JPS62256869A - Production of liquid aqueous composition of reactive dye - Google Patents

Abstract

PURPOSE:To improve the low-temperature storage stability of a liquid aq. compsn. of a reactive dye, by adding a lactam or an aminoalcohol to an aq. soln. of a reactive dye to dissolve it therein and cooling the aq. soln. of the dye to crystallize out inorg. salts present therein. CONSTITUTION:0.1-20wt% (based on the amount of a liquid aq. compsn.) at least one member selected from the group consisting of lactams and aminoal cohols is added to an aq. dye soln. contg. 5-50wt% at least one reactive dye of formula I (wherein D is a residue of an org. dye having 1-3 sulfo groups; n is 1 or 2; X is -CH=CH2 or -CH2CH2Y; and Y is a group which can be elimi nated by the action of an alkali) to dissolve it therein. The aq. dye soln. is cooled to a temp. of -10-5 deg.C to crystallize out inorg. salts present in the aq. dye soln. and to separate them. epsilon-Caprolactam is preferred as the lactam and triethanolamine is especially preferred as the aminoalcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a liquid aqueous composition containing a reactive dye and having excellent low-temperature storage stability.When industrially dyeing or printing with a reactive dye, it is usually a water-soluble composition. Powdered or granular dyes that are normally sold in commercial systems are first dissolved in boiling water and then used for dyeing or printing.On the other hand, in recent years there has been a movement toward automation and FMS in dyeing factories. Demand for a dye form that can be used in automatic dye weighing systems is increasing. Liquid aqueous compositions of reactive dyes do not contaminate the working environment due to dust scattering during handling, and do not require a dissolution process, which saves labor. It not only contributes to energy savings, but also takes advantage of its liquid properties and can be easily adapted to automatic weighing systems.Currently, it is attracting attention as a desirable product form for dyes, and is leading to the industrialization of liquid aqueous compositions. However, while liquid aqueous compositions of reactive dyes are relatively stable at room temperature, industrial products must be manufactured, stored, transported, stored, etc. at a temperature of 5°C during winter. In this case, the liquid aqueous composition of the reactive dye is often placed under low-temperature conditions such that the solubility of the reactive dye decreases and dye crystals precipitate, causing precipitation ◎ At low temperatures, the dye crystals precipitate In this case, it is inappropriate from a weighing point of view to dye the pipe up to t when crystals have precipitated.In addition, when using an automatic weighing device, there are not only problems in weighing, but also problems with the pipe's tb.
It also causes problems such as. Furthermore, if the crystals are redissolved,
If you want to return to the original uniform liquid dye, 80℃
However, there are many disadvantages in terms of operation and high-temperature stability of the dye itself.As such, low-temperature stability is the primary problem with liquid aqueous compositions of reactive dyes. can.

In order to prevent such troubles, it is effective to remove a large amount of inorganic salts that are produced as by-products during dye synthesis and are contained in the liquid aqueous composition of reactive dyes.

Various studies have been conducted on methods for desalting inorganic salts mixed in reactive dyes, such as Japanese Patent Application Laid-Open No. 59-188.
The reverse osmosis membrane desalting method is known, as shown in Publication No. 268. However, with this method, separation of sodium sulfate (an inorganic salt that is generally produced as a by-product in the synthesis of reactive dyes) is extremely difficult. Furthermore, as a desalination method, it cannot be said that it is economically efficient.Also, electrodialysis method is known as shown in Japanese Patent Application Laid-Open No. 54-12987, etc., but it requires expensive equipment and dye On the other hand, the so-called cooling method is an efficient desalination method that takes advantage of the fact that the solubility of inorganic salts in water varies depending on the temperature. The inorganic salt is crystallized and separated by cooling the dye solution containing the dye (+5 to -10° C.), but if the dye has low solubility at low temperatures, crystals of the dye itself will precipitate, so this method is not widely effective.

Although all of these methods have their own problems, this so-called cooling method can be said to be the most common method at present. However, as already mentioned, this method limits the number of reactive dyes that can be used. Only reactive dyes with problematic zero or very high solubility in water, especially in cold water (below 6° C.), can be desalted by this method.

If the solubility of the reactive dye is insufficient, first of all, the dye will precipitate as crystals at the same time as the inorganic salt, making it impossible to achieve the purpose of separating the dye and the inorganic salt. Second, if the dye concentration of the dye solution If desalting is carried out by lowering the solubility below the solubility at the temperature during desalting, the inorganic salt concentration will also drop at the same time, making efficient desalting impossible, or a step of concentrating to a practical product concentration will be required. However, as an industrial manufacturing method, it is not only complicated but also inefficient.
This can be cited as a problem.

The present inventors have completed the present invention as a result of intensive studies to solve the first and second problems.

That is, the present invention provides the following general formula CI), D-(80
,
, or -CH, CH, Y, where Y is a group that is eliminated by the action of an alkali. Lactams are added to an aqueous dye solution containing 5 to 50% by weight of at least one of the reactive dyes represented by 0). or at least one of amino alcohols
A reaction characterized by adding and dissolving 0.1 to 20 wt. Providing a method for producing a liquid aqueous composition of a dye In the present invention, for the dye represented by the general formula [l], as a residue of an organic dye having a sulfonic acid, polyazo dyes such as monoazo and disazo, metal complex monoazo Dyes or disazo dyes, metal formazan, anthofquinone, metal) talocyanine, stilbene, oxazine, dioxazine, triphenylmethane, phenazine, xanthine, thioxanthin, naphthoquinone, pyrenequinone,
Examples include dye residues such as berylene, boimide, nitro or azomethine. The central atom of the metal complex salt, metal formazan and metal phthalocyanine yarn dye is C.
u, Cr.

co%Nl, F, etc. ◇ Also, X represents a group -CH, CH, or a group -CH, CH, Y, where Y is a group that is eliminated with an alkali, such as sulfuric acid ester/ l' group, thiosulfate Nden group, v phosphoric acid x Nut/L'
This includes cocoons, acetate ester groups, halogen atoms, etc. The method of the present invention can be effectively applied to any reactive dye represented by the general formula CI), but it cannot be used for reactions that have problems with dissolution stability at low temperatures. It can be applied particularly effectively to dyes. Specifically, reactive dyes represented by the following formulas (1) to (6) in the form of free acids are exemplified. Lactams used in the present invention include C-caprolactam, γ-cabrolactam, , δ
-Cabrofuctam, T-Valerolactam, γ-Putilofuctam and the like, among which ε-Cabrofuctam is preferred.

Furthermore, examples of amino alcohols include triethanolamine, jetanolamine, monoethanol-ρ amine, and glyco/L' acid salts of triethanolamine, and among these, triethanolamine is preferred.

The dye aqueous solution containing 5 to 50% by weight of the reactive dye represented by the general formula [I] used in carrying out the method of the present invention refers to the reaction solution obtained in the synthesis step (in which case, the amount of water is If there is more than the specified amount, concentrate it until the dye content is appropriate.
...For example, the concentration is adjusted by distilling off part of the water under vacuum, or by drying part of the dye solution and adding the powdered dye obtained to the remaining dye solution VClT. . ), the usual method of separating the dye component from the dye reaction solution, i.e., salting out, filtration, and redissolving the wet cake in water, or redissolving the wet cake in water, or drying the wet cake and redissolving it in water. Refers to a dissolved dye aqueous solution ◇ To such a dye aqueous solution, at least one of lactams or aminoalcohol-p is added and dissolved to make a homogeneous solution ・Then, this aqueous solution is cooled to +5 to -10°C and 1 ~
By keeping it cool for 10 hours, the inorganic salt is crystallized and separated from the dye liquid by a method such as filtration to obtain the liquid aqueous composition of the reactive dye of the present invention.

In the above method, the amount of tuctams or aminoalcohol-μ added is 0.1 to 20% by weight, preferably 0.5 to 8% by weight, based on the weight of the liquid aqueous composition, and a predetermined total amount is added to the inorganic salt. Although it may be added before crystallization separation, a part thereof may be added after crystallization separation of the inorganic salt.

The liquid aqueous composition thus obtained is preferably adjusted to a pH value of 8 to 7 using a common mineral acid or alkali. The liquid aqueous composition is stable without precipitation of dye crystals even when stored at a low temperature of 5° C. or lower for a long period of time, for example, for 2 months at 5° C.

Furthermore, the liquid aqueous composition of the present invention has a low viscosity (10 cps
(below), it must be stable over a long period of time), and can be applied to various automatic #m devices, and its industrial application value is extremely high.

Further, the liquid aqueous composition of the reactive dye of the present invention exhibits dyeing properties that are no different from those of ordinary powder products in dyeing and printing natural or regenerated cellulose fibers, wool, silk, synthetic polyamide, and other fibers.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A reaction solution of a dye represented by the formula (1) in the form of free #la synthesized by a known method (aqueous solution containing 20% by weight of dye, 02 double quadrats of common salt, and 8.0% by weight of Glauber's salt) 990 important part C
- Added and dissolved 10 parts by weight of cabrotam, cooled to 0°C, and kept cold for about 6 hours to precipitate Glauber's salt crystals.During this time, the dye was stable without crystallization, and the inorganic salts could be separated from the dye solution. Efficiently carried out ◎ This desalted dye solution (dye content 22% by weight, salt 0.2% by weight)
, 1.8 wt.
The amount was 0 parts by weight. A part of this dye solution was stored at 0°C for 2 months, but the dye remained in a stable dissolved state without precipitation of crystals.Example 2 In the form of a free acid synthesized by a known method (1 ) Reaction solution of dye expressed by the formula (dye content 20% by weight, salt 0.2 weight 1
%, aqueous solution containing 8.0% by weight of Glauber's salt) 990 parts by weight 11
Add and dissolve 10 parts by weight of Ct-cabroctam, and heat to 0°C.
After cooling, it was kept cold for about 5 hours to precipitate Glauber's salt crystals.◎During this time, the dye was stable without being crystallized, and the dye solution and fW
Separation of the X machine salt was carried out efficiently.

This desalted dye solution (dye content 22% by weight, salt 0.2% by weight)
, Glauber's salt 1.8% by weight, C-cabroctam 1.1% by weight 1
Add and dissolve 950 parts by weight of Kt-Cabroxtam and 19 parts by weight, adjust the pH value of the dye solution to 5.0 with 1051 sulfuric acid, and bring the total amount to 1,000 parts by weight with water. Although stored at ℃ for 2 months, the dye remained in a stable dissolved state without precipitation of crystals. To 990 parts by weight of the solution (water IS solution containing 24% by weight of dye, 0.05% by weight of salt, 5.6% by weight of Glauber's salt, and 0.8% by weight of sodium acetate) was added 10% by weight of t-cabroctam.
If a certain amount was added and dissolved, the OCK was cooled and kept cold for about 5 hours to precipitate mirabilite crystals.During this time, the dye was stable without being crystallized, and the dye solution and inorganic salt were efficiently separated. 970 parts by weight of the desalinated dye solution (dye content 26% by weight, salt 0.05% by weight, mirabilite 1.6% by weight) was adjusted to pHff5.0 with 10% sulfuric acid, and the total amount was mixed with water to 1. ,000 parts by weight. A part of this dye solution was stored at 0°C for 2 months, but the dye remained in a stable dissolved state without precipitation of crystals.Example 4 In the form of a free acid synthesized by a known method (8 ) 980 parts by weight of a dye reaction solution (aqueous solution containing 15% by weight of dye, 0.6% by weight of salt, and 10% by weight of Glauber's salt) 11C
Add and dissolve 20 parts by weight of t-cabroctam, cool to 0°C, and keep cold for about 5 hours to precipitate mirabilite crystals.
During this period, the dye was stable without crystallization, and the separation of the dye solution and inorganic salt was carried out efficiently.
, 2.0 parts by weight of Glauber's salt*) 9 parts by weight of SO and 2 parts by weight of sodium acetate
Add 0 parts by weight, dissolve, and adjust the OpH value of the dye solution to 4 with 1096 sulfuric acid.
．． 6, and the total amount was made up to 1,000 parts by weight with water. A part of this dye solution was stored at 5°C for 2 months, but the dye remained in a stable dissolved state without precipitation of crystals. Example 5 A reaction solution of a dye represented by formula (1) in the form of a free acid synthesized by a known method (aqueous solution containing 20% by weight of dye, 0.2% by weight of common salt, and 8.0% by weight of mirabilite) ) 10 parts by weight of triethanolamine was added and dissolved in 990 parts by weight, and the solution was heated to 0°C.
After cooling, the mixture was kept cold for about 6 hours to precipitate Glauber's salt crystals. During this period, the dye was stable without crystallization, and the inorganic salts were efficiently separated from the dye solution.

This desalted dye solution (dye content 22% by weight, salt 0.2211
Adjust the pH value of the dye solution to 5.1 with 1091 sulfuric acid, and add 1,000 parts by weight of the total amount to 1,000 parts by weight with water. A portion of this dye solution was stored at 0° C. for 2 months, but the dye remained in a stable dissolved state without precipitation of crystals.

Example 6 A reaction solution of a dye represented by formula (4) in the form of a free acid synthesized by a known method (dye content 22% by weight, salt 0.1% by weight)
To 970 parts by weight of an aqueous solution containing 1% and 6.5% by weight of Glauber's salt, 80 parts by weight of ε-cabroctam was added and dissolved, and -8
After cooling to ℃, it was kept cold for about 5 hours to precipitate Glauber's salt crystals. During this period, the dye was stable without crystallization, and the inorganic salts were efficiently separated from the dye solution.

Desalinated dye solution (dye content 26% by weight, salt 0.1% by weight)
The pH value of the dye solution was adjusted to 5.5 with 1096 sulfuric acid, and the total amount was made up to 1,000 parts by weight with water. A part of this dye solution was stored at 0°C for 2 months, but the dye remained in a stable dissolved state without precipitation of crystals. Example 7 In the form of free acid synthesized by a known method (5 ) to 980 parts by weight of a dye reaction solution (aqueous solution containing 15% by weight of dye, 0.7% by weight of salt, and 8.5% by weight of Glauber's salt)
- Added and dissolved 20 parts by weight of Kabroktam. After cooling to 0° C. for about 5 hours, the mixture was kept cold to precipitate Glauber's salt crystals. During this period, the dye was stable without crystallization, and the dye solution and inorganic salt were efficiently separated.

This desalted dye solution (dye content 17% by weight, salt 0.7N#L)
Add and dissolve 20 parts by weight of sodium acetate into 950 parts by weight of 145 parts by weight*), adjust the pHff of the dye solution to 4.8 with 10% sulfuric acid, and add the entire amount i, oo with water.

Parts by weight. A portion of this dye solution was stored at 5° C. for 2 months, but the dye remained in a stable dissolved state without precipitation of crystals.

Example 8 A reaction solution of a dye represented by formula (6) in the form of a free acid synthesized by a known method (dye content 12% by weight, salt O, sxt
*, aqueous solution containing 10% by weight of Glauber's salt) 970 parts by weight of C-
80 parts by weight of Kabloktam was added and dissolved, and after cooling to 0° C., the mixture was kept cold for about 5 hours to precipitate Glauber's salt crystals. During this period, the dye was stable without crystallization, and the dye solution and inorganic salt were efficiently separated.

This de-dyeing solution (dye content 14% by weight, salt 0.8% by weight,
950 parts by weight of mirabilite (2.0% by weight) and 20 parts by weight of sodium acetate.
ItJfL part was added and dissolved, and the pH value of the dye solution was adjusted to 5.0 with 10 g of 6 sulfuric acid, and the total volume was made up to 1,000 parts by weight with water.

A part of this dye solution was stored at 5℃ for 2 months, but the dye remained in a stable dissolved state without precipitation of crystals.

Claims (1)

[Scope of Claims] The following general formula [I] D-(SO_2X)_n [I] (wherein, D is an organic dye residue having 1 to 3 sulfonic acid groups, and n represents 1 or 2) , X is a group -CH=CH
Indicates _2 or -CH_2CH_2Y. Here, Y is a group that is eliminated by the action of an alkali. 0.1 to 20% by weight of at least one of lactams or amino alcohols is added and dissolved in an aqueous dye solution containing 5 to 50% by weight of at least one of the reactive dyes represented by -. 1. A method for producing a liquid aqueous composition of a reactive dye, which comprises cooling to a temperature of 10 DEG C. to 5 DEG C. to crystallize and separate inorganic salts present in the aqueous dye solution.