JPH06104780B2 - Monoazo compound and dyeing or printing method using the same - Google Patents

Description

The present invention relates to a monoazo compound and a method for dyeing or printing a fiber material using the same.

<Prior Art> Japanese Patent Publication No. 35-10628 discloses, for example, the following formula in the form of free acid. And a yellow reactive dye represented by Further, Japanese Patent Publication No. 58-18471 discloses, for example, the following formula And a yellow reactive dye represented by

<Problems to be Solved by the Invention> Various reactive dyes are widely used for dyeing and printing fiber materials. However, at present, the known dyes of yellow to orange have a particular effect on dyeing performance, for example, lack of build-up property and variation of dyeing temperature, alkali agent, inorganic salt addition amount, and dyebath ratio. In view of high demands and high fastness, for example, fastness to sunlight, fastness to sweat and chlorine, fastness to chlorine, etc., the level is not yet satisfactory, and it is strongly desired to provide further improved dyes. It is rare.

As a result of intensive studies, the inventors of the present invention have completed the present invention by improving the drawbacks of known dyes and finding new compounds that can widely satisfy the requirements required for dyes.

<Means for Solving Problems> The present invention provides the following formula (I) in the form of a free acid. [In the formula, R ₁ , R ₂ and R ₃ are independently of each other a hydrogen atom or an optionally substituted lower alkyl group, and R ₄ is a hydrogen atom, an optionally substituted lower alkyl group or a group. And B is a group (R ₅ represents a hydrogen atom, a sulfonic acid group, a carboxylic acid group, a methyl group, a methoxy group or an ethoxy group, and when the number of (SO ₃ H) in this group is 0, R ₅ represents a carboxylic acid group. Or group And X is a chlorine atom, a fluorine atom, a lower alkoxy group,
Phenoxy group or group which may be substituted (R ₆ and R ₇ are each independently a hydrogen atom, an optionally substituted lower alkyl group, an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted benzyl group. And A is a phenylene or naphthylene group which may have a substituent, and Z is a group-.
SO ₂ CH = CH ₂ or a group —SO ₂ CH ₂ CH ₂ Y, where Y is a group capable of leaving with an alkali. ] The monoazo compound shown by these, or its salt, and the method of dyeing or printing a fiber material using it.

In the general formula (I), the lower alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ is preferably an alkyl group having 1 to 4 carbon atoms, and the optionally substituted group is A hydroxy group, a cyano group, an alkoxy group, a halogen group, a carboxy group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group and a sulfamoyl group are preferable.

Preferable R ₁ , R ₂ , R ₃ and R ₄ optionally substituted alkyl groups include, for example, a methyl group, an ethyl group and n-
Propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, 2-hydroxyethyl group, 2
-Hydroxypropyl group, 3-hydroxypropyl group,
2-hydroxybutyl group, 3-hydroxybutyl group, 4
-Hydroxybutyl group, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group, cyanomethyl group, 2
-Cyanoethyl group, 3-cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2
-Ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-hydroxy-3-methoxypropyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group, 3-bromopropyl group, 4-chlorobutyl group, 4-
Bromobutyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 1,2-dicarboxyethyl group, carbamoylmethyl group, 2-carbamoylethyl group, 3-carbamoylpropyl group, 4-carbamoylbutyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-
Methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 3-ethoxycarbonylpropyl group, 4-methoxycarbonylbutyl group, 4-ethoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group Group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 3-methylcarbonyloxypropyl group, 3-ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, Sulfomethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, sulfamoylmethyl group, 2-sulfamoylethyl group, 3-sulfamoylpropyl group, 4-sulfamoylbutyl group, etc. It can gel.

Among them, particularly preferable R ₁ , R ₂ and R ₃ include a hydrogen atom, a methyl group or an ethyl group.

A group represented by R ₄ in the general formula (I) Examples thereof include a phenyl group, a 3-sulfophenyl group, and a 4-sulfophenyl group.

Particularly preferred R ₄ is, for example, hydrogen atom, methyl group,
Examples thereof include an ethyl group, a phenyl group, a 3-sulfophenyl group and a 4-sulfophenyl group.

In the general formula (I), A is preferably substituted with 1 or 2 substituents selected from the group consisting of methyl group, ethyl group, methoxy group, ethoxy group, chlorine atom, bromine atom and sulfonic acid group. A phenylene group or a naphthylene group which may be substituted with one sulfonic acid group,
For example, (In the formula, the bond indicated by an asterisk is Means a bond leading to a group. ) And so on.

Z represents a group —SO ₂ CH═CH ₂ or a group —SO ₂ CH ₂ CH ₂ Y, and Y is a group capable of leaving with an alkali, such as a sulfate ester group, a thiosulfate ester group, or a phosphate ester. Base,
Acetate groups and the like correspond to this.

In the general formula (I), B is specifically [In the formula, the bond indicated by an asterisk is Means a bond leading to a group. ] Either.

In the general formula (I), the lower alkoxy group represented by X is preferably an alkoxy group having 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group and an n-propoxy group. -Butoxy group, iso
A butoxy group and the like.

Of these, a methoxy group, an ethoxy group, and n- are particularly preferable.
A propoxy group and an isopropoxy group.

In formula (I), the optionally substituted phenoxy group represented by X is, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group. Preferred is a phenoxy group which may be substituted with 1 or 2 substituents selected from the group consisting of a sulfonic acid group, a carboxylic acid group and a chlorine atom.

Among them, phenoxy group, 3- or 4-sulfophenoxy group, 2,4- or 3,5-disulfophenoxy group and the like are particularly preferable.

Group represented by X in formula (I) (Wherein R ₆ and R ₇ have the above-mentioned meanings), R ₆ and
Examples of the optionally substituted lower alkyl group represented by R ₇ include an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, a chlorine atom, a phenyl group and a sulfate group. Selected from a group,
Lower alkyl groups having 1 to 4 carbon atoms, which may be substituted by 1 or 2 substituents, are preferred.

Among them, particularly preferably, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, β-hydroxyethyl group, β-sulfatoethyl group, β -Sulfoethyl group, β-methoxyethyl group, carboxymethyl group and the like can be mentioned.

As the optionally substituted phenyl group represented by R ₆ and R ₇ , for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
Preference is given to phenyl groups which may be substituted by 1 or 2 substituents selected from the group of sulfonic acid groups, carboxylic acid groups and chlorine atoms.

Among them, phenyl group, 2-, 3- or 4 is particularly preferable.
Examples include -sulfophenyl group, 2-, 3- or 4-carboxyphenyl group, 3,4-, 3,5- or 3,6-disulfophenyl group.

Examples of the optionally substituted naphthyl group represented by R ₆ and R ₇ include a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an alkyl group having 1 to 4 carbon atoms, and 1 to 4
A naphthyl group optionally substituted with 1, 2 or 3 substituents selected from the group of alkoxy groups having 4 carbon atoms and chlorine atoms is preferred.

Among them, particularly preferably, 2-, 3-, 4-, 5-, 6-, 7- or 8-sulfo-1-naphthyl group, 1-, 5-, 6-, 7- or 8
-Sulfo-2-naphthyl group, 2,4-, 5,7-, 6,8-, 4,8
-, 4,7-, 3,8-, 4,6-, 3,7- or 3,6-disulfo-
1-naphthyl group, 5,7-, 6,8-, 1,5, 4,8-3,7- or
3,6, -disulfo-2-naphthyl group, 4,6,8-, 2,4,7- or 3,6,8-trisulfo-1-naphthyl group, 1,5,7-, 4,6,
8- or 3,6,8-trisulfo-2-naphthyl group and the like can be mentioned.

As the optionally substituted benzyl group represented by R ₆ and R ₇ , for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
A benzyl group optionally substituted by 1 or 2 substituents selected from the group of sulfonic acid and chlorine atom is preferable.

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

The compound of the present invention may be present in the form of a free acid, but is preferably an alkali metal salt or an alkaline earth metal salt,
For example, sodium salt and potassium salt may be mentioned.

In the general formula (I) of the present invention, the following general formula (I) ′ in which X is a chlorine atom or a fluorine atom. [In the formula, X ₁ represents a chlorine atom or a fluorine atom, and R ₁ , R ₂ ,
R ₃ , R ₄ , A, B and Z have the meanings given above. The monoazo compound represented by the following can be produced, for example, as follows.

The following general formula (II) [In the formula, R ₂ and B have the above-mentioned meanings. ] And the following general formula (III) [In the formula, R ₁ , A and Z have the above-mentioned meanings. ] In any order, in an aqueous medium, the compound represented by
PH to 1 to 10, preferably 2 to 7 at -50 ° C, preferably 0 to 30 ° C, and secondarily 0 to 70 ° C, preferably 10 to 50 ° C, pH 2 to 9 And preferably condensed to cyanuric chloride or cyanuric fluoride while adjusting the pH to 3 to 6 to give the following general formula (IV) [In the formula, R ₁ , R ₂ , A, B, Z and X ₁ have the above-mentioned meanings. ] The compound shown by these is obtained.

Subsequently, the compound of the general formula (IV) is diazotized at −10 to 20 ° C. by a conventional method to give the following general formula (V) [In the formula, R ₃ and R ₄ have the above-mentioned meanings. ] At -10 to 50 ℃, preferably 0 to 30 ℃
Then, the monoazo compound of the general formula (I) ′ can be obtained by coupling while adjusting the pH to 1 to 7, preferably pH 1 to 5.

Another method for producing the monoazo compound of the general formula (I) 'is as follows. The compound represented by the general formula (II) is diazotized by a conventional method at -10 to 20 ° C, and the compound of the general formula (V) is -10 to 50 ° C, preferably 0 to 30 ° C, and the pH is 1 to 10.
7, preferably while adjusting the pH to 1 to 5, or by coupling, or the following general formula (VI) H ₂ N-B-NO ₂ (VI) [wherein, B has the above-mentioned meaning. ] The compound represented by the general formula (V)
After coupling with the compound of (1), the compound was reduced in the presence of sodium sulfide at 40 to 100 ° C, and optionally alkylated,
The following general formula (VII) [In formula, R < ₂ >, R < ₃ >, R < ₄ > and B have a said meaning. ] The compound shown by these is obtained.

Subsequently, the compound of the general formula (VII) and the compound of the general formula (III) may be mixed in any order in an aqueous medium, primarily -10 to 50
C., preferably 0 to 30.degree. C., while adjusting to pH 1 to 10, preferably 2 to 7, secondarily at 0 to 70.degree. C., preferably 10 to 50.degree. C., to pH 2 to 9, The monoazo compound of the general formula (I) ′ can be obtained by condensation with cyanuric chloride or cyanuric fluoride, preferably while adjusting the pH to 3-6.

On the other hand, the following general formula (I) ″ in the form of free acid [In the formula, X ₂ is a lower alkoxy group, an optionally substituted phenoxy group or a group. (R ₆ and R ₇ have the above-mentioned meanings), and R ₁ , R ₂ ,
R ₃ , R ₄ , A, B and Z have the meanings given above. The monoazo compound represented by the following can be produced, for example, as follows.

In the monoazo compound represented by the general formula (I) ′, the following general formula (VIII) H—X ₂ (VIII) [wherein, X ₂ has the above meaning. ] The compound represented by the formula (I) ″ is condensed by condensing in an aqueous medium at 50 to 100 ° C., preferably 70 to 100 ° C., while adjusting to pH 2 to 9, preferably pH 3 to 7. A monoazo compound can be obtained.

Alternatively, as an alternative, the compound represented by the general formula (VII) and the compound represented by the general formula (VIII) can be obtained in any order,
In an aqueous medium, primarily -10 to 50 ° C, preferably 0 to 30
While adjusting to pH 1-10, preferably pH 4-7 at ℃,
Secondaryly at 10-70 ° C, preferably 20-50 ° C, pH 2-1
After condensing with cyanuric chloride or cyanuric fluoride while adjusting the pH to 0, preferably pH 4 to 9, the above-mentioned general formula (II
A compound represented by I) at 50 to 100 ° C, preferably 80 ° C
The monoazo compound of the general formula (I) ″ can also be obtained by condensation at ˜100 ° C. while adjusting to pH 2 to 9, preferably pH 3 to 7.

Examples of the compound represented by the general formula (V) include 2-
Aminonaphthalene-5-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 2-aminonaphthalene-7-sulfonic acid, 2-aminonaphthalene-8-sulfonic acid, aminonaphthalene-5,7-disulfonic acid, 2- Aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-
4,8-disulfonic acid, 2-aminonaphthalene-3,7-disulfonic acid, 2-aminonaphthalene-3,6-disulfonic acid and their N-methyl, N-ethyl, N-butyl, N, N ′ -Dimethyl body, N, N′-diethyl body, or
2-anilinonaphthalene-5-sulfonic acid, 2-anilinonaphthalene-6-sulfonic acid, 2-anilinonaphthalene-7-sulfonic acid, 2-anilinonaphthalene-8-sulfonic acid, 2- (3-sulfoanilino ) Naphthalene-6
-Sulfonic acid, 2- (4-sulfoanilino) naphthalene-6-sulfonic acid, 2-anilinonanaphthalene-6,8-disulfonic acid, 2-anilinonaphthalene-3,6-disulfonic acid and the like can be mentioned. .

Among them, particularly preferable compounds represented by the general formula (V) are 2-aminonaphthalene-5-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 2-aminonaphthalene-7-sulfonic acid and 2-aminonaphthalene-. 5,7-Disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-3,7-disulfonic acid, 2-
Aminonaphthalene-3,6-disulfonic acid, 2-methylaminonaphthalene-6-sulfonic acid, 2-methylaminonaphthalene-7-sulfonic acid, 2-ethylaminonaphthalene-5-sulfonic acid, 2-ethylaminonaphthalene-7
-Sulfonic acid, 2-ethylaminonaphthalene-5,7-disulfonic acid, 2-dimethylaminonaphthalene-6-sulfonic acid, 2-dimethylaminonaphthalene-8-sulfonic acid, 2-dimethylaminonaphthalene-3,7-disulfone Acid, 2-anilinonaphthalene-5-sulfonic acid, 2-anilinonanaphthalene-6-sulfonic acid, 2-anilinonaphthalene-7-sulfonic acid, 2- (3-sulfoanilino)
Naphthalene-6-sulfonic acid, 2- (4-sulfoanilino) naphthalene-6-sulfonic acid, 2-anilinonaphthalene-6,8-disulfonic acid, 2-anilinonaphthalene-
3,6-disulfonic acid and the like can be mentioned.

Examples of the compound represented by the general formula (VI) include Etc.

Examples of the compound represented by the general formula (VIII) include ammonia, 1-aminobenzene, and 1-amino-3.
-Or-4-methyl-benzene, 1-amino-3,4- or -3,5-dimethylbenzene, 1-amino-3- or-
4-ethylbenzene, 1-amino-3- or -4-methoxybenzene, 1-amino-4-ethoxybenzene, 1
-Amino-3- or -4-chlorobenzene, 3- or 4
-Amino-phenylmethanesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-
Methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid, 4-methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid, 5-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, 3- or 4-aminobenzoic acid, 5-aminobenzene-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,
Alternatively, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary 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, 1-
Aliphatic amines such as phenylethylamine, 1-phenyl-2-propylamine, and lower alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, etc., or Substituted phenols such as 3- or 4-sulfophenol, 2,4- or 3,5-disulfophenol, 2-nitro-4-sulfophenol, 2
-Chloro-4-sulfophenol and the like can be mentioned.

Of these, particularly preferred compounds represented by general formula (VIII) are, for example, aniline, N-methylaminobenzene, N-ethylaminobenzene, 3-aminobenzenesulfonic acid, 3-methylaminobenzenesulfonic acid, 3-
Ethylaminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 4-methylaminobenzenesulfonic acid, 4
-Ethylaminobenzenesulfonic acid, mono- or di-ethanolamine and the like can be mentioned.

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

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulosic fiber materials or regenerated products thereof and polyvinyl alcohol. Cellulosic fiber materials are cotton, as well as other vegetable fibers such as linen,
Hemp, jute and ramie fibers are preferred. Regenerated cellulose fibers are, for example, viscose staple and filament viscose.

Carbonamide group-containing materials are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers such as wool and other animal hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-
It is 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 exhaustion dyeing on cellulose fibers, sodium carbonate, sodium phosphate tribasic, in the presence of an acid binder such as caustic soda, optionally a neutral salt, such as sodium sulfate or salt,
If desired, a solubilizing agent, a penetrating agent, or a leveling agent is used in combination, and the reaction is performed at a relatively low temperature. The neutral salt, which accelerates the exhaustion of the dyestuff, can be added only after the original dyeing temperature has been reached or before, optionally in divided portions.

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

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

For printing pastes, pastes or emulsifiers, such as sodium alginate or starch ether, are used, if desired in combination with customary printing aids and / or dispersants, such as urea.

Suitable acid binders for fixing the compounds of the present 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 upon heating. In particular, alkali metal hydroxides and alkali metal salts of weak or medium-strength inorganic or organic acids are mentioned, of which soda salts and potassium salts are particularly preferable. Examples of such an acid binder include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, sodium dibasic or tribasic phosphate, sodium silicate, sodium trichloroacetate and the like.

Dyeing of synthetic and natural polyamide and polyurethane fibers should be carried out by first exhausting from an acidic or weakly acidic dyeing bath under the control of a pH value, and then changing it to a neutral, and possibly alkaline, pH value for fixing. Can be done by Dyeing is usually carried out at a temperature of 60 to 120 ° C., but in order to achieve level dyeing, a common leveling agent such as a condensation product of cyanuric chloride and 3 times moles 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. It is especially suitable for dyeing cellulose fiber materials and has extremely excellent fastness to sunlight, fastness to sweat sunlight, excellent fastness to wetness, for example, fastness to washing, fastness to peroxidation washing, fastness to chlorine, fastness to bleaching chlorine, sweat. It has fastness, acid hydrolysis fastness and alkali resistance, and also good rubbing fastness and iron fastness. It also has excellent build-up properties, level dyeing properties, and wash-off properties,
Furthermore, it is characterized in that it has good solubility, high exhaustion and stickiness, and that it is possible to obtain a dyed product of stable quality that is not easily affected by variations in dyeing temperature, alkali agent, inorganic salt addition amount, dyeing ratio. Have.

Further, the compound of the present invention shows excellent build-up property and excellent alkali stability in cold patch-up dyeing, and there is almost no difference in concentration between fixation at low temperature and fixation at 25 ° C., and hue difference. It has the property of being less susceptible to hydrolysis by agents.

The present invention is described in detail below with reference to examples. In the examples, parts and% mean parts by weight and% by weight, respectively.

Example 1 To a solution prepared by dispersing 18.5 parts of cyanuric chloride in 250 parts of ice water, 18.8 parts of 1,3-diaminobenzene-4-sulfonic acid was added, and the pH was adjusted to 2 to 4 using a 20% aqueous sodium carbonate solution. However, the first condensation is performed by stirring at 0 to 5 ° C for 6 hours.

Subsequently, 28.1 parts of 1-aminobenzene-3-β-sulfatoethyl sulfone was added, and the mixture was stirred at 10 to 20 ° C for 7 hours while adjusting the pH to 4 to 6 with a 20% aqueous sodium carbonate solution. Carry out dicondensation.

Then, 25.3 parts of concentrated hydrochloric acid is added, and 21.7 parts of a 35% sodium nitrite aqueous solution is injected at 0 to 5 ° C to carry out diazotization. After removing excess nitrous acid, 22.3 parts of 2-aminonaphthalene-6-sulfonic acid was added, and the mixture was stirred overnight at 0 to 5 ° C while adjusting the pH to 1 to 3 using 20% sodium carbonate. After coupling, the temperature is raised to 40 ° C, the pH is adjusted to 4 to 6, 20 parts of sodium chloride is added for salting out, washing, and drying at 60 ° C in the form of free acid. The following formula (1) A monoazo compound represented by

Examples 2 to 49 In Example 1, instead of 2-aminonaphthalene-6-sulfonic acid, compound (V) in the second column of the following table was replaced with 1,3-
Instead of diaminobenzene-4-sulfonic acid, the compound (II) in the third column of the following table is shown in the fourth column, cyanuric chloride or cyanuric fluoride (in the column, Cl represents cyanuric chloride and F represents cyanuric fluoride). .) Was synthesized in the same manner as in Example 1 by using the compound (III) shown in the fifth column of the following table in place of 1-aminobenzene-3-β-sulfatoethylsulfone. A monoazo compound was obtained.

Example 50 2-Methoxy-4-nitroaniline-5 in 150 parts of water
-Sulfonic acid 24.8 parts and 35% sodium nitrite aqueous solution 21.7
The solution containing 1 part is poured into a solution containing 300 parts of ice water and 35.5 parts of concentrated hydrochloric acid while maintaining 0 to 5 ° C., and diazotized by stirring at the same temperature for 1 hour.

Then, after removing excess nitrous acid, 30,3 parts of 2-aminonaphthalene-6,8-disulfonic acid was added, and 0 to 5 was added while adjusting the pH to 1 to 3 using a 20% sodium carbonate aqueous solution.
After stirring at ℃ for 2 hours and coupling, pH8 ~ 1
After adjusting to 0, 10.7 parts of sodium sulfide is added, the temperature is raised to 60 ° C., and the mixture is stirred at the same temperature for 3 hours for reduction. Then 40 parts of sodium chloride was added for salting out.
Wash to obtain a wet cake. This wet cake is dissolved in 400 parts of water, 16.7 parts of cyanuric chloride is added, and the first condensation is carried out by stirring at 0-10 ° C for 5 hours while adjusting the pH to 2-3 using a 20% aqueous sodium carbonate solution. . Then, into this solution, 37 parts of 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid was added, and using a 20% sodium carbonate aqueous solution,
After adjusting the pH to 4 to 5 and stirring at 20 to 30 ° C for 15 hours to carry out the second condensation, 40 parts of sodium chloride is added for salting out, excess washing, and drying at 60 ° C. The following formula (50) in the form of free acid A monoazo compound represented by

Examples 51 to 80 In Example 50, instead of 2-aminonaphthalene-6,8-disulfonic acid, compound (V) in the second column of the following table was replaced with 2-
Instead of methoxy-4-nitroaniline-5-sulfonic acid, the compound (VI) in the 8th column of the following table was replaced with cyanuric chloride or cyanuric fluoride shown in the 4th column (wherein Cl is cyanuric chloride and F is fluorine). In the same manner as in Example 50, except that the compound (III) shown in the fifth column of the following table is used instead of 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid. By the method, 51 to 80 monoazo compounds were obtained.

Example 81 The following formula in the form of the free acid obtained in Example 1 81.5 parts of the monoazo compound represented by is dissolved in 500 parts of water,
Add 34.6 parts of 3-aminobenzenesulfonic acid and adjust to pH 4-6 with 20% aqueous sodium carbonate solution.
After heating up to ~ 85 ° C and stirring at the same temperature and pH value for 7 hours, add 45 parts of sodium chloride to salt out, wash over, wash at 60 ° C and dry in the form of free acid. The following formula (81) A monoazo compound represented by

Examples 82 to 121 Instead of the monoazo compound obtained in Example 1 used in Example 81, the monoazo compound shown in the second column of the following table (indicated by the example number of the used monoazo compound in the column). ,
The compound (VIII) in the third column of the following table was used instead of 3-aminobenzenesulfonic acid, and synthesis was carried out in the same manner as in Example 81 to obtain monoazo compounds 82 to 121.

Example 122 A solution containing 27.4 parts of 2-amino-5-aminomethylnaphthalene-1-sulfonic acid and 35.5 parts of concentrated hydrochloric acid in 300 parts of ice water was added with 21.7 parts of 35% aqueous sodium nitrite solution at 0 to 5 ° C. While maintaining the temperature, the mixture is poured, and the mixture is stirred at the same temperature for 1 hour to diazotize. Then, after removing excess nitrous acid, 2-methylaminonaphthalene-6-sulfonic acid 23.7
And add 20 parts of 20% aqueous sodium carbonate solution to adjust the pH to
While adjusting to 5, coupling is performed by stirring at 0 to 5 ° C. for 12 hours to obtain a solution containing a monoazo compound.

On the other hand, in 300 parts of methanol, 30 parts of water and sodium carbonate
Add 8.4 parts, and then add 18.5 parts of cyanuric chloride, 0-1
The solution obtained by stirring for 30 minutes while maintaining it at 0 ° C was added to an aqueous solution containing the monoazo compound synthesized above, and the pH was adjusted to 7 to 8 with 20% aqueous sodium carbonate solution, while the pH was adjusted to 30 to 40%. Stir at 6 ° C for 6 hours.

Further, 30.9 parts of 1-ethylaminobenzene-4-β-sulfatoethyl sulfone was added, and the temperature was raised to 80 to 90 ° C. while adjusting the pH to 3 to 5 using a 20% aqueous sodium carbonate solution. After stirring at the same pH value for 15 hours, cooling to 40 ° C, adding 40 parts of sodium chloride, salting out, excess,
After washing, it is dried at 60 ℃, and in the form of free acid, the following formula (122) A monoazo compound represented by

Examples 123 to 141 In Example 122, instead of 2-amino-5-aminomethylnaphthalene-1-sulfonic acid, the compound (II) shown in the third column of the following table was replaced with 2-methylaminonaphthalene-6-sulfonic acid. In place of, the compound (V) in the second column of the table below, and in place of methanol, the compound (VIII) in the fourth column of the table below, 1
-Ethylaminobenzene-4-β-sulfatoethyl sulfone was used in the same manner as in Example 122, except that compound (III) shown in column 5 of the table below was used to obtain 123-141 monoazo compounds. It was

Dyeing Example 1 0.3 part of the monoazo compound (1) obtained in Example 1 is dissolved in 200 parts of water, 20 parts of Glauber's salt is added, 10 parts of cotton is added, and the temperature is raised to 50 ° C. Then, after 30 minutes, 4 parts of sodium carbonate is added and dyeing is carried out at the same temperature for 1 hour. After the completion of dyeing, washing with water and soaping were carried out to obtain a dyed product having a high concentration of orange and having various fastnesses, especially chlorine fastness, fastness to sunlight and fastness to sweat and sunlight, and good build-up properties.

Dyeing Example 2 0.3 part of the monoazo compound (50) obtained in Example 50 is dissolved in 150 parts of water, 30 parts of Glauber's salt is added, and 10 parts of cotton is added to 60 ° C.
The temperature rises to. Then, after 20 minutes, 4 parts of sodium carbonate is added and dyeing is carried out at the same temperature for 1 hour. After the completion of dyeing, washing with water and soaping were carried out to obtain a dyed product having a high concentration of orange and having various fastnesses, especially chlorine fastness, fastness to sunlight and fastness to sweat and sunlight, and good build-up properties.

Dyeing Example 3 0.3 part of each of the monoazo compounds obtained in Examples 1-80 was used as 3 parts.
Dissolve in 00 parts of water, add 30 parts of Glauber's salt, add 10 parts of cotton, and add 60 parts
Raise the temperature to ℃. Then, after 20 minutes have passed, 5 parts of sodium carbonate is added and dyeing is carried out at the same temperature for 1 hour. After the completion of dyeing, washing with water and soaping were carried out to obtain a dyed product having a high concentration of orange and having various fastnesses, particularly fastness to chlorine, fastness to sunlight and fastness to sweat and sun, and good build-up properties.

Dyeing Example 4 0.3 parts of each of the monoazo compounds obtained in Examples 81 to 141 was added.
Dissolve in 200 parts of water, add 30 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 50 ° C. Then, after 30 minutes, 4 parts of sodium phosphate tribasic is added and dyeing is carried out at the same temperature for 1 hour. After dyeing,
After washing with water and soaping, various fastnesses, especially chlorine fastness,
An orange dyed product having good fastness to sunlight and fastness to sweat and good build-up properties was obtained.

Dyeing product 5 Color paste composition Each of the monoazo compounds obtained in Examples 1-80 5 parts Urea 5 parts Sodium alginate (5%) Original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts Color paste having the above composition Is printed on mercerized cotton broad cloth, and after intermediate drying, steaming is performed at 100 ° C for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying to finish.

In this way, various fastnesses with high sticking rate, especially chlorine fastness,
An orange printed material having excellent fastness to sunlight and fastness to sweat and good build-up was obtained.

Dyeing Example 6 Color paste composition Each of the monoazo compounds obtained in Examples 81 to 141 4 parts Urea 5 parts Sodium alginate (5%) Original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 14 parts Color paste having the above composition The product is printed on mercerized cotton broad cloth, and after intermediate drying, steaming is performed for 5 minutes at 120 ° C, followed by hot water washing, soaping, hot water washing, and drying to finish.

In this way, various fastnesses with high sticking rate, especially chlorine fastness,
An orange printed material having excellent fastness to sunlight and fastness to sweat and good build-up was obtained.

Dyeing Example 7 25 parts of each of the monoazo compounds obtained in Examples 1 to 80 are dissolved in hot water and cooled to 25 ° C. Immediately after adding 5.5 parts of 32.5% caustic soda aqueous solution and 150 parts of 50 degree Baume water glass, and further adding water to bring the total amount to 1,000 parts at 25 ° C, use this solution as a padding solution to wind up a cotton fabric. Seal with polyethylene film and store in a room at 20 ℃.

The cotton fabric padded in the same manner and rolled up and sealed with a polyethylene film is stored in a room at 5 ° C. After leaving each padding cloth for 20 hours, the dyed product is washed with cold water and then with hot water, soaped in boiling detergent, further washed with cold water and dried to finish.

When the difference in density and the difference in density between the dyed product left at 20 ° C. for 20 hours and the dyed product left at 5 ° C. for 20 hours were examined, almost no difference was observed. In addition, a dyed product having good build-up properties was obtained by cold batch-up dyeing.

Dyeing Example 8 Using 25 parts of each of the monoazo compounds obtained in Examples 81 to 141, dyeing was performed by the cold batch-up method in the same manner as in Dyeing Example 7 to obtain a dyed product having good build-up properties,
Furthermore, when the difference in the density and the difference in hue of the dyed product left at 5 ° C. with respect to the dyed product left at 20 ° C. were examined, almost no difference was observed.

Dyeing Example 9 25 parts of each of the monoazo compounds obtained in Examples 1 to 80 are dissolved in hot water and cooled to 25 ° C. To this, 10 parts of 32.5% caustic soda aqueous solution and 30 parts of anhydrous sodium sulfate were added,
Immediately after adding water to make 1,000 parts at 25 ° C,
This solution is used as a padding solution to pad the viscose rayon fabric. The padded viscose rayon fabric is rolled up, sealed with a polyethylene film and stored in a room at 20 ° C.

In the same manner, the viscose rayon fabric padded and rolled up and sealed with a polyethylene film is stored in a room at 5 ° C.

After each padding cloth is left for 20 hours, the dyed product is washed with cold water and then with hot water, soaped in boiling detergent, further washed with cold water and dried to finish.

As a result of examining the density hue difference and the density difference between the dyed product left for 20 hours at 20 ° C. and the dyed product left for 20 hours at 5 ° C., almost no difference was observed.

Dyeing Example 10 Dyeing was carried out by the cold batch-up method in the same manner as in Dyeing Example 9 using 20 parts of each of the monoazo compounds obtained in Examples 81 to 141 to obtain a dyed product with good build-up properties, and further at 20 ° C. When the difference in the density and the difference in the hue of the density of the dyed product left at 5 ° C. with respect to the dyed product left in Step 2 were examined, almost no difference was observed.

Dyeing Example 11 Dyeing was performed in the same manner as in Dyeing Example 3 except that the amount of sodium carbonate used was changed from 5 parts to 3 parts, and the dyes obtained in Dyeing Example 3 were used for each of the monoazo compounds 1 to 80 used. A dyed product having the same quality as the product was obtained.

Dyeing example 12 Dyeing example 3 was dyed in exactly the same manner except that the temperature was changed from 60 ° C to 50 ° C, and the same quality as the dyed product obtained in dyeing example 3 for each of the monoazo compounds 1-80 used A dyed product having The same was true when the temperature was 70 ° C.

Dyeing Example 13 Dyeing products obtained in Dyeing Example 3 were dyed in exactly the same manner as in Dyeing Example 3, except that the amount of Glauber's salt used was changed from 30 parts to 15 parts. A dyed product having the same quality as

Dyeing Example 14 The same procedure as in Dyeing Example 4 was repeated except that the amount of water used was changed from 200 parts to 150 parts and the amount of Glauber's salt used was changed from 30 parts to 23 parts. A dyed product having the same quality as the dyed product obtained in Dyeing Example 4 was obtained for each.

Claims (5)

[Claims] 1. The following general formula (I) in the form of a free acid. [In the formula, R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or an optionally substituted lower alkyl group, and R ₄ is a hydrogen atom, an optionally substituted lower alkyl group or a group. And B is a group (In the formula, the bond indicated by an asterisk is Means a bond leading to a group. And X is a chlorine atom, a fluorine atom, a lower alkoxy group, an optionally substituted phenoxy group or a group (R ₆ and R ₇ are each independently a hydrogen atom, an optionally substituted lower alkyl group, an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted benzyl group. And A is a phenylene or naphthylene group which may have a substituent, and Z is a group-
SO ₂ CH = CH ₂ or a group —SO ₂ CH ₂ CH ₂ Y, where Y is a group capable of leaving with an alkali. ] The monoazo compound shown by these, or its salt. 2. R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
Represents a methyl group or an ethyl group, and A may be substituted with 1 or 2 substituents selected from the group consisting of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom, a bromine atom and a sulfonic acid group. The monoazo compound according to claim 1, which is a naphthylene group optionally substituted with one phenylene group or one sulfonic acid group, or a salt thereof. 3. Z is a group —SO ₂ CH═CH ₂ , a group —SO ₂ CH ₂ CH ₂ OSO.
₃ H, a group —SO ₂ CH ₂ CH ₂ OCOCH ₃ , a group —SO ₂ CH ₂ CH ₂ SSO ₃ H, or a group —SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ and X is a chlorine atom, a fluorine atom, or Basis (R ₈ represents a hydrogen atom, a methyl group or an ethyl group.) The monoazo compound according to claim 1 or 2, or a salt thereof. Wherein R ₄ is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, 3-sulfophenyl group or a 4-sulfophenyl claims first term of a phenyl group, according to the second term or third term A monoazo compound or a salt thereof. 5. The following general formula (I) in the form of a free acid. [In the formula, R ₁ , R ₂ and R ₃ are independently of each other a hydrogen atom or an optionally substituted lower alkyl group, and R ₄ is a hydrogen atom, an optionally substituted lower alkyl group or a group. And B is a group (In the formula, the bond indicated by an asterisk is Means a bond leading to a group. And X is a chlorine atom, a fluorine atom, a lower alkoxy group,
Phenoxy group or group which may be substituted (R ₆ and R ₇ are each independently a hydrogen atom, an optionally substituted lower alkyl group, an optionally substituted phenyl group, an optionally substituted naphthyl group or an optionally substituted benzyl group. And A is a phenylene or naphthylene group which may have a substituent, and Z is a group-.
SO ₂ CH = CH ₂ or a group —SO ₂ CH ₂ CH ₂ Y, where Y is a group capable of leaving with an alkali. ] The dyeing or printing method of the textile material characterized by using the monoazo compound shown by these, or its salt.