KR100506022B1 - Condensed azo compound and process for producing the same - Google Patents

Abstract

The present invention uses a bisamide compound of 2-hydroxynaphthalene-3,6-dicarboxylic acid, amide, or ester as a coupler, and has a novel condensed azo having excellent properties such as excellent water resistance, chemical resistance, solvent resistance and heat resistance. To provide a compound.

Description

A condensed azo compound and its manufacturing method {CONDENSED AZO COMPOUND AND PROCESS FOR PRODUCING THE SAME}

The present invention relates to novel condensed azo compounds and their preparation.

In recent years, development of new pigments and dyes and the like has been actively carried out in order to impart and improve high added value of paints, inks, photosensitive materials, and the like, and in particular, light resistance, solvent resistance, water resistance, chemical resistance, and the like. As a specific example, the condensed azo compound (for example, chromophthal scarlet RN or BRN; Japanese Unexamined-Japanese-Patent No. 48-11205 etc.) which uses bisamide of 2-hydroxy naphthalene-3-carboxylic acid as a raw material, and 2 Condensed azo compounds (for example, JP-A-7-238231) which use bisamides of -hydroxynaphthalene-6-carboxylic acid as a raw material are already known.

1 is an infrared absorption spectrum of a compound obtained in Example 1. FIG.

2 is an infrared absorption spectrum of the compound obtained in Example 38.

3 is an infrared absorption spectrum of the compound obtained in Example 39.

4 is an infrared absorption spectrum of the compound obtained in Example 40. FIG.

5 is an infrared absorption spectrum of the compound obtained in Example 41.

6 is an infrared absorption spectrum of the compound obtained in Example 42.

7 is an infrared absorption spectrum of the compound obtained in Example 43.

8 is an infrared absorption spectrum of the compound obtained in Example 44.

9 is an infrared absorption spectrum of the compound obtained in Example 45.

Hereinafter, an Example is given and this invention is demonstrated. In the examples, those used in parts or% represent parts by weight or% by weight unless otherwise indicated.

The present invention is characterized by obtaining an azo colorant having excellent water resistance, chemical resistance, solvent resistance, heat resistance and the like. Moreover, an object of this invention is to obtain the azo compound which can adjust a hue and sharpness by selecting a substituent suitably.

The present invention provides a novel condensed azo compound using a bisamide compound obtained as a raw material of 2-hydroxynaphthalene-3,6-dicarboxylic acid as a coupler, a colorant containing the same, and a method for producing the condensed azo compound. That is, the present invention relates to a condensed azo compound represented by the following formula [I], [II] or [III], a preparation method thereof, and a colorant containing the condensed azo compound:

[Wherein Y represents-(CONH) _n -X or -COR,

Y 'represents-(CONH) _n -X' or -COR ',

Each of X and X 'represents an alkyl group having 1 to 16 carbon atoms which may have a side chain, an aromatic group which may have a substituent, or a heterocyclic group having a conjugated double bond which may have a substituent,

n represents an integer of 1 or 2,

R and R 'each represent a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms which may have a side chain, a benzyloxy group, a phenyloxy group or a phenacyloxy group, provided that either R or R' is a hydroxyl group. May form an acceptable salt),

R ₂ and R ₂ ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a side chain, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group,

Q and Q 'are each an alkyl group having 1 to 6 carbon atoms which may have a side chain, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a halogen atom, a nitro group or a nitroso group,

m and m 'each represent an integer of 0 to 3, provided that when m or m' is 1, Q or Q 'may be bonded to either of two condensed rings, and m or m' is 2 or 3 May be bonded to one or both condensed rings, and may form a ring together with two condensed rings),

A represents a cyclic group having a C2-C12 alkylene group or a conjugated double bond which may have a side chain,

Z and Z 'each represents a monovalent aromatic group which may have a substituent.

The condensed azo compound of the present invention has a non-condensed amide group, a hydroxyl group or an alkoxy group, and when the amide group is an aromatic amide group, color and clarity can be adjusted by introducing an appropriate substituent to this aromatic group. In the present specification, the color material refers to dyes, pigments, inks, paints, printing inks, organic photoconductive materials and the like.

The present invention is also characterized by coupling an aromatic diazonium compound represented by the following formula [VII] or [VIIa] with a bisamide compound represented by the following formula [VIII], [IX] or [X] A method for preparing a condensed azo compound represented by the following formula [I], [II] or [III]:

[Formula VII]

Formula VIIa]

[Wherein, Z and Z 'each represent a monovalent aromatic group which may have a substituent];

[Formula VIII]

[Formula IX]

[Formula X]

[Wherein Y represents-(CONH) _n -X or -COR,

Y 'represents-(CONH) _n -X' or -COR ',

X and X 'each represents a heterocyclic group having a C1-C16 alkyl group which may have a side chain, an aromatic group which may have a substituent, or a conjugated double bond which may have a substituent,

n represents an integer of 1 or 2,

R and R 'each represent a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms, a benzyloxy group, a phenyloxy group or a phenacyloxy group, provided that either R or R' is a hydroxy group. May form an acceptable salt),

Each of R ₂ and R ₂ ′ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group,

Q and Q 'are each an alkyl group having 1 to 6 carbon atoms which may have a side chain, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a halogen atom, a nitro group or a nitroso group,

m and m 'each represent an integer of 0 to 3, provided that when m or m' is 1, Q or Q 'may be bonded to either of two condensed rings, and m or m' is 2 or 3 May be bonded to one or both condensed rings, and may form a ring together with two condensed rings),

A represents a cyclic group having a C2-C12 alkylene group or a conjugated double bond which may have a side chain;

[Formula I]

[Formula II]

[Formula III]

[Wherein Y represents-(CONH) _n -X or -COR,

Y 'represents-(CONH) _n -X' or -COR ',

Each of X and X 'represents an alkyl group having 1 to 16 carbon atoms which may have a side chain, an aromatic group which may have a substituent, or a heterocyclic group having a conjugated double bond which may have a substituent,

n represents an integer of 1 or 2,

R and R 'each represent a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms which may have a side chain, a benzyloxy group, a phenyloxy group or a phenacyloxy group, provided that either R or R' is a hydroxyl group. May form an acceptable salt),

R ₂ and R ₂ ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a side chain, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group,

Q and Q 'are each an alkyl group having 1 to 6 carbon atoms which may have a side chain, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a halogen atom, a nitro group or a nitroso group,

m and m 'each represent an integer of 0 to 3, provided that when m or m' is 1, Q or Q 'may be bonded to either of two condensed rings, and m or m' is 2 or 3 May be bonded to one or both condensed rings, and may form a ring together with two condensed rings),

A represents a cyclic group having a C2-C12 alkylene group or a conjugated double bond which may have a side chain,

Z and Z 'each represents a monovalent aromatic group which may have a substituent.

The present invention also relates to novel bis (aminocarbonylnaphthol) derivatives represented by the following formula [VIIIa], [IXa] or [Xa]:

[Wherein Y represents-(CONH) _n -X or -COR,

Y 'represents-(CONH) _n -X' or -COR ',

Each of X and X 'represents an alkyl group having 1 to 16 carbon atoms which may have a side chain, an aromatic group which may have a substituent, or a heterocyclic group having a conjugated double bond which may have a substituent,

n represents an integer of 1 or 2,

R and R 'each represent a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a benzyloxy group, a phenyloxy group or a phenacyloxy group, provided that either R or R' is a hydroxyl group. May form an acceptable salt),

R ₂ and R ₂ ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a side chain, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group,

Q and Q 'are each an alkyl group having 1 to 6 carbon atoms which may have a side chain, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a halogen atom, a nitro group or a nitroso group,

m and m 'each represent an integer of 0 to 3, provided that when m or m' is 1, Q or Q 'may be bonded to either of two condensed rings, and m or m' is 2 or 3 May be bonded to one or both condensed rings, and may form a ring together with two condensed rings),

A represents a cyclic group having a C2-C12 alkylene group or a conjugated double bond which may have a side chain,

Provided that at least one of Y and Y 'is a group wherein X or X' is an alkyl group having 1 to 16 carbon atoms which may have a side chain.

The present invention also relates to novel bis (aminocarbonylnaphthol) derivatives represented by the following formula [VIIIb], [IXb] or [Xb]:

[Wherein Y represents-(CONH) _n -X or -COR,

Y 'represents-(CONH) _n -X' or -COR ',

Each of X and X 'represents an alkyl group having 1 to 16 carbon atoms which may have a side chain, an aromatic group which may have a substituent, or a heterocyclic group having a conjugated double bond which may have a substituent,

n represents an integer of 1 or 2,

R and R 'each represent a hydroxyl group, an alkoxy group having 7 to 30 carbon atoms which may have a side chain, a benzyloxy group, a phenyloxy group or a phenacyloxy group (provided that either R or R' is a hydroxy group). May form an acceptable salt),

R ₂ and R ₂ ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a side chain, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group,

Q and Q 'are each an alkyl group having 1 to 6 carbon atoms which may have a side chain, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a halogen atom, a nitro group or a nitroso group,

m and m 'each represent an integer of 0 to 3, provided that when m or m' is 1, Q or Q 'may be bonded to either of two condensed rings, and m or m' is 2 or 3 , Q or Q 'may be bonded to one or both condensed rings, and may form a ring together with two condensed rings),

A represents a cyclic group having a C2-C12 alkylene group or a conjugated double bond which may have a side chain,

Provided that at least one of Y and Y 'is a group wherein R or R' is an alkoxy group having 7 to 30 carbon atoms which may have a side chain.

The compound of the present invention is a novel condensed azo containing a bisamide compound (eg, PCT / JP97 / 3638, etc.) in which either of the carboxyl groups of naphthol having a carboxyl group in the 3rd and 6th positions is amidated with an aromatic diamine. Characterized in that the compound.

In the present invention, A is a cyclic group having an alkylene group or a conjugated double bond which may have a side chain of 2 to 12 carbon atoms. As an alkylene group, it is preferable that it is linear, and it is especially preferable that it is C2-C6. As the cyclic group having a conjugated double bond, groups having an arylene group, a basic skeleton represented by the following general formula [IV] and the following general formula [VI] are preferable:

[Formula IV]

[In formula, Ar and Ar 'respectively independently represent the arylene group which may have a substituent, or the heterocyclic group which has a conjugated double bond,

M is a single bond, -CH _2- , -CH = C (E)-(wherein E represents hydrogen, a halogen atom, a lower alkyl group or a cyano group, etc.), -O-, -S-, -SS-, -CO-, -COO-, -SO _2- , -N (T)-(wherein T represents a phenyl group or lower alkyl group which may have a substituent), -N = N-, -CH = CH-ø- CH = CH- (o represents an arylene group) and a group selected from the group consisting of:

[Formula V]

(Wherein G represents -O-, -S- or -NH-);

[Formula VI]

[Wherein L represents> N-CH ₃ ,> C = O or> C = S].

Specific examples of these A are as follows:

(1) arylene groups such as phenylene, naphthylene, anthylene, etc. which may have a substituent;

(2) -Ar-M-Ar'- group, for example, a group of the formula wherein M is a single bond:

Wherein M is -CH _2-

A group of the formula wherein M is -CH = C (E):

A group of the formula wherein M is -O-, -S-, -SS-, -COO-, -SO _2- , -N (T)-or -N = N-:

A group of the formula wherein M is -CH = CH-ø-CH = CH-:

And the group of the following formula wherein M is a compound represented by the formula [V]:

(3) a group in which A is a group having a basic skeleton represented by the formula [VI]:

As a substituent of A, lower alkyl, for example, methyl, ethyl, isopropyl, propyl, n-butyl, isobutyl, tert-butyl, etc., lower alkoxy, for example, methoxy, ethoxy and the like, halogen, for example Examples thereof include fluorine, chlorine, bromine, iodine, cyano, nitro and the like.

In Y and Y ', as a compound which comprises group X or X', C1-C16, Preferably 1-12 alkyl group which may have a side chain, The aromatic group which may have a substituent, for example, Heterocyclic group which has phenyl group, naphthyl group, anthraquinonyl group, or the conjugated double bond which may have a substituent, for example, benzimidazoloyl group, carbazolyl group, pyridyl group, thiazolyl group, benzothiazolyl group, Imidazolyl group, indolyl group, thiofuryl group, phenothiazinyl group, acridinyl group, quinolinyl group and the like are exemplified (Y and Y 'in the formula [VIIIa], [IXa] and [Xa]). At least one is a group in which X or X 'represents an alkyl group having 1 to 16 carbon atoms which may have a side chain).

As a substituent of these aromatic groups or heterocyclic groups, a halogen, a nitro group, a lower alkyl group, a lower alkoxy group, a cyano group, a phenoxy group, an amide group (for example, a phenylaminocarbonyl group), etc. are illustrated, These phenoxy group, an amide, etc. are mentioned. The group may further have other substituents such as halogen, lower alkyl, lower alkoxy, alkylaminosulfonyl, nitrile and the like. When different kinds of substituents are introduced on these aromatic groups or heterocyclic groups, the color and the sharpness can be effectively changed, and therefore, azo compounds having different colors or sharpness can be easily obtained.

Y and Y 'may represent COR or COR'. R and R 'are an alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms which may have a hydroxy group and a side chain (however, in the formula [VIIIa], [IXa] and [Xa], they may have a side chain) An alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and in the formula [VIIIb], [IXb] and [Xb], alkoxy having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, which may have a side chain. Group, a benzyloxy group, a phenoxy group or a phenacyloxy group, wherein the aromatic ring contained in these groups may have a substituent, provided that Y and Y 'are represented in the formulas [VIIIb], [IXb] and [Xb]. At least one is a group in which R or R 'represents an alkoxy group having 7 to 30 carbon atoms which may have a side chain).

Y and Y 'are each preferably -CONH-X or -CONH-X'.

Groups R ₂ and R ₂ '' An alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which may have a hydrogen atom or a side chain, preferably a methyl group or an ethyl group; An acyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, particularly an acetyl group; Or a phenylalkyl group, the phenylalkyl group may have a substituent, for example, a halogen atom, a lower alkyl group, or the like, and the alkyl group preferably has 1 to 6 carbon atoms.

Z and Z 'which comprise an azo group are monovalent aromatic groups which may have a substituent. This aromatic group may be a condensed ring with a heterocyclic group. Typically, a phenyl group, naphthyl group, anthryl group, indenyl group, fluorenyl group, indolyl group, benzothiazolyl group, quinolinyl group, carbazolyl group and the like are exemplified. Examples of the substituent include halogen, lower alkyl, especially methyl, cyano, nitro, alkoxy, amide, sulfo, alkylaminosulfonyl, aminocarbonyl, phenoxy, alkoxycarbonyl, hydroxy, benzoylamino group and the like. Particularly preferred aromatic groups are phenyl groups.

In the present invention, the two naphthalene nuclei may have Q or Q 'as substituents, respectively, and as Q or Q', respectively, a lower alkyl group (preferably C1 to C4) and a lower alkoxy group (preferably C1) 4), a halogen atom, a nitro group, a nitroso group, etc. are illustrated. The number m or m 'of substituents is usually 0, but may have up to three. In addition, it should not have a substituent on 1 of naphthol.

What is necessary is just to manufacture this condensed azo compound of this invention according to the following Reaction Formula. Although the following reaction formula shows the condensed azo compound [Ia] which bisamide-ized the carboxyl group of 3, the condensed azo compound of Formula [II] and [III] can also be manufactured similarly.

The bisamide compound [VIIIa] is reacted with a diazonium compound to obtain a condensed azo compound [Ia]. In addition, 2-hydroxynaphthalene-3,6-dicarboxylic acid [XI] obtained by the Kolbe-Schmidt reaction or the like is used as a raw material, and the carboxyl group on the third position is protected by esterification or the like, and the carboxylic acid on the sixth position. To an acid chloride using thionyl chloride or the like, and then reacted with an aromatic amine to give 6-amide compound [XII]. The dicarboxylic acid [XI] can also be made into an amide compound by directly reacting with amines with phosphorus trichloride or dicyclohexyl carbodiimide. A diazonium compound is reacted with the obtained amide compound to give 1-azo-6-amide compound [XIII], and after changing the carboxyl group at the third position to acid chloride as desired, an aromatic diamine (for example, phenylenediamine ) To give a condensed azo compound [Ia].

Or the phenylenediamine at this time is made excess, and a monoamine compound [XIV] is obtained. The monoamine compound [XIV] can also be obtained by condensation reaction with an excess of phenylenediamine before the 6-amide compound [XII] is reacted with a diazo compound, followed by reaction with a diazonium compound.

The 3-carboxyl carboxyl group of the 6-amide compound [XII] is reacted with phenylamine having a nitro group in the presence of phosphorus trichloride and sulfolane, instead of phenylenediamine, to obtain a 3- (nitrophenylamide) compound, The nitro group is reduced in accordance with a conventional method to be converted to an amino group, and then reacted with a 6-amide compound [XII] or an acid chloride thereof to obtain a bisamide compound, which is reacted with a diazonium compound to give a condensed azo compound [ Ia] can also be obtained.

As described above, the reaction between the amino group and the carboxyl group of the aromatic amine can be carried out by changing the carboxyl group to an acid chloride and then reacting with the amine, or the carboxyl group can be directly reacted with the aromatic amine in the presence of phosphorus trichloride and sulfolane. . These reactions illustrate typical means, but are not limited to these.

As the amines, that is, the compounds constituting the group X or X ', an aromatic amino compound which may have a substituent, for example, aniline (X or X' is a phenyl group), α- or β-aminonaphthalene (X or X ' Heteronaphthyl group), aminoanthraquinone (X or X 'is an anthraquinonyl group), a heterocyclic compound having a conjugated double bond which may have a substituent, for example, aminobenzimidazolone (X or X' is benzimine Dazolonyl group), aminocarbazole (X or X 'is aminocarbazolyl group), aminopyridine (X or X' is pyridyl group), aminothiazole (X or X 'is thiazolyl group), aminobenzothia Sol (X or X 'is a benzothiazolyl group), aminoimidazole (X or X' is an imidazolyl group), also aminoindole (X or X 'is an indolyl group), aminothiophene (X or X' is Thiofuryl group), aminophenothiazine (X or X 'is a phenothiazinyl group), aminoacridine (X or X 'is an acridinyl group), an aminoquinoline (X or X' is a quinolinyl group), etc. are illustrated. As a substituent of these compounds, a halogen, a nitro group, a lower alkyl group, an alkoxy group, a cyano group, a phenoxy group, an amide group (for example, a phenylaminocarbonyl group), etc. are illustrated, and these substituents are other substituents, for example For example, it may further have halogen, lower alkyl, lower alkoxy, alkyl amino sulfonyl, nitrile and the like.

The azo compound of the present invention is a diazonium compound [VII] or [VIIa] obtained by diazotizing aromatic amines with sodium nitrite or the like, and the aforementioned 2-hydroxynaphthalene-3,6-dicarboxylic acid and derivatives thereof (Example For example, carboxyamide, carboxyureido or ester, etc.).

As aromatic amines, monoamino condensed polycyclic hydrocarbons such as aniline, α- or β-naphthylamine, monoaminoanthracene, monoaminoindene, monoaminofluorenone, monoaminoindole, monoaminobenzothiophene, monoamino Quinoline, monoaminocarbazole and the like. These aromatic amines may have a substituent, and as the substituent, halogen, lower alkyl (particularly methyl), cyano, nitro, lower alkoxy, amide, sulfo, alkylaminosulfonyl, aminocarbonyl, phenoxy, alkoxycarbonyl, Hydroxy, benzoylamino groups and the like.

Especially preferable aromatic amines are anilines which may have a substituent.

The method of obtaining a diazonium compound from amines is not specifically limited. What is necessary is just to use the general method of diazotizing aromatic primary amines with sodium nitrite.

Diazonium compounds are also coupled with the aforementioned 2-hydroxynaphthalene-3,6-dicarboxylic acids and derivatives thereof (eg, carboxyamides, carboxyureidos or esters, etc.), which methods are also conventional You can use

The azo compound of the present invention is excellent in water resistance, solvent resistance, chemical resistance and heat resistance, and can be used in pigments, printing inks, paints, mixed colorants for polymer materials, organic photoconductive materials and the like.

Example 1

1,4-bis {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino} phenyl Synthesis of Len

1.45 g of 2,5-dichloroaniline is suspended in 12.0 g of water as an amine component, and 2.3 g of 36% hydrochloric acid is added. Then, while maintaining 0-5 degreeC, the solution which dissolved 0.7 g of sodium nitrite in 10 g of water is added dropwise, and diazotization is performed. Subsequently, 0.8 g of acetic acid, 0.15 g of Pearlite® and 0.15 g of Carboraffin® are added, and then the mixture is filtered. The temperature at this time is kept at 10 degrees C or less. Meanwhile, as the coupler component, 3.1 g of 1,4-bis (2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino) phenylene was N-methyl-2-pi It is suspended in 124 g of ralidone, and the solution which dissolved 1.0 g of sodium hydroxide in 10 g of water is added, and it keeps at 15 degreeC after dissolving. The clear diazo solution mentioned above is added to this in 20-30 minutes, and a coupling reaction is performed. After stirring for 60 minutes, the temperature is raised to 70 ° C and stirred for about 30 minutes. Thereafter, the mixture was gradually cooled and suction filtered to room temperature. The product was ultrasonically washed with methanol and water, respectively, and then dried under reduced pressure to give a brownish red powder [1,4-bis {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy- 6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino} phenylene] was obtained (melting point, decomposition point: 396.6 ° C. (decomposition)).

This infrared absorption spectrum (diffusion spray method) is shown in FIG.

Table 1 shows various properties of the condensed azo compound obtained in Example 1, such as water resistance, chemical resistance, solvent resistance, light resistance and heat resistance.

Water resistance, chemical resistance, solvent resistance, light resistance and heat resistance were evaluated as follows:

Test Example 1 Water Resistance : 1 part of a sample is added to 20 parts of water, and dispersed for 20 minutes by ultrasonic waves. After boiling for 1 minute, the mixture was cooled and filtered, the color of the filtrate was observed and evaluated according to the following A to E.

Test Example 2 Chemical Resistance : 1 part of the sample is added to 20 parts of 5% aqueous solution of hydrochloric acid or sodium hydroxide and dispersed for 5 minutes by ultrasonic wave. After filtration, the color of the filtrate was observed and evaluated according to the following A to E.

Test Example 3 Solvent Resistance : 1 part of the sample is added to 20 parts of acetone, methanol, xylene or ethyl acetate and dispersed for 5 minutes by ultrasonic wave. After filtration, the color of the filtrate was observed and evaluated according to the following A to E.

Evaluation of the above three items : A = no coloration at all, B = very little coloration, C = little coloration, D = coloration, E = significant coloration.

Test Example 4 Light Resistance :

1) Mix 1.0 parts of the sample, 0.7 parts of dioctylphthalate and 0.7 parts of castor oil with a Hoover Muller (100 turns × 3 times).

2) Add 10.0 parts of hardener becosol (ER-3653-60) and 0.1 part of manganese naphthenic acid to 1.0 part of the mixture kneaded in 1 and knead well on a glass plate using a spatula.

3) After applying the sample obtained in 2 to 0.5 mil (1.27 x 10 ^-5 m) on an iron plate using an applicator, it is heated with an air dryer at 145 degreeC for 30 minutes, and the test piece of a print paint is obtained.

4) After masking 3 specimens halfway, irradiate for 100 hours with a feather meter (manufactured by Shimadzu Corporation): Suntester (registered trademark) XF-180, xenon lamp). The color of the masked part and the unmasked part is observed, respectively, and evaluated by the difference (DELTA) E of both colors.

ΔE <2 A

ΔE = 2-3 B

ΔE = 3 to 5 C

ΔE = 5 to 8 D

ΔE> 8 E

Test Example 5 Heat Resistance :

1) To 100 parts of the composition consisting of 100 parts of softened polyvinyl chloride, 50 parts of dioctylphthalate, 2 parts of tin maleate, 0.4 part of calcium stearate, and 0.6 part of barium stearate, 1 part of a sample was added, and 140 degreeC was carried out with 2 roll mills. After kneading for 5 minutes, pressure was applied at 100 kgf / cm ² to obtain a test piece having a thickness of 1 mm.

2) Cut the test piece obtained in 1 to 30 mm x 30 mm.

3) The test piece of 2 was left to stand in a thermostat at 170 degreeC for 60 minutes, the color of the test piece before and after heating was measured, and the color difference (E) was evaluated.

ΔE <2 A

ΔE = 2-3 B

ΔE = 3 to 5 C

ΔE = 5 to 8 D

ΔE> 8 E

Example 2

1,4-bis {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino} phenyl Synthesis of Len

As the coupler component, 1,4-bis (2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino) phenylene of Example 1 was substituted with 1,4-bis (2 Reddish brown powder in the same manner as in Example 1 except for changing to 3.1 g of '-hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino) phenylene [1, 4-bis {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino} phenylene] 3.28 g were obtained (melting point, decomposition point: 368.6 ° C. (decomposition)).

Example 3

1- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino} -4- { Synthesis of 1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-6'-phenylaminocarbonylnaphth-3'-yl-carbonylamino} phenylene

 As a coupler component, 1,4-bis (2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino) phenylene of Example 1 was substituted with 1- (2'-hydride. Hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino) -4- (2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonyl A brownish red powder [1- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy, in the same manner as in Example 1 except for changing to 3.1 g of amino) phenylene -3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino} -4- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-6' 2.67 g of -phenylaminocarbonyl-naphth-3'-yl-carbonylamino} phenylene were obtained (melting point and decomposition point: 356.1 ° C. (decomposition)).

Example 4

1- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino} -3- { Synthesis of 1'-2 '', 5 ''-dichlorophenylazo) -2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino} phenylene

 As a coupler component, 1,4-bis (2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino) phenylene of Example 1 was substituted with 1- (2'-hydride. Hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino) -3- (2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonyl A brownish red powder [1- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy, in the same manner as in Example 1 except for changing to 3.1 g of amino) phenylene -3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino} -3- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-6' -Phenylaminocarbonyl-naphth-3'-yl-carbonylamino} phenylene] was obtained (melting point, decomposition point: 339.6 ° C. (decomposition)).

Example 5

Bis [4- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino} phenyl] Synthesis of methane

 As the coupler component, 1,4-bis (2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino) phenylene of Example 1 was used as bis {4- (2 ' Yellowish red powder [bis [] [except for changing to 3.5 g of -hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino) phenyl} methane, 4- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino} phenyl] methane] 2.32 g were obtained (melting point, decomposition point: 353.0 ° C. (decomposition)).

Example 6

Bis [4- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino} phenyl] Synthesis of methane

 As the coupler component, 1,4-bis (2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino) phenylene of Example 1 was used as bis {4- (2 ' Except for changing to 3.5 g of -hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino) phenyl} methane, the same method as in Example 1 was carried out. 4- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-3'-phenylaminocarbonyl-naphth-6'-yl-carbonylamino} phenyl] methane] 1.54 g was obtained (melting point, decomposition point: 332.0 ° C. (decomposition)).

Example 7

Bis [4- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-6'phenylaminocarbonyl-naphth-3'-yl-carbonylamino} phenyl] ether Synthesis of

 As the coupler component, 1,4-bis (2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino) phenylene of Example 1 was used as bis {4- (2 ' A yellowish red powder [bis [] was prepared in the same manner as in Example 1, except that 3.5 g of -hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino) phenyl} ether was used. 4- {1 '-(2' ', 5' '-dichlorophenylazo) -2'-hydroxy-6'-phenylaminocarbonyl-naphth-3'-yl-carbonylamino} phenyl] ether] 1.61 g was obtained (melting point / decomposition point: 368.1 ° C. (decomposition)).

Examples 8-28

As an amine component and a coupler component, the azo compound was synthesize | combined by the method similar to Example 1 except having used the amine and coupler shown in Table 3, respectively.

The melting point and decomposition point of the synthesized azo compound are shown in Table 2.

Example 29

1.25 g of 2-hydroxy-3-hydroxycarbonyl-6-methoxycarbonylnaphthalene and 2.2 g of diazonium borofluoride prepared by conventional methods from 4-nitrotoluidine were prepared using N, N-dimethylformamide 100 dissolve in g. While keeping at 10-15 degreeC, the solution which dissolved 7.4 g of sodium acetate in 20 g of water is slowly added to this. After stirring for about 2 hours, the precipitate is recovered by filtration. Wash thoroughly with water and methanol and dry. 1.03 g of the monoazo compound thus obtained is suspended in 20 g of tetrahydrofuran, and 0.75 g of thionyl chloride is added thereto. Furthermore, after adding a small amount of N, N-dimethylformamide, it raises temperature to 60-70 degreeC. After stirring for about 15 hours and allowing sufficient reaction, the excess thionyl chloride is distilled off. A solution obtained by dissolving 0.33 g of 2,5-di (4'-aminophenyl) -3,4-oxadiazole in 20 g of N-methyl-2-pyrrolidone is added thereto. After stirring at 70-80 degreeC for about 20 hours, 10 g of methanol is added. The precipitate was recovered by filtration, sufficiently washed with water and methanol, and dried to yield 1.21 g of a yellowish red powder having a target substance as a main component (melting point / decomposition point: 292.2 ° C. (decomposition)).

Example 30

Except for preparing the corresponding diazonium borofluoride in place of 4-nitrotoluidine of Example 29 with 2-methoxy-5-diethylaminosulfonylaniline, the target product was used as a main component in the same manner as in Example 29. 1.08 g of dark blueish red powders were obtained (melting point and decomposition point: 248.4 ° C (melting), 301.7 ° C (decomposition)).

Test Example 6 Photoconductive Characteristics :

One part of the azo compound obtained in Example 26 was dispersed by a ball mill together with one part of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., SLEC BH-3) and 10 parts of cyclohexanone. The dispersion of this azo compound was applied to an aluminum plate with a bar coater and then dried. The film thickness at this time is about 0.5 micrometer. On the charge generating layer thus obtained, 1 part of N-ethylcarbazole-3-aldehydephenylhydrazone and 1 part of polycarbonate resin (made by Teijin Kasei Co., Ltd., Panlite K-1285) are 1,2-dichloro The solution dissolved in 20 parts of ethane was applied so as to have a dry film thickness of 20 m, and a charge transport layer was formed. In this way, an electrophotographic photosensitive member having a photosensitive layer composed of two layers was obtained.

As a sensitivity of the photosensitive member, the half-sensitive exposure amount (E _1/2 ) measured the photosensitive member described above by an electrostatic radiation paper test apparatus (Model Kawaguchi Denki Seisakusho Model EPA-8100).

First, in the dark, it was charged by corona discharge at -5.0 kV, and then exposed to white light having an illuminance of 20 lux, and the exposure amount necessary for the surface potential to attenuate to half of the initial surface potential was determined.

The half-life exposure amount (E _1/2 ) thus obtained is 6.8 lux sec. The surface potential (residual potential) after sufficient exposure (after 200 lux sec exposure) is -1V.

With respect to the azo compounds obtained in Examples 22, 27 and 28, an electrophotographic photosensitive member was produced in the same manner as above, and the half exposure (E _1/2 ) and the surface potential (residual potential) were obtained. Each half-life exposure (E _1/2 ) and surface potential (residual potential) are shown in Table 4.

Example 31

1.89 g of 4-aminotoluene-3-sulfonic acid (4B-Acid) is dispersed in 50 g of water and dissolved by adding 2.57 g of 35% hydrochloric acid. Thereafter, while maintaining the temperature at 0 ° C., a solution obtained by dissolving 0.84 g of sodium nitrite in 5 g of water is added dropwise to effect diazotization. Meanwhile, 2.72 g of 1,6-bis (2'-hydroxy-3'-hydroxynaphth-6'-ylcarbonylamino) hexane was suspended in 100 g of water, and 7.0 g and 5% aqueous 10% sodium hydroxide solution. 4.0 g of% rosin aqueous solution is added and dissolved, and then maintained at 13 (± 2) ° C. The diazo solution mentioned above is added dropwise over about 30 minutes, and further stirred for 90 minutes. After adjusting the pH of the reaction solution to 9.0 to 9.5, a solution obtained by dissolving 2.20 g of calcium chloride dihydrate in 20 g of water is added dropwise to this solution and quenched. After 30 minutes, the temperature was raised to 70 ° C, left for about 30 minutes, and then gradually cooled to room temperature, 200 g of water was added to adjust the pH to 6.0 to 6.5, and then the precipitate was recovered by filtration. The product was washed with water and dried to give 4.12 g of a dark red powder (melting point, decomposition point: 501.6 ° C. (decomposition)).

Example 32

The 1,6-bis (2'-hydroxy-3'-hydroxynaphth-6'-ylcarbonylamino) hexane of Example 31 was replaced with 1,4-bis (2'-hydroxy-6'-hydroxy 3.92 g of a dark blue-red powder was obtained in the same manner as in Example 31 except that the oxynaphth-3-ylcarbonylamino) phenylene was changed to 2.68 g (melting point / decomposition point: 472.8 ° C. (decomposition)) ).

Test Example 7 Color Data as Print Ink :

For the azo compounds obtained in Examples 31 and 32, printing inks were made and colored according to JIS K5101. The color data is shown in Table 5. As color data, dominant wavelength lambda d, stimulation purity pe and brightness Y described in JIS Z8701 are shown.

Dominant wavelength Stimulation purity Pe Brightness Y Example 31 627 nm 43.3% 11.8% Example 32 636 nm 28.7% 15.4%

Examples 33-37

As an amine component and a coupler component, the azo compound was synthesize | combined by the method similar to Example 1 except having used the amine and coupler shown in Table 7, respectively.

The melting point and decomposition point of the synthesized azo compound are shown in Table 6.

Example 38

7.39 g of 2-hydroxy-6-hydroxycarbonyl-3-methoxycarbonyl naphthalene are acid chlorinated by a conventional method, and 6.82 g of n-dodecylamine is converted to N-methyl-2-pyrrolidone 25 The solution dissolved in g and 13 g of xylenes is added dropwise thereto at 80 ° C. After the reaction for about 18 hours, ice-cooled, and the precipitate is recovered by filtration. A solution of 10.48 g washed with acetone was dissolved in 100 g of N, N-dimethylformamide at 60 ° C., and a solution of 3.2 g of sodium carbonate dissolved in 100 g of water and 30 g of methanol was added. After making it react at 80 degreeC for 2 hours, and removing an insoluble matter, 100 g of water is further added. The pH of this solution is adjusted to 2, and the precipitate is recovered by filtration. Wash with hot water and methanol and dry. 1.02 g of the crystal thus obtained is suspended in 22.16 g of tetrahydrofuran, and 0.35 g of thionyl chloride is added, followed by reacting for about 15 hours in an ice bath. After the remaining thionyl chloride is distilled off, a solution in which 0.13 g of 1,5-diamino naphthalene is dissolved in 7.35 g of N-methyl-2-pyrrolidone is added. After about 40 hours of reaction, the precipitate was recovered by filtration, washed with water and methanol, and dried to yield 0.15 g of an off-blue powder (melting point / decomposition point: 371.6 ° C. (decomposition)).

This infrared absorption spectrum (KBr method) is shown in FIG.

Example 39

0.38 g of a flesh-colored powder was obtained in the same manner as in Example 38 except that the n-dodecylamine used in Example 38 was changed to n-octyl alcohol (melting point / decomposition point: 95.2 ° C (melting), 320.8 ° C ( decomposition)).

This infrared absorption spectrum (KBr method) is shown in FIG.

Example 40

0.61 g of a flesh-colored powder was obtained in the same manner as in Example 38 except that the n-dodecylamine used in Example 38 was changed to 1-hexadecanol (melting point / decomposition point: 127.5 ° C (melting), 329.5 ° C ( decomposition)).

This infrared absorption spectrum (KBr method) is shown in FIG.

Example 41

After suspending 8.2 g of 2-hydroxy-6-hydroxycarbonyl-3-methoxycarbonyl naphthalene in 60 g of tetrahydrofuran, 7.8 g of thionyl chloride and a small amount of N, N-dimethylformamide are added, Heat to 50 ° C. After the reaction for about 3 hours, the solvent and the like were distilled off, and a solution obtained by dissolving 1.62 g of p-phenylenediamine in 13 g of tetrahydrofuran and 3.5 g of N-methyl-2-pyrrolidone was added to the residue, followed by reflux. Under reaction for about 20 hours. The precipitate was recovered by filtration and washed with methanol. The obtained solid is suspended in 200 g of methanol, and 50 g of an aqueous 24% sodium hydroxide solution is added thereto and reacted at 50 ° C for 6 hours. 200 g of water is added, pH is adjusted to 2, and a precipitate is collect | recovered by filtration. After washing with warm water and methanol, it was dried to give 2.6 g of 1,4-bis (2'-hydroxy-3'-methoxycarbonyl-naphth-6'-ylcarbonylamino) phenylene.

After further acid chlorination by a conventional method, a solution in which 2.6 g of n-amyl alcohol is dissolved in 20 g of N-methyl-2-pyrrolidone is added. After reaction at 80 ° C for 18 hours, 50 g of methanol is added, and the precipitate is recovered by filtration. It was sufficiently washed with methanol and dried to give 0.68 g of an off-white powder (melting point, decomposition point: 300.4 ° C. (melting)).

This infrared absorption spectrum (KBr method) is shown in FIG.

Example 42

0.83 g of an off-white powder was obtained in the same manner as in Example 41 except that the n-amyl alcohol used in Example 41 was changed to 7.3 g of 2-hexyldecanol (melting point / decomposition point: 225.8 ° C. (melting)).

This infrared absorption spectrum (KBr method) is shown in FIG.

Example 43

0.76 g of an off-white powder was obtained in the same manner as in Example 41 except that the n-amyl alcohol used in Example 41 was changed to 3.2 g of benzyl alcohol (melting point / decomposition point: 283.0 ° C. (melting)).

This infrared absorption spectrum (KBr method) is shown in FIG.

Example 44

1.00 g of 2-hydroxy-6-hydroxycarbonyl-3-methoxycarbonyl naphthalene is suspended in 10.0 g of tetrahydrofuran, 0.94 g of thionyl chloride and a small amount of N, N-dimethylformamide are added, and 50 Heated to ° C. After the reaction for about 3 hours, the solvent and the like are distilled off, and a solution obtained by dissolving 1.27 g of n-decanol in 10.0 g of tetrahydrofuran is added to the residue and reacted under reflux for about 20 hours. Subsequently, after distilling a solvent off, 15.0 g of N, N- dimethylformamide, 15.0 g of methanol, and 180.0 g of 5% sodium hydrogencarbonate aqueous solution are added, and it reacts at 60 degreeC for 20 hours. After removing an insoluble matter, pH is adjusted to 2 at 50 degreeC, and a precipitate is collect | recovered by filtration. The product was washed with hot water and methanol, and dried to yield 1.33 g of 2-hydroxy-3-hydroxycarbonyl-6-decyloxycarbonyl naphthalene as an off-white powder (melting point, decomposition point: 269.2 ° C. (decomposition)). ).

Further, after acid chlorination by a conventional method, 1.00 g of 2-hydroxy-6- (4'-aminophenyl aminocarbonyl) -3-phenylaminocarbonyl naphthalene was N-methyl-2-pi A solution dissolved in 60.0 g of ralidone is added. After reaction at 80 ° C for 18 hours, 200 g of methanol is added, and the precipitate is recovered by filtration. It was sufficiently washed with methanol and dried to give 0.99 g of an off-white powder (melting point, decomposition point: 296.8 ° C. (decomposition)).

This infrared absorption spectrum (KBr method) is shown in FIG.

Example 45

2-hydroxy-6- (4'-aminophenyl aminocarbonyl) -3-phenylaminocarbonyl naphthalene was used as the 2-hydroxy-6- (3'-aminophenyl aminocarbonyl) -3. 0.93 g of a tan powder was obtained in the same manner as in Example 44 except for changing to 1.00 g of -phenylaminocarbonyl naphthalene (melting point / decomposition point: 311.2 ° C. (decomposition)).

 The infrared absorption spectrum (KBr method) is shown in FIG.

Claims (12)

Condensed azo compounds represented by the following formula [I], [II] or [III]: [Formula I] [Formula II] [Formula III] [Wherein Y represents-(CONH) _n -X or -COR, Y 'represents-(CONH) _n -X' or -COR ', Each of X and X 'represents an alkyl group having 1 to 16 carbon atoms which may have a side chain, an aromatic group which may have a substituent, or a heterocyclic group having a conjugated double bond which may have a substituent, n represents an integer of 1 or 2, R and R 'each represent a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms which may have a side chain, a benzyloxy group, a phenyloxy group or a phenacyloxy group, provided that either R or R' is a hydroxyl group. May form an acceptable salt), R ₂ and R ₂ ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a side chain, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group, Each of Q and Q 'represents an alkyl group having 1 to 6 carbon atoms which may have a side chain, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a halogen atom, a nitro group or a nitroso group, m and m 'each represent an integer of 0 to 3, provided that when m or m' is 1, Q or Q 'may be bonded to either of two condensed rings, and m or m' is 2 or 3 May be bonded to one or both condensed rings, and may form a ring together with two condensed rings), A represents a cyclic group having a C2-C12 alkylene group or a conjugated double bond which may have a side chain, Z and Z 'each represents a monovalent aromatic group which may have a substituent. The condensed azo compound according to claim 1, wherein A is a group selected from an arylene group which may have a substituent, a group represented by the following formula [IV], or a group represented by the following formula [VI]: [Formula IV] -Ar-M-Ar'- [Wherein Ar and Ar 'each independently represent an arylene group which may have a substituent or a heterocyclic group having a conjugated double bond, M is a single bond or -CH _2- , -CH = C (E)-(wherein E represents hydrogen, a halogen atom, a lower alkyl group or a cyano group, etc.), -O-, -S-, -SS- , -CO-, -COO-, -SO _2- , -N (T)-(wherein T represents a phenyl group or a lower alkyl group which may have a substituent), -N = N-, -CH = CH-ø -CH = CH- (o represents an arylene group) and a group selected from the group consisting of the following formula [V]: [Formula V] (Wherein G represents -O-, -S- or -NH-); [Formula VI] [Wherein, L represents> N-CH ₃ ,> C = O or> C = S]. The condensed azo compound according to claim 1, wherein Y is-(CONH) _n -X and Y 'is-(CONH) _n -X' (n, X and X 'are the same as defined above). The condensed azo compound according to claim 1, wherein Z and Z 'are a monovalent phenyl group which may have a substituent. A pigment containing the condensed azo compound according to claim 1. A printing ink containing the condensed azo compound according to claim 1. A paint containing the condensed azo compound according to claim 1. The mixing coloring material for polymer materials containing the condensed azo compound of Claim 1. An organic photoconductor containing the condensed azo compound according to claim 1. Condensation of Claim 1 characterized by coupling the aromatic diazonium compound represented by following formula [VII] or [VIIa] with the bisamide compound represented by following formula [VIII], [IX], or [X]. Preparation of Azo Compounds: [Formula VII] ZN ⁺ ≡ N Formula VIIa] Z'-N ⁺ ≡ N [Wherein, Z and Z 'represent a monovalent aromatic group which may have a substituent]; [Formula VIII] [Formula IX] [Formula X] [Wherein Y represents-(CONH) _n -X or -COR, Y 'represents-(CONH) _n -X' or -COR ', Each of X and X 'represents an alkyl group having 1 to 16 carbon atoms which may have a side chain, an aromatic group which may have a substituent, or a heterocyclic group having a conjugated double bond which may have a substituent, n represents an integer of 1 or 2, R and R 'each represent a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms which may have a side chain, a benzyloxy group, a phenyloxy group or a phenacyloxy group, provided that either R or R' is a hydroxyl group. May form an acceptable salt), R ₂ and R ₂ ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a side chain, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group, Each of Q and Q 'represents an alkyl group having 1 to 6 carbon atoms which may have a side chain, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a halogen atom, a nitro group or a nitroso group, m and m 'each represent an integer of 0 to 3, provided that when m or m' is 1, Q or Q 'may be bonded to either of two condensed rings, and m or m' is 2 or 3 May be bonded to one or both condensed rings, and may form a ring together with two condensed rings), A represents a C2-C12 alkylene group which may have a side chain or a cyclic group which has a conjugated double bond. Bis (aminocarbonylnaphthol) derivatives represented by the following formula [VIIIa], [IXa] or [Xa]: Formula VIIIa Formula IXa Formula Xa [Wherein Y represents-(CONH) _n -X or -COR, Y 'represents-(CONH) _n -X' or -COR ', Each of X and X 'represents an alkyl group having 1 to 16 carbon atoms which may have a side chain, an aromatic group which may have a substituent, or a heterocyclic group having a conjugated double bond which may have a substituent, n represents an integer of 1 or 2, R and R 'each represent a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a benzyloxy group, a phenyloxy group or a phenacyloxy group, provided that either R or R' is a hydroxyl group. May form an acceptable salt), R ₂ and R ₂ ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a side chain, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group, Each of Q and Q 'represents an alkyl group having 1 to 6 carbon atoms which may have a side chain, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a halogen atom, a nitro group or a nitroso group, m and m 'each represent an integer of 0 to 3, provided that when m or m' is 1, Q or Q 'may be bonded to either of two condensed rings, and m or m' is 2 or 3 May be bonded to one or both condensed rings, and may form a ring together with two condensed rings), A represents a cyclic group having a C2-C12 alkylene group or a conjugated double bond which may have a side chain, Provided that at least one of Y and Y 'is a group wherein X or X' is an alkyl group having 1 to 16 carbon atoms which may have a side chain. Bis (aminocarbonylnaphthol) derivatives represented by the following formula [VIIIb], [IXb] or [Xb]: Formula VIIIb Formula IXb [Formula Xb] [Wherein Y represents-(CONH) _n -X or -COR, Y 'represents-(CONH) _n -X' or -COR ', Each of X and X 'represents an alkyl group having 1 to 16 carbon atoms which may have a side chain, an aromatic group which may have a substituent, or a heterocyclic group having a conjugated double bond which may have a substituent, n represents an integer of 1 or 2, R and R 'each represent a hydroxyl group, an alkoxy group having 7 to 30 carbon atoms which may have a side chain, a benzyloxy group, a phenyloxy group or a phenacyloxy group (provided that either R or R' is a hydroxy group). May form an acceptable salt), R ₂ and R ₂ ′ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a side chain, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group, Each of Q and Q 'represents an alkyl group having 1 to 6 carbon atoms which may have a side chain, an alkoxy group having 1 to 6 carbon atoms which may have a side chain, a halogen atom, a nitro group or a nitroso group, m and m 'each represent an integer of 0 to 3, provided that when m or m' is 1, Q or Q 'may be bonded to either of two condensed rings, and m or m' is 2 or 3 , Q or Q 'may be bonded to one or both condensed rings, and may form a ring together with two condensed rings), A represents a cyclic group having a C2-C12 alkylene group or a conjugated double bond which may have a side chain, Provided that at least one of Y and Y 'is a group wherein R or R' is an alkoxy group having 7 to 30 carbon atoms which may have a side chain.