JP2004300422A - Azo compound, method for producing the same and material for photosensitive layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new azo compound suitably used as an electrophotographic photosensitive material having high sensitivity in practical use, to provide a method for efficiently producing the azo compound, and to obtain a material for a photosensitive layer. <P>SOLUTION: The azo compound expressed by formula (I) (r<SB>1</SB>and r<SB>2</SB>are each H, a halogen, an alkyl, an alkoxy or nitro; and two Cp's are each a coupler residue) is used as the electrophotographic photosensitive material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

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 since ancient times. For example, they are also used for dyeing fibers, as color materials for color photographic light materials, and recently for photochromic applications. Is a very important group of compounds. This azo compound is generally synthesized by performing a coupling reaction between a “diazonium compound” and a “coupler compound”. Regarding the diazonium compound and the 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 the coupler compound is used. , The absorption wavelength and intensity, the solubility in water, the fastness to light, and the dispersion characteristics for resin are determined.

  In particular, in the field of electrophotographic photoreceptors, certain azo compounds may be useful as organic photoconductors used in laminated photoreceptors, which are one form of electrophotographic photoreceptors, and particularly as charge-generating pigments. Are known. As is well known, the laminated photoreceptor includes a charge generation layer mainly composed of a charge generation pigment capable of generating charge carriers by light on a conductive support, and a charge carrier generated by the charge generation layer thereon. And a charge transporting layer having a charge transporting material as a main component capable of transporting the same. Examples of the azo compound used for such a photoconductor include benzidine-based bisazo compounds (see Patent Documents 1 and 2), stilbenzene-based bisazo compounds (see Patent Document 3), and diphenylhexatriene-based bisazo compounds (see Patent Document 3). Patent Document 4), diphenylbutadiene-based bisazo compounds (see Patent Document 5), and the like are known.

  On the other hand, examples of coupler compounds used in such azo pigments include naphthol-based couplers (see Patent Document 6), benzocarbazole-based couplers (see Patent Document 7), and naphthalimide-based couplers (see Patent Document 8). Perinone-based couplers (see Patent Document 9), azulene-based couplers (see Patent Document 10), anthracene-based couplers (see Patent Document 11), and the like are already known.

  However, conventional photoreceptors using an azo compound generally have low sensitivity and durability, so that they are not always sufficient for practical use, and have been able to satisfy various requirements required for an electrophotographic process. At present, it is desired that the sensitivity and durability be further improved.

JP-A-47-37543 JP-A-52-55643 JP-A-52-8832 JP-A-58-222152 JP-A-58-222153 JP-A-47-37543 JP-A-58-122967 JP-A-54-79632 JP-A-57-176055 JP-A-60-10256 JP-A-61-257953

  The present invention has been made in view of such circumstances, and has as its object to solve the above-described various problems in the related art and achieve the following objects. 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. .

  The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a novel azo compound using a specific coupler can be easily produced, and particularly, it is practically used when used in an electrophotographic photosensitive member. It was found that it had high sensitivity and durability.

ただし、前記一般式（１）中、ｒ_１及びｒ_２は、それぞれ独立して水素原子、ハロゲン原子、アルキル基、アルコキシ基、又はニトロ基を表す。２つのＣｐはカップラー残基を表し、該２つのＣｐの少なくとも１つは下記一般式（２）、下記一般式（３）及び下記一般式（４）のいずれかで表されるカップラー残基である。

ただし、前記一般式（２）、一般式（３）、及び一般式（４）中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して水素原子、ハロゲン原子、アルキル基、又はアルコキシ基を表す。ただし、Ｒ_１とＲ_２は互いに結合して置換又は無置換のアルキレンによる環、置換又は無置換の不飽和脂肪族環、又は置換又は無置換の芳香族環を形成してもよい。Ｘは、水素原子、アルキル基、シクロアルキル基、環状不飽和脂肪族基、芳香族基、複素環基、又はアミノ基を表し、これらは置換基により更に置換されていてもよい。Ｙは、置換又は無置換のアルキレン基、置換又は無置換のシクロアルキレン基、置換又は無置換のアラルキレン基、置換又は無置換の芳香族性を有する２価の有機残基、置換又は無置換の複素芳香族性を有する２価の有機残基、又はＣＯ−Ｚ−で示される２価のカルボニル基含有有機残基（ただし、Ｚは、アルキレン基、シクロアルキレン基、芳香族性を有する２価の有機残基、複素芳香族性を有する２価の有機残基を表し、これらは置換基により更に置換されていてもよい）を表す。
＜２＞ 一般式（１）において、２つのＣｐの少なくとも１つは、下記一般式（５）で表されるカップラー残基である前記＜１＞に記載のアゾ化合物である。

ただし、前記一般式（５）中、Ａ_１は、芳香族基、又は複素環基を表し、これらは置換基により更に置換されていてもよい。ｍは、１〜６の整数を示す。
＜３＞ 一般式（１）において、２つのＣｐの少なくとも１つは、下記一般式（６）、及び下記一般式（７）のいずれかで表されるカップラー残基である前記＜１＞に記載のアゾ化合物である。

ただし、前記一般式（７）中、Ｙは、置換又は無置換のアルキレン基、置換又は無置換のシクロアルキレン基、置換又は無置換のアラルキレン基、置換又は無置換の芳香族性を有する２価の有機残基、置換又は無置換の複素芳香族性を有する２価の有機残基、又はＣＯ−Ｚ−で示される２価のカルボニル基含有有機残基（ただし、Ｚは、アルキレン基、シクロアルキレン基、芳香族性を有する２価の有機残基、複素芳香族性を有する２価の有機残基を表し、これらは置換基により更に置換されていてもよい）を表す。
＜４＞ 一般式（１）において、２つのＣｐの少なくとも１つは、下記一般式（８）で表されるカップラー残基である前記＜１＞に記載のアゾ化合物である。

ただし、前記一般式（８）中、Ｚ_１は、式中のベンゼン環と縮合して置換又は無置換の炭化水素環を形成する２価の有機残基、又は式中のベンゼン環と縮合して置換又は無置換の複素環を形成する２価の有機残基を表す。Ｒ_１４は、水素原子、置換又は無置換のアルキル基、又は置換又は無置換のフェニル基を表す。Ｙ_２は、置換又は無置換の炭化水素環基、又は置換又は無置換の複素環基を表す。
＜５＞ 一般式（１）において、２つのＣｐの少なくとも１つは、下記一般式（２３）及び下記一般式（２４）のいずれかで表されるカップラー残基である前記＜１＞に記載のアゾ化合物である。

ただし、前記一般式（２３）及び一般式（２４）中、ｙ₂は、芳香族炭化水素の２価基又は窒素原子を環内に含む複素環の２価基を表す。これらの環は更に置換基により置換されていてもよい。
＜６＞ 下記一般式（９）で表わされるジアゾニウム塩化合物と、下記一般式（１０）で表わされるカップラー化合物とを反応させることを特徴とするアゾ化合物の製造方法である。

ただし、前記一般式（９）中、ｒ_１及びｒ_２は、それぞれ独立して水素原子、アルキル基、アルコキシ基、ハロゲン原子、又はニトロ基を表す。Ｚ⁻は、アニオン基を表す、
ＨＣｐ 一般式（１０）
ただし、前記一般式（１０）中、Ｃｐは、カップラー残基を表す。
＜７＞ 前記＜１＞から＜５＞のいずれかに記載のアゾ化合物からなることを特徴とする感光層用材料である。 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, in the general formula (1), r ₁ and r ₂ each independently represent 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 of the following general formulas (2), (3) and (4). is there.

However, in the general formulas (2), (3) and (4), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or Represents an alkoxy group. However, R ₁ and R ₂ may combine with 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, and these 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 divalent organic residue having aromaticity, a substituted or unsubstituted A divalent organic residue having a heteroaromatic property, or a divalent carbonyl group-containing organic residue represented by CO-Z- (where Z is an alkylene group, a cycloalkylene group, or a divalent aromatic compound having an aromatic property) And a divalent organic residue having heteroaromaticity, which may be further substituted with a substituent.
<2> In the general formula (1), at least one of the two Cp is the azo compound according to the above <1>, which is a coupler residue represented by the following general formula (5).

However, in the general formula (5), A ₁ represents an aromatic group or a heterocyclic group, which may be further substituted by a substituent. m shows the integer of 1-6.
<3> In the general formula (1), at least one of the two Cp is a coupler residue represented by any of the following general formulas (6) and (7). It is an azo compound described.

In the general formula (7), Y represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted aralkylene group, or a substituted or unsubstituted aromatic divalent group. An organic residue, a substituted or unsubstituted divalent organic residue having a heteroaromatic property, or a divalent carbonyl group-containing organic residue represented by CO-Z- (where Z is an alkylene group, An alkylene group, a divalent organic residue having aromaticity, or a divalent organic residue having heteroaromaticity, which may be further substituted by a substituent.
<4> In the general formula (1), at least one of the two Cp is the azo compound according to the above <1>, which is a coupler residue represented by the following general formula (8).

However, in the general formula (8), Z ₁ is a divalent organic residue that forms a substituted or unsubstituted hydrocarbon ring by condensing with a benzene ring in the formula or a benzene ring in the formula. Represents a divalent organic residue which 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.
<5> The general formula (1), wherein at least one of the two Cp is a coupler residue represented by any of the following general formulas (23) and (24). Is an azo compound.

Here, in the general formulas (23) and (24), y ₂ 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 further substituted by substituents.
<6> A method for producing an azo compound, comprising reacting a diazonium salt compound represented by the following general formula (9) with a coupler compound represented by the following general formula (10).

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. And Z ^- represents an anion group,
HCp General formula (10)
Here, in the general formula (10), Cp represents a coupler residue.
<7> A photosensitive layer material comprising the azo compound according to any one of <1> to <5>.

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

ただし、前記一般式（１）中、ｒ_１及びｒ_２は、それぞれ独立して水素原子、ハロゲン原子、アルキル基、アルコキシ基、又はニトロ基を表す。２つのＣｐはカップラー残基を表し、該２つのＣｐの少なくとも１つは下記一般式（２）、下記一般式（３）及び下記一般式（４）のいずれかで表されるカップラー残基である。

ただし、前記一般式（２）、一般式（３）、及び一般式（４）中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して水素原子、ハロゲン原子、アルキル基、又はアルコキシ基を表す。ただし、Ｒ_１とＲ_２は互いに結合して置換又は無置換のアルキレンによる環、置換又は無置換の不飽和脂肪族環、又は置換又は無置換の芳香族環を形成してもよい。Ｘは、水素原子、アルキル基、シクロアルキル基、環状不飽和脂肪族基、芳香族基、複素環基、又はアミノ基を表し、これらは置換基により更に置換されていてもよい。Ｙは、置換又は無置換のアルキレン基、置換又は無置換のシクロアルキレン基、置換又は無置換のアラルキレン基、置換又は無置換の芳香族性を有する２価の有機残基、置換又は無置換の複素芳香族性を有する２価の有機残基、又はＣＯ−Ｚ−で示される２価のカルボニル基含有有機残基（ただし、Ｚは、アルキレン基、シクロアルキレン基、芳香族性を有する２価の有機残基、複素芳香族性を有する２価の有機残基を表し、これらは置換基により更に置換されていてもよい）を表す。
本発明のアゾ化合物の製造方法は、下記一般式（９）で表わされるジアゾニウム塩化合物と、下記一般式（１０）で表わされるカップラー化合物とを反応させる。

ただし、前記一般式（９）中、ｒ_１、ｒ_２は、それぞれ独立して水素原子、アルキル基、アルコキシ基、ハロゲン原子、又はニトロ基を表わし、Ｚ⁻はアニオン基を表す、
ＨＣｐ 一般式（１０）
ただし、前記一般式（１０）中、Ｃｐはカップラー残基を表す。
以下、本発明のアゾ化合物の製造方法の説明を通じて、本発明のアゾ化合物の詳細も明らかにする。 (Azo compound and production method thereof)
The azo compound of the present invention is represented by the following general formula (1).

However, in the general formula (1), r ₁ and r ₂ each independently represent 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 of the following general formulas (2), (3) and (4). is there.

However, in the general formulas (2), (3) and (4), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or Represents an alkoxy group. However, R ₁ and R ₂ may combine with 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, and these 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 divalent organic residue having aromaticity, a substituted or unsubstituted A divalent organic residue having a heteroaromatic property, or a divalent carbonyl group-containing organic residue represented by CO-Z- (where Z is an alkylene group, a cycloalkylene group, or a divalent aromatic compound having an aromatic property) 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 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, and Z ⁻ represents an anion group.
HCp General formula (10)
Here, in the 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 method for producing the azo compound of the present invention.

The azo compound of the present invention and a 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 subjected to the following reaction (Diels-Alder reaction) to give the following general formula ( A naphthalene compound represented by 13) is obtained.

ただし、前記反応は酸化反応を伴うＤｉｅｌｓ−Ａｌｄｅｒ反応であり、Ｌｉｅｂｉｇｓ Ａｎｎ．Ｃｈｅｍ．，５９５，１（１９５５）には、ハイドロキノン類とヨウ素による反応が、Ｂｅｒ．，６９，１６８６（１９３６）には、ニトロベンゼン溶媒中で、無水マレイン酸による反応が記載されている。本発明においては、ニトロベンゼン溶媒中、アセチレンジカルボン酸エステルによる反応を、反応温度を１００℃〜１６０℃、更に好適には１３０℃〜１５０℃に制御することにより、１段階の反応で、高収率で上記一般式（１３）で表されるナフタレン化合物を得ることができる。

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

ただし、前記一般式（１４）中、Ｒ_６は、ＯＨ基の保護基であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、メチル基、ｉｓｏ−プロピル基、ｔ−ブチル基、ベンジル基、アリル基、メトキシメチル基、テトラヒドロピラニル基、トリメチルシリル基等が挙げられ、これらの中でも、更に好適には、酸触媒下、室温で除去可能なｉｓｏ−プロピル基、ｔ−ブチル基、メトキシメチル基である。前記酸触媒としては、例えば、硫酸、トリフルオロ酢酸、臭化水素酸、メタンスルホン酸、トリフルオロメタンスルホン酸、などを挙げることができる。 Next, the protecting group R ₆ 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) Base).

However, in the general formula (14), R ₆ is not particularly limited as long as it is a protecting group for an OH group, and can be appropriately selected depending on the purpose. Examples thereof include a methyl group, an iso-propyl group, and a t- group. Examples thereof include a butyl group, a benzyl group, an allyl group, a methoxymethyl group, a tetrahydropyranyl group, and a trimethylsilyl group. Among them, more preferably, an iso-propyl group which can be removed at room temperature under 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, and trifluoromethanesulfonic acid.

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 obtain the following general formula (16) ) Can be obtained.

  Generally, the ester / amide exchange reaction is carried out in the presence of a basic catalyst. Am. Chem. Soc. , 71, 1245 (1945) describes that the addition of a glycol-based, water, or glycerol-based solvent 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 a cyclization reaction). In addition, by controlling the reaction temperature in a system containing at least one kind to 100 ° C. to 170 ° C., preferably 110 ° C. to 150 ° C., the coupler compound of the general formula (16) can be obtained in high yield. Can be

  The coupler compound of the following general formula (18) or the following general formula (19) is obtained by synthesizing the naphthalene compound of the above general formula (14) obtained by the above synthesis with the following general formula (17) as shown by the following formula: It is manufactured from the diamine compound of.

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.
The coupler compounds represented by the general formulas (16), (18) and (19) can also be produced by the following method.

即ち、式（１３）のナフタレン化合物を酸触媒存在下で反応させることにより、一般式（２０）で示されるナフタレン化合物を得ることができる。この場合、Ｒ_６は保護基であれば特に制約はないが、メチル基、ｉｓｏ−プロピル基などが一般に使用でき、好適にはメチル基が使用できる。前記酸触媒としては、例えば、臭化水素酸、三臭化ホウ素などを挙げることができる。

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

  Next, the naphthalene compound of the general formula (20) obtained by the synthesis and the amine compound of the general formula (15) are reacted under an acid catalyst to obtain a coupler compound of the general formula (16). it can. As the acid catalyst, for example, acetic acid, sulfuric acid, or the like can be used, and if necessary, water produced by the reaction can be taken out of the reaction system to achieve a more efficient reaction.

  Further, 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 with the diamine compound represented by the general formula (17) under an acid catalyst. It can be obtained by doing. As the acid catalyst, for example, acetic acid, sulfuric acid, or the like can be used, and if necessary, water produced by the reaction can be taken out of the reaction system to achieve a more efficient reaction.

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

  Among the azo compounds 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) is replaced by the general formula (16) , The coupler compound of the general formula (18) or the general formula (19) and the coupler compounds exemplified by the general formulas (Cp1) to (Cp15) described below are reacted in two steps in order, or After isolating the diazonium salt compound obtained by the ring reaction, the compound 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 an alkyl group having 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. Not something. The alkoxy group of r ₁ and r ₂ is preferably an alkoxy group having 1 to 25 carbon atoms, more preferably an alkoxy group having 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. Examples of the halogen atom for r ₁ and r ₂ include a fluorine atom, a chlorine atom, and a bromine atom. Furthermore, Z ^{- may, Cl -, Br -, I} -, BF -, PF -, B (C 6 H 5) 4 -, ClO 4 -, SO 4 2-, AsF 6 -, represented by the following formula group, SbF ₆ ^- denotes an anion functional group, such as, among these, BF ₄ ^- is particularly preferable.

Also, the general formulas (2), (3), (4), (11), (13), (14), (16), and (18) In general formulas (19) and (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 combine with 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 an alkyl group having 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. Not something. The alkoxy group is preferably an alkoxy group having 1 to 25 carbon atoms, more preferably an alkoxy group having 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, 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 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 and an ethoxy group, and a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom. .

In the general formulas (12), (13) and (14), R ₅ is preferably a group having 1 to 25 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, more preferably Examples thereof include an alkyl group having 1 to 8 carbon atoms, an aralkyl group such as a benzyl group, and a substituted alkyl group such as a 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, or 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, but not limited thereto.

  In the general formulas (2), (15) and (16), X represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cyclic group. 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 an alkyl group having 1 to 12 carbon atoms, for example, 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 an octyl group and a decyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 8 carbon atoms, such as a cyclopentyl group and a cyclohexyl group, but is not limited thereto. 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, phenyl, naphthyl, anthracenyl, phenanthrenyl, and pyrenyl. The heterocyclic group contains at least one heteroatom such as nitrogen, oxygen or sulfur in the atoms forming the ring. Group, benzothiazolyl group, imidazolyl group, benzimidazolyl group, indolyl group and the like. Examples of the amino group include an alkylamino group such as a methylamino group and an ethylamino group, an aromatic amino group such as a phenylamino group and a naphthylamino group, and a carbamino group such as an acetylamino group and a benzoylamino group. It is not limited to.

Substituents of these alkyl groups, cycloalkyl groups, cyclic unsaturated aliphatic groups, aromatic groups, heterocyclic groups and amino groups include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; benzyl group Substituted alkenyl 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 An aromatic group such as a phenanthrenyl group or a pyrenyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a hydroxy group; an amino group which may have a substituent; Carboamino groups such as amino group and benzoylamino group; nitro group; cyano group; acetyl group; benzoyl group which may have a substituent; 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. Among these, a coupler residue represented by the general formula (5) is preferable. 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, phenyl, naphthyl, anthracenyl, phenanthrenyl, and pyrenyl. . The heterocyclic group includes at least one heteroatom such as nitrogen, oxygen, and sulfur in the atoms forming the ring. Benzothiazolyl group, imidazolyl group, benzimidazolyl group, indolyl group and the like. Examples of the amino group include an alkylamino group such as a methylamino group and an ethylamino group; an aromatic amino group such as a phenylamino group and a naphthylamino group; and an carbamino group such as an acetylamino group and a benzoylamino group. It is not limited. Examples of the substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; a substituted alkyl group such as a benzyl group, a phenethyl group and a methoxymethyl group; and an alkoxy group such as a methoxy group, an ethoxy group, and a phenoxy group. A phenyl group which may have a substituent, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a trifluoromethyl group, a cyano group, an alkoxycarbonyl group, and a carbamoyl group which may have a substituent. Can be

  In the general formulas (3), (4), (6), (7), (18) and (19), Y represents a substituted or unsubstituted alkylene group. Substituted or unsubstituted cycloalkylene group, substituted or unsubstituted aralkylene group, substituted or unsubstituted aromatic divalent organic residue, substituted or unsubstituted heteroaromatic divalent organic residue Or a divalent carbonyl group-containing organic residue represented by CO—Z— (where Z is a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted aromatic group) Or a divalent organic residue having a substituted or unsubstituted heteroaromatic property, wherein the alkylene group preferably has 1 to 25 carbon atoms, and more preferably has 1 to 25 carbon atoms. 1-12 alkylene groups, for example, methylene And alkylene groups such as, but not limited to, ethylene groups, propylene groups, butylene groups, pentylene groups, hexylene groups, octylene groups, decylene groups, etc. The alkylene group forms an aromatic ring at its carbon-carbon bond. The cycloalkylene group is preferably a cycloalkylene group having 5 to 8 carbon atoms, such as, but not limited to, a cyclopentylene group and a cyclohexylene group. An aralkylene group having 7 to 20 carbon atoms, such as, for example, a toluylene group, a xylylene group, an ethylenephenyleneethylene group, a phenylenemethylene group, and a phenyleneethylene group, but is not limited thereto. The residue is preferably an aryl group having 6 to 30 carbon atoms or an aryl group. A group in which a saturated aliphatic ring or unsaturated aliphatic ring is further condensed to the skeleton of the group, 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 aromatic property includes at least a heteroatom such as nitrogen, oxygen or sulfur as an atom forming a ring. In addition to the heterocyclic aromatic group, the skeleton of the heterocyclic aromatic group further includes a condensed saturated aliphatic ring, unsaturated aliphatic ring, or heterocyclic ring. -Pyrazolediyl group, 2,3-pyridinediyl group, 5,6-pyrimidindiyl group, 6,7-benzimidazolediyl group, 6,7quinolinediyl group, etc., but not limited thereto, including carbonyl group Examples of the divalent organic residue include a 2-benzoyl group and a 2-naphthylcarbonyl group, but are not limited thereto.

  Substituents of these alkylene group, cycloalkylene group, aralkylene group, divalent organic residue having aromaticity, and divalent organic residue having heteroaromaticity include a methyl group, an ethyl group, and a propyl group. An alkyl group such as a butyl group, a substituted alkyl group such as a benzyl group, a phenethyl group and a methoxymethyl group; an alkoxy group such as a methoxy group, an ethoxy group and a phenoxy group; a phenyl group which may have a substituent; Aromatic groups such as naphthyl group, anthracenyl group, phenanthrenyl group and pyrenyl group which may be present, halogen atoms such as fluorine atom, chlorine atom and bromine atom, hydroxy group, amino group which may have a substituent, acetyl Amino group, carboxyamino group such as benzoylamino group which may have a substituent, nitro group, cyano group, acetyl group, having a 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 formulas (3) and (4), the coupler residues represented by the general formulas (6) and (7) are preferable, and among these, Y is substituted. Alternatively, a coupler residue which is an unsubstituted alkylene group or a substituted or unsubstituted carbonyl group-containing divalent organic residue is preferable, and among these, Y is particularly preferably represented by the following general formulas (21) and (22). The indicated coupler residues are preferred.

  B1 in the general formula (21) and B2 in the general formula (22) each represent, for example, a divalent group of an aromatic hydrocarbon ring such as an o-phenylene group or a 2,3-naphthylene group, for example, 2, Represents a divalent group of an aromatic heterocyclic ring such as a 3-pyrinyl group, a 3,4-pyrazolyl group, a 2,3-pyridineyl group, a 4,5-pyridineyl group, a 4,5-imidazoleyl group, and substitution thereof. Examples of the group 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, and a phenoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; and a nitro group. Is mentioned.

  Hereinafter, examples of the novel coupler (Cp) of the present invention will be described.

  In Cp of the general formula (1), examples of the coupler residue which may coexist in addition to the coupler residues represented by the general formulas (2), (3) and (4) include: For example, phenols, compounds having a phenolic hydroxyl group such as naphthols, aromatic amino compounds having an amino group or aminonaphthols having an amino group and a phenolic hydroxyl group, having an aliphatic or aromatic enol ketone group And a compound (a compound having an active methylene group). Preferably, the coupler residue Cp has the following general formula (Cp1), general formula (Cp2), general formula (Cp3), general formula (Cp4) or general formula (Cp4). 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).

ただし、前記一般式（Ｃｐ１）、一般式（Ｃｐ２）、一般式（Ｃｐ３）、及び一般式（Ｃｐ４）中、Ｘ_１、Ｙ_１、Ｚ_１、ｌ及びｍは、それぞれ以下のものを表す。

However, 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は−ＯＨ又はＮＨＳＯ_２−Ｒ_１３を表す。
ただし、Ｒ_１１及びＲ_１２は水素原子又は置換もしくは無置換のアルキル基を表し、Ｒ_１３は置換もしくは無置換のアルキル基又は置換もしくは無置換のアリール基を表す。
Ｙ_１は水素原子、ハロゲン、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、スルホ基、置換もしくは無置換のスルファモイル基又は下記式で表される機を表す。

X ₁ represents -OH or NHSO ₂ -R _13.
Here, R ₁₁ and R ₁₂ represent a hydrogen atom or a substituted or unsubstituted alkyl group, and 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.

ただし、Ｒ_１４は水素原子、アルキル基又はその置換体、フェニル基又はその置換体を表わし、Ｙ_２は炭化水素環基又はその置換体、複素環基又はその置換体、あるいは、下記式で表される基を表す。

Here, R ₁₄ represents a hydrogen atom, an alkyl group or a substituted product thereof, a phenyl group or a substituted product thereof, and Y ₂ represents a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or a compound represented by the following formula. Represents a group to be formed.

ただし、Ｒ_１５は炭化水素環基又はその置換体、複素環基又はその置換体、あるいはスチリル基又はその置換体、Ｒ_１６は水素原子、アルキル基、フェニル基又はその置換体を表すか、あるいはＲ_１５及びＲ_１６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。
Ｚ_１は炭化水素環又はその置換体あるいは複素環又はその置換体を表す。
ｌは１又は２の整数である。
ｍは、１又は２の整数である。

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 to which they are attached.
Z ₁ represents a hydrocarbon ring or a substituted body thereof, or a heterocyclic ring or a substituted body thereof.
l is an integer of 1 or 2.
m is an integer of 1 or 2.

ただし、式（Ｃｐ５）中、Ｒ_１７は置換もしくは、無置換の炭化水素基を表わし、Ｘ_１は前記に同じである。

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

ただし、式（Ｃｐ６）中、Ｙ_２は芳香族炭化水素の２価基又は窒素原子を環内に含む複素環の２価基を表す。これらの環は、置換又は無置換でもよい。Ｘ_１は前記に同じである。

Here, in the formula (Cp6), Y ₂ 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 ₁ is as defined above.

ただし、式（Ｃｐ７）中、Ｒ_１８はアルキル基、カルバモイル基、カルボキシ基又はそのエステルを表わし、Ａｒ_１は炭化水素環基又はその置換体を表わし、Ｘ_１は前記と同じである。

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.

ただし、上記一般式（Ｃｐ８）及び一般式（Ｃｐ９）中、Ｒ_１９は水素原子又は置換もしくは無置換の炭化水素基を表わし、Ａｒ_２は炭化水素環基又はその置換体を表す。

However, in the general formulas (Cp8) and (Cp9), R ₁₉ 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 Z1 in the general formula (Cp1), the general formula (Cp2), the general formula (Cp3) or the general formula (Cp4) include a benzene ring and a naphthalene ring. Examples of the heterocyclic ring which may have a substituent include an indole ring, a carbazole ring, a benzolane ring, a dibenzofuran ring and the like. The substituent in the ring of Z ₁ may be exemplified halogen atom such as chlorine atom, a 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. And a ring formed by combining R ₁₅ and R ₁₆ with each other, and 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 an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a methoxy group, Alkoxy groups such as ethoxy group, propoxy group and 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, and cyano group , a carboxyl group or an ester thereof, a hydroxyl group, such as sulfonate groups, such as _-SO 3 Na and the like.

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

Representative examples of the hydrocarbon group represented by 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, and 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, Examples thereof include a halogen atom such as a bromine atom, a hydroxyl group, and a nitro group.

Representative 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 thereof include an alkoxy group such as an alkyl group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group, a halogen atom such as a nitro group, a chlorine atom and a bromine atom, and a dialkylamino group such as a cyano group, a dimethylamino group and a diethylamino group. .
Further, among 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 preferable. Of these, X ₁ in the general formula is preferably a hydroxyl group. Further, among the coupler residues represented by the general formula (Cp2), a coupler residue represented by the general formula (Cp10) is particularly preferable.

ただし、Ｙ_１及びＺ_１は前記に同じである。
さらに好ましくは一般式で表わされるカップラー残基である。

However, Y ₁ and Z ₁ are the same as described above.
More preferred are coupler residues represented by the general formula.

ただし、Ｚ_１、Ｙ_２及びＲ_１２は前記と同じである。

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

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

ただし、Ｚ_１、Ｒ_１４、Ｒ_１５及びＲ_１６は前記と同じである。また、Ｒ_２０としては上記のＹ_２の置換基が例示できる。
また、前記一般式（Ｃｐ６）で示されるカップラー残基の中でも、特に下記一般式（Ｃｐ１４）あるいは下記一般式（Ｃｐ１５）で示されるカップラー残基が好ましい。

ただし、前記一般式（Ｃｐ１４）及び（Ｃｐ１５）中、Ｗ_１は、芳香族炭化水素の２価基又は窒素原子を環内に含む複素環の２価基を表す。これらの環は、置換又は無置換でもよい。

However, Z ₁ , R ₁₄ , R ₁₅ and R ₁₆ are the same as described above. Examples of R ₂₀ include the substituents of Y ₂ described above.
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.

  Below, the example of a coupler residue (Cp) is shown.

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

  Next, the present invention will be specifically described with reference to examples, but the embodiments of the present invention are not limited thereto.

(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)) compounds of H ₉₎ manufacturing>
35.25 g (0.2 mol) of pt-butoxystyrene and 56.84 g (0.4 mol) of dimethyl acetylenedicarboxylate are dissolved in 200 ml of nitrobenzene, reacted at 140 ° C. for 5 hours, and allowed to cool. Further, after nitrobenzene was distilled off 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. Was.
Next, the product was recrystallized from diisopropyl ether to obtain 36.63 g (yield 57.9%) of the target naphthalene compound. Melting point was 82.0-83.0 ° C. Elemental analysis values are shown in the table below.

(Synthesis example 2)
<Production of 2-hydroxy-7,8-naphthalic acid dimethyl ester (compound of general formula (14) in which R ₁ = R ₂ = R ₃ = R ₄ = H, R ₅ = CH ₃ )>
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) was added dropwise over 10 minutes, and the stirring reaction was continued for 3 hours under the same conditions (room temperature). After the reaction, the reaction product is poured on ice, water is added, and the phases are separated. The methylene chloride phase is washed twice more with water and dried over anhydrous magnesium sulfate. Magnesium sulfate was removed by filtration, and the residue from which methylene chloride was distilled off 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. 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 the general formula (16), X = C ₆ H ₁₃ -n [coupler No. Production of Compound C1])>
Nitrogen gas stream of 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 in 100 ml of ethylene glycol A stirring reaction was performed at 120 ° C. for 4 hours. After completion of the reaction and cooling, the reaction product was poured on ice, acidified with hydrochloric acid, and the precipitated crystals were collected by filtration, washed with 500 ml of ion-exchanged water, and dried at 60 ° C. under reduced pressure to obtain a crude product. 9.73 g were 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 a yellow coupler compound < Coupler No. C1> was obtained. The melting point was 165.5-166.5 ° C. Elemental analysis values are shown in the table below.

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

合成例２で得られた２−ヒドロキシ−７，８−ナフタル酸ジメチルエステル１０．４１ｇ（０．０４ｍｏｌ）、及びベンジルアミン８．５７ｇ（０．０８ｍｏｌ）をエチレングリコール１００ｍｌ中、窒素ガス気流下１４０℃で６時間、攪拌反応を行なった。反応終了、放冷後、反応物を氷上に注ぎ、塩酸酸性とした後、析出した結晶をろ取し、５００ｍｌのイオン交換水で洗浄後、６０℃で減圧下に乾燥して、粗製の目的物１０．２１ｇを得た。得られた粗製物をｎ−ブタノールより再結晶して９．５７ｇ（収率７８．９％）の橙色のカップラー化合物＜カップラーＮｏ．Ｃ５＞を得た。融点は、２５５．２〜２５９．０℃であった。元素分析値を下表に示す。

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 were added to 100 ml of ethylene glycol in a nitrogen gas stream at 140 g. Stirring reaction was performed at 6 ° C. for 6 hours. After the reaction was completed and allowed to cool, the reaction product was poured onto ice, acidified with hydrochloric acid, and the precipitated crystals were collected by filtration, washed with 500 ml of ion-exchanged water, and dried at 60 ° C. under reduced pressure to obtain a crude product. 10.21 g of the product were obtained. The obtained crude product was recrystallized from n-butanol to give 9.57 g (yield 78.9%) of an orange coupler compound <coupler No. C5> was obtained. Melting point was 255.2-259.0 ° C. 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 the general formula (16), X = phenylethyl of the following formula [ Production of Compound No. C14]>

ベンジルアミン８．５７ｇ（０．０８ｍｏｌ）をフェネチルアミン９．６９ｇ（０．０８ｍｏｌ）使用する以外は、合成例４と同様に反応して、粗製の目的物１０．４８ｇを得た。得られた粗製物をｎ−ブタノールより再結晶して９．９５ｇ（収率７８．４％）の黄色のカップラー化合物＜カップラーＮｏ．Ｃ１４＞を得た。融点は、２３３．５〜２３６．５℃であった。元素分析値を下表に示す。

The same reaction as in Synthesis Example 4 was carried out except that 8.57 g (0.08 mol) of benzylamine and 9.69 g (0.08 mol) of phenethylamine were used to obtain 10.48 g of a crude target product. The obtained crude product was recrystallized from n-butanol to give 9.95 g (yield 78.4%) of a yellow coupler compound <coupler No. C14> was obtained. The melting point was 233.5-236.5 ° C. 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 the general formula (16), X = phenylpropyl of the following formula [ Production of Compound of Coupler No. C24]>

ベンジルアミン８．５７ｇ（０．０８ｍｏｌ）を３−フェニルプロピルアミン１０．８２ｇ（０．０８ｍｏｌ）使用する以外は、合成例４と同様に反応して、粗製の目的物１３．２５ｇを得た。得られた粗製物をｎ−ブタノールより再結晶して１１．１７ｇ（収率８４．３％）の黄色のカップラー化合物＜カップラーＮｏ．Ｃ２４＞を得た。融点は、２０６．９〜２１２．０℃であった。元素分析値を下表に示す。

Except that 8.57 g (0.08 mol) of benzylamine was used and 10.82 g (0.08 mol) of 3-phenylpropylamine, the reaction was carried out in the same manner as in Synthesis Example 4 to obtain 13.25 g of a crude target product. The obtained crude product was recrystallized from n-butanol to obtain 11.17 g (yield: 84.3%) of a yellow coupler compound <coupler No. C24> was obtained. Melting point was 206.9-212.0 ° C. Elemental analysis values are shown in the table below.

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

ベンジルアミン８．５７ｇ（０．０８ｍｏｌ）をアニリン７．４５ｇ（０．０８ｍｏｌ）使用する以外は、合成例４と同様に反応して、粗製の目的物１２．０４ｇを得た。得られた粗製物をｎ−ブタノール／トルエン（１／１ｖｏｌ）より再結晶して、８．１５ｇ（収率６９．７％）の黄色のカップラー化合物＜カップラーＮｏ．Ｃ２８＞を得た。融点は、２４５．５〜２４８．９℃であった。元素分析値を下表に示す。

The same reaction as in Synthesis Example 4 was carried out except that 8.57 g (0.08 mol) of benzylamine and 7.45 g (0.08 mol) of aniline were 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 a yellow coupler compound <coupler No. C28> was obtained. The melting point was 245.5-248.9 ° C. 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 Preparation of ON (R ₁ ＲR ₂ ＲR ₃ R ₄ ＹH in the general formula (18) or the general formula (19), Y = a compound of naphthylene <coupler No. E23> of the following formula)>

合成例２で得られた２−ヒドロキシ−７，８−ナフタル酸ジメチルエステル１０．４１ｇ（０．０４ｍｏｌ）、及び１，８−ジアミノナフタレン１２．６６ｇ（０．０８ｍｏｌ）をエチレングリコール１００ｍｌ中、窒素ガス気流下１６０℃で８時間、攪拌反応を行なった。反応終了、放冷後、反応物を氷上に注ぎ、塩酸酸性とした後、析出した結晶をろ取し、５００ｍｌのイオン交換水で洗浄後、６０℃で減圧下に乾燥して、粗製の目的物９．９６ｇを得た。得られた粗製物をニトロベンゼンより再結晶して８．８０ｇ（収率６５．４％）の赤色のカップラー化合物＜カップラーＮｏ．Ｅ２３＞を得た。分解点は３９８℃であった。元素分析値を下表に示す。

10.41 g (0.04 mol) of 2-hydroxy-7,8-naphthalic acid dimethyl ester obtained in Synthesis Example 2 and 12.66 g (0.08 mol) of 1,8-diaminonaphthalene in 100 ml of ethylene glycol were mixed with nitrogen. A stirring reaction was performed at 160 ° C. for 8 hours under a gas stream. After the reaction was completed and allowed to cool, the reaction product was poured onto ice, acidified with hydrochloric acid, and the precipitated crystals were collected by filtration, washed with 500 ml of ion-exchanged water, and dried at 60 ° C. under reduced pressure to obtain a crude product. 9.96 g of the product were obtained. The obtained crude product was recrystallized from nitrobenzene to obtain 8.80 g (yield 65.4%) of a red coupler compound <coupler No. E23> was obtained. The decomposition point was 398 ° C. 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 (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. Then, 4.92 g of a 10% by mass aqueous sodium acetate solution was added dropwise over 10 minutes, and the mixture was stirred and reacted at room temperature for 6 hours. The formed precipitate was separated by filtration, washed three times with 120 ml of DMF at room temperature, and then twice with 120 ml of water. Drying at 70 ° C. under reduced pressure gave an azo compound (azo compound No. P3).
The yield (yield), infrared absorption spectrum, and elemental analysis result of 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 (compound of coupler No. C5) was dissolved in 60 ml of DMF, and 2,7-diaminodibenzo [a , C] phenazine synthesized, and 0.76 g (1.5 mmol) of dibenzo [a, c] phenazine-2,7-bisdiazonium tetrafluoroborate was added, followed by stirring at room temperature for 30 minutes. Next, a solution consisting of 0.39 g (1.5 mmol) of 2-hydroxy-3-phenylcarbamoylnaphthalene (the compound of coupler No. 17) and 40 ml of DMF is added.
Then, 4.92 g of a 10% by mass aqueous sodium acetate solution was added dropwise over 10 minutes, and the mixture was stirred and reacted at room temperature for 6 hours. The formed precipitate was separated by filtration, washed three times with 120 ml of DMF at room temperature, and then twice with 120 ml of water. Drying under reduced pressure at 70 ° C. gave an azo compound (azo compound No. P4).
The yield (yield), infrared absorption spectrum, and elemental analysis result of the obtained azo compound are collectively shown in Table 64.

(Example 3)
-Production of azo compound (azo compound No. P20)-
In Example 1, N- (2-phenylethyl) -2-hydroxy was replaced with 0.91 g (3 mmol) of N-benzyl-2-hydroxy-7,8-naphthalimide (compound of coupler No. C5). An azo compound (azo compound No. P20) was obtained in the same manner as in Example 1, except that 0.95 g (3 mmol) of -7,8-naphthalic acid imide (compound of coupler No. C14) was used.
The yield (yield), infrared absorption spectrum, and elemental analysis result of the obtained azo compound are collectively shown in Table 64.

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

(Example 5)
-Production of azo compound (azo compound No. P27)-
In Example 1, N- (3-phenylpropyl) -2-hydroxy was replaced with 0.91 g (3 mmol) of N-benzyl-2-hydroxy-7,8-naphthalimide (compound of coupler No. C5). An azo compound (azo compound No. P27) was obtained in the same manner as in Example 1, except that 0.99 g (3 mmol) of -7,8-naphthalic acid imide (the compound of coupler No. C24) was used.
The yield (yield), infrared absorption spectrum, and elemental analysis result of the obtained azo compound are collectively shown in Table 64.

(Example 6)
-Production of azo compound (azo compound No. P28)-
In Example 1, N- (3-phenylpropyl) -2 was used instead of 0.46 g (1.5 mmol) of N-benzyl-2-hydroxy-7,8-naphthalimide (the compound of coupler No. C5). An azo compound (azo compound No. P28) was produced in the same manner as in Example 1 except that 0.50 g (1.5 mmol) of -hydroxy-7,8-naphthalimide (the compound of coupler No. C24) was used. Got.
The yield (yield), infrared absorption spectrum, and elemental analysis result of 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 (compound of coupler No. C24) is dissolved in 60 ml of DMF and 2,7 g 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, and the mixture was added for 30 minutes. Stirred at room temperature. Next, a solution consisting of 0.57 g (1.5 mmol) of 2-hydroxy-3-phenylcarbamoyl-11H-benzo [a] carbazole (compound of coupler No. 73) and 40 ml of DMF is added. Then, 4.92 g of a 10% by mass aqueous sodium acetate solution was added dropwise over 10 minutes, and the mixture was stirred and reacted at room temperature for 6 hours. The formed precipitate was separated by filtration, washed three times with 120 ml of DMF at room temperature, and then twice with 120 ml of water. Drying under reduced pressure at 70 ° C. gave an azo compound (azo compound No. P169).
The yield (yield), infrared absorption spectrum, and elemental analysis result of 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 (compound of coupler No. C24) is dissolved in 100 ml of DMF, and 2,7-diamino 11-Chlorodibenzo [a, c] phenazine-2,7-bisdiazonium tetrafluoroborate 0.0.81 g (1.5 mmol) synthesized from -11-chlorodibenzo [a, c] phenazine was added. Then, 4.92 g of a 10% by mass aqueous sodium acetate solution was added dropwise over 10 minutes, and the mixture was stirred and reacted at room temperature for 6 hours. The formed precipitate was separated by filtration, washed three times with 120 ml of DMF at room temperature, and then twice with 120 ml of water. Drying at 70 ° C. under reduced pressure gave an azo compound (azo compound No. P207).
The yield (yield), infrared absorption spectrum, and elemental analysis result of 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 (compound of coupler No. C24) is dissolved in 60 ml of DMF and 2,7 g 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, and the mixture was added for 30 minutes. Stirred at room temperature. Next, a solution consisting of 0.57 g (1.5 mmol) of 2-hydroxy-3-phenylcarbamoyl-11H-benzo [a] carbazole (compound of coupler No. 73) and 40 ml of DMF is added. Then, 4.92 g of a 10% by mass aqueous sodium acetate solution was added dropwise over 10 minutes, and the mixture was stirred and reacted at room temperature for 6 hours. The formed precipitate was separated by filtration, washed three times with 120 ml of DMF at room temperature, and then twice with 120 ml of water. Drying under reduced pressure at 70 ° C. gave an azo compound (azo compound No. P209).
The yield (yield), infrared absorption spectrum, and elemental analysis result of 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 (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 Was added 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 (the compound of coupler No. 195) and 20 ml of DMSO was added. Was. Then, 1.65 g of a 10% by mass aqueous sodium acetate solution was added dropwise over 10 minutes, and the mixture was stirred and reacted at room temperature for 6 hours. The resulting precipitate was filtered off, washed three times with 60 ml of DMSO at room temperature, and then twice with 60 ml of water. Drying at 70 ° C. under reduced pressure gave an azo compound (azo compound No. P289).
The yield (yield), infrared absorption spectrum, and elemental analysis result of the obtained azo compound are collectively shown in Table 64.

Further, the present invention will be specifically described with reference to the following application examples, but this does not stabilize the embodiments of the present invention.
(Application Example 1)
7.5 parts by mass of an azo compound of Example 5 of the present invention (azo compound No. P27) and 500 parts by mass of a 0.5% by mass tetrahydrofuran solution of a polyester resin (Vylon 200: Toyobo) were pulverized and mixed in a ball mill. The resulting dispersion was applied onto an aluminum-evaporated polyester film with a doctor blade and air-dried to form a charge generating 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 was prepared. The composition was coated on the charge generation layer 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 photoreceptor thus obtained was subjected to a corona of -6 kV in a dark place using an electrostatic copying paper tester EPA-8200 (manufactured by Kawaguchi Electric Works) in an environment of 25 ° C./55% RH. After discharging for 20 seconds to charge, the device is left in a dark place for another 20 seconds, the surface potential V0 (V) at that time is measured, and then the illuminance of the photosensitive member surface is adjusted to 5.3 lux by a tungsten lamp. Then, a time (sec) until the surface potential becomes 1/2 of V0 was determined, and an exposure amount E1 / 2 (lux · sec) was calculated. The result was V0 = -1382 volts, E1 / 2 = 1.94 lux-seconds.

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

FIG. 1 is a diagram showing 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 yet 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 yet another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 5). FIG. 6 is yet another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 6). FIG. 7 is yet another diagram showing an 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 yet another diagram showing an infrared absorption spectrum of the azo compound of the present invention (Example 10).

Claims (7)

An azo compound represented by the following general formula (1).

However, in the general formula (1), r ₁ and r ₂ each independently represent 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 of the following general formulas (2), (3) and (4). is there.

However, in the general formulas (2), (3) and (4), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or Represents an alkoxy group. However, R ₁ and R ₂ may combine with 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, and these 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 divalent organic residue having aromaticity, a substituted or unsubstituted A divalent organic residue having a heteroaromatic property, or a divalent carbonyl group-containing organic residue represented by CO-Z- (where Z is an alkylene group, a cycloalkylene group, or a divalent aromatic compound having an aromatic property) And a divalent organic residue having heteroaromaticity, which may be further substituted with a substituent. The azo compound according to claim 1, wherein, in the general formula (1), at least one of the two Cp is a coupler residue represented by the following general formula (5).

However, in the general formula (5), A ₁ represents an aromatic group or a heterocyclic group, which may be further substituted by a substituent. m shows the integer of 1-6. The azo compound according to claim 1, wherein in the general formula (1), at least one of the two Cp is a coupler residue represented by any of the following general formulas (6) and (7). .

In the general formula (7), Y represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted aralkylene group, or a substituted or unsubstituted aromatic divalent group. An organic residue, a substituted or unsubstituted divalent organic residue having a heteroaromatic property, or a divalent carbonyl group-containing organic residue represented by CO-Z- (where Z is an alkylene group, An alkylene group, a divalent organic residue having aromaticity, or a divalent organic residue having heteroaromaticity, which may be further substituted by a substituent. The azo compound according to claim 1, wherein in the general formula (1), at least one of the two Cp is a coupler residue represented by the following general formula (8).

However, in the general formula (8), Z ₁ is a divalent organic residue that forms a substituted or unsubstituted hydrocarbon ring by condensing with a benzene ring in the formula or a benzene ring in the formula. Represents a divalent organic residue which 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. The azo compound according to claim 1, wherein in the general formula (1), at least one of the two Cp is a coupler residue represented by any of the following general formulas (23) and (24).

Here, in the general formulas (23) and (24), y ₂ 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 further substituted by substituents. A method for producing an azo compound, comprising reacting a diazonium salt compound represented by the following general formula (9) with a coupler compound represented by the following general formula (10).

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. And Z ^- represents an anion group,
HCp General formula (10)
Here, in the general formula (10), Cp represents a coupler residue. A photosensitive layer material comprising the azo compound according to claim 1.

Images