JPH07109424A - Liquid composition of reactive dye and method for dyeing by using the same - Google Patents

Abstract

PURPOSE:To obtain a liquid composition excellent in storage stability at low and high temperatures by using specified reactive dye(s) and tertiary amine salt(s) as the constituents and adjusting the pH to a specified value. CONSTITUTION:This liquid composition (e.g. an aqueous solution) of reactive dye(s) contains 5-50wt.% of at least one reactive dye of formula I [wherein D1 and D2 are each a substituted aromatic residue, provided that at least one of them is a group of formula II (wherein A is an aromatic or aliphatic amine residue or a substituted alkoxy group)] in free acid form and 0.1-40wt.% of at least one tertiary amine salt (e.g. triethanolamine hydrochloride), and which has the pH adjusted to 5.0-8.5.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to liquid compositions. More specifically, it relates to a liquid composition containing a reactive dye having a specific structure and excellent in low temperature storage stability and high temperature storage stability.

[0002]

2. Description of the Related Art In dyeing with a reactive dye, a commercially available powdery or granular dye is once dissolved in hot water and then provided for dyeing. On the other hand, in the dyeing factory, in recent years, the movement for automation and FA has been active, and a liquid form of many reactive dyes has already been put on the market because a dye form that can be applied to an automatic weighing system is required.

A liquid composition of a reactive dye is industrially used during production, storage, transportation, storage, etc., and at 5 ° C. in winter.
It may be placed under the following conditions, or in the summer at about 50 ° C. Therefore, the liquid composition of the reactive dye must exhibit good stability at low and high temperatures.

If the stability at low temperature is poor, the solubility of the reactive dye is lowered, and crystals of the dye are precipitated and precipitate. It is not only inadequate in terms of measurement that dyeing is performed while crystals are deposited, but also troubles such as pipe clogging occur. Furthermore, if the crystals are re-concentrated to return to a uniform liquid dye, then 50 to 70 ° C
Since it has to be heated to a high temperature, there are many inconveniences in terms of operation and high temperature stability of the dye itself.

On the other hand, there are many dyes which are very difficult to liquefy due to their structure, and the reactive dye represented by the formula (1) described later tends to cause precipitation of dye crystals due to its high salt sensitivity. Liquefaction was one of the very difficult things.

Further, regarding this dye, a solubilizer or hydrotrope which is generally said to be effective for liquefaction, for example, caprolactams, N-substituted ureas, special nonionic surfactants, pyrrolidones, The use of glycols and the like did not improve the low temperature storage stability, and it was necessary to highly remove the inorganic salt in the dye solution.

When the stability at high temperature is poor, the reactive group is decomposed and the original reactivity of the reactive dye is not exhibited.
This will cause poor dyeing. Usually, when a tertiary amine is added to a reactive dye having a chlorotriazinyl group, the chlorotriazinyl group and the tertiary amine react with each other during storage at high temperature, and the original dyeing property to the fiber is There was a drawback that it would decrease.

The dye represented by the formula (1) described below is usually
It has blue, navy, black and green.
When blue or navy is used as one of the three primary colors, it is necessary to use it at a concentration corresponding to yellow and red, and since the amount used is large, industrially high concentration liquid products are desired. There is.

[0009]

With respect to the reactive dye having high salt sensitivity represented by the formula (1) described below, it is desired to produce a liquid composition having good storage stability at low temperature and high temperature. ing.

[0010]

The present inventors have accomplished the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention provides the free acid of the formula (1)

[0011]

[Chemical 1]

(D ₁ and D ₂ in the formula (1) are substituted aromatic residues, and at least one of them is represented by the following formula (2).

[0013]

[Chemical 2]

A in the formula (2) means a residue of aromatic or aliphatic amine, or a substituted alkoxy group. ) 5 to 50% by weight of at least one reactive dye and 0.1 to 40% by weight of at least one salt of a tertiary amine, and a pH of 5.0 to 5.0%.
A liquid composition of a reactive dye adjusted to 8.5 and a method for dyeing cellulose fiber or polyamide fiber using the same or a fiber product containing the same are provided.

The liquid composition of the present invention will be described in detail. In the present invention, specific examples of the aromatic amino group among the specific examples of the residue A in the group represented by the formula (2) include:
For example, there are a phenylamino group, a substituted phenylamino group, and a substituted naphthylamino group. Specific examples of the aliphatic amino group include an alkylamino group, an alkoxyamino group, a substituted alkylamino group, an alkenylamino group and a substituted alkenylamino group. Further, specific examples of the substituted alkoxy group include a lower alkoxy group, a hydroxyalkoxy group, an alkoxyalkoxy group, and an allyloxy group.

The reactive dye used in the present invention may be any one represented by the above formula (1).
The reactive group is a chlorotriazinyl group represented by the above formula (2), but may be a nicotinotriazinyl, isonicotinotriazinyl or fluorotriazinyl group. At the same time, a vinyl sulfone group or a precursor of a vinyl sulfone group may be included in the dye structure as another reactive group.

Examples of the reactive dye represented by the formula (1) include C.I. I. The reactive green 19 or the one represented by the following formula is exemplified and these are easily obtained from the market.

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

[0021]

[Chemical 6]

Specific examples of the tertiary amines used in the present invention include triethanolamine, N-methyldiethanolamine, N, N-diethylethanolamine,
Examples thereof include N-ethyldiethanolamine, and triethanolamine is particularly preferable.

Specific examples of the acid used for neutralizing the tertiary amines include mineral acids such as hydrochloric acid and sulfuric acid, hydroxy acids and alkoxy acids, and the use of hydrochloric acid is preferable. Three
As a method of adding a salt of a primary amine, a dye obtained by neutralizing a tertiary amine in advance may be added to the dye solution. Alternatively, the tertiary amine may be added to the dye solution and then neutralized with the above-mentioned acid. The amount of the tertiary amine salt used is 0.1 in the dye composition.
-40% by weight, preferably 0.5-10% by weight. A known solubilizer, hydrotrope, or pH buffer may be used in combination with the liquid composition of the present invention.

The pH of the liquid composition of the reactive dye of the present invention is adjusted to 5.0 to 8.5, more preferably pH.
It is adjusted to 6.5 to 7.5. The acid for pH adjustment is preferably an acid used for neutralizing tertiary amines, and the alkali for pH adjustment is preferably tertiary amines or alkali hydroxide.

The dye represented by the formula (1) has high salt sensitivity,
The presence of small amounts of inorganic salts significantly reduces stability at low temperatures. However, when a salt of a tertiary amine is added according to the present invention, the stability is conversely improved although the concentration of the inorganic salt in the liquid composition is increased. Therefore, the step of removing the inorganic salt in advance is also greatly simplified. The liquid composition of the reactive dye represented by the formula (1) thus produced is stored at a low temperature of 0 ° C. or lower for a long time, for example, −5 ° C.
Even after being stored for 2 months, it was stable without precipitation of dye crystals.

Usually, when a tertiary amine is added to a reactive dye having a chlorotriazinyl group, the chlorotriazinyl group and the tertiary amine react with each other during storage at a high temperature to cause the original dyeing property to the fiber. However, there was a drawback that it decreased. However, by adjusting the pH of the reactive dye having the structure represented by the formula (1) to suppress the reaction at high temperature,
A liquid composition having good dyeability is also provided.

These liquid compositions did not decompose the reactive groups of the dye even when stored at a high temperature of 50 ° C. or higher, for example, at 60 ° C. for 2 weeks, and exhibited the same dyeability as that of a powder dye usually used. . The liquid composition of the present invention has a low viscosity (1
Since it is stable at 0 cps or less and 25 ° C. for a long time, it can be applied to various automatic weighing devices and its industrial value is extremely high.

Next, the dyeing method using the liquid composition of the present invention will be described. Cellulose fiber and cellulose-containing fiber are particularly suitable for dyeing the reactive dye used in the present invention, and the dyeing method includes a dip dyeing method and a textile printing method.
In the dip dyeing method, the dyeing bath is usually prepared with an inorganic salt such as sodium sulfate or sodium chloride and the compound of the formula (1), the fibers are dipped, and the temperature is raised to 50 to 90 ° C. under a heating temperature of 1 to 1.
After dyeing for 0 to 60 minutes, acid binders such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, tripotassium phosphate, potassium pyrophosphate, trichloro. Sodium acetate is added alone or as a mixture of two or more kinds, and dyeing is further carried out at the same temperature for 20 to 60 minutes. In this case, the acid binder may be added to the dye bath from the beginning, or it may be dyed neutral and then treated in a separate bath containing the acid binder and the inorganic salt. In the printing method, sodium alginate, an emulsion paste, etc. are used as a base paste, and a printing paste containing an acid binder such as sodium bicarbonate is printed and then dried or steamed. Further, a so-called two-phase printing method in which after printing, a high temperature treatment is carried out with a solution containing an acid binder such as sodium hydroxide or sodium silicate can be performed. When the dyeing according to the present invention is carried out, there is no problem in using the liquid composition of the reactive dye of the present invention by further mixing them with each other, and if necessary, known additives such as a dissolution aid and a dispersion may be used. An agent, a leveling agent, a slow-dyeing agent, a color-developing accelerator, a pH adjusting agent, a sequestering agent for a metal ion, an antioxidant or an anti-reducing agent can be used.

The liquid composition of the reactive dye of the present invention is a powdered product which is usually used for dyeing natural or regenerated cellulose fibers, fiber products such as wool, silk and synthetic polyamide, or a fiber product in which these fibers and other fibers are mixed. Shows the same dyeability.

[0030]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 A reaction solution of a reactive dye represented by the above formula (3) obtained by a known method (dye content: 5.2% by weight, salt: 1.1).
An aqueous solution containing 50% by weight) was concentrated using a reverse osmosis membrane made of acetylcellulose to obtain a concentrated dye solution containing 20% by weight of dye and 0.5% by weight of salt. This concentrated liquid 8
Add 5 parts by weight of triethanolamine to 0 parts by weight and add 3 parts of hydrochloric acid.
After adding parts by weight to adjust the pH to 7.2, the total amount was adjusted to 100 parts by weight with water to obtain a composition of the present invention. -5 part of this thing
It was stored at ℃ for 2 months, but kept stable dissolved state without precipitation of dye crystals. Even when a part of this product was stored at 60 ° C. for 2 weeks and subjected to dyeing of cellulose fibers, no change in hue of the dyed product and decrease in density were observed.

Example 2 A reaction solution of a reactive dye represented by the above formula (4) obtained by a known method (dye content: 5.5% by weight, salt: 1.2%).
An aqueous solution containing 50% by weight) was concentrated using a reverse osmosis membrane made of acetylcellulose to obtain a concentrated dye solution containing 20% by weight of dye and 0.5% by weight of salt. This concentrated liquid 7
10 parts by weight of triethanolamine was added to 0 parts by weight, and 6 parts by weight of hydrochloric acid was added to adjust the pH to 7.3.
The composition of the present invention was obtained in an amount of 0 part by weight. A part of this product was stored at -5 ° C for 2 months, but a stable dissolved state was maintained without precipitation of dye crystals. 60 of this thing
Even when stored at 2 ° C. for 2 weeks and subjected to dyeing of cellulose fibers, no change in hue or decrease in density was observed.

Example 3 A reaction solution of a reactive dye represented by the above formula (5) obtained by a known method (dye content: 5.0% by weight, salt: 1.2).
An aqueous solution containing 50% by weight) was concentrated using a reverse osmosis membrane made of acetylcellulose as a raw material to obtain a concentrated dye solution containing 21% by weight of dye and 0.6% by weight of salt. This concentrated liquid 8
Triethanolamine (7 parts by weight) was added to 0 parts by weight, and hydrochloric acid (4.2 parts by weight) was added to adjust the pH to 7.0. Then, the total amount was adjusted to 100 parts by weight with water to obtain a composition of the present invention. A part of this product was stored at -5 ° C for 2 months, but a stable dissolved state was maintained without precipitation of dye crystals. Even when a part of this product was stored at 60 ° C. for 2 weeks and subjected to dyeing of cellulose fibers, no change in hue of the dyed product and decrease in density were observed.

Example 4 A reaction solution of a reactive dye represented by the above formula (6) obtained by a known method (dye content: 5.3% by weight, salt: 1.2%).
Aqueous solution containing 10% by weight) was concentrated using a reverse osmosis membrane made of acetylcellulose to obtain a concentrated dye solution containing 20% by weight of dye and 0.6% by weight of salt. This concentrated liquid 8
Triethanolamine (7 parts by weight) was added to 0 parts by weight, and hydrochloric acid (4.2 parts by weight) was added to adjust the pH to 7.5. Then, the total amount was adjusted to 100 parts by weight with water to obtain the composition of the present invention. A part of this product was stored at -5 ° C for 2 months, but a stable dissolution state was maintained in which crystals of the dye were precipitated. Even when a part of this product was stored at 60 ° C. for 2 weeks and subjected to dyeing of cellulose fibers, no change in hue of the dyed product and decrease in density were observed.

Example 5 A reaction solution of a reactive dye represented by the above formula (7) obtained by a known method (dye content: 5.8% by weight, salt: 1.4).
(Aqueous solution containing 10% by weight) was concentrated using a reverse osmosis membrane made of acetylcellulose to obtain a concentrated dye solution containing 22% by weight of dye and 0.6% by weight of salt. This concentrated liquid 8
After adding 10 parts by weight of triethanolamine hydrochloride to 0 parts by weight and adjusting the pH to 6.8 by adding dilute hydrochloric acid, the total amount is adjusted to 10 with water.
The composition of the present invention was obtained in an amount of 0 part by weight. A part of this product was stored at -5 ° C for 2 months, but a stable dissolved state was maintained without precipitation of dye crystals. 60 of this thing
Even when stored at 2 ° C. for 2 weeks and subjected to dyeing of cellulose fibers, no change in hue or decrease in density was observed.

Example 6 C.I. I. Reaction liquid of Reactive Green 19 (Dye content 5.1% by weight, salt 1.0
Aqueous solution containing 10% by weight) was concentrated using a reverse osmosis membrane made of acetylcellulose to obtain a concentrated dye solution containing 20% by weight of dye and 0.6% by weight of salt. This concentrated liquid 8
5 parts by weight of triethanolamine hydrochloride was added to 0 parts by weight, diluted hydrochloric acid was added to adjust the pH to 6.8, and the total amount was adjusted to 100 parts by weight with water to obtain a composition of the present invention. -5 part of this thing
It was stored at 0 ° C for 2 months, but a stable dissolved state was maintained without precipitation of dye crystals. Some of this thing is 60 ℃
Even when the dyed product was stored for 2 weeks and dyed with a cellulose fiber, neither the hue change nor the density decrease of the dyed product was observed.

Example 7 2.0 parts of the dye composition obtained in Example 1 was diluted with 20 parts of water and 16 parts of sodium sulfate was added to prepare a dye bath. Into this dyeing bath, 10 parts of unmercured cotton knitted fabric was heated to 80 ° C. with stirring, allowed to stand for 20 minutes, then added with 4 parts of sodium carbonate and dyed at the same temperature for 1 hour. Then, the material to be dyed is taken out and washed with water, and then 100 parts of an aqueous solution containing 1 part of the anionic surfactant is used at 100 ° C.
It was soaped for 10 minutes, washed with water and dried.

Example 8 The dye composition obtained in Example 2 and a powdery product of the reactive dye represented by the formula (4) in the form of a free acid obtained by a known method were used. Comparison was performed by the same staining as shown in 7. The dyed product obtained from the dye solution exhibited properties comparable to those of the dyed product obtained from the powder product such as density, hue, and various fastnesses.

Example 9 Water was added to 10 parts of the dye composition obtained in Example 5 to 50 parts of 5% by weight sodium alginate, 10 parts of urea and 2 parts of sodium bicarbonate to obtain 100 parts of a color paste. . This was printed on a mercerized cotton broad cloth, dried at 60 ° C. for 10 minutes, and then steamed at 100 ° C. for 10 minutes.
The dyed product thus obtained was washed with water and then soaped at 1000C for 10 minutes using 1000 parts of an aqueous solution containing 2 parts of an anionic surfactant, followed by washing with water and drying.

Comparative Example 1 To 80 parts of the dye concentrate obtained in Example 1 was added 7 parts by weight of ε-caprolactam, and the total amount was adjusted to 100 parts by weight with water.
A part of this was stored at -5 ° C, but crystals were deposited on the second day.

Comparative Example 2 To 80 parts of the dye concentrate obtained in Example 1 was added 10 parts by weight of N-methylpyrrolidone, and the total amount was adjusted to 100 parts by weight with water. A part of this was stored at -5 ° C, but crystals were deposited on the first day.

Comparative Example 3 10 parts by weight of diethylene glycol was added to 80 parts by weight of the dye concentrate obtained in Example 4, and the total amount was made up to 100 parts by weight with water. A part of this was stored at -5 ° C, but crystals were deposited on the first day.

Comparative Example 4 A powdery product of a reactive dye represented by the formula (7) in the form of free acid obtained by a known method was prepared as a color paste so as to have the same composition as in Example 9. Then, dyeing was performed in the same manner to obtain a dyed object. The obtained dyed product showed no difference in density, hue, various fastnesses, etc. as compared with the dyed product obtained in Example 9.

Comparative Example 5 A powdery product of a reactive dye represented by the formula (3) in the form of a free acid obtained by a known method was dissolved to the same concentration as in Example 7, It was diluted and dyed in the same manner to obtain a dyed object. The obtained dyed product showed no difference in density, hue, various fastnesses, etc. as compared with the dyed product obtained in Example 7.

[0045]

EFFECTS OF THE INVENTION A liquid composition of a reactive dye having high salt sensitivity and having excellent storage stability at low and high temperatures was obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location D06P 3/66 B

Claims (2)

[Claims] 1. A free acid of the formula (1): (D ₁ and D ₂ in the formula (1) are each a substituted aromatic residue, and at least one of them is a group represented by the formula (2)) (A in the formula (2) means a residue of an aromatic or aliphatic amine, or a substituted alkoxy group.) 5 to 50% by weight of at least one reactive dye represented by the formula and a tertiary amine A liquid composition of a reactive dye, which comprises 0.1 to 40% by weight of at least one salt of the same class and is adjusted to pH 5.0 to 8.5. 2. A method for dyeing a cellulose fiber, a polyamide fiber or a fiber product containing these, which comprises using the liquid composition according to claim 1.