described in Ber. 69, 1686 (1936) describe a reaction with maleic anhydride in a nitrobenzene solvent. In the present invention, the reaction with acetylenedicarboxylic acid ester in a nitrobenzene solvent is controlled at a reaction temperature of 100 ° C. to 160 ° C., and more preferably 130 ° C. to 150 ° C. The naphthalene compound represented by the general formula (13) can be obtained.

Next, R ₆ which is a protecting group of the naphthalene compound of the general formula (13) obtained above is removed as follows to obtain a naphthalene compound represented by the following general formula (14) (deprotection). Group).
However, in the general formula (14), R ₆ is not particularly limited as long as it is a protecting group for the OH group, and can be appropriately selected according to the purpose. For example, R ₆ can be selected from methyl group, iso-propyl group, t- And a butyl group, a benzyl group, an allyl group, a methoxymethyl group, a tetrahydropyranyl group, a trimethylsilyl group, and the like. Among these, an iso-propyl group that can be removed at room temperature in the presence of an acid catalyst, t- A butyl group and a methoxymethyl group. Examples of the acid catalyst include sulfuric acid, trifluoroacetic acid, hydrobromic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and the like.

Next, the naphthalene compound of the general formula (14) obtained by the above synthesis and the amine compound of the following general formula (15) are subjected to an ester / amide exchange reaction as shown below to give the following general formula (16 ) Can be obtained.

  In general, the ester / amide exchange reaction is carried out under a basic catalyst. Am. Chem. Soc. , 71, 1245 (1945) describes that addition of glycol-based, water, or glycerol-based solvents is effective for the ester / amide exchange reaction. In the present invention, the naphthalene compound of the general formula (14) and the amine compound of the general formula (15) are selected from glycol-based or glycerol-based solvents in an ester / imide exchange reaction (including cyclization reaction). In addition, by controlling the reaction temperature to 100 ° C. to 170 ° C., preferably 110 ° C. to 150 ° C. in a system containing at least one kind, the coupler compound of the general formula (16) is obtained in high yield. It is done.

  Further, the coupler compound represented by the following general formula (18) or the following general formula (19) is obtained by the synthesis of the naphthalene compound represented by the general formula (14) and the following general formula (17). It is manufactured from the diamine compound.

In this case, the same ester / imide exchange reaction (including two cyclization reactions) as in the production of the coupler compound of the general formula (16) can be used. However, the reaction temperature is 130 ° C to 180 ° C, preferably 140 ° C to 170 ° C.
Moreover, the coupler compound shown by General formula (16), General formula (18), and General formula (19) can be manufactured also by the method shown below.

That is, the naphthalene compound represented by the general formula (20) can be obtained by reacting the naphthalene compound of the formula (13) in the presence of an acid catalyst. In this case, R ₆ is not particularly limited as long as it is a protecting group, but a methyl group, an iso-propyl group, or the like can be generally used, and a methyl group can be preferably used. Examples of the acid catalyst include hydrobromic acid and boron tribromide.

  Next, the coupler compound of the general formula (16) can be obtained by reacting the naphthalene compound of the general formula (20) obtained in the synthesis and the amine compound of the general formula (15) in the presence of an acid catalyst. it can. As the acid catalyst, for example, acetic acid, sulfuric acid and the like can be used, and the reaction can be performed more efficiently by removing water generated by the reaction from the reaction system as necessary.

  The coupler compound represented by the general formula (18) or the general formula (19) is obtained by reacting the naphthalene compound represented by the general formula (20) obtained by the synthesis and the diamine compound represented by the general formula (17) in the presence of an acid catalyst. It can be obtained by making it. As the acid catalyst, for example, acetic acid, sulfuric acid and the like can be used, and the reaction can be performed more efficiently by removing water generated by the reaction from the reaction system as necessary.

The azo compound represented by the general formula (1) can be synthesized by the following reaction formula. First, the corresponding 2,7-diaminodibenzo [a, c] phenazine compound is used as a starting material, this is diazotized and isolated as a diazonium salt represented by the general formula (9), and then this is mixed with a suitable organic solvent ( N, N-dimethylformamide, etc.) in the presence of an alkali and a coupler compound represented by the general formula (10) corresponding to each pigment.

  In the azo compound of the general formula (1) of the present invention, two or more types of coupler compounds (10) can be used. In this case, the diazonium compound represented by the general formula (9) can be used as the general formula (16). The coupler compound of the general formula (18) or the general formula (19) and the coupler compound exemplified by the following general formula (Cp1) to the general formula (Cp15) are reacted in order in two stages, or the first cup After the diazonium salt compound obtained by the ring reaction is isolated, it can be further obtained by reacting the corresponding coupler compound.

In the general formula (1), r ₁ and r ₂ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a nitro group. In this case, the alkyl group is preferably an alkyl group having 1 to 25 carbon atoms, more preferably 1 to 8 carbon atoms, and examples thereof include, but are not limited to, a methyl group, an ethyl group, a propyl group, and a butyl group. It is not a thing. The alkoxy group of r ₁ and r ₂ is preferably an alkoxy group having 1 to 25 carbon atoms, more preferably 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. It is not limited to. halogen atoms r _{1, r 2,} for example, a fluorine atom, a chlorine atom, a bromine atom. Z ⁻ is Cl ⁻ , Br ⁻ , I ⁻ , BF ⁻ , PF ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , ClO ₄ ⁻ , SO ₄ ²⁻ , AsF ₆ ⁻ and represented by the following formula. An anion functional group such as SbF ₆ ^— , among which BF ₄ ^— is particularly preferable.

The general formula (2), the general formula (3), the general formula (4), the general formula (11), the general formula (13), the general formula (14), the general formula (16), and the general formula (18). In general formula (19) and general formula (20), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, provided that R ₁ And R ₂ may be bonded to each other to form a substituted or unsubstituted alkylene ring, a substituted or unsubstituted unsaturated aliphatic ring, or a substituted or unsubstituted aromatic ring. In this case, the alkyl group is preferably an alkyl group having 1 to 25 carbon atoms, more preferably 1 to 8 carbon atoms, and examples thereof include, but are not limited to, a methyl group, an ethyl group, a propyl group, and a butyl group. It is not a thing. The alkoxy group is preferably an alkoxy group having 1 to 25 carbon atoms, more preferably 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, but are not limited thereto. Absent. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. When R ₁ and R ₂ are bonded to each other to form a ring, the atomic group formed by bonding R ₁ and R ₂ to each other includes a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted group Or a substituted or unsubstituted alkylene group such as an unsubstituted pentylene group, a substituted or unsubstituted propenylene group, a substituted or unsubstituted butenylene group, a substituted or unsubstituted alkenylene group such as a substituted or unsubstituted pentenylene group, or An aromatic ring such as a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring may be formed. In this case, examples of the substituent include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, alkoxy groups such as methoxy group and ethoxy group, halogen atoms such as fluorine atom, chlorine atom, and bromine atom. .

In the general formula (12), general formula (13), and general formula (14), R ₅ is preferably a methyl group, an ethyl group, a propyl group, a butyl group, etc., preferably 1 to 25 carbon atoms, more preferably. Examples thereof include an alkyl group having 1 to 8 carbon atoms, an aralkyl group such as benzyl group, and a substituted alkyl group such as 2-methoxyethyl group.

  In the general formulas (11) and (13), R6 is not particularly limited as long as it is a protecting group for an OH group, but is preferably a methyl group, an iso-propyl group, a t-butyl group, a benzyl group. , An allyl group, a methoxymethyl group, a tetrahydropyranyl group, a trimethylsilyl group and the like, and more preferably, an iso-propyl group and a t-butyl group are not limited thereto.

  In the general formula (2), general formula (15), and general formula (16), X is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cyclic group. It represents an unsaturated aliphatic group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted amino group. In this case, the alkyl group is preferably an alkyl group having 1 to 25 carbon atoms, more preferably 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Examples include, but are not limited to, alkyl groups such as octyl group and decyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 8 carbon atoms, and examples thereof include, but are not limited to, a cyclopentyl group and a cyclohexyl group. Examples of the cyclic unsaturated aliphatic group include, but are not limited to, an indanyl group and a tetralinyl group. The aromatic group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and examples thereof include, but are not limited to, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. The heterocyclic group contains at least one hetero atom such as nitrogen, oxygen or sulfur in the atoms forming the ring. For example, a pyridyl group, pyrazino group, quinolino group, oxazolyl group, benzoxazolyl group, thiazolyl Group, benzothiazolyl group, imidazolyl group, benzoimidazolyl group, indolyl group and the like. Examples of the amino group include alkylamino groups such as methylamino group and ethylamino group, aromatic amino groups such as phenylamino group and naphthylamino group, and carboamino groups such as acetylamino group and benzoylamino group. It is not limited to.

These alkyl groups, cycloalkyl groups, cyclic unsaturated aliphatic groups, aromatic groups, heterocyclic groups, and amino group substituents include alkyl groups such as methyl, ethyl, propyl, and butyl groups; benzyl groups Substituted alkyl groups such as phenethyl group and methoxymethyl group; alkoxy groups such as methoxy group, ethoxy group and phenoxy group; phenyl group which may have a substituent; naphthyl group and anthracenyl which may have a substituent Group, aromatic group such as phenanthrenyl group and pyrenyl group; halogen atom such as fluorine atom, chlorine atom and bromine atom; hydroxy group; amino group which may have a substituent; acetyl which may have a substituent Carboamino groups such as amino groups and benzoylamino groups; nitro groups; cyano groups; acetyl groups; benzoyl groups that may have substituents; Good alkoxycarbonyl group; an optionally substituted phenoxycarbonyl group; a substituent and the like may carbamoyl group.
Among the coupler residues represented by the general formula (2), a coupler residue in which X is a substituted or unsubstituted alkyl group is preferable, and among these, the coupler residue represented by the general formula (5) is Particularly preferred.

In the general formula (5), A ₁ represents a substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group. In this case, the aromatic group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and examples thereof include, but are not limited to, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. . Heterocyclic groups contain at least one heteroatom such as nitrogen, oxygen, or sulfur in the atoms forming the ring. For example, pyridyl group, pyrazino group, quinolino group, oxazolyl group, benzoxazolyl group, thiazolyl group Benzothiazolyl group, imidazolyl group, benzoimidazolyl group, indolyl group and the like. Examples of the amino group include alkylamino groups such as methylamino group and ethylamino group, aromatic amino groups such as phenylamino group and naphthylamino group, and carboamino groups such as acetylamino group and benzoylamino group. It is not limited. These substituents include alkyl groups such as methyl, ethyl, propyl, and butyl groups, substituted alkyl groups such as benzyl, phenethyl, and methoxymethyl groups, and alkoxy groups such as methoxy, ethoxy, and phenoxy groups. A phenyl group which may have a substituent, a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, a trifluoromethyl group, a cyano group, an alkoxycarbonyl group or a carbamoyl group which may have a substituent. It is done.

  In the general formula (3), general formula (4), general formula (6), general formula (7), general formula (18), and general formula (19), Y represents a substituted or unsubstituted alkylene group. Substituted or unsubstituted cycloalkylene group, substituted or unsubstituted aralkylene group, divalent organic residue having substituted or unsubstituted aromaticity, divalent organic having substituted or unsubstituted heteroaromaticity Residue or divalent carbonyl group-containing organic residue represented by CO-Z- (where Z is a substituted or unsubstituted alkylene group, substituted or unsubstituted cycloalkylene group, substituted or unsubstituted aromaticity) Or a divalent organic residue having a substituted or unsubstituted heteroaromaticity, wherein the alkylene group preferably has 1 to 25 carbon atoms, more preferably carbon atoms. 1 to 12 alkylene groups such as methylene , Ethylene groups, propylene groups, butylene groups, pentylene groups, hexylene groups, octylene groups, decylene groups, and the like, but not limited to these, an alkylene ring forms an aromatic ring at its carbon-carbon bond. The cycloalkylene group is preferably a cycloalkylene group having 5 to 8 carbon atoms, and examples thereof include, but are not limited to, a cyclopentylene group and a cyclohexylene group. C 7-20 aralkylene group, for example, toluylene group, xylylene group, ethylene phenylene ethylene group, phenylene methylene group, phenylene ethylene group, but are not limited to these. The residue is preferably an aryl group or aryl having 6 to 30 carbon atoms. A skeleton of the group further condensed with a saturated aliphatic ring or an unsaturated aliphatic ring. For example, o-phenylene group, 1,8-naphthylene group, 2,3-naphthylene group, 1,2-anthrylene group, 9 , 10-phenanthrylene group, etc. The divalent organic residue having a heterocyclic aromaticity has at least a hetero atom such as nitrogen, oxygen, or sulfur as a ring-forming atom. In addition to a heterocyclic aromatic group, it includes a heterocyclic aromatic group skeleton and a saturated aliphatic ring, unsaturated aliphatic ring, or heterocyclic ring condensed to the skeleton of the heterocyclic aromatic group. -A pyrazolediyl group, a 2,3-pyridinediyl group, a 5,6-pyrimidinediyl group, a 6,7-benzimidazolediyl group, a 6,7quinolinediyl group, and the like, but are not limited thereto. Examples of the divalent organic residue include, but are not limited to, a 2-benzoyl group and a 2-naphthylcarbonyl group.

  The substituents of these alkylene groups, cycloalkylene groups, aralkylene groups, divalent organic residues having aromaticity, and divalent organic residues having heteroaromaticity include methyl group, ethyl group, propyl group An alkyl group such as a butyl group, a substituted alkyl group such as a benzyl group, a phenethyl group or a methoxymethyl group, an alkoxy group such as a methoxy group, an ethoxy group or a phenoxy group, a phenyl group which may have a substituent, or a substituent. Aromatic groups such as naphthyl group, anthracenyl group, phenanthrenyl group and pyrenyl group, halogen atoms such as fluorine atom, chlorine atom and bromine atom, hydroxy group, amino group which may have a substituent, acetyl Amino group, Carboamino group such as benzoylamino group which may have a substituent, Nitro group, Cyano group, Acetyl group, Substituent Good benzoyl group, an alkoxycarbonyl group, an optionally substituted phenoxycarbonyl group, and the like may carbamoyl group which may have a substituent.

  Among the coupler residues represented by the general formula (3) and the general formula (4), the coupler residues represented by the general formula (6) and the general formula (7) are preferable, and among these, Y is substituted. Alternatively, an unsubstituted alkylene group or a coupler residue which is a substituted or unsubstituted carbonyl group-containing divalent organic residue is preferable. Among these, Y is particularly represented by the following general formula (21) and general formula (22). The coupler residues shown are preferred.

  B1 in the general formula (21) and B2 in the general formula (22) are, for example, a divalent group of an aromatic hydrocarbon ring such as an o-phenylene group or a 2,3-naphthylene group, such as 2, Represents a divalent group of an aromatic heterocyclic ring such as 3-pyrinyl group, 3,4-pyrazolyl group, 2,3-pyridylyl group, 4,5-pyridylyl group, 4,5-imidazolyl group, and substitution thereof Examples of the group include alkyl groups such as methyl, ethyl, propyl, and butyl groups, alkoxy groups such as methoxy, ethoxy, and phenoxy groups, halogen atoms such as fluorine, chlorine, and bromine, and nitro groups. Is mentioned.

  The example of the novel coupler (Cp) of this invention is shown below.

  In Cp of the general formula (1), examples of coupler residues that may coexist other than the coupler residues represented by the general formula (2), the general formula (3), and the general formula (4) are as follows: For example, a compound having a phenolic hydroxyl group such as phenols or naphthols, an aromatic amino compound having an amino group, an aminonaphthol having an amino group and a phenolic hydroxyl group, an aliphatic or aromatic enol ketone group Compounds (compounds having an active methylene group) and the like. Preferably, the coupler residue Cp has the following general formula (Cp1), general formula (Cp2), general formula (Cp3), general formula (Cp4), general formula ( Cp5), general formula (Cp6), general formula (Cp7), general formula (Cp8), general formula (Cp9), general formula (Cp10), general formula (Cp11), It is represented by the general formula (Cp12) or the general formula (Cp13).

In the general formula (Cp1), the general formula (Cp2), the general formula (Cp3), and the general formula _{(Cp4), X 1, Y} 1, Z 1, l and m represent the following, respectively.

X ₁ represents —OH or NHSO ₂ —R ₁₃ .
However, R ₁₁ and R ₁₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group, R ₁₃ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
Y ₁ represents a hydrogen atom, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a carboxy group, a sulfo group, a substituted or unsubstituted sulfamoyl group, or a machine represented by the following formula.

Table However, R ₁₄ is a hydrogen atom, an alkyl group or a substitution product thereof, a phenyl group or a substitution product thereof, Y ₂ is a hydrocarbon ring group or a substitution product thereof, a heterocyclic group or a substitution product thereof, or by the following formula Represents a group.

However, R ₁₅ represents 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 ₁₆ represents a hydrogen atom, an alkyl group, a phenyl group or a substituted product thereof, or R ₁₅ and R ₁₆ may form a ring together with the carbon atom bonded to them.
Z ₁ represents a hydrocarbon ring or a substituted product thereof or a heterocyclic ring or a substituted product thereof.
l is an integer of 1 or 2.
m is an integer of 1 or 2.

However, in the formula (Cp5), R ₁₇ represents a substituted or unsubstituted hydrocarbon group, and X ₁ is the same as described above.

However, in formula (Cp6), Y ₂ represents an aromatic hydrocarbon divalent group or a heterocyclic divalent group containing a nitrogen atom in the ring. These rings may be substituted or unsubstituted. X ₁ is the same as described above.

However, in the formula (Cp7), R ₁₈ 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 ₁ is the same as described above.

However, the general formula (Cp8) and the general formula (Cp9), R ₁₉ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, Ar ₂ represents a hydrocarbon ring group or a substitution product thereof.

Examples of the hydrocarbon ring of Z1 in the general formula (Cp1), general formula (Cp2), general formula (Cp3), or general formula (Cp4) include a benzene ring and a naphthalene ring. Examples of the heterocyclic ring that may have a substituent include an indole ring, a carbazole ring, a benzolane ring, and a dibenzofuran ring. Examples of the substituent in the ring of Z ₁ include halogen atoms such as chlorine atom and bromine atom.

Examples of the hydrocarbon ring group for Y ₂ or R ₁₅ include a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group, and examples of the heterocyclic group include a pyridyl group, a phenyl 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 ₁₅ and R ₁₆ include a fluorene ring.

Examples of the substituent in the hydrocarbon ring group or heterocyclic group of Y ₂ or R ₁₅ or the ring formed by R ₅ and R ₁₆ include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, methoxy group, Alkoxy groups such as ethoxy group, propoxy group, butoxy group, halogen atoms such as chlorine atom and bromine atom, dialkylamino groups such as dimethylamino group and diethylamino group, halomethyl groups such as trifluoromethyl group, nitro group, cyano group position , Carboxyl groups or esters thereof, hydroxyl groups, sulfonate groups such as —SO ₃ Na, and the like.

Examples of the substituent of the phenyl group of R ₁₄ include a halogen atom such as a chlorine atom or a bromine atom.

Typical examples of the hydrocarbon group for R ₁₇ or R ₁₉ include an alkyl group such as a methyl group, an ethyl group, a propyl group, and 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 an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a chlorine atom, Illustrative are halogen atoms such as 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 examples of the substituent in these groups include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples include alkyl groups, methoxy groups, ethoxy groups, propoxy groups, butoxy groups and other alkoxy groups, nitro groups, chlorine atoms, bromine atoms and other halogen atoms, cyano groups, dimethylamino groups, diethylamino groups and other dialkylamino groups. .
In X1, a hydroxyl group is particularly suitable.

Among the above coupler residues, those represented by the above general formula (Cp2), general formula (Cp5), general formula (Cp6), general formula (Cp7), general formula (Cp8) and general formula (Cp9) are preferred. Among them, those in which X ₁ in the general formula is a hydroxyl group are preferable. Among the coupler residues represented by the general formula (Cp2), the coupler residue represented by the general formula (Cp10) is particularly preferable.

However, Y ₁ and Z ₁ are the same as described above.
More preferably, it is a coupler residue represented by the general formula.

However, Z ₁ , Y ₂ and R ₁₂ are the same as described above.

  Furthermore, among the above preferred coupler residues, those represented by general formula (Cp12) or general formula (Cp13) are suitable.

However, Z ₁ , R ₁₄ , R ₁₅ and R ₁₆ are the same as described above. _Moreover, substituents of the above _{Y 2} can be exemplified as _{R 20.}
Further, among the coupler residues represented by the general formula (Cp6), a coupler residue represented by the following general formula (Cp14) or the following general formula (Cp15) is particularly preferable.
However, in the general formulas (Cp14) and (Cp15), W ₁ 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.

  Examples of coupler residues (Cp) are shown below.

Specific examples of the azo compound of the present invention are shown in the following table. For simplicity, the central skeleton shown in Table 47 below, Ar ₁ , Ar ₂ , and two coupler compounds shown in Tables 48 to 55 are shown. (Cp) is indicated, and azo compounds are indicated by combinations of their respective numbers. In addition, the azo compound of this invention is not limited to these specific examples.

  Next, although an Example demonstrates this invention concretely, the aspect of this invention is not limited by this.

(Synthesis Example 1)
<2- (t-butoxy) 7,8-naphthalic acid dimethyl ester (R ₁ = R ₂ = R ₃ = R ₄ = H, R ₅ = CH ₃ , R ₆ = t-C _{4 in the} general formula (13) Production of H ₉ Compound)>
35.25 g (0.2 mol) of pt-butoxystyrene and 56.84 g (0.4 mol) of acetylenedicarboxylic acid dimethyl ester are dissolved in 200 ml of nitrobenzene, reacted at 140 ° C. for 5 hours and allowed to cool. Further, after distilling off nitrobenzene under reduced pressure, the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 9: 1 as a developing solvent) to obtain 40.78 g of a crude target product. It was.
Next, recrystallization from diisopropyl ether gave 36.63 g (yield 57.9%) of the desired naphthalene compound. The melting point was 82.0-83.0 ° C. The elemental analysis values are shown in the table below.

(Synthesis Example 2)
<Production of 2-hydroxy-7,8-naphthalic acid dimethyl ester (compound of R ₁ = R ₂ = R ₃ = R ₄ = H, R ₅ = CH _{3 in} the general formula (14))>
31.63 g (0.1 mol) of 2- (t-butoxy) 7,8-naphthalic acid dimethyl ester obtained in Synthesis Example 1 was dissolved in 120 ml of methylene chloride, and 57.01 g of trifluoroacetic acid was stirred at room temperature. (0.5 mol) is added dropwise over 10 minutes, and the stirring reaction is continued for 3 hours under the same conditions (room temperature). After the reaction, the reaction is poured onto ice, water is added and the phases are separated. The methylene chloride phase is further washed twice with water and dehydrated with anhydrous magnesium sulfate. The magnesium sulfate was removed by filtration, and the residue obtained by distilling off methylene chloride was recrystallized from toluene to obtain 24.31 g (yield 93.4%) of the desired naphthalene compound. The melting point was 139.0-139.8 ° C. The elemental analysis values are shown in the table below.

(Synthesis Example 3)
<Nn-hexyl-2-hydroxy-7,8-naphthalimide (R ₁ = R ₂ = R ₃ = R ₄ = H in general formula (16), X = C ₆ H ₁₃ -n [coupler No. .C1] compound)>
Nitrogen gas stream in 100 ml of ethylene glycol with 10.41 g (0.04 mol) of 2-hydroxy-7,8-naphthalic acid dimethyl ester obtained in Synthesis Example 2 and 12.14 g (0.12 mol) of n-hexylamine The stirring reaction was carried out at 120 ° C. for 4 hours. After completion of the reaction and allowing to cool, the reaction product is poured onto ice and acidified with hydrochloric acid, and then the precipitated crystals are collected by filtration, washed with 500 ml of ion-exchanged water, dried at 60 ° C. under reduced pressure, and the crude target product. 9.73 g was obtained. The obtained crude product was treated with silica gel column chromatography (toluene: ethyl acetate = 4: 1 as a developing solvent) and recrystallized from toluene to give 7.12 g (yield 59.9%) of yellow coupler compound < Coupler No. C1> was obtained. The melting point was 165.5 to 166.5 ° C. The elemental analysis values are shown in the table below.

(Synthesis Example 4)
<N-benzyl-2-hydroxy-7,8-naphthalimide (R ₁ = R ₂ = R ₃ = R ₄ = H in general formula (16), X = benzyl [coupler No. C5] of the following formula) Compound)>

10.41 g (0.04 mol) of 2-hydroxy-7,8-naphthalic acid dimethyl ester obtained in Synthesis Example 2 and 8.57 g (0.08 mol) of benzylamine in 100 ml of ethylene glycol under a nitrogen gas stream 140 The stirring reaction was carried out at 6 ° C. for 6 hours. After completion of the reaction and allowing to cool, the reaction product was poured onto ice to make it acidic with hydrochloric acid, and the precipitated crystals were collected by filtration, washed with 500 ml of ion-exchanged water, dried at 60 ° C. under reduced pressure, 10.21 g of product was obtained. The obtained crude product was recrystallized from n-butanol, and 9.57 g (yield 78.9%) of orange coupler compound <coupler No. C5> was obtained. The melting point was 255.2-259.0 ° C. The elemental analysis values are shown in the table below.

(Synthesis Example 5)
<N- (2-phenylethyl) -2-hydroxy-7,8-naphthalimide (R ₁ = R ₂ = R ₃ = R ₄ = H in general formula (16), X = phenylethyl of the following formula [ Production of Compound No. C14]>

The reaction was performed in the same manner as in Synthesis Example 4 except that 8.57 g (0.08 mol) of benzylamine was used and 9.69 g (0.08 mol) of phenethylamine was used to obtain 10.48 g of a crude target product. The obtained crude product was recrystallized from n-butanol, and 9.95 g (yield 78.4%) of yellow coupler compound <coupler No. C14> was obtained. The melting point was 233.5-236.5 ° C. The elemental analysis values are shown in the table below.

(Synthesis Example 6)
<N- (3-Phenylpropyl) -2-hydroxy-7,8-naphthalimide (R ₁ = R ₂ = R ₃ = R ₄ = H in General Formula (16), X = Phenylpropyl of the following formula [ Production of Compound No. C24]>

The reaction was performed in the same manner as in Synthesis Example 4 except that 10.57 g (0.08 mol) of 3-phenylpropylamine was used in the amount of 8.57 g (0.08 mol) of benzylamine to obtain 13.25 g of a crude target product. The obtained crude product was recrystallized from n-butanol to yield 11.17 g (yield 84.3%) of yellow coupler compound <coupler No. C24> was obtained. The melting point was 206.9-212.0 ° C. The elemental analysis values are shown in the table below.

(Synthesis Example 7)
<N-phenyl-2-hydroxy-7,8-naphthalic acid imide (R ₁ = R ₂ = R ₃ = R ₄ = H in general formula (16), X = phenyl of the following formula [coupler No. C28] Compound)>

The reaction was performed in the same manner as in Synthesis Example 4 except that 8.45 g (0.08 mol) of benzylamine was used and 7.45 g (0.08 mol) of aniline was used to obtain 12.04 g of a crude target product. The obtained crude product was recrystallized from n-butanol / toluene (1/1 vol) to give 8.15 g (yield 69.7%) of yellow coupler compound <coupler No. C28> was obtained. The melting point was 245.5-248.9C. The elemental analysis values are shown in the table below.

(Synthesis Example 8)
<12-hydroxy-benzo [6,7] isoindole [2,1-a] perimidin-14-one or 9-hydroxy-benzo [4,5] isoindole [2,1-a] perimidine-14- ON (Production of R ₁ = R ₂ = R ₃ = R ₄ = H, Y = Naphthylene <Coupler No. E23> in the following Formula> in General Formula (18) or General Formula (19)>

2-hydroxy-7,8-naphthalic acid dimethyl ester obtained in Synthesis Example 2 (10.41 g, 0.04 mol) and 1,8-diaminonaphthalene, 12.66 g (0.08 mol), were added to 100 ml of ethylene glycol in nitrogen. Stirring reaction was performed at 160 ° C. for 8 hours under a gas stream. After completion of the reaction and allowing to cool, the reaction product was poured onto ice to make it acidic with hydrochloric acid, and the precipitated crystals were collected by filtration, washed with 500 ml of ion-exchanged water, dried at 60 ° C. under reduced pressure, 9.96 g of product was obtained. The obtained crude product was recrystallized from nitrobenzene, and 8.80 g (yield 65.4%) of red coupler compound <coupler no. E23> was obtained. The decomposition point was 398 ° C. The elemental analysis values are shown in the table below.

Example 1
-Production of Azo Compound (Azo Compound No. P3)-
0.91 g (3 mmol) of N-benzyl-2-hydroxy-7,8-naphthalimide (a compound of coupler No. C5) was dissolved in 100 ml of DMF, and 2,7-diaminodibenzo [a, c ] 0.76 g (1.5 mmol) of dibenzo [a, c] phenazine-2,7-bisdiazonium tetrafluoroborate synthesized from phenazine was added. Subsequently, 4.92 g of 10 mass% sodium acetate aqueous solution was dripped over 10 minutes, and it stirred at room temperature for 6 hours. The resulting precipitate was filtered off and washed 3 times with 120 ml DMF at room temperature and then twice with 120 ml water. It dried under reduced pressure at 70 degreeC and obtained the azo compound (Azo compound No. P3).
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

(Example 2)
-Production of Azo Compound (Azo Compound No. P4)-
0.46 g (1.5 mmol) of N-benzyl-2-hydroxy-7,8-naphthalimide (a compound of coupler No. C5) was dissolved in 60 ml of DMF, and 2,7-diaminodibenzo [a , C] phenazine 0.76 g (1.5 mmol) of dibenzo [a, c] phenazine-2,7-bisdiazonium tetrafluoroborate synthesized from phenazine was added and stirred at room temperature for 30 minutes. Next, a solution consisting of 0.39 g (1.5 mmol) of 2-hydroxy-3-phenylcarbamoylnaphthalene (a compound of coupler No. 17) and 40 ml of DMF is added.
Subsequently, 4.92 g of 10 mass% sodium acetate aqueous solution was dripped over 10 minutes, and it stirred at room temperature for 6 hours. The resulting precipitate was filtered off and washed 3 times with 120 ml DMF at room temperature and then twice with 120 ml water. It dried under reduced pressure at 70 degreeC and obtained the azo compound (Azo compound No. P4).
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

(Example 3)
-Production of Azo Compound (Azo Compound No. P20)-
In Example 1, instead of 0.91 g (3 mmol) of N-benzyl-2-hydroxy-7,8-naphthalimide (a compound of coupler No. C5), N- (2-phenylethyl) -2-hydroxy Production was carried out in the same manner as in Example 1 except that 0.95 g (3 mmol) of -7,8-naphthalimide (a compound of coupler No. C14) was used to obtain an azo compound (azo compound No. P20).
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

Example 4
-Production of Azo Compound (Azo Compound No. P21)-
In Example 1, instead of 0.46 g (1.5 mmol) of N-benzyl-2-hydroxy-7,8-naphthalimide (a compound of coupler No. C5), N- (2-phenylethyl) -2 Produced in the same manner as in Example 1 except that 0.48 g (1.5 mmol) of -hydroxy-7,8-naphthalimide (a compound of coupler No. C14) was used, an azo compound (azo compound No. P21) Got.
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

(Example 5)
-Production of Azo Compound (Azo Compound No. P27)-
In Example 1, instead of 0.91 g (3 mmol) of N-benzyl-2-hydroxy-7,8-naphthalimide (a compound of coupler No. C5), N- (3-phenylpropyl) -2-hydroxy Manufactured in the same manner as in Example 1 except that 0.99 g (3 mmol) of -7,8-naphthalimide (a compound of coupler No. C24) was used, an azo compound (azo compound No. P27) was obtained.
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

(Example 6)
-Production of Azo Compound (Azo Compound No. P28)-
In Example 1, instead of 0.46 g (1.5 mmol) of N-benzyl-2-hydroxy-7,8-naphthalimide (a compound of coupler No. C5), N- (3-phenylpropyl) -2 Produced in the same manner as in Example 1 except that 0.50 g (1.5 mmol) of -hydroxy-7,8-naphthalimide (a compound of coupler No. C24) was used, an azo compound (azo compound No. P28) Got.
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

(Example 7)
-Production of Azo Compound (Azo Compound No. P169)-
0.50 g (1.5 mmol) of N- (3-phenylpropyl) -2-hydroxy-7,8-naphthalimide (a compound of coupler No. C24) was dissolved in 60 ml of DMF, and 2,7 in advance at room temperature. -0.78 g (1.5 mmol) of 11-methyldibenzo [a, c] phenazine-2,7-bisdiazonium tetrafluoroborate synthesized from diamino-11-methyldibenzo [a, c] phenazine was added for 30 minutes. Stir at room temperature. Next, a solution consisting of 0.57 g (1.5 mmol) of 2-hydroxy-3-phenylcarbamoyl-11H-benzo [a] carbazole (a compound of coupler No. 73) and 40 ml of DMF is added. Subsequently, 4.92 g of 10 mass% sodium acetate aqueous solution was dripped over 10 minutes, and it stirred at room temperature for 6 hours. The resulting precipitate was filtered off and washed 3 times with 120 ml DMF at room temperature and then twice with 120 ml water. It dried under reduced pressure at 70 degreeC and obtained the azo compound (Azo compound No.P169).
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

(Example 8)
-Production of Azo Compound (Azo Compound No. P207)-
0.99 g (3 mmol) of N- (3-phenylpropyl) -2-hydroxy-7,8-naphthalimide (coupler No. C24 compound) was dissolved in 100 ml of DMF, and 2,7-diamino was previously prepared at room temperature. 11-Chlordibenzo [a, c] phenazine-2,7-bisdiazonium tetrafluoroborate 0.0.81 g (1.5 mmol) synthesized from -11-chlorodibenzo [a, c] phenazine was added. Subsequently, 4.92 g of 10 mass% sodium acetate aqueous solution was dripped over 10 minutes, and it stirred at room temperature for 6 hours. The resulting precipitate was filtered off and washed 3 times with 120 ml DMF at room temperature and then twice with 120 ml water. It dried under reduced pressure at 70 degreeC and obtained the azo compound (Azo compound No.P207).
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

Example 9
-Production of Azo Compound (Azo Compound No. P209)-
0.50 g (1.5 mmol) of N- (3-phenylpropyl) -2-hydroxy-7,8-naphthalimide (a compound of coupler No. C24) was dissolved in 60 ml of DMF, and 2,7 in advance at room temperature. -0.81 g (1.5 mmol) of 11-chlorodibenzo [a, c] phenazine-2,7-bisdiazonium tetrafluoroborate synthesized from diamino-11-chlorodibenzo [a, c] phenazine was added for 30 minutes. Stir at room temperature. Next, a solution consisting of 0.57 g (1.5 mmol) of 2-hydroxy-3-phenylcarbamoyl-11H-benzo [a] carbazole (a compound of coupler No. 73) and 40 ml of DMF is added. Subsequently, 4.92 g of 10 mass% sodium acetate aqueous solution was dripped over 10 minutes, and it stirred at room temperature for 6 hours. The resulting precipitate was filtered off and washed 3 times with 120 ml DMF at room temperature and then twice with 120 ml water. It dried under reduced pressure at 70 degreeC and obtained the azo compound (Azo compound No. P209).
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

(Example 10)
-Production of Azo Compound (Azo Compound No. P289)-
0.159 g (0.50 mmol) of N- (2-phenylethyl) -2-hydroxy-7,8-naphthalimide (a compound of coupler No. C14) was dissolved in 20 ml of DMSO, 0.268 g (0.50 mmol) of 11,12-dimethyldibenzo [a, c] phenazine-2,7-bisdiazonium tetrafluoroborate synthesized from 7-diamino-11,12-dimethyldibenzo [a, c] phenazine And stirred at room temperature for 10 minutes. Next, a solution consisting of 0.143 g (0.50 mmol) of 2 (5) -hydroxy-7H-benzimidazo [2,1-a] benzisoquinolinone-7 (a compound of coupler No. 195) and 20 ml of DMSO was added. It was. Subsequently, 1.65 g of 10 mass% sodium acetate aqueous solution was dripped over 10 minutes, and it stirred at room temperature for 6 hours. The resulting precipitate was filtered off and washed three times with 60 ml DMSO at room temperature and then twice with 60 ml water. It dried under reduced pressure at 70 degreeC and obtained the azo compound (Azo compound No.P289).
The yield (yield), infrared absorption spectrum, and elemental analysis results for the obtained azo compound are collectively shown in Table 64.

Furthermore, the present invention will be specifically described by the following application examples, but this does not stabilize the embodiment of the present invention.
(Application 1)
7.5 parts by mass of an azo compound of Example 5 (azo compound No. P27) of the present invention and 500 parts by mass of a 0.5% by mass tetrahydrofuran solution of a polyester resin (Byron 200: manufactured by Toyobo) were pulverized and mixed in a ball mill. The obtained dispersion was applied onto an aluminum vapor-deposited polyester film with a doctor blade and naturally dried to form a charge generation layer having a thickness of about 1 μm.
Next, a charge transport layer coating solution of 1 part by mass of a charge transport material represented by the following structural formula (D-1), 1 part by mass of a polycarbonate resin (Panlite K1300: manufactured by Teijin Chemicals) and 8 parts by mass of tetrahydrofuran is prepared, The charge generation layer was coated with a doctor blade and dried at 80 ° C. for 2 minutes and then at 120 ° C. for 5 minutes to form a charge transport layer having a thickness of 20 μm.

  The electrophotographic photosensitive member obtained as described above was subjected to a corona of −6 kV in the dark using an electrostatic copying paper test apparatus EPA-8200 (manufactured by Kawaguchi Electric Manufacturing Co., Ltd.) in an environment of 25 ° C./55% RH. After charging for 20 seconds, the battery is left in a dark place for 20 seconds, and the surface potential V0 (V) at that time is measured. Then, the illuminance on the surface of the photoreceptor is 5.3 lux by a tungsten lamp. Then, the time (second) until the surface potential was reduced to 1/2 of V0 was obtained by calculating the exposure amount E1 / 2 (looks / second). The results were V0 = −1382 volts and E1 / 2 = 1.94 lux · second.

  The production raw material (coupler compound) of the azo compound of the present invention is easier to produce than conventional coupler compounds, and an azo compound using this production raw material (coupler compound) can also be produced easily. Further, by using the azo compound of the present invention as a material for a photosensitive layer, it is possible to provide a highly sensitive electrophotographic photoreceptor.

FIG. 1 is an infrared absorption spectrum of the azo compound of the present invention (Example 1). FIG. 2 is another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 2). FIG. 3 is still another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 3). FIG. 4 is still another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 4). FIG. 5 is still another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 5). FIG. 6 is still another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 6). FIG. 7 is yet another diagram showing the infrared absorption spectrum of the azo compound of the present invention (Example 7). FIG. 8 is yet another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 8). FIG. 9 is yet another diagram showing the infrared absorption spectrum of the azo compound of the present invention (Example 9). FIG. 10 is still another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 10).

Claims (5)

An azo compound represented by the following general formula (1):
However, the general formula (1), r ₁ and r ₂ represent each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a nitro group. Two Cp represent a coupler residue, and one of the two Cp is a coupler residue represented by any one of the following general formula (2) and the following general formula (5). One is a coupler residue represented by any one of the following general formula (2), the following general formula (5), the following general formula (8), and the following general formula (24).
However, in said general formula (2), R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group each independently. However, R ₁ and R ₂ may be bonded to each other to form an unsubstituted alkylene ring, an unsubstituted unsaturated aliphatic ring, or an unsubstituted aromatic ring. These may be further substituted with an alkyl group, an alkoxy group or a halogen atom. X represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyclic unsaturated aliphatic group, an aromatic group, a heterocyclic group, or an amino group.
However, the general formula (5) in, A ₁ represents a non-substituted aromatic group, or unsubstituted heterocyclic group, these alkyl group, alkoxy group, a phenyl group, a halogen atom, a trifluoromethyl group, It may be further substituted with a cyano group, an alkoxycarbonyl group, or a carbamoyl group. m shows the integer of 1-6.
However, in the general formula (8), Z ₁ is condensed with a benzene ring in the formula to form an unsubstituted hydrocarbon ring or condensed with a benzene ring in the formula. Represents a divalent organic residue that forms a substituted heterocycle. These may be further substituted with a halogen atom. R ₁₄ represents a hydrogen atom, an unsubstituted alkyl group, or an unsubstituted phenyl group. Y ₂ represents an unsubstituted hydrocarbon ring group or an unsubstituted heterocyclic group.
However, the general formula (24), y ₂ represents the divalent group of a heterocyclic ring containing divalent group or a nitrogen atom of the aromatic hydrocarbon in the ring. In the general formula (1), one of the two Cp is a coupler residue represented by the following general formula (2) or the following general formula (5), and the other one of Cp is the following general formula ( The azo compound according to claim 1, which is a coupler residue represented by 8).
However, in the general formula (2), R ₁ , R ₂ , R ₃ And R ₄ Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. However, R ₁ And R ₂ May be bonded to each other to form an unsubstituted alkylene ring, an unsubstituted unsaturated aliphatic ring, or an unsubstituted aromatic ring. These may be further substituted with an alkyl group, an alkoxy group or a halogen atom. X represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyclic unsaturated aliphatic group, an aromatic group, a heterocyclic group, or an amino group.
However, in the general formula (5), A ₁ Represents an unsubstituted aromatic group or an unsubstituted heterocyclic group, which are further substituted with an alkyl group, an alkoxy group, a phenyl group, a halogen atom, a trifluoromethyl group, a cyano group, an alkoxycarbonyl group, or a carbamoyl group. May be. m shows the integer of 1-6.
However, in the general formula (8), Z ₁ Is a divalent organic residue that is condensed with a benzene ring in the formula to form an unsubstituted hydrocarbon ring, or a divalent organic residue that is condensed with a benzene ring in the formula to form an unsubstituted heterocyclic ring. Represents a group. These may be further substituted with a halogen atom. R ₁₄ Represents a hydrogen atom, an alkyl group, or a phenyl group. Y ₂ Represents a hydrocarbon ring group or a heterocyclic group. In the general formula (1), one of the two Cp is a coupler residue represented by the following general formula (2) or the following general formula (5), and the other one of Cp is the following general formula ( The azo compound according to claim 1, which is a coupler residue represented by 24).
However, in the general formula (2), R ₁ , R ₂ , R ₃ And R ₄ Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. However, R ₁ And R ₂ May be bonded to each other to form an unsubstituted alkylene ring, an unsubstituted unsaturated aliphatic ring, or an unsubstituted aromatic ring. These may be further substituted with an alkyl group, an alkoxy group or a halogen atom. X represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyclic unsaturated aliphatic group, an aromatic group, a heterocyclic group, or an amino group.
However, in the general formula (5), A ₁ Represents an unsubstituted aromatic group or an unsubstituted heterocyclic group, which are further substituted with an alkyl group, an alkoxy group, a phenyl group, a halogen atom, a trifluoromethyl group, a cyano group, an alkoxycarbonyl group, or a carbamoyl group. May be. m shows the integer of 1-6.
However, in the general formula (24), y ₂ Represents an aromatic hydrocarbon divalent group or a heterocyclic divalent group containing a nitrogen atom in the ring. A method for producing an azo compound according to any one of claims 1 to 3, wherein a diazonium salt compound represented by the following general formula (9) is reacted with a coupler compound represented by the following general formula (10). A process for producing an azo compound characterized by the above.
However, in the general formula (9), r ₁ And r ₂ Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a nitro group. Z ⁻ Represents an anionic group.
HCp General formula (10)
However, in said general formula (10), Cp represents a coupler residue. A photosensitive layer material comprising the azo compound according to claim 1.