KR100282263B1 - Bisazo compounds and their use as fiber-reactive dyes - Google Patents

Abstract

The present invention provides a bisazo compound or a salt thereof represented by the following general formula:

Wherein R ¹ and R ³ are each hydrogen or alkyl; D is phenylene or naphthylene; And one of X ¹ and X ² is NH ₂ , the other is OH; Z ¹ and Z ² are each -CH = CH ₂ or -CH ₂ CH ₂ Z '(wherein Z' is a removable group); B is monosulfophenylene, monosulfophenylene-methylene or mono- or di-sulfonaphthylene-methylene; U is a phenylene or aliphatic bridging group; When J is an amino-derivative group or when X is ¹ and Y is phenylene, J may be alkoxy, and when X ¹ is OH and U is an aliphatic bridging group, J may be alkoxy or phenoxy.

The compound of the present invention is useful for dyeing or printing textile materials, and provides dyestuffs or prints having excellent build-up properties and excellent color fastness properties.

Description

Bisazo compounds and their use as fiber-reactive dyes

The present invention is suitable for dyeing and printing of materials containing hydroxyl groups and / or amide groups, especially cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather and blend fibers thereof, and is characterized by a light fastness, a sweat- Which are capable of obtaining superior navy-blue dyes, and the use of these compounds.

Bisazo compounds having a triazinyl group and a plurality of vinyl sulfone type reactors are known, for example, from U.S. Pat. Nos. 5,053,494 and 5,112,959. However, these compounds are still inadequate in dyeing performance, especially in dyeing power, build-up properties and various fastnesses.

Conventionally, various reactive dyes have been extensively used in the field of dyeing and printing of textile materials, and at the present level of technology, there is a need for a dyeing technique, a dyeing process or a dyeing process, It is still not fully satisfactory.

The above-mentioned known reactive dyes are strongly required to develop more improved dyes because of poor durability such as dyeability or build-up property and insufficient fastness such as light fastness, sweat-light fastness and wet fastness.

Excellence in buildability is crucial for today's demanding economical dyeing approaches, and robustness is also important in today's world of high quality in the clothing sector.

The inventors of the present invention have made extensive studies in order to find new compounds capable of sufficiently satisfying the requirements of the dyes while improving the drawbacks of the known dyes.

The present invention provides a bisazo compound represented by the following general formula (I) or a salt thereof.

Wherein R < ¹ > is hydrogen, or unsubstituted or substituted alkyl; D is phenylene, unsubstituted or substituted with one or two substituents selected from sulfo, alkoxy, alkyl, halogeno and carboxy, or naphthylene substituted once or twice or unsubstituted with a sulfo; And one of X ¹ and X ² is NH ₂ , the other is OH; Z ¹ is -CH = CH ₂ or -CH ₂ CH ₂ Z '(wherein Z' is a group which can be removed by the action of an alkali); B is a group represented by the following general formula (1) or (2)

(Wherein, Represents a bond connected to the azo group, and R < ² > is hydrogen, methyl or methoxy; When X ¹ is OH, L is a triazinyl group represented by any one of the following general formulas (II) to (V);

(Wherein, R ³ is hydrogen, or unsubstituted or substituted alkyl; R ⁴ is hydrogen, alkyl, alkoxy or halogenoalkyl, and; R ⁵ and R ⁶ are either each hydrogen or unsubstituted alkyl, or R ⁵ and R ⁶ may be mutually bonded to form a heterocyclic ring which may contain nitrogen, oxygen or sulfur as a ring atom, and R < ⁷ > represents a heterocyclic ring which may contain an alkoxy, sulfo, carboxy, carboxylic acid ester, hydroxy, cyano, sulfato, halo R ⁸ is selected from the group consisting of alkoxy, sulfo, carboxy, carboxylic acid ester, hydroxy, cyano, sulphato , Straight or branched chain alkyl substituted with one or two substituents selected from halogen, phenyl, substituted phenyl, carbamoyl and sulfamoyl, or alkyl, substituted alkyl, alkoxy, substituted alkoxy, DE hydroxy, sulfo, cyano, carboxy, carboxylic ester, sulfamoyl, carbamoyl, optionally substituted with one or two substituents selected from the group consisting of substituted amino, halogeno or unsubstituted phenyl; R ¹⁰ is hydroxy, Chain or branched alkyl substituted or unsubstituted with one or two substituents selected from the group consisting of halogen, alkoxy, cyano, sulfo, sulfato, carboxy, carboxylic acid ester, carbamoyl, Or R ¹¹ is one or two substituents selected from hydroxy, halogeno, alkoxy, cyano, sulfo, sulfato, carboxy, carboxylic acid ester, carbamoyl, sulfamoyl, amino and substituted amino Alkyl, substituted alkyl, alkoxy, substituted alkoxy, hydroxy, halogeno, cyano, carboxy, substituted or unsubstituted straight or branched chain alkyl, When the carboxylic acid ester, carbamoyl, sulfamoyl, amino, substituted amino, -SO ₂ CH ₂ CH ₂ OH and SO ₂ Z ³ (here, Z ³ is -CH = CH ₂ or -CH ₂ CH ₂ ' Z ' and Z ' is as defined above), or hydrogen, which is unsubstituted or substituted with one or two substituents selected from halogen; Or R ¹⁰ and R ¹¹ may be mutually bonded to form a heterocyclic ring which may contain nitrogen, oxygen or sulfur as a ring atom; Z ² is -CH = CH ₂ or -CH ₂ CH ₂ Z ', wherein Z' is as defined above; A is a divalent aliphatic group represented by the following general formula (3), (4) or (5);

-CH ₂ -W (3)

- (CH ₂ ) _m -O- (CH ₂ ) _n - (4)

Wherein W is selected from the group consisting of a chlorine atom, a bromine atom, a fluorine atom, a hydroxy, a sulfato, a cyano, a C ₁ -C ₄ alkylcarbonyloxy, a C ₁ -C ₅ alkylcarbonyloxy, a carboxy or a carbamoyl substituted or unsubstituted straight or branched chain C ₁ -C ₆ alkylene; W ¹ and W ² are each a straight-chain or branched alkylene C ₂ -C ₆ alkyl; R ⁹ is hydrogen, unsubstituted lower alkyl or phenyl m and n are each independently an integer of 2 to 6), and when X ¹ is NH ₂ , L is a triazinyl group represented by the above general formula (III) or (V).

The present invention also provides a method for dyeing or printing a fiber material using the bisazo compound of the formula (I) or a salt thereof.

Examples of R ^{1 in} the above general formula (I) include linear or branched C ₁ -C ₆ alkyl substituted by hydroxy, halogeno, cyano, carboxy or sulfo, unsubstituted straight or branched C ₁ -C ₆ Alkyl, or hydrogen. Of these, preferred R ¹ is hydrogen or unsubstituted straight or branched C ₁ -C ₆ alkyl, particularly preferably hydrogen or methyl.

D, preferred groups include, for example, unsubstituted phenylene, C ₁ -C ₄ alkyl (eg methyl or ethyl), C ₁ -C ₄ alkoxy (eg methoxy or ethoxy), halogeno Or bromine atoms), sulfo and carboxy, unsubstituted naphthylene, and naphthylene substituted once or twice with a sulfone. A concrete example of D is as follows:

(Wherein, Represents a bond connected to the azo group. Among them, particularly preferable is a group having a sulfo group at the ortho position with respect to the azo group. An example of a particularly preferred D is as follows:

(Wherein, Are as defined above.

Examples of the group that can be separated by the action of an alkali represented by Z ¹ include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetic acid ester group and a halogen. Of these, sulfuric ester groups and halogen are preferable. Preferred Z ¹ , Z ^2, and Z ³ are each independently butyl, β-sulfatoethyl or β-chloroethyl.

An example of group B is:

(Wherein, Are as defined above. Of these, preferred are

(Wherein, Are as defined above.

In the general formulas (II), (III), (IV) and (V), examples of R ³ include the same groups as those in R ^1. Of these, preferably hydrogen and unsubstituted straight- C ₁ -C ₄ alkyl, particularly preferably hydrogen, methyl and ethyl.

Examples of R ⁴ in the general formulas (II) and (III) include hydrogen, lower alkyl, lower alkoxy, chlorine atom, bromine atom and fluorine atom. Of these, preferred are hydrogen, methyl and methoxy.

In the general formula (III), R ⁵ and R ⁶ may be hydrogen or unsubstituted, linear or branched C ₁ -C ₄ alkyl. Of these, preferred are hydrogen, methyl and ethyl.

In the above general formula (III), when R ⁵ and R ⁶ mutually combine to form a heterocyclic ring, the -NR ⁵ R ⁶ group may be a 5- or 6-membered heterocyclic residue. Examples of the above-mentioned heterocyclic residues include those containing only one nitrogen atom as a hetero atom, those containing one nitrogen atom and one or two hetero atoms selected from nitrogen, oxygen and sulfur. Specific examples of the heterocyclic residue include residues derived from pyrrolidine, piperidine, piperazine, N-alkylpiperazine, morpholine, pyrrole, imidazole, and the like. Of these, preferred is a moiety derived from morpholine, i.e. morpholino.

In the combination of -R ⁵ and R ⁶ , preferably -NR ⁵ R ⁶ is morpholino and at least one of R ⁵ and R ⁶ is hydrogen and the other is hydrogen, methyl or ethyl.

In the above general formula (III), the compound represented by H-NR ⁵ R ⁶ , which can be used for forming the residue -NR ⁵ R ⁶ , is, for example, ammonia, methylamine, ethylamine, Amine, n-butylamine, isobutylamine, sec-butylamine, dimethylamine, diethylamine, methylethylamine, pyrrolidine, piperazine, morpholine, piperidine, pyrrole and imidazole. Of these, particularly preferred are ammonia, methylamine, ethylamine and morpholine.

In the above general formula (II), R ⁷ is a straight or branched chain unsubstituted or substituted with alkoxy, sulfo, carboxy, carboxylic acid ester, hydroxy, cyano, sulfato, halogeno, carbamoyl or sulfamoyl Alkyl. Examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, 2- hydroxyethyl, 2- sulfatoethyl, 2- sulfoethyl, 2- methoxyethyl, Ethyl, 2-carboxyethyl and the like. Of these, preferred are unsubstituted C ₁ -C ₄ alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and the like, and particularly preferred are methyl and ethyl.

In the above general formula (II), the compound represented by R ⁷ OH, which may be used for forming the triazine ring-substituted -OR ⁷ group, may be, for example, methanol, ethanol, n-propanol, isopropanol, , 2-butoxyethanol, 2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol, 2-hydroxyethanesulfonic acid, 3-hydroxy- Sulfonic acid, 2-cyanoethanol, 2-sulfatoethanol, glycolic acid, 3-hydroxypropionic acid and the like.

Among them, preferred -OR ⁷ is a residue derived from methanol, ethanol, n-propanol and isopropanol, namely methoxy, ethoxy, n-propoxy and isopropoxy, particularly preferably methoxy and ethoxy.

In the general formulas (IV) and (V), A is a divalent aliphatic group represented by any one of the formulas (3), (4) and (5). Any of these free bonds may be connected to -SO ₂ Z ² .

In the general formula (5), R ⁹ may be hydrogen, C ₁ -C ₄ alkyl or phenyl. Of these, preferred are hydrogen, methyl and ethyl.

Particularly preferred for A is a residue represented by the following formulas (6), (7) and (8):

-CH ₂ -CH ₂ - (6)

-CH ₂ CH ₂ CH ₂ - (7)

-CH ₂ CH ₂ OCH ₂ CH ₂ - (8)

In the general formula (IV), the unsubstituted or substituted alkyl represented by R ⁸ is preferably a straight-chain or branched C ₁ -C ₄ lower alkyl group. Preferred substituents which may be present in the alkyl group are C ₁ -C ₄ alkoxy, sulfo, carboxy, carboxylic acid ester, hydroxy, cyano, sulfato, halogeno, phenyl, sulfophenyl, carbamoyl and sulfamo It is a collective. When a plurality of substituents are present, these substituents may be the same or different from each other. Preferred R ⁸ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, benzyl, 2-hydroxyethyl, 2-sulfatoethyl, , 2-chloroethyl, 2-carboxyethyl and the like. Of these, particularly preferred are C ₁ -C ₄ alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and the like, most preferably methyl and ethyl. Unsubstituted or substituted phenyl represented by R ⁸ is from, for example C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, hydroxy, sulfo, carboxy, sulfamoyl, carbamoyl, a chlorine atom and a bromine atom Preference is given to phenyl which is unsubstituted or substituted by one or two substituents selected. Of these, particularly preferred are phenyl, 2-, 3- or 4-sulfophenyl, 2,4- or 2,5-disulfophenyl, 2-, 3- or 4- chlorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl and the like. More preferably, R < ⁸ > is an unsubstituted or substituted phenyl group in the above alkyl and phenyl groups.

Examples of compounds represented by R ⁸ OH, which can be used to form the triazine ring substituent -OR ⁸ in the above general formula (IV) are: phenol, 1-hydroxy-2-, Methylbenzene, 1-hydroxy-3, 4- or -3,5-dimethylbenzene, 1-hydroxy-2-, 3- or 4- ethylbenzene, 1- 3- or 4-methoxybenzene, 1-hydroxy-2-, 3- or 4- ethoxybenzene, 1-hydroxy-2-, Hydroxybenzene-1, 3-disulfonic acid, 6-hydroxybenzene-1,4-disulfonic acid, 4-hydroxybenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, Aromatic hydrocarbons such as hydroxybenzene-1,2-disulfonic acid, 3- or 4-hydroxybenzoic acid, 5-hydroxybenzene-1,3-dicarboxylic acid and 5-hydroxy- compound; And at least one solvent selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, 2-chloroethanol, 2- methoxyethanol, Propanol, 2-hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2-cyanoethanol, 2-sulfatoethanol, glycolic acid, 3-hydroxypropionic acid, benzyl alcohol, Aliphatic compounds such as chlorobenzyl alcohol, 4-methylbenzyl alcohol, 2-, 3- or 4-sulfobenzyl alcohol, 2-phenylethanol, 1-phenyl-2-propanol and the like.

Of these, preferably the unsubstituted or methyl, methoxy or sulpho substituted phenols or the -OR ⁸ groups derived from methanol, ethanol, n-propanol and isopropanol, i.e. phenoxy, 2-, 3- or Methoxyphenoxy, 2-, 3- or 4-sulfophenoxy, methoxy, ethoxy, n-propoxy and isopropoxy, particularly preferred is 2- Is phenoxy, methylphenoxy, methoxyphenoxy and sulfophenoxy.

In the general formula (V), R ¹⁰ is substituted or unsubstituted with hydroxy, halogeno, alkoxy, cyano, sulfo, sulfato, carboxy, carboxylic acid ester, carbamoyl, sulfamoyl, Substituted straight or branched chain alkyl, or hydrogen. Preferable examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2- hydroxyethyl, 3- hydroxypropyl, 2- Ethoxyethyl, 2-chloroethyl, 2-bromoethyl, 2-sulfoethyl, 2-carboxyethyl, 2-carbamoylethyl, 2-sulfatoethyl, 2-sulfamoylethyl and the like. Of these, preferred are methyl, ethyl, 2-hydroxyethyl, 2-sulfoethyl and 2-carboxyethyl.

In the above general formula (V), R ¹¹ is selected from the group consisting of hydroxy, halogeno, alkoxy, cyano, sulfo, sulfato, carboxy, carboxylic acid ester, carbamoyl, sulfamoyl, amino and substituted amino Alkyl, alkoxy (wherein the alkyl and alkoxy may be further substituted), hydroxy, halogeno, cyano, carboxy, carboxyl, amino, acid ester, sulfamoyl, carbamoyl, amino, substituted amino (eg, _{dimethylamino), -SO 2 CH 2 CH 2} OH and -SO ₂ Z ³ (wherein, Z ³ is the same as Z defined in ¹⁾ Lt; / RTI > is phenyl or unsubstituted phenyl or is hydrogen. The above-mentioned alkyl may be an alkyl group as exemplified in the case of R < ¹⁰ >. Of these, preferred are methyl, ethyl, 2-hydroxyethyl, 2-sulfoethyl and 2-carboxyethyl. In the case of the above-mentioned phenyl, preferably phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4- 3- or 4-hydroxyphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, Phenyl, 2-, 3- or 4-sulfophenyl, 2,4- or 2,5-disulfophenyl, 2- methoxy-5-methylphenyl, 2,5-dimethoxyphenyl,

.

In the group represented by -NR ¹⁰ R ^11, preferably it is a to the same group as well as derived from an amine represented by the following H-NR ¹⁰ R ¹¹ groups as those exemplified in the case of H-NR ⁵ R ^6:

Aniline, N-methylaniline, N-ethyl aniline, o-, m- or p-toluidine, o-, m- or p-anisidine, 2-, 3- or 4- 3- or 4-chloroaniline, 2-, 3- or 4-bromoaniline, 2-, 3- or 4-fluoroaniline, 2-, 3- or 4- (O-, m- or p-isomer), N-methylchloroaniline (2-, 3- or 4-isomer) Isomer), N-ethylchloroaniline (2-, 3- or 4-isomer), aminophenol (o-, m- or p-

Among them, preferred -NR ¹⁰ R ¹¹ is ammonia, methylamine, ethylamine, 2-hydroxyethylamine, 2-sulfoethylamine, 2-carboxyethylamine, aniline, N-methylaniline, -, 3- or 4-anilinesulfonic acid,

to be.

When R ¹⁰ and R ¹¹ are mutually bonded to form a ring, this ring may be the same as exemplified in -NR ⁵ R ⁶ .

Particularly preferred among the amines exemplified above as H-NR ¹⁰ R ¹¹ and used in the formation of -NR ¹⁰ R ¹¹ groups are aromatic amines (such as aniline and its derivatives).

The compounds of the invention are present in the free acid or salt form thereof. Among these salts, preferred are alkali metal salts and alkaline earth metal salts, particularly preferred are sodium salts, potassium salts and lithium salts.

The compound of the present invention can be produced, for example, by the following method. Therefore, the compound of formula (I) of the present invention is a compound represented by the following formula (XII): 2,4,6-trihalogeno-s-triazine:

(Wherein T is a halogen), in the form of the free acid, a bisazo compound represented by the following general formula (VI):

(VIIa) and (VIIb): (wherein B, D, R ¹ , X ¹ , X ² and Z ¹ are as defined above)

(Wherein R ³ , R ⁴ , A and Z ² are as defined above) and compounds represented by the following general formulas (VIII) to (XI):

H-OR ⁷ (VIII), H-OR ⁸ (IX),

H-NR ⁵ R ⁶ (X), H-NR ¹⁰ R ¹¹ (XI),

(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are as defined above) in any order.

2,4,6-trihalogeno-s-triazine, preferably cyanuric chloride and cyanuric fluoride.

The preferred condensation procedure with 2,4,6-trihalogeno-s-triazine is as follows. When L is a group represented by the general formula (II) or (IV) and the compound represented by the general formula (I) is synthesized from the compound represented by the general formula (VIII) or (IX) It is preferable to conduct the condensation of the compound represented by the general formula (VIII) or (IX) first. When L is a group represented by the general formula (III) and the compound represented by the general formula (I) is synthesized from the compound represented by the general formula (X), the condensation of the compound represented by the general formula (X) .

When L is a group represented by the general formula (II) or (III) and the compound represented by the general formula (I) is synthesized from the compound represented by the general formula (VIIa), the condensation of the compound represented by the general formula (VIIa) , Secondarily or thirdarily to obtain excellent results, preferably secondarily or thirdarily.

When L is a group represented by the general formula (IV) and the compound represented by the general formula (I) is synthesized from the compound represented by the general formula (VIIb), the condensation of the compound represented by the general formula (VIIb) .

When L is a group represented by the general formula (V) and the compound represented by the general formula (I) is synthesized from the compound represented by the general formula (VIIb), the condensation of the compound represented by the general formula (VIIb) It is preferable to perform this operation in the first place.

When L is synthesized from the compound represented by the general formula (Ⅰ) compound group represented by the general formula (Ⅴ) by the general formula (XI), the condensation of the compound represented by the general formula (XI) is, R ¹¹ is an aliphatic group , It is preferable to carry out the reaction in a primary or secondary manner, and when R ¹¹ is an aromatic group, it is preferably carried out in a secondary or tertiary manner.

However, in all the cases mentioned above, the condensation reaction sequence is not limited, and the reaction conditions are not limited. Generally speaking, the primary condensation reaction is carried out at a temperature of from -10 ° C to + 40 ° C and a pH of from 1 to 10, a secondary reaction at a temperature of from 0 ° C to 70 ° C and a pH of from 2 to 10 and a tertiary reaction of from 10 ° C to 100 And at a pH of 2 to 9 to obtain a compound represented by the general formula (I) or a salt thereof.

Alternatively, the compounds of the present invention can also be synthesized in the following manner. Therefore, instead of the bisazo intermediate compound represented by the general formula (IV) used in the above production method, a diamine compound represented by the following general formula (XIII) as a condensation component:

(XIV), using the same synthetic procedure as above, using a compound of the general formula (XIV): wherein B and R ¹ are as defined above.

(Wherein B and R < ¹ > and L are as defined above). Further, an amine compound represented by the following general formula (XV):

Z ¹ -SO ₂ -D-NH ₂ (XV)

(Wherein Z ¹ and D are as defined above) is also prepared. These two amine compounds are diazotically separated in a conventional manner and, in the form of the free acid, the compound represented by the following general formula (XVI)

In any order, to obtain a compound represented by the general formula (I). The coupling reaction can be carried out primarily at a temperature of -10 ° C to + 30 ° C and at a pH of 0 to 4, secondly at a temperature of 0 ° C to 40 ° C and at a pH of 2 to 8.

Is a compound represented by the general formula (XVI), preferably a H acid represented by the following formula (9) and a K acid represented by the following formula (10):

Of these, more preferred is H acid represented by the formula (9).

In the third method, the compound represented by the general formula (I) is obtained by reacting the compound represented by the general formula (XVI) with the diacid component constituting the amine compound represented by the general formula (XV) One kind of diacid component in the compounds represented by the formulas (XIII) to (XXII)

(Wherein T, R ¹ , B, R ⁵ , R ⁶ , R ³ , R ⁴ , Z ² , A, R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are as defined above) , Followed by secondary and / or tertiary condensation reaction. In this method, when the diazo compound selected from the compounds represented by the general formulas (XVII) to (XXIII) is firstly coupled with the compound represented by the general formula (XVI), the secondary and / May be carried out at the monoazo intermediate compound stage before the compound is prepared.

The groups represented by Z ¹ and Z ² are each -CH ₂ CH ₂ Z '(wherein Z ^{1, that} is, Z ^{1, which} is a group capable of being separated by the action of an alkali, is an ester group such as a sulfate ester group or a phosphate ester group ), The ester group may be formed after condensation or coupling reaction. That is, the compound represented by the general formula (I) can be obtained by reacting the compound (XXIV), (XXV), (XXV), (XXV), XXVI) and (XXVII), the precursor of the ester compound obtained at any stage is esterified by a conventional method, and the product is treated in the same manner as described above.

(Wherein R ³ , R ⁴ , A, X ¹ , X ² , B, R ¹ and D are as defined above)

Examples of the compound represented by the general formula (IV) in which chromophore groups usable in the present invention, that is, SO ₂ Z ¹ is hydrogen, are as follows:

(5 " -amino-2 " -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid,

(5 " -amino-2 " -sulfophenylazo) -8-aminonaphthalene-3, 5-disulfonic acid,

Amino-2'-sulfophenylazo) -7- (1 "-sulfonaphth-2" -ylza) -8- aminonaphthalene-3,6-disulfonic acid,

Amino-2'-sulfophenylazo) -7- (1 "-sulfonaphth-2" -ylza) -8- aminonaphthalene-3,5-disulfonic acid,

(5 " -amino-2 " -sulfophenylazo) -8-aminonaphthalene-3,6-dicarbamoyl- Disulfonic acid,

Amino-2'-sulfophenylazo) -7- (1 ", 7" -disulfophenylnaphth-2 "-ylza) -8-aminonaphthalene- Disulfonic acid,

Amino-2'-sulfophenylazo) -7- (6 "-sulfonaphth-2" -ylza) -8- aminonaphthalene-

Amino-2'-sulfophenylazo) -7- (8 "-sulfonaphth-2" -ylza) -8- aminonaphthalene-3,6-disulfonic acid,

Amino-2'-sulfophenylazo) -7- (6 "-sulfonaphth-2" -ylza) -8- aminonaphthalene-

(4 " -amino-2 " -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid,

(2 " -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid (hereinafter referred to as " ,

(1 " -sulfo-5 " -aminomethylnaphth-2 " -yrazo) -8-aminonaphthalene-3,6-disulfonic acid ,

(1 " -sulfonaphth-2 ' -yrazo) -8-aminonaphthalene- 3, 6-disulfonic acid,

(1 " -sulfo-5 " -aminomethylnaphth-2 ' -yrazo) -8-aminonaphthalene- 3, 6-disulfonic acid,

(2 " -sulfophenylazo) -8-aminonaphthalene-3, 5-aminomethylnaphth-2'- Disulfonic acid,

(1 ", 7 "-disulfo-aminomethylnaphth-2" -ylza) -8-aminonaphthalene-3,6-di Sulfonic acid,

Aminomethyl-4'-methyl-2'-sulfophenylazo) -7- (1 "-sulfonaphth-2" -ylza) -8- , 6-disulfonic acid,

(5 " -aminomethyl-4 " -methyl-2 " -sulfophenylazo) -8-aminonaphthalene-3 , 6-disulfonic acid,

Amino-2 " -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid,

Amino-2-sulfophenylazo) -7- (2 " -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid,

(1 ", 7 " -disulfo-5 " -aminomethylnaphth-2 ' -yl azo) -7- ) -8-aminonaphthalene-3, 6-disulfonic acid,

Amino-4-methyl-2 ' -sulfophenylazo) -8-aminonaphthalene-3, Disulfonic acid,

Amino-2-sulfophenylazo) -7-phenylazo-8-aminonaphthalene-3,6-disulfonic acid,

Amino-5 " -methoxy-2 " -sulfophenylazo) -8-aminonaphthalene-3 , 6-disulfonic acid,

(5 " -Amino-4 " -methoxy-2 " -sulfophenylazo) -8-aminonaphthalene-3 , 6-disulfonic acid,

Amino-5 "-methoxy-2" -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid,

Amino-5'-methoxy-2'-sulfophenylazo) -7- (1 "-sulfonaphth-2" -ylza) -8-aminonaphthalene- , 6-disulfonic acid,

Amino-4-methoxy-2'-sulfophenylazo) -7- (1 "-sulfonaphth-2" -ylza) -8-aminonaphthalene- , 6-disulfonic acid,

Amino-5'-methoxy-2'-sulfophenylazo) -7- (2 "-sulfophenylazo) -8- aminonaphthalene-

Among the compounds represented by the general formula (I) according to the present invention, the free acid forms are preferably the compounds represented by the following general formulas (E) and (F)

Wherein Z ¹ and L are as defined above, R ¹² is hydrogen or sulfo, and R ²² and R ²³ are each independently of the other hydrogen, methyl, methoxy or sulfo.

Preferred compounds represented by the general formula (E) are, for example, compounds represented by the following general formulas (E-1) to (E-4) in the free acid form:

[Wherein, Z ¹ and R ¹² are as defined above, R ¹⁴ is methyl or ethyl, Q is then represented by the formula (K-1) or (K-2) group:

(Wherein R < ¹³ > is hydrogen, methyl or ethyl and Z < ² > is as defined above);

Wherein Z ¹ , Z ² , R ¹² and R ¹³ are as defined above, R ¹⁵ is hydrogen, R ¹⁶ is hydrogen, methyl or ethyl, or NR ¹⁵ R ¹⁶ is morpholino. ;

Wherein Z ¹ , Z ² and R ¹² are as defined above and R ¹⁷ is hydrogen and R ¹⁸ is hydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl, sulfophenyl, methylphenyl, methoxyphenyl , Hydroxyphenyl or carboxyphenyl, or NR ¹⁷ R ¹⁸ is morpholino R ¹⁸ is particularly preferably unsubstituted or substituted phenyl as defined above);

Wherein Z ¹ , Z ² and R ¹² are as defined above and R ²⁴ and R ²⁵ are each hydrogen, sulfo, methyl, ethyl, methoxy, ethoxy, chlorine atom or carboxy.

Other preferred compounds included in the general formula (E) are, for example, compounds represented by the following general formulas (E-5) to (E-12) in the form of free acid:

(Wherein R ¹³ and R ¹⁴ are as defined above);

(Wherein R ¹⁴ is as defined above and G is two aliphatic groups represented by the above-mentioned formula (6), (7) or (8));

(Wherein R ¹³ , R ¹⁵ and R ¹⁶ are as defined above);

(Wherein G, R ¹⁷ and R ¹⁸ are as defined above);

(Wherein R ¹³ and R ¹⁴ are as defined above);

(Wherein R ¹³ , R ¹⁵ and R ¹⁶ are as defined above);

(Wherein G, R ²⁴ and R ²⁵ are as defined above); and

(Wherein G, R ²⁴ and R ²⁵ are as defined above).

A preferred compound represented by the general formula (F) is, for example, a compound represented by the following general formula (F-1) in a free acid form:

(Wherein, Z ^1, Z ^2, R ²² and R ²³ are as defined above, R ¹⁹ is hydrogen, methyl or ethyl, R ²⁰ is hydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl, phenyl , Methoxyphenyl, sulfophenyl, carboxyphenyl, chlorophenyl, hydroxyphenyl, or 3- or 4- (ssulfatoethylsulfonyl) phenyl, or NR ¹⁰ R ²⁰ is morpholino.

Another preferred compound contained in the general formula (F) is, for example, a compound represented by the following general formula (F-2) in a free acid form:

Wherein G and R ¹⁹ are as defined above and R ²¹ is phenyl, methylphenyl, methoxyphenyl, chlorophenyl, sulfophenyl, carboxyphenyl, or 3- or 4- (ssulfatoethylsulfonyl) Phenyl.)

The compounds of the present invention are fiber-reactive and useful for dyeing or printing hydroxy group- or amide group-containing materials in the form of non-blend or blend fibers.

Hydroxy group containing materials include cellulose fiber materials, their regenerated products, and natural or synthetic hydroxy group containing materials such as polyvinyl alcohol. Cellulose fiber materials are preferably cotton, and other plant fibers such as linen, flax, hemp, jute and ramie fibers. Examples of the regenerated cellulose fibers include viscose rayon staples and viscose rayon filaments.

Examples of the amide group-containing material include synthetic or natural polyamides and polyurethanes. In particular, the fibrous material is exemplified by wool and other pure cotton, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The fiber material may be dyed in any suitable manner selected according to the physical and chemical properties of the fiber material described above.

The cellulose fiber material can be dyed by absorption, padding, cold batch-up dyeing or printing using the compounds of the present invention.

The absorption dyeing can be carried out in the presence of an acid binder (for example sodium carbonate, tribasic sodium phosphate or sodium hydroxide) at a relatively low temperature, together with a neutral salt (for example sodium sulphate or sodium chloride), if necessary together with a dissolution aid, It can be dyed and dyed. The neutral salt used to accelerate the absorption of the dye can be added in portions before, after, and after the temperature of the dye bath reaches a predetermined dyeing temperature.

Also, padding dyeing can be done by padding the fiber material at room or elevated temperature, drying and then stimming or dry heat to fix the dye.

The printing can be carried out in one-phase or two-phase. The single-phase printing can be carried out by printing the fiber material with a printing paste containing an acid binder such as sodium bicarbonate, and steaming the printed fibers at 95 ° C to 160 ° C. The two-phase printing can be achieved by printing the fiber material with a neutral or weakly acidic printing paste, passing the printed fibers through a heated alkaline solution bath containing the electrolyte, or over-padding the printed fibers with an electrolyte containing alkali padding solution, Or may be carried out by steam annealing or dry heat treatment.

For the production of printing paste, a thickener or emulsifier such as sodium alginate or starch ether or the like may be used together with a conventional printing preparation and / or dispersing agent such as an element, if necessary.

Suitable acid binders for fixing the compounds of the present invention to cellulose fibers include water-soluble basic salts formed between an alkali metal or alkaline metal and an inorganic or organic acid, or compounds which liberate alkali in the heated state . Preferably an alkali metal hydroxide, and an alkali metal salt of an inorganic or organic acid having a weak or moderate strength. Of these, sodium salts and potassium salts are particularly preferred. Specific examples of such an acid binding agent include sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium phosphate, potassium carbonate, primary, secondary and tertiary phosphates, sodium silicate and trichloroacetosal sodium.

In addition, the dyeing of the synthetic or natural polyamide and polyurethane fiber materials can be accomplished by damping while adjusting the pH value in an acidic or slightly acidic salt bath and then changing the pH to a neutral, if appropriate, alkaline pH value in a salt bath. The dyeing can be carried out usually at a temperature of 60 ° C to 120 ° C. In order to uniformly dye, a conventional leveling agent such as a condensation product of cyanuric chloride with aminobenzenesulfonic acid or aminonaphthalenesulfonic acid at 3-fold moles or an adduct of stearylamine with ethylene oxide may be used.

The compounds of the invention are distinguished in particular by their excellent dye performance in dyeing and printing of cellulose fiber materials. For example, the compound of the present invention can be used as a dyeing material having excellent wet fastness, wear fastness and iron fastness such as light fastness, sweat-day light fastness, wash fastness, internal oxide washing ability, chlorine resistance, perspiration resistance, internal hydrolysis resistance and alkali resistance .

In addition, the compound of the present invention exhibits excellent dyeability, build-up property, leveling property, wash-off property and high solubility as well as excellent adsorption and fixation ratio. Moreover, since the compound of the present invention is hardly affected by the change of the dyeing temperature, the amount of the dyeing auxiliary such as the salt and alkali, and the salt bath ratio, it is possible to obtain a dyeing with a constant quality.

Furthermore, the dyed product obtained according to the present invention is less discolored during the fixing treatment and the resin finishing treatment, and has little change upon contact with the basic substance during the storage period.

When the compound of the present invention is used in the form of a mixture with the fiber-reactive dyes disclosed in the following patent publications, excellent dyes can be obtained:

Japanese Patent Application Laid-open No. 61-155469 (= European Patent Publication 184071), Japanese Patent Application Laid-open No. 59-161463, Japanese Patent Application Laid-open No. 56-15481 (= European Patent Publication No. 21105) Japanese Patent Application Laid-open No. 57-89679 (= European Patent Publication No. 52985), Japanese Patent Application Laid-open No. 60-6754, Japanese Patent Laid-Open Publication No. 50-178, Japanese Patent Laid-open No. 56-118976 Japanese Patent Application Laid-open No. 35171), Japanese Patent Application Laid-Open No. 63-77974 (= European Patent Publication No. 239847), Japanese Patent Application No. 57-2365 (= European Patent Publication No. 42108) -15451 (= European Patent Publication No. 99721), Japanese Patent Application Laid-open No. 56-9483 (= European Patent Publication No. 22265), Japanese Patent Application Laid-open No. 60-123559 and Japanese Patent Laid- number.

In addition, when the compound of the present invention is used in the form of a mixture mixed with dyes commercially available under the trade names such as Sumipix Supra, Sumipix, Levapix, and Ramesol, excellent results can be obtained.

Hereinafter, the present invention will be described in more detail by way of examples. However, these embodiments are provided only for facilitating understanding of the present invention, and the present invention is not limited to these embodiments. In the examples, "parts" and "%" used herein mean parts by weight and% by weight, respectively, unless otherwise specified.

[Example 1]

(3.76 parts) of 2,4-diaminobenzenesulfonic acid and 3.69 parts of cyanuric chloride were condensed and reacted at a pH of 2 to 4 at a temperature of 0 to 15 ° C, and the resulting condensation product and 2- (β -Hydroxyethylsulfonyl) ethylamine (3.06 parts) was condensed with a pH of 6 to 9 at a temperature of 15 to 40 ° C. Diazotization reaction of the obtained condensation product with the diazotization product and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at a pH of 1 to 3.5 and a temperature of 0 to 15 ° C Coupling reaction, followed by diazotization of the resulting coupling product with 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23 parts) at pH 4 to 8 and at a temperature of 0 to 30 ° C. Coupling reaction. Subsequently, the obtained coupling product and 3-aminobenzenesulfonic acid (3.47 parts) were subjected to condensation reaction at a pH of 2 to 5 at a temperature of 50 to 80 ° C. Subsequently, the condensation product thus obtained was converted into a sulfuric acid ester by a conventional method and salted out to give a bisazo compound represented by the following structural formula.

(? max = 610 nm, in aqueous medium)

[Example 2]

2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, The synthesis method of Example 1 was repeated except that the 2- (β-hydroxyethylsulfonyl) ethalamine was replaced with the compounds shown in Columns 2, 3, 4, 5 and 6 of the following Table 1 To give the corresponding bisazo compound. The thus-obtained bisazo compound was used to stain the fiber material to obtain a dyeing material having the color shown in column 7 of Table 1. Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride. Similar results were obtained when the compound of column 6 was replaced with the corresponding sulfur ester derivative and the last step, i. E., The conversion to the sulfuric acid ester was omitted.

[Example 3]

(3.47 parts) and cyanuric chloride (3.69 parts) were subjected to condensation reaction at a pH of 2 to 5 at a temperature of 0 to 15 ° C, and then the resulting condensation product and 2- (? -Hydroxy Ethylsulfonyl) ethylamine (3.06 parts) was condensed with a pH of 6 to 9 at a temperature of 15 to 40 ° C. Then, the resulting condensation product and 2,4-diaminobenzenesulfonic acid (3.76 parts) were subjected to condensation reaction at a pH of 2 to 5 at a temperature of 50 to 80 ° C. Diazotization reaction of the obtained condensation product with the diazotization product and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at a pH of 1 to 3.5 and a temperature of 0 to 15 ° C Coupling reaction, followed by diazotization of the resulting coupling product with 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23 parts) at pH 4 to 8 and at a temperature of 0 to 30 ° C. Coupling reaction. Subsequently, the obtained coupling product was converted to a sulfuric acid ester in a usual manner and salted out to give a bisazo compound represented by the following structural formula.

[Example 4]

As used in Example 3, 2-aminonaphthalene-6-ssulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid , 2-aminobenzenesulfonic acid and 2- (β-hydroxyethylsulfonyl) ethylamine were replaced by the compounds shown in column 2, column 3, column 4, column 5 and column 6 in the following Table 2 The synthesis method of Example 3 was repeated to obtain the corresponding bisazo compound. The bisazo compound thus obtained was dyed on a fiber material to obtain a dyeing material having the color shown in column 7 in Table 2. [ Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride. In addition to 6 is a compound (and / or -SO ₂ C ₂ H ₄ and 5, the second column is the compound (s) in the case having OH group) and the corresponding substituted acid ester derivative, and the last step, that is, sulfuric acid esters of Similar results were obtained when switching was omitted.

[Example 5]

(3.76 parts) of 2,4-diaminobenzenesulfonic acid and 3.69 parts of cyanuric chloride were condensed and reacted at a pH of 2 to 4 at a temperature of 0 to 15 ° C, and the resulting condensation product and 3- (β -Chloroethylsulfonyl) propylamine (3.72 parts) was condensed with a pH of 6 to 9 at a temperature of 15 to 40 ° C. The resulting condensation product and 4-aminobenzenesulfonic acid (3.47 parts) were subjected to condensation reaction at a pH of 2 to 5 at a temperature of 50 to 80 ° C. Diazotization reaction of the obtained condensation product with the diazotization product and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at a pH of 1 to 3.5 and a temperature of 0 to 15 ° C Coupling reaction, followed by diazotization of the resulting coupling product with 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23 parts) at pH 4 to 8 and at a temperature of 0 to 30 ° C. Coupling reaction. Subsequently, the obtained coupling product was salted out and expressed in the form of a free acid, to give a bisazo compound represented by the following structural formula.

[Example 6]

As used in Example 5, 2-aminonaphthalene-6-ssulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid , 4-aminobenzenesulfonic acid and 3- (? -Hydroxyethylsulfonyl) propylamine were replaced by the compounds shown in column 2, column 3, column 4, column 5 and column 6 in the following Table 3 The synthesis method of Example 5 was repeated to obtain the corresponding bisazo compound. The thus-obtained bisazo compound was used to stain the fiber material to obtain a dyeing material having the hue shown in column 7 of Table 3. Similar results were obtained when the above synthesis was repeated by changing the order of the first, second and third condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride.

[Example 7]

The synthesis method of Example 1 was repeated except that the coupling reaction between 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and two diazo compounds was carried out in the reverse order, , A bisazo compound represented by the following structural formula was obtained.

[Example 8]

The corresponding bisazo compounds were obtained by repeating the synthesis method of Example 7 using the compounds of Columns 2 to 6 of Table 4 as used in Example 2. [ Thus, a dye material having a navy blue color was obtained by staining the fiber material with a bisazo compound. Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride. Similar results were obtained when the compound of column 6 was replaced by the corresponding sulfuric acid ester derivative and the last step, i.e., the conversion to the sulfuric acid ester was omitted.

[Example 9]

2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4- The synthesis method of Example 7 was repeated except that the 2- (β-hydroxyethylsulfonyl) ethylamine was replaced with the compounds shown in Columns 2, 3, 4, 5 and 6 of Table 4 below To give the corresponding bisazo compound. The thus-obtained bisazo compound was stained on a fiber material to obtain a dyeing material having the color shown in column 7 of Table 4. [ Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric chloride. It is also possible to replace the compound of column 6 (and the compound of column 2 in the case of having -SO ₂ C ₂ H ₄ OH group) with the corresponding sulfuric acid ester derivative and, if the conversion to the last step, .

[Example 10]

The synthesis method of Example 3 was repeated except that the coupling reaction of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid with two diazo compounds was carried out in the reverse order, , A bisazo compound represented by the following structural formula was obtained.

[Example 11]

The corresponding bisazo compound was obtained by repeating the synthesis method of Example 10 using the compounds of Columns 2 to 6 of Table 5 as used in Example 4. [ The thus-obtained bisazo compound was used to stain a fiber material to obtain a dye having a navy blue color. Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride. In addition to 6 is a compound (and / or -SO ₂ C ₂ H ₄ and 5, the second column is the compound (s) in the case having OH group) and the corresponding substituted acid ester derivative, and the last step, that is, sulfuric acid esters of Similar results were obtained when switching was omitted.

[Example 12]

2-aminonaphthalene-6-ssulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, 2- The synthesis method of Example 10 was repeated except that 2- (β-hydroxyethylsulfonyl) ethylamine was replaced by the compounds shown in Columns 2, 3, 4, 5 and 6 of Table 5 below To give the corresponding bisazo compound. The thus-obtained bisazo compound was used to stain the fiber material to obtain a dyeing material having the color shown in column 7 in Table 5. [ Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride. In addition to 6 is a compound (and / or -SO ₂ C ₂ H ₄ and 5, the second column is the compound (s) in the case having OH group) and the corresponding substituted acid ester derivative, and the last step, that is, sulfuric acid esters of Similar results were obtained when switching was omitted.

[Example 13]

The synthesis method of Example 5 was repeated except that the coupling reaction between 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and two diazo compounds was carried out in the reverse order, , A bisazo compound represented by the following structural formula was obtained.

[Example 14]

The corresponding bisazo compounds were obtained by repeating the synthesis method of Example 13 using the compounds of Columns 2 to 6 of Table 6 as used in Example 6. The thus-obtained bisazo compound was used to stain a fiber material to obtain a dye having a navy blue color. Similar results were obtained when the above synthesis was repeated by changing the order of the first, second and third condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride.

[Example 15]

As used in Example 13, 2-aminonaphthalene-6-ssulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid , 4-aminobenzenesulfonic acid and 3- (β-hydroxyethylsulfonyl) propylamine were replaced by the compounds shown in column 2, column 3, column 4, column 5 and column 6 of the following Table 6 The synthesis method of Example 13 was repeated to obtain the corresponding bisazo compound. The thus obtained bisazo compound was dyed on the fiber material to obtain a dyeing material having the color shown in column 7 of Table 6. [ Similar results were obtained when the above synthesis was repeated by changing the order of the first, second and third condensation reactions using cyanuric chloride. Similar results were obtained when the synthesis was repeatedly carried out by replacing cyanuric chloride with cyanuric fluoride.

[Example 16]

In a usual manner, cyanuric chloride (3.69 parts) and 2,4-diaminobenzenesulfonic acid (3.76 parts) were subjected to condensation reaction with a pH of 2 to 4 at a temperature of 0 to 10 ° C, and the resulting condensation product and ethylamine Part) was subjected to condensation reaction with stirring at a pH of 6 to 10 and a temperature of 20 to 40 ° C. Diazotization reaction of the obtained condensation product with the diazotization product and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at a pH of 1 to 3.5 and a temperature of 0 to 15 ° C Coupling reaction and then diazotizing the resulting coupling product with 2-aminonaphthalene-6 -? - sulfatoethylsulfone-1-sulfonic acid (8.23 parts) at pH 4 to 8 and at a temperature of 0 to 20 ° C Coupling reaction. Finally, the obtained coupling product and 1-aminobenzene-3-β-sulfatoethylsulfone (5.63 parts) were subjected to a condensation reaction at a pH of 2 to 5 at a temperature of 50 to 80 ° C. Then, the condensation product obtained was salted out and expressed in the form of a free acid, to give a bisazo compound represented by the following structural formula.

[Example 17]

2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, Benzene-3 -? - sulfatoethylsulfone was replaced with the compounds shown in column 2, column 3, column 4, column 5 and column 6 in the following Table 7, the procedure of Example 16 was repeated, To obtain a bisazo compound. The thus-obtained bisazo compound was stained on a fiber material to obtain a dyeing material having the color shown in column 7 in Table 7. [ Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride.

[Example 18]

The cyanuric chloride (3.69 parts) and 1-aminobenzene-4-sulphatoethylsulfone (5.63 parts) were subjected to a condensation reaction with a pH of 2 to 5 at a temperature of 5 to 20 ° C, followed by methylamine 0.63 part) was added with stirring at a pH of 6 to 10 and a temperature of 15 to 40 ° C to continue the condensation reaction. The resulting condensation product and 2,4-diaminobenzenesulfonic acid (3.76 parts) were subjected to condensation reaction at a pH of 2 to 5 at a temperature of 50 to 80 ° C. Diazotization reaction of the obtained condensation product and coupling reaction of the resulting diazotised product with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at pH 0.5 to 3.5 at a temperature of 0 to 15 ° C , And the product obtained by diazotizing the resulting coupling product with 2-aminonaphthalene-6 -? - sulfatoethylsulfone-1-sulfonic acid (8.23 parts) was subjected to coupling reaction at a pH of 4 to 8 at a temperature of 0 to 20 ° C . Finally, the obtained coupling condensation product was salted out with potassium chloride and expressed in the form of a free acid, to give a bisazo compound represented by the following structural formula.

[Example 19]

Sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, methylamine and 1-amino Benzene-4-β-sulfatoethylsulfone was replaced with the compound shown in column 2, column 3, column 4, column 5 and column 6 of the following Table 8, the procedure of Example 18 was repeated, To obtain a bisazo compound. The thus-obtained bisazo compound was stained on a fiber material to obtain a dyeing material having the color shown in column 7 of Table 8. [ Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride.

[Example 20]

The synthesis method of Example 16 was repeated except that the coupling reaction of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid with two diazo compounds was carried out in the reverse order, , A bisazo compound represented by the following structural formula was obtained.

[Example 21]

The corresponding bisazo compounds were obtained by repeating the procedure of Example 20 using the compounds of Columns 2 to 6 of Table 9 as used in Example 17. The bisazo compound thus obtained was dyed on a fiber material to obtain a dye having a navy color.

[Example 22]

As used in Example 20, 2-aminonaphthalene-6-ssulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid , Ethylamine and 1-aminobenzene-3-β-sulfatoethylsulfone were replaced by the compounds shown in column 2, column 3, column 4, column 5 and column 6 of the following Table 9 The synthesis method was repeated to obtain the corresponding bisazo compound. The thus-obtained bisazo compound was dyed on the fiber material to obtain a dyeing material having the color shown in column 7 in Table 9. [ Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride.

[Example 23]

The synthesis method of Example 18 was repeated, except that the coupling reaction of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid with two diazo compounds was carried out in the reverse order, , A bisazo compound represented by the following structural formula was obtained.

[Example 24]

The corresponding bisazo compounds were obtained by repeatedly carrying out the synthesis method of Example 23 using the compounds of Columns 2 to 6 of Table 10 as used in Example 19. The bisazo compound thus obtained was dyed on a fiber material to obtain a dye having a navy color.

[Example 25]

As used in Example 23, 2-aminonaphthalene-6-ssulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid , Methylamine and 1-aminobenzene-4-β-sulfatoethylsulfone were replaced by the compounds shown in column 2, column 3, column 4, column 5 and column 6 of the following Table 10 The synthesis method was repeated to obtain the corresponding bisazo compound. The thus-obtained bisazo compound was used to stain a fiber material to obtain a dyed material having the color shown in column 7 in Table 10. Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were obtained when the synthesis was repeatedly carried out by replacing cyanuric chloride with cyanuric fluoride.

[Example 26]

Methanol (0.64 parts) and cyanuric chloride (3.69 parts) were subjected to condensation reaction in the usual manner, and the resulting condensation product and 2,4-diaminobenzenesulfonic acid (3.76 parts) were subjected to condensation reaction. Diazotization reaction of the obtained condensation product with the diazotization product and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at a pH of 1 to 3.5 and a temperature of 0 to 15 ° C Coupling reaction, followed by diazotization of the resulting coupling product with 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23 parts) at pH 3 to 8 and at a temperature of 0 to 30 ° C. Coupling reaction. Finally, the obtained coupling product and 1-aminobenzene-3-β-sulfatoethylsulfone (5.63 parts) were subjected to a condensation reaction with a pH of 2 to 5 at a temperature of 50 to 80 ° C., and the resulting condensation product was salted out with potassium chloride, When expressed in the form of the free acid, a bisazo compound represented by the following structural formula was obtained.

[Example 27]

As used in Example 26, 2-aminonaphthalene-6-ssulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid , Methylol and 1-aminobenzene-3-β-sulfatoethylsulfone were replaced by the compounds shown in column 2, column 3, column 4, column 5 and column 6 of the following Table 11 The synthesis method was repeated to obtain the corresponding bisazo compound. The thus-obtained bisazo compound was dyed on the fiber material to obtain a dyeing material having the color shown in column 7 of Table 11. [ Similar results were obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride.

[Example 28]

Methanol (0.64 parts) and cyanuric chloride (3.69 parts) were subjected to a condensation reaction in the usual manner, and the resulting condensation product was condensed with 1-ethylaminobenzene-4-β-sulfatoethylsulfone (6.19 parts) . The resulting condensation product and 2, 4-diaminobenzenesulfonic acid (3.76 parts) were subjected to condensation reaction at a pH of 2 to 5 at a temperature of 50 to 80 ° C. Diazotization reaction of the obtained condensation product with the diazotization product and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at a pH of 1 to 3.5 and a temperature of 0 to 15 ° C Coupling reaction and then diazotizing the resulting coupling product with 2-aminonaphthalene-5-sulphatoethylsulfone-1-sulfonic acid (7.23 parts) at pH 3 to 8 and at a temperature of 0 to 30 ° C Coupling reaction. Finally, the obtained coupling product was salted out with potassium chloride and expressed in the form of a free acid, to give a bisazo compound represented by the following structural formula.

[Example 29]

As used in Example 26, 2-aminonaphthalene-5-ssulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid , Methylol and 1-ethylaminobenzene-4-β-sulfatoethylsulfone were replaced by the compounds shown in column 2, column 3, column 4, column 5 and column 6 in the following Table 12 Was repeatedly carried out to obtain the corresponding bisazo compound. The thus-obtained bisazo compound was stained on a fiber material to obtain a dyeing material having the color shown in column 7 in Table 12. [ Similar results were obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride.

[Example 30]

Methanol (0.64 parts) and cyanuric chloride (3.69 parts) were subjected to a condensation reaction in the usual manner, and the resulting condensation product was then condensed with 2,4-diaminobenzenesulfonic acid (3.76 parts). The resulting condensation product and condensation reaction were carried out at a pH of 6 to 10 and at a temperature of 50 to 90 ° C with 2- (β-hydroxyethylsulfonyl) ethylamine (3.06 parts). Diazotization reaction of the obtained condensation product with the diazotization product and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (6.39 parts) at a pH of 1 to 3.5 and a temperature of 0 to 15 ° C Coupling reaction, followed by diazotization of the resulting coupling product with 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid (8.23 parts) at pH 3 to 8 and at a temperature of 0 to 30 ° C. Coupling reaction. Finally, the obtained coupling product was converted to a sulfuric acid ester by a conventional method and salted out to give a bisazo compound represented by the following structural formula.

[Example 31]

As used in Example 30, 2-aminonaphthalene-6-ssulfatoethylsulfone-1-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid , Methanol and 2- (β-hydroxyethylsulfonyl) ethylamine were replaced by the compounds shown in column 2, column 3, column 4, column 5 and column 6 of Table 13 below The procedure was repeated to give the corresponding bisazo compound. The thus-obtained bisazo compound was stained on a fiber material to obtain a dyeing material having the color shown in column 7 in Table 13. [ Similar results were obtained when the above synthesis was repeated by changing the order of the first and second condensation reactions using cyanuric chloride. Similar results were also obtained when the above synthesis was repeated by replacing cyanuric chloride with cyanuric fluoride.

[Example 32]

Each of the bisazo compounds obtained in Examples 1 to 31 (0.1 part, 0.3 part and 0.6 part) was dissolved in water (200 parts). Sodium sulfate (10 parts) and cotton (10 parts) were added to the resulting solution. The reaction bath was heated to 60 DEG C and sodium carbonate (4 parts) was added. After dyeing at the same temperature for 1 hour, the dyed surface was washed, soaked, and rinsed, and then dried to obtain each dyeing having navy blue color with excellent buildability and excellent fastness.

[Example 33]

Each of the bisazo compounds described in Examples 1 to 31 was used to prepare each color paste having the following composition.

Bisazo compound 5 parts

Element Five

Sodium alginate (5%) stock paste 50 parts

25 pieces of hot water

Sodium bicarbonate 2 parts

Water 13 part

Mercerized cotton broad cloth was printed with color paste having the above composition, preliminarily dried, steamed at 100 DEG C for 5 minutes, washed with hot water, then sopped, then washed again with hot water and dried. Thus, a printing material having a navy blue hue and excellent in various fastnesses was obtained.

Claims (14)

A bisazo compound represented by the following formula (I) or a salt thereof: Wherein R < ¹ > is hydrogen, or unsubstituted or substituted alkyl; D is phenylene substituted or unsubstituted with one or two substituents selected from sulfo, alkoxy, alkyl, halogeno and carboxy, or naphthylene substituted once or twice or unsubstituted with a sulfo; And one of X ¹ and X ² is NH ₂ , the other is OH; Z ¹ is -CH = CH ₂ or -CH ₂ CH ₂ Z '(wherein Z' is a group which can be removed by the action of an alkali); B is a group represented by the following general formula (1) or (2) (Wherein, Represents a bond connected to the azo group, and R < ² > is hydrogen, methyl or methoxy; When X ¹ is OH, L is a triazinyl group represented by any one of the following general formulas (II) to (V); (Wherein, R ³ is hydrogen, or unsubstituted or substituted alkyl; R ⁴ is hydrogen, alkyl, alkoxy or halogenoalkyl, and; R ⁵ and R ⁶ are either each hydrogen or unsubstituted alkyl, or R ⁵ and R ⁶ are mutually bonded to form a heterocyclic ring which may contain nitrogen, oxygen or sulfur as a ring atom, and R ⁷ is a group selected from the group consisting of alkoxy, sulfo, carboxy, carboxylic acid ester, hydroxy, cyano, sulfato, halo R ⁸ is selected from the group consisting of alkoxy, sulfo, carboxy, carboxylic acid ester, hydroxy, cyano, sulphato Substituted or unsubstituted alkyl, substituted or unsubstituted alkyl, alkoxy, substituted alkoxy, hydroxycarbamoyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkoxy, substituted or unsubstituted alkoxy, R ¹⁰ is phenyl substituted with one or two substituents selected from the group consisting of hydrogen, cyano, sulfo, cyano, carboxy, carboxylic acid ester, sulfamoyl, carbamoyl, substituted amino and halogeno; Which is unsubstituted or substituted by one or two substituents selected from halogen, alkoxy, cyano, sulfo, sulfato, carboxy, carboxylic acid, ester, carbamoyl, sulfamoyl, Alkyl, or hydrogen; R ¹¹ is one or two selected from hydroxy, halogeno, alkoxy, cyano, sulfo, sulfato, carboxy, carboxylic acid, ester, carbamoyl, sulfamoyl, Alkyl, substituted alkyl, alkoxy, substituted alkoxy, hydroxy, halogeno, cyano, carboxy, substituted or unsubstituted alkyl, Diplopia, carboxylic ester, carbamoyl, sulfamoyl, amino, substituted amino, -SO ₂ CH ₂ CH ₂ OH and SO ₂ Z ³ (here, Z ³ is -CH = CH ₂ or -CH ₂ CH ₂ ' Z ' and Z ' is as defined above), or hydrogen, which is unsubstituted or substituted with one or two substituents selected from halogen; Or R ¹⁰ and R ¹¹ may be mutually bonded to form a heterocyclic ring which may contain nitrogen, oxygen or sulfur as a ring atom; Z ² is -CH = CH ₂ or -CH ₂ CH ₂ Z '(wherein Z ¹ is as defined above); A is a divalent aliphatic group represented by the following general formula (3), (4) or (5); -CH ₂ -W- (3) - (CH ₂ ) _m -O- (CH ₂ ) _n - (4) (Wherein W is a chlorine atom, a bromine atom, a fluorine atom, a hydroxy, a sulfato, a cyano, a C ₁ -C ₄ alkylcarbonyloxy, a C ₁ -C ₅ alkoxycarbonyl, a carboxy or a carbamoyl or unsubstituted linear or branched C ₁ -C ₆ alkylene; W ¹ and W ² are each a straight-chain or branched C ₂ -C ₆ alkylene; R ⁹ is hydrogen, unsubstituted lower alkyl or phenyl; m And n are each independently an integer of 2 to 6), and when X ¹ is NH ₂ , L is a triazinyl group represented by the above general formula (III) or (V). A bisazo compound or a salt thereof according to claim 1, wherein R ¹ is hydrogen or methyl. 2. A bisazo compound or a salt thereof according to claim 1, wherein R < ³ > is hydrogen, methyl or ethyl. A bisazo compound or a salt thereof according to claim 1, wherein B is a group represented by the following structural formula in the form of a free acid. (Wherein, Are as defined in claim 1. The bisazo compound or a salt thereof according to claim 1, wherein L is represented by the general formula (III) wherein R ⁵ is hydrogen, or R ¹⁰ is hydrogen. (IV) wherein L is phenyl represented by the general formula (II) wherein R ⁷ is methyl or ethyl, or R ⁸ is methyl, methoxy or sulfone, or unsubstituted phenyl, ≪ / RTI > or a salt thereof. The bisazo compound or its salt according to claim 1, wherein A is a residue represented by the following formula (6), (7) or (8). -CH ₂ -CH ₂ - (6) -CH ₂ CH ₂ CH ₂ - (7) -CH ₂ CH ₂ OCH ₂ CH ₂ - (8) The bisazo compound or its salt according to claim 1, wherein Z ¹ , Z ² and Z ³ are each vinyl,? -Sulfatoethyl or? -Chloroethyl. The bisazo compound or a salt thereof according to claim 1, wherein the compound is a compound represented by the following formula (E-1). Wherein Z ¹ is as defined in claim 1, R ¹² is hydrogen or sulfo, R ¹⁴ is methyl or ethyl and Q is a group represented by the following general formula (K-1) or (K-2) group: (Wherein R ¹³ is hydrogen, methyl or ethyl and Z ² is as defined in claim 1). The bisazo compound or a salt thereof according to claim 1, wherein the compound is a compound represented by the following formula (E-2): (Wherein, Z ¹ and Z ² are as defined in claim 1, R ¹² is hydrogen or sulfo, R ¹³ is hydrogen, methyl or ethyl, R ¹⁵ is hydrogen, R ¹⁶ is hydrogen, methyl or ethyl Or NR < ¹⁵ > R < ¹⁶ > is morpholino). The bisazo compound or a salt thereof according to claim 1, wherein the compound is a compound represented by the following formula (E-3). Wherein Z ¹ and Z ² are as defined in claim 1, R ¹² is hydrogen or sulfo, R ¹⁷ is hydrogen and R ¹⁸ is hydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl, sulfo Phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl or carboxyphenyl, or NR ¹⁵ R ¹⁶ is morpholino). The bisazo compound or a salt thereof according to claim 1, wherein the compound is a compound represented by the following formula (E-4). Wherein Z ¹ and Z ² are as defined in claim 1, R ¹² is hydrogen or sulfo and R ²⁴ and R ²⁵ are each hydrogen, sulfo, methyl, ethyl, methoxy, ethoxy, Carboxy.) The bisazo compound or a salt thereof according to claim 1, wherein the compounding room is a compound represented by the following formula (F-1). Wherein Z ¹ and Z ² are as defined in claim 1 and R ¹⁹ is hydrogen, methyl or ethyl and R ²⁰ is hydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl, methylphenyl, methoxyphenyl , Or sulfinyl, carboxyphenyl, chlorophenyl, hydroxyphenyl, or 3- or 4- (ssulfatoethylsulfonyl) phenyl, or NR ¹⁹ R ²⁰ is morpholino, R ²² and R ²³ are each Hydrogen, methyl, methoxy or sulfo.) A method for dyeing or printing a fiber material comprising applying a bisazo compound according to claim 1 to a fiber material.