JPH06136281A - Dye water-based liquid composition - Google Patents

Abstract

PURPOSE:To provide a dye water-base liquid composition containing a specific reactive dye, improved in workplace environment such as prevention of dust pollution, excellent in long-term storage stability and handleability, suitable for e.g. dyeing cellulosic fibers, etc. CONSTITUTION:The composition containing a reactive dye of the formula [R is 1-4C alkyl or alkoxyalkyl; X is H or SO3M (M is H, Li, Na or K; where, at least one of Ms being Li)].

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous liquid composition of a yellow dye. More specifically, it relates to a concentrated aqueous liquid composition having excellent storage stability of a reactive dye.

[0002]

2. Description of the Related Art Conventionally, powdered products have been widely used as product forms of dyes, but in recent years, improvement of work environment such as prevention of dust pollution, easy handling in weighing and dissolving, and automatic weighing As a result, liquid products have come to be widely used.

As the liquid product, storage stability which does not cause decomposition, crystal precipitation, etc. during storage is a major requirement, and the highest possible concentration is a problem from the viewpoint of transportation, storage and use.

In order to improve stability, desalting treatment in liquid products and addition of various solubilizing agents have been carried out. Free acid, sodium salt or potassium salt is used as a type of sulfonic acid group of dye. , In many cases, the solubility is not sufficient and there is a problem such as crystal precipitation, so that the stability is improved by a complicated desalting treatment, a combination of various dissolution aids, and a complicated operation such as large addition, Furthermore, there are naturally limits to stability at low temperatures and higher dye concentrations. Liquid dyes of the free acid, sodium salt or potassium salt of formula (1) (M is hydrogen, Na or K) described below are not exceptions, and long-term storage stability at low temperature to room temperature, especially dyes It has problems at high concentrations.

[0005]

With respect to the reactive dye of the formula (1) described below, there is a demand for a concentrated aqueous liquid composition which is stable in storage at low temperature to room temperature (-10 ° C to 40 ° C) for a long period of time.

[0006]

The present inventors have completed the present invention as a result of intensive studies to solve the above-mentioned problems.

That is, the present invention uses the formula (1)

[0008]

[Chemical 2]

(In the formula, R represents a C ₁ -C ₄ alkyl group or an alkoxyalkyl group, X represents hydrogen or a —SO ₃ M group, and each M independently represents hydrogen, Li, Na or K. However, regarding the aqueous liquid composition of the reactive dye represented by the formula (1), at least one of M represents Li), which is stored at low temperature to room temperature for a long time by an efficient and industrially advantageous method. The present invention provides a stable concentrated aqueous liquid composition.

The present invention will be described in detail. The reactive dye represented by the formula (1) in which M is hydrogen, Na or K is known per se from Japanese Patent Publication No. 57-14779, and is produced, for example, as follows. Formula (2) as free acid

[0011]

[Chemical 3]

A compound represented by the formula (wherein X represents hydrogen or a --SO ₃ H group) and cyanuric chloride are condensed,
The product is then diazotized and then used as the free acid of formula (3)

[0013]

[Chemical 4]

(Wherein R represents a C ₁ -C ₄ alkyl group or an alkoxyalkyl group), and then, as a free acid, 4- or 3-aminobenzenesulfonic acid. It can be obtained by reacting.

Specific examples of the compound represented by the formula (2) include 2,4-diaminobenzenesulfonic acid and 2,4-diamino-1,5-benzenedisulfonic acid.

Further, specific examples of the compound represented by the formula (3) include 3-sulfomethyl-1,4-dimethyl-6-.
Hydroxy-2-pyridone, 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone, 1
-Propyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone, 1-butyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone, 1-methoxypropyl-3-sulfomethyl-4- Methyl-6-
Hydroxy-2-pyridone and the like can be mentioned. Further, in the formula (3), the compound having a —CONH2 group at the 5-position itself leaves during coupling, so that corresponding compounds can also be used in the reaction.

In the aqueous liquid composition of the present invention, at least one of the three or four sulfonic acid groups of the reactive dye represented by the formula (1) forms a —SO ₃ Li group. However, the method for forming this salt is not particularly limited, for example, in the case of producing a reactive dye, a solubilizer,
Usually sodium carbonate used as a neutralizing agent, sodium bicarbonate, sodium hydroxide, a part in place, such as potassium hydroxide or, all lithium hydroxide, depending on the use of lithium carbonate, -SO ₃ Li groups Can be converted to. At this time, the amount used is 1 to 10 with respect to 1 mol of the reactive dye.
The amount is more preferably 2 to 5 mol and can be appropriately used in each step of the reaction.

It is also possible to produce a reactive dye by an ordinary method, filter and separate the obtained crystal, and redissolve it with lithium hydroxide or lithium carbonate to convert it into a --SO ₃ Li group. Further, the reaction solution obtained by a usual method can be cation exchanged by a dialysis method using a lithium chloride solution to form a —SO ₃ Li group.

In the present invention, in order to form the reaction solution obtained into an aqueous liquid composition having a desired dye concentration, it is concentrated by evaporation or, more preferably, desalted and concentrated by a reverse osmosis method.
The reverse osmosis method is usually carried out under a pressure of 10 to 30 kg using polybenzimidazolone, cellulose acetate, polyamide or the like as a filtration membrane.

In order to obtain a stable concentrated liquid composition, it is desirable to reduce inorganic salts such as NaCl, Na ₂ SO ₄ and KCl in the liquid as much as possible, and a complicated desalting treatment operation is carried out. In the case of the liquid composition of the present invention, the solubility and stability are extremely high, and no advanced or high-order desalting treatment is required.

Regarding the degree of desalting, a concentration of about 1% in the liquid is sufficient to achieve the purpose, and in this respect, the simplification of the operation in practice, efficiency improvement, and industrial advantage are noted.

The aqueous liquid composition of the present invention is usually 20 to 4
It contains 0% by weight of dye, but is adjusted to the desired concentration by adding water if necessary. Additives that are usually used in the liquid composition, for example, ε-caprolactone, urea, ethylene glycols, sodium polyacrylate, dissolution aids such as condensed phosphates, sequestering agents, pH adjusting agents, antibacterial agents, etc. It is effective to add 0.5 to 50% by weight of a fungicide, etc., if necessary, and to adjust the pH of the liquid composition to about 6.0 to 8.0 to improve the stability with time. is there.

The aqueous liquid composition of the reactive dye of the present invention is excellent in stability without problems such as decomposition and crystal precipitation even during long-term storage at low temperature to room temperature (-10 ° C to 40 ° C). , It is significant that the dye concentration can be increased in the moderate desalting process.

The liquid composition is applied for dyeing cellulose fibers and fibers containing cellulose. Cotton, rayon,
The usual dyeing method is applied to hemp and blended fabrics of these and mixed woven products, and further to cellulose / synthetic fiber blended fabrics and mixed woven products such as cotton / polyester blended products.

[0025]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, parts are parts by weight and% is% by weight.

Example 1 14.8 parts of 2,4-diaminobenzenesulfonic acid was added to sodium hydroxide and dissolved in 300 parts of water. 19 parts of cyanuric chloride was added to the solution, and primary condensation was performed at 0 to 5 ° C and pH 6 to 7. During the reaction, sodium carbonate was added to complete the reaction. Then, the product was diazotized with hydrochloric acid and sodium nitrite by a conventional method. Then 1
-Ethyl-5-carbamoyl-3-sulfomethyl-4-
Methyl-6-hydroxy-2-pyridone 29 parts water 20
It was dissolved in 0 part and added, and coupling was performed at 10 ° C. and pH 6 to 7. During the reaction, 4.8 parts of lithium hydroxide was added to complete the reaction. Then, 18 parts of 4-aminobenzenesulfonic acid is dissolved in 150 parts of water and added, and the mixture is added at 50 ° C. and pH 7 to 7.
Secondary condensation was carried out at 8. During the reaction, lithium hydroxide 4.
8 parts were added to complete the reaction. The reaction solution was desalted and concentrated by a reverse osmosis apparatus to obtain 210 parts of an aqueous liquid composition.
A polyamide membrane (manufactured by Teijin Engineering Co., Ltd.) was used as the reverse osmosis device at a pressure of 15 kg / cm ² . As a result of analyzing the dye structure in the obtained liquid composition, among the three M's in the dye represented by the formula (4),
Two were Li and one was Na. Dye density is 32.9
%, NaCl 0.9%, Na ₂ SO ₄ 0.2%.

[0027]

[Chemical 5]

Example 2 A dye was prepared according to Example 1, except that in the secondary condensation, 4-aminobenzenesulfonic acid and lithium hydroxide as a reaction neutralizing agent were used instead of 3-aminobenzene, respectively. It was carried out using 18 parts of sulfonic acid and 8 parts of sodium hydroxide. Similarly, the reaction solution is desalted and concentrated by the reverse osmosis method,
220 parts of liquid composition was obtained. Regarding the dye structure in the obtained liquid composition, in the dye represented by the formula (5), among 3 M, 1 was Li and 2 was Na. Dye density is 3
2.3%, NaCl 1.1%, Na ₂ SO ₄ 0.2%
Was included.

[0029]

[Chemical 6]

Example 3 A dye was prepared according to Example 1, except that 7.4 parts of lithium carbonate was used instead of sodium carbonate as a reaction neutralizing agent in the primary condensation, and coupling and secondary condensation were carried out. Sodium hydroxide was used instead of lithium hydroxide in. The reaction solution was similarly desalted and concentrated by the reverse osmosis method to obtain 220 parts of a liquid composition. Regarding the dye structure in the obtained liquid composition, in the dye represented by the formula (4), among 3 M, 1 was Li and 2 was Na. The dye concentration is 32.5%, NaCl 1.0%, Na ₂ SO ₄ 0.
It contained 2%.

Example 4 A dye was prepared according to Example 1, except that potassium hydroxide was used instead of lithium hydroxide as a reaction neutralizing agent in the secondary condensation. The reaction solution was similarly desalted and concentrated by the reverse osmosis method to obtain 210 parts of a liquid composition. Regarding the dye structure in the obtained liquid composition, in the dye represented by the formula (4), among 3 M, 1 was Li and 2 was K. Dye concentration is 33.0%, NaCl 0.3%, K
Cl 0.7%, Na ₂ SO ₄ 0.1%, K ₂ SO ₄ 0.
It contained 1%.

Example 5 2,4-Diamino-1,5-benzenedisulfonic acid 2
Sodium hydroxide was added to 6.8 parts and dissolved in 250 parts of water. Add 19 parts of cyanuric chloride to the solution, and add 0-5
Primary condensation was performed at a temperature of 6 to 7. During the reaction, 4 parts of lithium carbonate was added to complete the reaction. The product was then diazotized with hydrochloric acid and sodium nitrite. Then 1-butyl-5-carbamoyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone 31.8
Part was dissolved in 250 parts of water and added, and coupling was performed at 10 ° C. and pH 6 to 7. During the reaction, lithium hydroxide 4.8
Parts were added to complete the reaction. Then, 18 parts of 4-aminobenzenesulfonic acid is dissolved in 150 parts of water and added,
Secondary condensation was performed at a temperature of 7 to 8 ° C. During the reaction, 4.8 parts of lithium hydroxide was added to complete the reaction. Similarly, the reaction solution was desalted and concentrated by the reverse osmosis method to give a liquid composition 230
I got a part. The dye structure in the obtained liquid composition is as follows. Of the four M's in the dye represented by the formula (6), three are L's.
i, one was Na. Dye concentration is 33.3%, N
It contained aCl 1.1% and Na ₂ SO ₄ 0.1%.

[0033]

[Chemical 7]

Examples 6 to 12 In the formula (7), the results obtained for the dyes having the structures shown in the following table are shown.

[0035]

[Chemical 8]

[0036]

[Table 1]

Comparative Example In order to measure the low temperature storage stability of the aqueous liquid compositions of the present invention, these compositions were diluted with water to obtain a dye concentration of 30%.
The stability test shown in Table 1 below was performed. The objects of comparison are the following equations (8), (9), (10), (11)
Further, the dye having the structure of (12) was also desalted and concentrated by the reverse osmosis method to obtain a concentrated liquid having a dye concentration of 30%.
The content of the inorganic salt in the liquid composition was adjusted to 0.8 to 1.2%, and the pH of the composition was adjusted to 6.5 to 7.5.

[0038]

[Chemical 9]

[0039]

[Chemical 10]

[0040]

[Chemical 11]

[0041]

[Chemical 12]

[0042]

[Chemical 13]

Results of low temperature storage stability test (-5 ° C. storage)

[Table 2] In the table, ◯ indicates a completely dissolved state, Δ indicates a slightly crystallized state, and x indicates a crystallized state as a whole.

Separately, when the liquid composition of Example 2 was prepared, the composition containing 5% of ε-caprolactone was 9%.
It was in a completely dissolved state until 0 days later. Further, similarly to the liquid composition of Example 3, the composition containing 5% of ε-caprolactone was in a completely dissolved state until 90 days later. Also, similarly to the liquid composition of Example 9, the composition containing 10% of ε-caprolactone was in a completely dissolved state until 60 days later.

Dyeing Example The liquid composition obtained in Example 1 was diluted with water to give a dye concentration of 30%.
A printing paste having the following composition was prepared using the liquid composition described above. The color paste was printed on a cotton cloth, intermediately dried at 80 ° C., and then steamed at 102 ° C. for 10 minutes. Then, soaping, washing with water and drying were carried out to obtain a vivid green-yellow print dyeing product. Composition of printing paste Liquid composition of Example 1 (dye concentration 30%) 7 parts 5% sodium alginate aqueous solution 50 ″ sodium bicarbonate 3 ″ urea 10 ″ water 30 ″ 100 copies

[0046]

Industrial Applicability A concentrated aqueous liquid composition of a reactive dye is obtained which is stable even during long-term storage, particularly at low temperature storage.

Claims (1)

[Claims] 1. A general formula: (In the formula, R represents a C _{1 to} C ₄ alkyl group or an alkoxyalkyl group, X represents hydrogen or a —SO ₃ M group, and M
Each independently represent hydrogen, Li, Na or K. However, among M, at least one M represents Li. ) An aqueous liquid composition of a reactive dye represented by: