JP2861174B2 - Monoazo compound and method for dyeing or printing fiber material using the same - Google Patents

Description

The present invention relates to a material containing a hydroxy group and / or an amide group, particularly cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers or leather, and blends thereof. The present invention relates to an improved compound suitable for dyeing and printing fibers and enabling light-fast and wet-fast yellow dyeing, and its application.

<Prior Art> Compounds having a vinylsulfone-based reactive group and a pyridinium triazine-reactive group in the same molecule are disclosed in
Although it is known in Japanese Patent No. 173060, it is insufficient in dyeing performance, for example, build-up property, and further improvement is desired.

<Problems to be Solved by the Invention> Conventionally, various reactive dyes have been widely used in the field of dyeing and printing of fiber materials. However, the state of the art is not yet fully satisfactory in view of the high requirements for suitability for particular dyeing processes and the sophistication of the requirements for the fastness of dyeings.

The above-mentioned known reactive dyes are insufficient in solubility, dyeing performance (eg, build-up property) and fastness,
There is a strong desire to provide further improved dyes.

The importance of good build-up properties is a very important factor in today's increasingly demanding economics of dyeing methods.

Means for Solving the Problems The present inventors have intensively studied for the purpose of improving the above-mentioned disadvantages of the known dyes and finding new compounds that can widely satisfy the requirements required for the dyes, and as a result, completed the present invention.

<Means for Solving the Problems> The present invention provides the following general formula (I) Wherein X is -NR ₂ R _3, -SO ₂ C the -OR ₄ or -SR _5, Y is a substituted or unsubstituted pyridinio group, Z ₁ and Z ₂ independently of one another
H = CH ₂ or —SO ₂ CH ₂ CH ₂ Z ′, wherein Z ′ represents a group which is eliminated by the action of an alkali. A represents an optionally substituted phenylene, naphthylene or alkylene group.

R ₁ is hydrogen or an optionally substituted alkyl group,
R ₂ , R ₃ , R ₄ and R ₅ independently represent hydrogen or an optionally substituted alkyl, phenyl, naphthyl or benzyl group.

R ₆ may be hydrogen, halogen, an alkyl group, an alkoxy group, an acylamino group or a ureido group, R ₇ may form a ring together with hydrogen or R ₆ , and R ₈ may be a hydrogen, an alkyl group, an alkoxy group or a sulfo group. Represent.

D represents a phenylene or naphthylene group which may be substituted. And a method for dyeing or printing a fiber material characterized by using the same.

In the general formula (I), the phenylene and naphthylene represented by A are preferably substituted by one or two substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo. Examples of phenylene or naphthylene which may be substituted with sulfo, for example, (In the formula, the bond indicated by an asterisk is Means a bond leading to a group. ) And so on. The alkylene represented by A is represented by the following formula: (In the formula, the bond indicated by an asterisk is Means a bond leading to a group. alk is a polymethylene group having 1 to 6 carbon atoms or a branched isomer thereof, R 'is hydrogen, chlorine, bromine, fluorine, hydroxy, sulfato, acyloxy having 1 to 4 carbon atoms, cyano, carboxy, An alkoxycarbonyl or carbamoyl having 1 to 5 carbon atoms, R "is
Hydrogen or C _1-6 alkyl, alk ′ is independently 2
A polymethylene group having from 6 to 6 carbon atoms or a branched isomer thereof, wherein alk 'and R "may form a ring with each other through a methylene group; n is 1 to 6, m is 1 to 6 Which is an integer.).

The polymethylene group represented by alk in the above formulas (a), (b) and (c) is preferably methylene, ethylene, methylmethylene, propylene and butylene.

R "represents hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-
Examples include butyl, pentyl, hexyl and the like, preferably hydrogen. The polymethylene group represented by alk 'is preferably ethylene, propylene or butylene.

The numbers n and m are preferably independently of one another 2, 3 or 4.

D is preferably methyl, ethyl, methoxy,
Ethoxy, chloro, bromo and sulfo selected from the group consisting of phenylene which may be substituted by one or two substituents or naphthylene which may be substituted by sulfo, for example, (In the formula, the bond indicated by ** means a bond leading to the -N = N- group.).

Among them, those having a sulfo group are preferable, for example, (In the formula, the bond indicated by ** has the same meaning as described above.).

Examples of the group capable of leaving under the action of an alkali represented by Z ′ include sulfate, thiosulfate, phosphate, acetate, and halogen.
Of these, sulfates are preferred.

The alkyl optionally having a substituent represented by R ₁ is preferably a C _{1 to} C ₄ alkyl, and the optionally substituted group includes hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, Alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl are preferred.

Particularly preferred R ₁ is, for example, hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-
-Butyl, sec-butyl, 2-hydroxyethyl, 2-
Hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl , Ethoxymethyl, 2-
Methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3-
Methoxypropyl, chloromethyl, bromomethyl, 2-
Chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl,
3-carboxypropyl, 4-carboxybutyl, 1,2
-Dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2
-Ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2
-Ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfo Famoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl and 4-sulfamoylbutyl can be mentioned. Among them, particularly preferred is hydrogen, methyl or ethyl.

Examples of the optionally substituted alkyl represented by R ₂ and R ₃ include, for example, alkoxy having 1 to 4 carbon atoms,
Alkyl having 1 to 4 carbon atoms which may be substituted by one or two substituents selected from the group of sulfo, carboxy, hydroxy, chloro, phenyl and sulfate is preferred.

Among them, particularly preferably, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-
Butyl, β-hydroxyethyl, β-sulfatoethyl, β-sulfoethyl, β-methoxyethyl, β-carboxyethyl and the like.

Examples of the optionally substituted phenyl represented by R ₂ and R ₃ include, for example, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, and chloro. And bromo,
Preferred is phenyl optionally substituted by one or two substituents.

Among them, particularly preferred is phenyl, 2-, 3- or 4
-Sulfophenyl, 2,4- or 2,5-disulfophenyl,
2-, 3- or 4-carboxyphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methylphenyl and 2-, 3- or 4-methoxyphenyl and the like.

Examples of the optionally substituted naphthyl represented by R ₂ and R ₃ include, for example, hydroxy, carboxy, sulfo, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms And naphthyl which may be substituted with 1, 2 or 3 substituents selected from the group of chloro and chloro.

Among them, particularly preferred are 2-, 3-, 4-, 5-, and 6
-, 7- or 8-sulfo-1-naphthyl, 1-, 5-,
6-, 7- or 8-sulfo-2-naphthyl, 1,5-, 5,7
-, 6,8-, 4,8-, 4,7-, 3,8-, 4,6-, 3,7- or 3,
6-disulfo-2-naphthyl, 4,6,8-, 2,4,7- or 3,
Examples include 6,8-trisulfo-1-naphthyl, 1,5,7-, 4,6,8- or 3,6,8-trisulfo-2-naphthyl.

Examples of the optionally substituted benzyl represented by R ₂ and R ₃ include alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo and chloro. Preferred is benzyl optionally substituted with one or two substituents selected from

Among them, particularly preferred is benzyl, 2-, 3- or 4
-Sulfobenzyl and the like.

In the present invention, one of R ₂ and R ₃ is hydrogen,
Methyl or ethyl, the other being C _1-4 alkyl, C
_The case of phenyl which may be substituted with _1-4 alkoxy, sulfo, carboxy or halogeno is particularly preferred in terms of dye properties.

In the general formula (I), when X is —NR ₂ R ₃ , the compound represented by HNR ₂ R ₃ used for forming such a group includes, for example, ammonia or 1-aminobenzene, 1-amino-2-, -3- or-
4-methyl-benzene, 1-amino-3,4- or 3,5-dimethylbenzene, 1-amino-2-, -3- or 4-ethylbenzene, 1-amino-2-, -3- or -4 -Methoxybenzene, 1-amino-2-, -3- or 4-ethoxybenzene, 1-amino-2-, -3- or -4-
Chlorobenzene, 3- or 4-amino-phenylmethanesulfonic acid, 2-, 3- or 4-aminobenzenesulfonic acid, 3-methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid, 4-methylaminobenzenesulfonic Acid, 4-ethylaminobenzenesulfonic acid,
5-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-
1,4-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid, 4-amino-5-methylbenzene-1,2-disulfonic acid, 2-, 3- or 4-aminobenzoic acid, 5-amino Benzene-1,3-dicarboxylic acid, 5-amino-2-
Hydroxybenzenesulfonic acid, 4-amino-2-hydroxybenzenesulfonic acid, 5-amino-2-ethoxybenzenesulfonic acid, N-methylaminobenzene, N-
Ethylaminobenzene, 1-methylamino-3- or-
4-methylbenzene, 1-ethylamino-4-chlorobenzene, 1-ethylamino-3- or -4-methylbenzene, 1- (2-hydroxyethyl) -amino-3-methylbenzene, 3- or 4- Methylaminobenzoic acid, 3
-Or 4-methylaminobenzenesulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-2-sulfonic acid, 5-
Aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-2-sulfonic acid, 7-aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-2-sulfonic acid, 7-ethylaminonaphthalene-2-sulfonic acid, 7
-Butylaminonaphthalene-2-sulfonic acid, 7-isobutylaminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-
1,3-disulfonic acid, 5-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 8-
Aminonaphthalene-1,3-disulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene -1,6-disulfonic acid, 8-aminonaphthalene-1,6-disulfonic acid, 4-
Aminonaphthalene-1,7-disulfonic acid, 3-aminonaphthalene-2,6-disulfonic acid, 4-aminonaphthalene-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic acid, 4-aminonaphthalene -2,7-disulfonic acid, 6-aminonaphthalene-1,3,5-trisulfonic acid,
7-aminonaphthalene-1,3,5-trisulfonic acid, 4-
Aminonaphthalene-1,3,6-trisulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid and 4-aminonaphthalene-1, Aromatic amines such as 3,7-trisulfonic acid,
Or methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, dimethylamine, diethylamine, methylethylamine, allylamine, 2-
Chloroethylamine, 2-methoxyethylamine, 2-
Aminoethanol, 2-methylaminoethanol, bis- (2-hydroxyethyl) amine, 2-acetylaminoethylamine, 1-amino-2-propanol, 3-
Methoxypropylamine, 1-amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid, aminomethanesulfonic acid, 2-methylaminoethanesulfonic acid,
3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, ε-aminocaproic acid, benzylamine, 2-, 3- or 4-chlorobenzylamine, 4-methylbenzylamine, N -Methylbenzylamine, 2-, 3- or 4
-Sulfobenzylamine, 2-phenylethylamine,
Examples thereof include aliphatic amines such as 1-phenylethylamine and 1-phenyl-2-propylamine.

Among them, particularly preferred compounds include, for example, aniline, N-methylaniline, N-ethylaniline, 2-,
3- or 4-chloroaniline, N-methyl-2-,-
3- or -4-chloroaniline, N-ethyl-2-,
-3- or -4-chloroaniline, 2-, 3- or 4
-Methylaniline, 2-, 3- or 4-sulfoaniline, aniline-2,4- or -2,5-disulfonic acid, 3
-Or 4-methylaminobenzenesulfonic acid, 3- or 4-ethylaminobenzenesulfonic acid, 2-, 3- or 4-carboxyaniline, taurine, N-methyltaurine, mono- or di-ethanolamine and the like. Can be.

As the optionally substituted alkyl represented by R ₄ and R ₅ , for example, selected from the group consisting of alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, hydrokilos, chloro, phenyl, cyano and sulfate, 1 to 2 carbon atoms which may be substituted by one or two substituents
Alkyl having 4 is preferred.

Among them, preferably, methyl, ethyl, n-propyl,
iso-propyl, n-butyl, iso-butyl, sec-butyl, β-hydroxyethyl, β-sulfatoethyl,
β-sulfoethyl, β-methoxyethyl, β-ethoxyethyl, β-chloroethyl, β-carboxyethyl and the like.

Examples of the optionally substituted phenyl represented by R ₄ and R ₅ include, for example, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, and chloro. And bromo,
Preferred is phenyl optionally substituted by one or two substituents.

Among them, particularly preferred is phenyl, 2-, 3- or 4
-Sulfophenyl, 2,4- or 2,5-disulfophenyl,
2-, 3- or 4-chlorophenyl, 2-, 3- or 4
-Methylphenyl and 2-, 3- or 4-methoxyphenyl and the like.

Examples of the optionally substituted naphthyl represented by R ₄ and R ₅ include, for example, hydroxy, carboxy, sulfo, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms And naphthyl which may be substituted with 1, 2 or 3 substituents selected from the group of chloro and chloro.

Among them, particularly preferred are 2-, 3-, 4-, 5-, and 6
-, 7- or 8-sulfo-1-naphthyl, 1-, 5-,
6-, 7- or 8-sulfo-2-naphthyl, 1,5-, 5,7
-, 6,8-, 4,8-, 4,7-, 3,8-, 4,6-, 3,7- or 3,
6-disulfo-2-naphthyl, 4,6,8-, 2,4,7- or 3,
Examples include 6,8-trisulfo-1-naphthyl, 1,5,7-, 4,6,8- or 3,6,8-trisulfo-2-naphthyl.

Examples of the optionally substituted benzyl represented by R ₄ and R ₅ include alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo and chloro. Preferred is benzyl optionally substituted with one or two substituents selected from

Among them, particularly preferred is benzyl, 2-, 3- or 4
-Sulfobenzyl and the like.

In formula (I), when X is -OR _4,
The compound represented by R ₄ OH used to form such a group includes, for example, phenol, 1-hydroxy-2-, -3- or -4-methylbenzene, 1-hydroxy-3,4- Or -3,5-cimethylbenzene, 1-hydroxy-2-, -3- or -4-ethylbenzene, 1-hydroxy-2-, -3- or -4-methoxybenzene,
1-hydroxy-2-, -3- or -4-ethoxybenzene, 1-hydroxy-2-, -3- or -4-chlorobenzene, 3- or 4-hydroxy-phenylmethanesulfonic acid, 3-hydroxybenzene Sulfonic acid, 4-hydroxybenzenesulfonic acid, 5-hydroxybenzene-1,3-disulfonic acid, 6-hydroxybenzene-1,4-
Disulfonic acid, 4-hydroxybenzene-1,2-disulfonic acid, 4-hydroxy-5-methylbenzene-1,2-
Disulfonic acid, 3- or 4-hydroxybenzoic acid, 5-
Hydroxybenzene-1,3-dicarboxylic acid, 5-hydroxy-2-ethoxybenzenesulfonic acid, 2-hydroxynaphthalene-1-sulfonic acid, 4-hydroxynaphthalene-1-sulfonic acid, 5-hydroxynaphthalene-1
-Sulfonic acid, 6-hydroxynaphthalene-1-sulfonic acid, 7-hydroxynaphthalene-1-sulfonic acid, 8
-Hydroxynaphthalene-1-sulfonic acid, 1-hydroxynaphthalene-2-sulfonic acid, 4-hydroxynaphthalene-2-sulfonic acid, 5-hydroxynaphthalene-
2-sulfonic acid, 6-hydroxynaphthalene-2-sulfonic acid, 7-hydroxynaphthalene-2-sulfonic acid,
8-hydroxynaphthalene-2-sulfonic acid, 4-hydroxynaphthalene-1,3-disulfonic acid, 5-hydroxynaphthalene-1,3-disulfonic acid, 6-hydroxynaphthalene-1,3-disulfonic acid, 7-hydroxynaphthalene 1,3-disulfonic acid, 8-hydroxynaphthalene-1,3-disulfonic acid, 2-hydroxynaphthalene-1,5
-Disulfonic acid, 3-hydroxynaphthalene-1,5-disulfonic acid, 4-hydroxynaphthalene-1,5-disulfonic acid, 4-hydroxynaphthalene-1,6-disulfonic acid, 8-hydroxynaphthalene-1,6-disulfone acid,
4-hydroxynaphthalene-1,7-disulfonic acid, 3-
Hydroxynaphthalene-2,6-disulfonic acid, 4-hydroxynaphthalene-2,6-disulfonic acid, 3-hydroxynaphthalene-2,7-disulfonic acid, 4-hydroquinaphthalene-2,7-disulfonic acid, 6-hydroxy Aromatic compounds such as naphthalene-1,3,5-trisulfonic acid, 7-hydroxynaphthalene-1,3,5-trisulfonic acid and 4-hydroxynaphthalene-1,3,6-trisulfonic acid;
Alternatively, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, se
c-butanol, 2-chloroethanol, 2-methoxyethanol, 2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol, 2-hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2-cyanoethanol , 2-sulfatoethanol, glycolic acid, 3-hydroxypropionic acid, benzyl alcohol, 2-, 3- or 4-chlorobenzyl alcohol, 4-methylbenzyl alcohol, 2-, 3- or 4-sulfobenzyl alcohol,
2-phenylethanol, include either such aliphatic compounds 1-phenyl-2-propanol, also, the above formula (I), when X is -SR _5, in order to form such a group Examples of R ₅ SH to be used include compounds in which the hydroxy of the above compound is mercapto.

Represented by R _6, the acylamino group, an acetylamino group, propionylamino group, butyrylamino group, etc. methylsulfonylamino group and the like, preferred R _6, acetylamino group, propionylamino group and ureido group include And a ureido group is particularly preferred.

When Y is a substituted pyridinio group, examples of the substituent include carboxy, carbamoyl, sulfo, halogeno, and substituted or unsubstituted alkyl having 1 to 4 carbon atoms. Β is a substituted alkyl group
-Hydroxyethyl, β-sulfoethyl and the like. As the pyridinio group represented by Y, a carboxy or carbamoyl-substituted pyridinio group is preferable, and a carboxypyridinio group is particularly preferable in terms of dye properties.

Preferably as the pyridine optionally having a substituent, pyridine, 2-, 3- or 4-carboxypyridine,
2-, 3- or 4-carbamoylpyridine, 3-sulfopyridine, 4-β-sulfoethylpyridine, 3-β-hydroxyethylpyridine, 4-chloropyridine, 3-methylpyridine, 3,5-dicarboxypyridine, etc. Is mentioned. Among them, particularly preferred is 3- or 4-carboxypyridine (nicotinic acid, isonicotinic acid).

The compound of the present invention exists in the form of a free acid or a salt thereof, and particularly, an alkali metal salt and an alkaline earth metal salt, particularly, a soda salt, a potassium salt, and a lithium salt are preferable.

The compound of the present invention can be produced, for example, as follows. The following general formula (II) [Wherein, D, R ₆ , R ₇ , R ₈ and Z ₁ have the above-mentioned meaning. And a compound represented by the following general formulas (III) to (VI) (Wherein, A, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and Z ₂ have the above-mentioned meanings), and 2,4,6-trihalogeno-s- By condensing triazine in any order, the following general formula (VII) [Wherein T represents a halogen, and D, X, R ₆ , R ₇ , R ₈ , and Z ₁ have the above-mentioned meanings. Is obtained, by condensing a pyridine compound,
The compound of the general formula (I) can be obtained.

The order of the condensation reaction with 2,4,6-trihalogeno-s-triazine is not particularly limited, and the reaction conditions are not particularly limited.
PH 2 to 9 at 40 ° C to 40 ° C, and secondarily at temperature 0 to 70 ° C.
H2 to 9 and, if tertiary, p
The compound represented by the general formula (I) or a salt thereof can be obtained by condensation while adjusting to H2 to 7.

As the raw material 2,4,6-trihalogeno-s-triazine, cyanuric chloride and cyanuric fluoride are particularly preferable.

Examples of the dye matrix of the present invention [compounds in which the vinylfluone-based reactive group in the general formula (II) is a hydrogen atom] include, for example, 2- (4'-amino-2'-ureidophenylazo)
Naphthalene-1-sulfonic acid, 2- (4'-amino-2'-ureidophenylazo)
Naphthalene-1,7-disulfonic acid, 2- (4'-amino-2'-ureidophenylazo)
Naphthalene-6-sulfonic acid, 2- (4'-amino-2'-ureidophenylazo)
Naphthalene-8-sulfonic acid, 4-amino-2-ureidoazobenzene-2'-sulfonic acid, 2- (4'-amino-2'-acetylaminophenylazo) naphthalene-1-sulfonic acid, 2- (4 '-Amino-2'-acetylaminophenylazo) naphthalene-1,7-disulfonic acid, 2- (4'-amino-2'-acetylaminophenylazo) naphthalene-6-sulfonic acid, 2- (4'-amino -2'-acetylaminophenylazo) naphthalene-8-sulfonic acid, 4-amino-2-acetylaminoazobenzene-2 '
-Sulfonic acid, 2- (4'-amino-2'-methylphenylazo) naphthalene-1-sulfonic acid, 2- (4'-amino-2'-methylphenylazo) naphthalene-1,7-disulfonic acid, 2- (4'-amino-2'-methylphenylazo) naphthalene-6-sulfonic acid, 2- (4'-amino-2'-methylphenylazo) naphthalene-8-sulfonic acid, 4-amino-2- Methylazobenzene-2'-sulfonic acid, 2- (4'-amino-2'-methyl-5'-methoxyphenylazo) naphthalene-1-sulfonic acid, 2- (4'-amino-2'-methyl-5 '-Methoxyphenylazo) naphthalene-1,7-disulfonic acid, 2- (4'-amino-2'-methyl-5'-methoxyphenylazo) naphthalene-6-sulfonic acid, 2- (4'-amino-2 -Methyl-5'-methoxyphenylazo) naphthalene-8-sulfonic acid, 4-amino-2-methyl-5-methoxyazobenzene-2'-sulfonic acid, 2- (4'-amino-2'-propionylaminophenyl Azo) naphthalene-1-sulfonic acid, 2- (4'-amino-2'-propionylaminophenylazo) naphthalene-1,7-disulfonic acid, 2- (4'-amino-2'-propionylaminophenylazo) Naphthalene-6-sulfonic acid, 2- (4'-amino-2'-ureido-5'-methoxyphenylazo) naphthalene-1-sulfonic acid, 2- (4'-amino-2'-ureido-5'- Methoxyphenylazo) naphthalene-6-sulfonic acid, 2- (4'-amino-2'-ureido-5'-methoxyphenylazo) naphthalene-1,7-di Sulfonic acid, 2- (4'-amino-2'-methyl-5'-ethoxyphenylazo) naphthalene-1,7-disulfonic acid, 2- (4'-amino-2'-methyl-5'-ethoxyphenyl Azo) naphthalene-6-sulfonic acid, 2- (4'-amino-2 ', 5'-dimethoxyphenylazo) naphthalene-6-sulfonic acid, 2- (4'-amino-2', 5'-dimethoxyphenyl Azo) naphthalene-1-sulfonic acid, 1-amino-4- (1'-sulfonaphth-2'-ylazo) naphthalene-8-sulfonic acid, 1-amino-4- (6'-sulfonaphth-2'-ylazo) Naphthalene-8-sulfonic acid, 1-amino-4- (1 ', 7'-disulfonaphth-2'
-Ylazo) naphthalene-8-sulfonic acid, 1-amino-4- (1'-sulfonaphth-2'-ylazo) naphthalene-7-sulfonic acid, 1-amino-4- (6'-sulfonaphtho-2'-ylazo ) Naphthalene-7-sulfonic acid, 1-amino-4- (1'-sulfonaphth-2'-ylazo) naphthalene-6-sulfonic acid, 1-amino-4- (6'-sulfonaphth-2'-ylazo) naphthalene -6-sulfonic acid, 1-amino-4- (8'-sulfonaphth-2'-ylazo) naphthalene-8-sulfonic acid, 2- (4'-amino-2'-ethylphenylazo) naphthalene-1-sulfone Acid, 2- (4'-amino-2'-ethylphenylazo) naphthalene-6-sulfonic acid, 2- (4'-amino-2'-methoxyphenylazo)
Naphthalene-1-sulfonic acid, 2- (4'-amino-2'-methoxyphenylazo)
Naphthalene-6-sulfonic acid, 2- (4'-amino-2'-acetylamino-5'-
Methoxyphenylazo) naphthalene-1-sulfonic acid, 2- (4'-amino-2'-acetylamino-5'-
Methoxyphenylazo) naphthalene-6-sulfonic acid, 2- (4'-amino-2'-acetylamino-5'-
Methoxyphenylazo) naphthalene-1,7-disulfonic acid;

The compound of the present invention has fiber reactivity and can be used for dyeing or printing a material containing a hydroxy group or a carbonamide group. The material is preferably used in the form of a fibrous material or a blend thereof.

The hydroxy-containing material is a natural or synthetic hydroxy-containing material, such as a cellulosic fibrous material or a regenerated product thereof and polyvinyl alcohol. The cellulosic fiber material is preferably cotton and other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, viscose staples and filament viscose.

Carbonamide-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-
4.

The compound of the present invention can be dyed or printed on the above-mentioned material, particularly on the above-mentioned fiber material, by a method depending on physical and chemical properties.

For example, in the case of exhaust dyeing on cellulose fibers, sodium carbonate, tertiary sodium phosphate, in the presence of an acid binder such as caustic soda, optionally a neutral salt, for example, sodium sulfate or sodium chloride,
If desired, dissolution aids, penetrants or leveling agents may be used in combination at relatively low temperatures. Neutral salts which promote the exhaustion of the dye can be added only after the original dyeing temperature has been reached or before, optionally in portions.

When dyeing cellulose fibers according to the padding method,
After padding and drying at room temperature or elevated temperature, it can be fixed by steaming or dry heat.

When printing on cellulose fibers, printing is carried out in one phase, for example with a printing paste containing baking soda or another acid condensing agent, followed by steaming at 100-160 ° C., or in two phases, for example in medium. The printing can be carried out by printing with an acidic or weakly acidic printing paste and passing it through a hot electrolyte-containing alkaline bath, or over-padding with an alkaline electrolyte-containing padding solution, and steaming or dry heat treatment.

In the printing paste, a sizing or emulsifying agent such as sodium alginate or starch ether is optionally used,
For example, it is used in combination as a usual printing aid and / or dispersant such as urea.

Acid binders suitable for immobilizing the compounds of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali under heating. In particular, mention may be made of hydroxides of alkali metals and alkali metal salts of inorganic or organic acids of weak to moderate strength, of which soda salts and potassium salts are particularly preferred. Such acid binders include, for example, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate and the like.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out by first exhausting the acid or weakly acidic dye bath under control of the pH value and then changing it to a neutral and possibly alkaline pH value for fixing. I can do it. Dyeing can usually be carried out at a temperature of 60 to 120 ° C, but in order to achieve levelness, a conventional leveling agent, for example, a condensation product of cyanuric chloride with 3 times mol of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, an addition product of stearylamine and ethylene oxide can be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing on fiber materials. Particularly suitable for dyeing cellulosic fiber materials, good light fastness and sweat and sun fastness, excellent wet fastness, such as washing, washing, peroxide washing, chlorine, sweat and acid hydrolysis resistance And it has alkali resistance, and also good friction resistance and iron resistance.

In addition, it has excellent build-up properties, leveling properties and wash-off properties, and also has good solubility and exhaustion / fixing properties,
It is characterized by the fact that it is hardly affected by fluctuations in the dyeing temperature and the dyeing bath ratio and a dyed product of stable quality can be obtained.

It is also characterized by little discoloration of the obtained dyed product during fixation or resin processing, and little change due to contact with a basic substance during storage.

Hereinafter, the present invention will be described in detail with reference to examples. In the example,
Parts and% represent parts by weight and% by weight, respectively.

Example 1 49.1 parts of 2-naphthylamine-5-β-sulfatoethylsulfone-1,7-disulfonic acid were diazotized by a conventional method, and coupled with 15.2 parts of m-ureidoaniline to give a free acid in the form of a free acid. A compound represented by the formula was obtained.

To this monoazo compound, 18.4 parts of cyanuric chloride was condensed by a conventional method, then 9.3 parts of aniline was added to perform a second condensation, and 12.3 parts of 3-carboxypyridine was further added to carry out a substitution reaction. The reaction solution was salted out with sodium chloride to obtain a monoazo compound represented by the following formula in the form of a free acid.

Example 2 2-Naphthylamine-5- used in Example 1
In place of β-sulfatoethylsulfone-1,7-disulfonic acid, m-ureidoaniline, aniline and 3-carboxypyridine, the following table, column 2, column 3, column 4
Synthesis was performed in the same manner as in Example 1 using the compounds in the columns and the fifth column to obtain the corresponding monoazo compounds. These compounds were stained to give dyeings of the shades shown in column 6 of the table below.

Example 3 2-naphthylamine-6-β-sulfatoethylsulfone-1-sulfonic acid (41.1 parts) is diazotized by a conventional method and coupled with m-ureidoaniline (15.2 parts) to give a free acid in the form of the following formula. The indicated compound was obtained.

On the other hand, 15.3-aminobenzene-2,5-disulfonic acid 25.3
And 18.4 parts of cyanuric chloride were condensed. The condensate was condensed with the previously synthesized monoazo compound, and then 12.3 parts of 3-carboxypyridine was added to carry out a substitution reaction. The reaction solution was salted out with sodium chloride to obtain a monoazo compound represented by the following formula in the form of a free acid.

Example 4 2-Naphthylamine-6- used in Example 3
β-sulfatoethyl sulfone-1-sulfonic acid, m
Using the compounds in the following table, column 2, column 3, figure 4 and column 5 in place of ureidoaniline, 1-aminobenzene-2,5-disulfonic acid and 3-carboxypyridine in order Synthesis was performed in the same manner as in Example 3 to obtain corresponding monoazo compounds. These compounds were stained to give dyeings of the shades shown in the following table, column 6.

Example 5 In place of the compound described in column 4 of the table of Example 2 and the compound described in column 4 of the table of Example 4, synthesis was carried out in the same manner using the compounds shown below, and the corresponding monoazo compound was obtained. The compound was obtained.

Phenol, phenol-2-, -3- or -4-sulfonic acid, phenol-2,4- or -2,5-disulfonic acid, benzylamine, benzylamine-2-,-3-,
Or -4-sulfonic acid, taurine, N-methyltaurine, β-alanine, mono- or di-ethanolamine Example 6 Each monoazo compound 0.1, 0.3 described in Examples 1-5.
And 0.6 parts were dissolved in 200 parts of water, 10 parts of sodium sulfate and 10 parts of cotton were added, the temperature was raised to 60 ° C., and 4 parts of sodium carbonate was added, followed by dyeing for 1 hour. Washing, soaping, washing and drying were carried out to obtain a yellow dyed product having excellent fastness properties and good build-up properties.

Example 7 A color paste having the following composition was prepared using each of the monoazo compounds described in Examples 1 to 5.

Monoazo compound 5 parts Urea 5 parts Sodium alginate (5%) base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts This color paste is printed on mercerized cotton broad, intermediate dried and steamed at 100 ° C for 5 minutes The resultant was washed with water, soaped, washed with hot water and dried to obtain a yellow print having excellent fastnesses.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takashi Omura 3-1-1, Kasuganaka, Konohana-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. (72) Naoki Harada Inventor Naoki Harada, Osaka-shi No. 3-98, No. 98, Sumitomo Chemical Industries, Ltd. (56) References JP-A-60-173060 (JP, A) JP-A-62-43466 (JP, A) JP-A-61-47887 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 62/51 D06P 1/38 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (8)

(57) [Claims] 1. A compound of the following general formula (I) in the form of a free acid: [Where X is —NR ₂ R ₃ , —OR ₄ or —SR ₅ , wherein Y is an unsubstituted pyridinio group, or carboxy, carbovamoyl, sulfo, halogeno, unsubstituted alkyl having 1 to 4 carbon atoms, β-
Represents a pyridinio group substituted with a substituent selected from the group consisting of hydroxyethyl and β-sulfoethyl, wherein Z ₁ and Z ₂ independently of one another are —SO ₂ CH ＝ CH ₂ or —SO ₂ CH ₂ CH
₂ represents Z ', wherein Z' represents a sulfate group, a thiosulfate group, a phosphate group, an acetate group or a halogen group. A represents an unsubstituted naphthylene group, a sulfo-substituted naphthylene group, an unsubstituted phenylene group, a phenylene group substituted with a substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo. Represent or
Alternatively, the following formula (a), (b) or (c) 結合 In the formula, the bond indicated by * means a bond leading to the —N (R ₁ ) — group. alk represents a polymethylene group having 1 to 6 carbon atoms or a branched isomer thereof, and R 'represents hydrogen, chlorine, bromine, fluorine, hydroxy, sulfate, alkylcarbonyloxy having 1 to 4 carbon atoms, cyano, carboxy. Represents alkoxycarbonyl or carbamoyl having 1 to 5 carbon atoms, and R ″ represents hydrogen or 1 to 5 carbon atoms.
And alk ′ independently of each other has 2 to 2 carbon atoms
6 means a polymethylene group or its branched isomer,
k ′ and R ″ may form a ring with each other through a methylene group. n represents an integer of 1 to 6, m represents an integer of 1 to 6. R ₁ represents an alkylene group represented by｝. Represents a hydrogen, an unsubstituted alkyl group, or an alkyl group substituted with a substituent selected from the group consisting of hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl. R ₂ and R ₃ independently of one another are hydrogen, unsubstituted alkyl, unsubstituted phenyl, unsubstituted naphthyl, unsubstituted benzyl, alkoxy, sulfo, carboxy, hydroxy, chloro, phenyl and An alkyl group substituted by a substituent selected from the group of sulfate, alkyl, alkoxy, sulfo, carboxy, A phenyl group substituted with a substituent selected from the group of chloro and bromo, hydroxy, carboxy, sulfo, alkyl, naphthyl group substituted with a substituent selected from the group of chloro, or alkyl, alkoxy, sulfo and A benzyl group substituted by a substituent selected from the group of chloro, and R ₄ and R ₅ independently of each other are hydrogen, an unsubstituted alkyl group, an unsubstituted phenyl group, an unsubstituted naphthyl group, an unsubstituted group; A benzyl group, an alkoxy, a sulfo, a carboxy, a hydroxy, a chloro, a phenyl, an alkyl group substituted by a substituent selected from the group of cyano and sulfate,
Alkyl, alkoxy, sulfo, carboxy, phenyl and phenyl substituted by a substituent selected from the group of bromo, hydroxy, carboxy, sulfo, alkyl, naphthyl group substituted by a substituent selected from the group of alkoxy and chloro, Alternatively, it represents a benzyl group substituted by a substituent selected from the group consisting of alkyl, alkoxy, sulfo and chloro. R ₆ is hydrogen, halogen, alkyl group, alkoxy group, acetylamino group, propionylamino group, butyrylamino group, a methylsulfonylamino group or H ₂ NCONH-- group, or R ₇ represents a hydrogen, or together with R ₆ It may form a ring, and R ₈ represents hydrogen, an alkyl group, an alkoxy group or a sulfo group. D is an unsubstituted phenylene group, an unsubstituted naphthylene group,
Represents a phenylene group substituted by a substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo, or a naphthylene group substituted by sulfo. ] The monoazo compound represented by these. (2) D is a phenylene group having a sulfo group and optionally further substituted by a substituent selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo; The compound according to claim 1, which is a naphthylene group having a sulfo group and optionally further substituted with a sulfo. Wherein R ₇ and R ₈ are hydrogen, R ₆ is an acetylamino group,
The compound according to claim 1, which is a propionylamino group, a butyrylamino group, a methylsulfonylamino group, or an H ₂ NCONH— group. 4. The compound according to claim 1, wherein Y is a pyridinio group substituted with a carboxyl group or a carbamoyl group. 5. The compound according to claim 1, wherein Z ₁ and Z ₂ are each independently —SO ₂ CH ＝ CH ₂ or —SO ₂ CH ₂ CH ₂ OSO ₃ H. 6. X is --NR ₂ R ₃ , wherein R ₂ and R ₃ are each independently substituted by a substituent selected from the group consisting of hydrogen, alkoxy, sulfo, carboxy, hydroxy, chloro, phenyl and sulfate. An alkyl group, which may be
Alternatively, the compound according to any one of claims 1 to 5, which is a phenyl group which may be substituted with a substituent selected from the group consisting of alkyl, alkoxy, sulfo, carboxy, chloro and bromo. 7. X is --NR ₂ R ₃ , wherein R ₂ is hydrogen, methyl or ethyl, R ₃ is substituted by a substituent selected from the group consisting of alkyl, alkoxy, sulfo, carboxy, chloro and bromo. The compound according to claim 6, which is a phenyl group. 8. A method for dyeing or printing a fiber material, comprising using the monoazo compound according to claim 1.