JP3068351B2 - Dye aqueous liquid composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 In the past, powdery dyes have been widely used as product forms. However, in recent years, improvement of working environment such as prevention of dust contamination, easiness of handling in weighing and dissolving, etc., and improvement of automatic weighing. Liquid products have come to be widely used due to measures and the like.

As a liquid product, storage stability that does not cause decomposition, crystal precipitation, or the like during storage is a major requirement, and there is a need to increase the concentration as much as possible for convenience of transportation, storage, and use.

In order to improve the stability, desalting of the liquid product and addition of various solubilizers have been carried out. However, as the type of sulfonic acid group of the dye, free acid, sodium salt or potassium salt is used. In many cases, the solubility is not sufficient, and since there are problems such as crystal precipitation, complicated operations such as advanced desalination treatment, combination of various dissolution aids and addition of a large amount are required to improve the stability. In addition, there are naturally limitations on stability at low temperatures and high concentration of dyes. Dye liquids of the free acid, sodium salt or potassium salt of the following formula (1) (when M is hydrogen, Na or K) are no exception, and long-term storage stability at low to room temperature, especially dyes Has problems at high concentrations.

[0005]

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

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.

That is, the present invention provides the following formula (1)

[0008]

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

The present invention will be described in detail. In the formula (1), the reactive dyes in which M is hydrogen, Na or K are known per se from JP-B-57-14779, and are produced, for example, as follows. Formula (2) as a free acid

[0011]

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Wherein X represents hydrogen or a —SO ₃ H group, and cyanuric chloride,
The product is then diazotized and the free acid of formula (3)

[0013]

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(Wherein R represents a C ₁ -C ₄ alkyl group or an alkoxyalkyl group), followed by coupling with 4- or 3-aminobenzenesulfonic acid as a free 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. Further, in the formula (3), the compound having a -CONH2 group at the 5-position itself is eliminated at the time of coupling, so that each corresponding compound can be used for 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, when producing a reactive dye, a dissolving agent,
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 mole of the reactive dye.
Mol, more preferably 2 to 5 mol, and can be used as appropriate at each stage of the reaction.

Alternatively, a reactive dye may be prepared by a conventional method, and the crystals obtained by filtration and separation may be re-dissolved using lithium hydroxide or lithium carbonate to convert them into -SO ₃ Li groups. Further, the reaction solution obtained by the usual method can be subjected to cation exchange by a dialysis method using a lithium chloride solution to form a —SO ₃ Li group.

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

In order to obtain a stable concentrated liquid composition, it is desirable to reduce the amount of inorganic salts such as NaCl, Na ₂ SO ₄ , and KCl in the liquid as much as possible. In the case of the liquid composition of the present invention, the solubility and stability are extremely high, and a high or higher order desalting treatment is not required.

As for the degree of desalting, a concentration in the liquid of about 1% sufficiently satisfies the purpose, and in this respect, simplification of operation, efficiency, and industrial advantage are particularly noted.

The aqueous liquid composition of the present invention usually contains 20 to 4
It contains a dye content of 0% by weight, but is adjusted to a desired concentration by adding water as required. In addition, additives usually used in the liquid composition, for example, dissolution aids such as ε-caprolactone, urea, ethylene glycols, sodium polyacrylate, condensed phosphates, sequestering agents, pH adjusters, and antibacterial protection It is effective to add 0.5 to 50% by weight of a fungicide or the like as needed, or to adjust the pH of the liquid composition to about 6.0 to 8.0, etc., to improve stability over time. is there.

The aqueous liquid composition of the reactive dye of the present invention has excellent stability without problems such as decomposition and crystallization even during long-term storage at low temperature to room temperature (-10 ° C to 40 ° C). It is significant that the dye can be highly concentrated in a suitable desalting treatment.

The liquid composition is applied to dye cellulose fibers and cellulose-containing fibers. Cotton, rayon,
Hemp and blended and mixed fabrics thereof, and cellulose / synthetic fiber blended fabrics such as cotton / polyester blended fabrics and mixed fabrics are subjected to a usual dyeing method.

[0025]

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

Example 1 18.8 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. Next, the product was diazotized by a conventional method using hydrochloric acid and sodium nitrite. Then 1
-Ethyl-5-carbamoyl-3-sulfomethyl-4-
29 parts of methyl-6-hydroxy-2-pyridone were added to water 20
After dissolving in 0 parts, coupling was performed at 10 ° C. and pH 6-7. During the reaction, 4.8 parts of lithium hydroxide was added to complete the reaction. Next, 18 parts of 4-aminobenzenesulfonic acid was dissolved in 150 parts of water, and added at 50 ° C., pH 7 to
In 8, secondary condensation was performed. During the reaction, lithium hydroxide4.
Eight parts were added to complete the reaction. The reaction solution was desalted and concentrated using a reverse osmosis device to obtain 210 parts of an aqueous liquid composition.
The reverse osmosis device was performed at a pressure of 15 kg / cm ² using a polyamide-based membrane (manufactured by Teijin Engineering Limited). As a result of analyzing the dye structure in the obtained liquid composition, among the three Ms in the dye represented by the formula (4),
Two were Li and one was Na. The dye concentration is 32.9
%, Contained 0.9% NaCl, 0.2% Na ₂ SO ₄ .

[0027]

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Example 2 A dye was produced in the same manner as in Example 1, except that 4-aminobenzenesulfonic acid and lithium hydroxide as a reaction neutralizing agent were replaced with 3-aminobenzene in the secondary condensation. Performed using 18 parts of sulfonic acid and 8 parts of sodium hydroxide. The reaction solution is similarly desalted and concentrated by the reverse osmosis method,
220 parts of a liquid composition were obtained. The dye structure in the obtained liquid composition was one of Li and two of Na among three M in the dye represented by the formula (5). Dye concentration is 3
In _{2.3%, NaCl1.1%, Na 2} SO 4 0.2%
Was contained.

[0029]

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

Example 4 A dye was produced in the same manner as in 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. The dye structure in the obtained liquid composition was one of Li and two of K of three M in the dye represented by the formula (4). The dye concentration was 33.0%, NaCl 0.3%, K
Cl 0.7%, Na ₂ SO ₄ 0.1%, K ₂ SO ₄ 0.1%
It contained 1%.

Example 5 2,4-Diamino-1,5-benzenedisulfonic acid 2
6.8 parts of sodium hydroxide were added and dissolved in 250 parts of water. To the solution was added 19 parts of cyanuric chloride, and 0 to 5
Primary condensation was carried out at a temperature of 6 ° C. and pH 6-7. During the reaction, 4 parts of lithium carbonate was added to complete the reaction. The product was then diazotized using hydrochloric acid and sodium nitrite. Then 1-butyl-5-carbamoyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone 31.8.
Was dissolved in 250 parts of water, and coupling was performed at 10 ° C. and pH 6 to 7. During the reaction, lithium hydroxide 4.8
Was added to complete the reaction. Next, 18 parts of 4-aminobenzenesulfonic acid was dissolved in 150 parts of water and added.
The secondary condensation was performed at a temperature of 7 ° C. and a pH of 7 to 8. During the reaction, 4.8 parts of lithium hydroxide was added to complete the reaction. The reaction solution was similarly desalted and concentrated according to the reverse osmosis method to obtain a liquid composition 230.
Got a part. The dye structure in the obtained liquid composition is such that three of the four Ms in the dye represented by the formula (6) are L
i, one was Na. Dye concentration is 33.3%, N
It contained 1.1% aCl and 0.1% Na ₂ SO ₄ .

[0033]

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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]

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[0036]

[Table 1]

COMPARATIVE EXAMPLE In order to measure the aqueous liquid compositions of the present invention, especially the low-temperature storage stability, the compositions were diluted with water and the dye concentration was reduced to 30%.
And the stability test shown in Table 1 below was performed. The following expressions (8), (9), (10), and (11)
And, the dye having the structure of (12) was similarly desalted and concentrated by a reverse osmosis method to obtain a concentrated solution having a dye concentration of 30%.
The inorganic salt content 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]

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[0039]

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[0040]

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[0041]

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[0042]

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

[Table 2] In the table, ○ indicates a completely dissolved state, Δ indicates a state of slightly precipitated crystals, and X indicates a state of completely precipitated crystals.

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

Dyeing Example The liquid composition obtained in Example 1 was diluted with water to give a dye concentration of 30%.
Using the above liquid composition, a printing paste having the following composition was prepared. The color paste was printed on a cotton cloth, intermediate-dried at 80 ° C., and steamed at 102 ° C. for 10 minutes. Subsequently, the fabric was soaped, washed with water and dried to obtain a clear green-yellow printed dyeing. Composition of printing paste 7 parts of liquid composition of Example 1 (dye concentration 30%) 7 parts 5% aqueous sodium alginate solution 50 "sodium bicarbonate 3" urea 10 "water 30" 100 copies in total

[0046]

According to the present invention, a concentrated aqueous liquid composition of a reactive dye is obtained, which is stable even during long-term storage, especially at low temperatures.

Continuation of the front page (56) References JP-A-62-74964 (JP, A) JP-A-62-246968 (JP, A) JP-A-64-20268 (JP, A) JP-A-47-34425 (JP) JP-A-57-161174 (JP, A) JP-A-6-49380 (JP, A) JP-A-47-13429 (JP, A) JP-A-47-8285 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 67/26 C09B 62/085 C09B 62/008

Claims (1)

(57) [Claims] 1. A compound of the general formula (Wherein, R represents a C ₁ -C ₄ alkyl group or an alkoxyalkyl group, X represents hydrogen or a —SO ₃ M group,
Each independently represents hydrogen, Li, Na or K. However, among M, at least one M represents Li. An aqueous liquid composition of the reactive dye represented by the formula (1).