JPH0776310B2 - Monoazo compound and method for dyeing or printing fiber material using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel monoazo compound in the field of dyeing or printing a fiber material as a reactive dye.

2. Description of the Related Art It has been widely practiced to dye or print a fiber material in a brown color using a fiber-reactive monoazo compound.

Problems to be Solved by the Invention Due to recent changes in technical and economic conditions in the demand industry, existing fiber-reactive monoazo compounds have not always been able to meet all the needs of the demand industry. For example, looking at the dyeing performance, which is one of the basic required performances of dyes, many unsatisfactory points have been found.

Means for Solving the Problems In order to find a novel monoazo compound having performance capable of responding to the sophistication of needs as described above, the present inventors have developed a dye base, the type and number of fiber-reactive groups, and As a result of diligent studies on the types of linking groups to which they are connected and the linking sites, etc., a compound having specific performance was found by optimally combining specific ones, and the present invention was completed. That is, the present invention has 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 hydrogen or lower alkyl which may have a substituent, R ₄ is hydrogen, lower alkyl which may have a substituent or acyl, B ₁ and B ₂ independently of each other are phenylene or sulfo optionally substituted by 1 or 2 substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo. Optionally substituted naphthylene, Z ₁ and Z ₂ independently of each other are vinyl or --CH ₂ CH ₂ L
(L is a group capable of leaving by the action of an alkali), l is 0 or 1,
And A is of formula (II) (In the formula, X ₁ represents hydrogen, methyl, ethyl, methoxy, ethoxy, chloro, carboxy or sulfo, R ₅ represents hydrogen, methyl, methoxy or sulfo, and m represents 0 or 1.) or the formula (III). (In the formula, X ₂ represents hydrogen or sulfo). ] And a method for dyeing or printing a fiber material using the monoazo compound represented by:

In the general formula (I), when R ₁ , R ₂ and R ₃ are independently lower alkyl which may have a substituent, such a group is described in, for example, JP-A-59-176355. The groups described above correspond to this. Preferably, R ₁ and R ₂ independently of one another are hydrogen, methyl or ethyl, of which at least one of R ₁ and R ₂ is preferably hydrogen. on the other hand,
A preferred group for R ₃ is hydrogen or methyl.

When R ₄ is lower alkyl which may have a substituent, a group such as sulfomethyl, methyl, ethyl, carboxymethyl, carboxyethyl or sulfoethyl is preferable, and when acyl is, for example, acetyl, propionyl and the like are preferable. .

As B ₁ and B ₂ , known groups are applicable, for example, the groups shown in the above-mentioned publication correspond, and particularly unsubstituted or methyl, methoxy or sulfo substituted phenylene, or unsubstituted Or .beta.-naphthylene substituted with sulfo is preferred.

In the case where Z ₁ or Z ₂ is —CH ₂ CH ₂ L, what is known as a group capable of leaving by the action of an alkali corresponds to this, and examples thereof include sulfate, thiosulfate, acetoxy and Examples include chloro. Preferable Z ₁ and Z ₂ are both β-sulfatoethyl, and vinyl may be partially mixed therein.

As A, the case where X ₁ of the formula (II) is carboxy or sulfo, R ₅ is hydrogen, methyl or sulfo, and m is 0 or 1, and the case of the formula (III) are preferable.

Among the monoazo compounds represented by the formula (I), particularly preferable ones are those represented by the following general formula (IV) in the form of free acid. [In the formula, R ₆ is hydrogen, methyl or ethyl, R ₇ is hydrogen, methyl or sulfo, R ₈ and R ₉ are independently of each other hydrogen, methyl,
Methoxy or sulfo, l and m independently of each other are 0 or 1
Represents ] And the following general formula (V) [In the formula, R ₁₀ represents hydrogen, methyl or ethyl, R ₁₁ and R ₁₂ each independently represent hydrogen, methyl, methoxy or sulfo, X ₂ represents hydrogen or sulfo, and l represents 0 or 1. ] It is a monoazo compound shown by these. In the general formula (IV), in particular, R ₇ is hydrogen, methyl or sulfo, and m is 0, or R ₇ is hydrogen or methyl,
And it is preferable that m is 1.

The compound of the present invention is preferably an alkali metal or alkaline earth metal salt, and particularly preferably a sodium or potassium salt.

The compounds of the present invention have the following formulas (VI) to (IX) [In the formula, l, R ₄ , A, R ₃ , R ₁ , B ₁ , Z ₁ , R ₂ , B ₂ and Z ₂ have the above-mentioned meanings, and X is a hydrogen or a temporary such as acetyl. It is a group capable of protecting amino. ] It can manufacture with a compound shown by and a cyanuric chloride or a cyanuric fluoride by a conventional method. That is, a compound of formula (VII) (wherein X is preferably a method using a group capable of temporarily protecting an amino group such as acetyl) is diazotized and coupled with a compound of formula (VI), If it is hydrolyzed in the presence of an alkali or acid to convert X into hydrogen, this and the formula (VI
It can be prepared by sequentially condensing the compound II) and the compound of formula (IX) with cyanuric chloride or cyanuric fluoride. Alternatively, in the reaction of a compound of formula (VII) (where X is hydrogen) with cyanuric chloride or fluoride, the compound of formula (VII)
Compound When (X is hydrogen and R ₃ has the above meanings) is more reactive than the group H ₂ N-, this reaction is carried out, and then the compound of formula (VIII) and formula (IX) It can also be produced by sequentially condensing, finally diazotizing, and coupling with the compound of the formula (VI). Alternatively, a precursor of a compound of formula (VII) (wherein X and R ₃ are both hydrogen), H ₂ N-
A-NO ₂ (A is as defined above) was used, and after diazotization, the compound was coupled with a compound of the formula (VI), and the nitro was reduced with sodium sulfide or sodium hydrosulfide to give an amino. Further, by introducing a group R ₃ into this amino, After that, the compound of the present invention can be produced according to the above method.

Examples of the compound of the formula (VI) include 7- (o, m or p-sulfophenylamino) -1-naphthol-3-sulfonic acid and 7-phenylamino-1-naphthol-3-
Sulfonic acids and their N-acetylated, N-propionylated, N-sulfomethylated, N-methylated, N-ethylated, N-carboxymethylated, N-carboxyethylated or N-sulfoethylated compounds Is mentioned.

Examples of the compound of formula (VII) include 2,4- or 2,5
-Diaminobenzenesulfonic acid, 2,4-diaminobenzene-1,5-disulfonic acid, 2,5-diaminobenzene-1,4
-Disulfonic acid, 5-methyl, methoxy or chloro-2,4-diaminobenzenesulfonic acid, 5-acetylamino-5-aminobenzoic acid, 2-methyl, methoxy, ethyl, ethoxy or chloro-1,4- or 1 , 5-Diaminobenzene, 4-aminomethyl-2-amino-5-
Methylbenzenesulfonic acid, 4- or 5-aminomethyl-2-aminobenzenesulfonic acid, 6-aminomethyl-2-amino-3-methoxybenzenesulfonic acid, 3
-Aminomethyl-2-amino-5-methylbenzenesulfonic acid, 4-aminomethyl-2-amino-5-methoxybenzenesulfonic acid, 5-aminomethyl-2-aminobenzene-1,4-disulfonic acid, 4- Aminomethyl-2-
Amino-5-ethylbenzenesulfonic acid and, of these, compounds having aminomethyl include N-lower alkyl-substituted compounds of amino, particularly N-methylated compounds, or their primary groups. Alternatively, a compound in which the secondary amino is temporarily protected with a group such as acetyl is also included. Furthermore, as the compound of formula (VII) having a naphthalene ring, 2-amino-5
-Aminomethylnaphthalene-1-sulfonic acid or-
1,7-disulfonic acid is also included.

The above-mentioned starting compound is an acid and / or salt depending on reaction conditions,
In particular, it is used in the form of an alkali metal salt or an alkaline earth metal salt.

The monoazo compound produced according to the present invention can be made into a liquid product by removing an inorganic salt and optionally adding a stabilizer or a dyeability improving agent, or evaporating the liquid product or the reaction solution. For example, it can be made into a powder product by spray drying, or can be made into a liquid product or a powder product through salting-out separation by addition of an electrolyte by a generally known method.

The monoazo compounds according to the invention can be used as fiber-reactive dyes and can dye fiber materials, for example materials containing hydroxy groups or carboxylic acid amide groups.

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 staples and filament viscose.

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

For dyeing, a method depending on the reactive group of the fiber reactive dye can be applied.

For example, in the case of cellulosic fibers, dyeing is carried out using the dye of the present invention and an acid binder such as caustic soda, sodium carbonate, phosphate, silicate or sodium hydrogen carbonate. The dyeing method can be selected according to the nature of the fiber and the physical shape,
For example, an exhaust method, a printing method, a cold pad-patch-up method, etc. can be adopted.

In the case of the exhaust method, sodium carbonate, sodium triphosphate,
It is carried out at a relatively low temperature in a dyebath containing Glauber's salt or salt in the presence of an acid binder such as caustic soda. In the case of printing processes, pastes or emulsified pastes such as sodium alginate or starch ether and sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, sodium triphosphate, sodium trichloroacetate or the corresponding potassium or alkaline earth compounds Along with the alkaline or alkali-releasing agents, if desired, is applied to the fibers with the addition of conventional printing aids or dispersants such as urea, dried and heat-treated, especially in the presence of steam. It can be dyed by In the case of cold pad-batch-up dyeing, caustic soda alone, or sodium silicate, sodium carbonate or sodium triphosphate as an acid binder is used in combination, and in some cases, sodium sulfate or sodium chloride is added to dissolve urea such as urea. At around room temperature with the addition of auxiliary agents or penetrants, pad on the fiber and wind it up on a roll.
It can be dyed by leaving it for 3 hours or overnight and washing with water and drying.

The compound of the present invention is characterized in that it exhibits excellent performance on fiber materials, and is particularly suitable for dyeing cellulosic fibers. It has a high exhaustion rate and sticking rate, extremely excellent build-up property, level dyeing property and detergency property, and even if there is some variation in dyeing conditions such as temperature, bath ratio and salt concentration, it has almost no effect on dyeing property. It has features such as not being present. Excellent in fastness such as light resistance, sweat light resistance, sweat resistance, acid hydrolysis resistance, washing resistance, chlorine resistance, etc., especially when A is represented by the formula (II) in the general formula (I). the, X ₁ is a group other than hydrogen, i.e. a relatively large group, in particular sulfo, and groups in the para-position of the base - when there is a (CH _{2 m,} and a is represented by formula (III) Occasionally, it shows even higher robustness.

Next, the present invention will be described in more detail with reference to examples. In the text, parts indicate parts by weight.

Example 1 2,4-Diaminobenzenesulfonic acid (4.70 parts), cyanuric chloride (4.61 parts), and then 1-aminobenzene-4-β-sulfatoethylsulfone (6.95 parts) were sequentially condensed by a conventional method, and then 1-amino was prepared. It was condensed with 6.95 parts of benzene-3-β-sulfatoethyl sulfone at 60 to 70 ° C. under weak acidity, and diazotized by a conventional method, and 7- (m-sulfophenylamino) -1-naphthol-3- Coupling with 4.70 parts of sulfonic acid, salting out, the following formula in the form of free acid A monoazo compound represented by

0.3 part of this monoazo compound was added to 200 parts of water, 10 parts of cotton and 8 parts of sodium sulfate were added and the temperature was raised to 60 ° C., 4 parts of sodium carbonate was added, and dyeing was carried out at the same temperature for 1 hour, followed by washing with water and soaping. A brown dyed product having excellent fastness and dyeing performance was obtained. This compound changes dyeing temperature, bath ratio, salt concentration a little,
The reproducibility was excellent.

Example 2 2,4-diaminebenzenesulfonic acid, 1-aminobenzene-4-β-sulfatoethylsulfone, 1-aminobenzene-3-β-sulfatoethylsulfone and 7- (m used in Example 1 -Sulfophenylamino) -1-naphthol-3-sulfonic acid in place of the compounds in columns 1, 2, 3 and 4 of the following table,
Corresponding monoazo compounds were obtained. The color tone of these compounds on cotton is as shown in the fifth column.
It showed the same performance as the compound.

Example 3 9.1 parts of 2-amino-5-acetylaminobenzoic acid was diazotized by a conventional method to give 7- (m-sulfophenylamino).
After coupling with 19.8 parts of -1-naphthol-3-sulfonic acid, the acetyl group was alkali-hydrolyzed. Then, 9.3 parts of cyanuric chloride and 14.1 parts of 1-aminobenzene-3-β-sulfatoethyl sulfone were sequentially condensed by a conventional method. Furthermore, 1-N-ethylaminobenzene-4-β-sulfatoethyl sulfone 16.2 parts and 70-80 ° C under weak acidity.
In the following formula in the form of free acid A monoazo compound represented by

Example 4 12.4 parts of 5-amino-4-methoxy-2-nitrobenzenesulfonic acid was diazotized by a conventional method to give 7- (p-sulfophenylamino) -1-naphthol-3-sulfonic acid 1
After coupling with 9.8 parts, the nitro group was reduced with sodium sulfide. 9.3 parts of cyanuric chloride based on the obtained compound, 2-
20.6 parts of naphthylamine-6-β-sulfatoethylsulfone-1-sulfonic acid were successively condensed by a conventional method. Further, it is condensed with 14.3 parts of 1-aminobenzene-3-β-sulfatoethyl sulfone under mild acidity at 65 to 75 ° C. and salted out to give the following formula in the form of free acid. A monoazo compound represented by

Example 5 For each of the monoazo compounds obtained in Examples 3 and 4,
Dyeing was performed according to the method described in Example 1 to obtain a brown dyed product having excellent build-up properties.

Claims (10)

[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 independently of each other hydrogen or lower alkyl which may have a substituent, R ₄ is hydrogen, lower alkyl or acyl which may have a substituent, B ₁ and B ₂ are each independently substituted with phenylene or sulfo optionally substituted with 1 or 2 substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo. Optionally naphthylene, Z ₁ and Z ₂ independently of each other are vinyl or --CH ₂ CH ₂ L
(L is a group capable of leaving by the action of an alkali), l is 0 or 1,
And A is of formula (II) (In the formula, X ₁ is hydrogen, methyl, ethyl, methoxy, ethoxy, chloro, carboxy or sulfo, R ₅ is hydrogen, methyl, methoxy or sulfo, and m is 0 or 1.) or Formula (III) (In the formula, X ₂ represents hydrogen or sulfo). ] The monoazo compound shown by these. 2. A compound according to claim ₁ wherein R ₁ and R ₂ are independently of each other hydrogen, methyl or ethyl. _3. A compound according to claim 1 or 2 in which R ₃ is hydrogen or methyl. Wherein R ₄ is hydrogen, acetyl, propionyl, sulfomethyl, methyl, ethyl, carboxymethyl, first the claims is a carboxyethyl or sulfoethyl
Item 4. The compound according to any one of Items 3 to 3. 5. The compound according to any one of claims 1 to 4, wherein Z ₁ and Z ₂ are each independently vinyl or β-sulfatoethyl. 6. A compound according to claim 1, wherein X _{1 in} formula (II) is carboxy or sulfo, R ₅ is hydrogen, methyl or sulfo, and m is 0 or 1. The compound according to any of the above. 7. The following general formula (IV) in the form of a free acid. [In the formula, R ₆ is hydrogen, methyl or ethyl, R ₇ is hydrogen, methyl or sulfo, R ₈ and R ₉ are independently of each other hydrogen, methyl,
Methoxy or sulfo, l and m independently of each other are 0 or 1
Represents ] The monoazo compound of Claim 1 shown by these. 8. The following general formula (V) in the form of a free acid. [In the formula, R ₁₀ represents hydrogen, methyl or ethyl, R ₁₁ and R ₁₂ each independently represent hydrogen, methyl, methoxy or sulfo, X ₂ represents hydrogen or sulfo, and l represents 0 or 1. ] The monoazo compound of Claim 1 shown by these. 9. R ₇ is hydrogen, methyl or sulfo and m is 0, or R ₇ is hydrogen or methyl,
The compound according to claim 7, wherein m is 1. 10. 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 hydrogen or lower alkyl which may have a substituent, R ₄ is hydrogen, lower alkyl or acyl which may have a substituent, B ₁ and B ₂ are each independently substituted with phenylene or sulfo optionally substituted with 1 or 2 substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, nitro, carboxy and sulfo. Optionally naphthylene, Z ₁ and Z ₂ independently of each other are vinyl or --CH ₂ CH ₂ L
(L is a group capable of leaving by the action of an alkali), l is 0 or 1,
And A is of formula (II) (In the formula, X ₁ is hydrogen, methyl, ethyl, methoxy, ethoxy, chloro, carboxy or sulfo, R ₅ is hydrogen, methyl, methoxy or sulfo, and m is 0 or 1.) or Formula (III) (In the formula, X ₂ represents hydrogen or sulfo). ] The method of dyeing or printing the fiber material characterized by using the monoazo compound shown by these.