Method of recovering sulfur and vat dyes


D06P1/651 -
D06P1/30 - using sulfur dyes
C09B67/30 - in liquid form

 

(57) Abstract:

The invention relates to a method for recovery of sulfur and VAT dyes, and is intended for use in the methods of dyeing sulfur or kovovymi dyes cellulose textile materials. The invention consists in that the recovery of sulfur or VAT dyes is carried out in an aqueous-alkaline medium with isomaltulose or a mixture containing isomaltulose and trehalose as a reducing agent, at a concentration of reducing agent is from 1 to 50 g/L. the Method allows to prevent sverhvosstanovlenie sensitive to restore dyes and, thus, to increase the output of the pigment to the textile material. 4 C. and 9 C. p. F.-ly, 4 Il. , 6. table.

The invention relates to a method for recovering dye from the group consisting of sulfur dyes and VAT dyes.

Methods of dyeing cellulose-containing textile materials sulfur and kovovymi dyes known. As VAT and sulfur dyes before the dyeing process or during it should be removed from their water-insoluble form by recovery in water-soluble form with SRO sodium or sodium sulfite. However, these methods have the disadvantage that in particular in the case of sensitive dyes is the so-called sverhvosstanovlenie, which leads to the fact that the dye after restoring and applying to the textile material may not be re-oxidized to the desired pigment. Moreover, the released sulfide ions create problems for the environment due to their unpleasant odor and toxicity. From the patent DE 4115452 A1 it is known recovery of VAT dyes under the influence of fructose, mannose or glucose. From the patent EP 0699797 A2 is known, the recovery of sulfur dyes under the influence of fructose, galactose, glucose, mannose, maltose or lactose. Described in these patents recovery of dyes by means of reducing sugars has the advantage that it eliminates caused by the release of sulfide ions negative impact on the environment. Due to minor redoxpotential, for example, glucose it is able to restore most of the dyes used, and simultaneously eliminates the danger of sverchuvstvovanie. The disadvantage is, however, relatively slow equilibrium oxidation-vosstanovitelnoj the things kinetics of recovery requires a relatively long period of time for recovery of the used dyes.

Underlying the present invention technical problem consists, therefore, in developing a way to recover VAT and sulfur dyes, which overcomes the above disadvantages, in particular not of concern from the point of view of ecology, can restore a wide range of commonly used dyes, reduces the risk of sverchuvstvovanie and has improved the kinetics of recovery.

Underlying the present invention, the technical problem is solved by a method according to the main claim. Accordingly, in this invention, a method for recovering dye from the group consisting of sulfur dyes, VAT dyes, and restoration is carried out in an aqueous-alkaline medium with isomaltulose or containing isomaltulose, and in particular trehalose, the mixture as a reducing agent and concentration of reducing agent is chosen preferably 10 to 30 g/l Reducing agent further comprises isomaltose, sucrose, glucose, fructose or oligomer of carbohydrate.

The reducing agent contains from 10 to 90 weight. % trehalose, from 10 to 90 weight. % isomaltulose, from 0 to 15 weight. % sucrose, from 0 to 20 on the dry matter).

Preferably the reducing agent contains 42 weight. % trehalose, 20 weight. % isomaltulose, 10 weight. % sucrose, 12 weight. % fructose, 10 weight. % glucose, 3 weight. % isomaltose and 3 weight. % of oligomers of carbohydrate (calculated on dry substance).

The reducing agent may contain 42 weight. % trehalose, 20 weight. % isomaltulose, 17 weight. % fructose, 15 weight. % glucose, 3 weight. % isomaltose and 3 weight. % of oligomers of carbohydrate (calculated on dry substance).

It is advisable that when this water is alkaline medium had a pH greater than 11.

The restoration is carried out at a temperature of at least 50oC, preferably at 80oC-100oC.

The restoration carried out under the action of ultrasound. The use of isomaltulose, in particular mixtures with isomaltulose containing trehalose, as a reducing agent in the recovery of sulfur and VAT dyes from water-insoluble form in water-soluble lacovara has the advantage that the equilibrium redox potential, in particular mixtures which contain this sugar set much faster than in the cases commonly used sugars. More rapid establishment of equilibrium oxidation-vosstanovitelnaya, which ultimately leads to cost reduction. The reducing agent according to the invention does not affect the environment, has a low redox potential, so that can be restored almost all commonly used dyes, and does not lead to their sverhotstalostyu.

In connection with this invention under sulfur dyes understand those that can be obtained by boiling chemical compounds in the polysulfides or sulfur. In connection with this invention under kovovymi dyes understand such dyes, which can be represented as derivatives of anthraquinone.

This invention considers the use as a reductant isomaltulose, in particular a mixture, which contains the sugar. In particular, preferably the reducing agent contains, along with isomaltulose additional trehalose, isomaltose, sucrose, glucose, fructose or oligomeric carbohydrates. In particular this invention relates to a reducing agent, which contains from 10 to 90 weight. % trehalose, from 10 to 90 weight. % isomaltulose, from 0 to 15 weight. % sucrose, from 0 to 20 weight. % fructose, from 0 to 20 weight. % glucose, 0 to 5 weight. % isomaltose and from 0 to 5 weight. % oligomeric carbohydrates. Price sucrose in isomaltulose followed by the separation of isomaltulose, so form a product containing netdelivery isomaltulose and trehalose. The method of preparation and the composition of the mixture containing isomaltulose and trehalose described in the patent EP 0625578 A1, which in respect of both these points of view is an essential part of the disclosure of the present invention. The reducing agent according to the invention in addition to the sugars may also contain other reductants or secondary recovery methods such as dithionite sodium, buffer systems, complexing agents or similar.

The restoration should be carried out in alkaline conditions in an aqueous solution, especially suitable pH > 11, in particular from 11 to 12.5.

The invention provides especially advisable to pursue a recovery for at least 50oC, preferably at from 80oC to 100oC.

This invention provides a particularly appropriate use of recovery funds in a concentration of from 1 to 50 g/l, preferably from 10 to 30 g/L.

This invention relates also to a method for dyeing or printing cellulose-containing textile material, the above proposed method are converted into water-soluble lacovara, rodstvennuju to the fiber.

In connection with the proposed invention under cellulose-containing textile materials refers to materials that contain cellulose fibers and, if necessary, the fibers of other materials, such as semi-synthetic or fully synthetic fabric, as cellulose acetate, polyolefins, polyacrylonitrile, esters or polyamides.

Method of dyeing or printing cellulose-containing textile materials according to the invention comprise the above proposed restoration according to the invention using isomaltulose or reductant containing isomaltulose and trehalose; and the dye was applied to the coated textile material before, during or after recovery.

After application and recovery of the dye it again oxidized and thus fixed on the textile material; and achieve the desired manifestation of color and durability dyed textile material. The oxidation is expediently carried out with the aid of gaseous oxygen or oxidizing salts.

In a preferred embodiment of the invention provides that prima of the dyeing process was exposed to ultrasound.

The invention is explained in more detail below using drawings and related examples of execution.

In the drawings:

Fig. 1: graphical representation of the degree of light reflection (sulfur dyes);

Fig. 2: graphical representation of the degree of light reflection (VAT dyes);

Fig. 3: graphical representation of the establishment of the redox potentials of various sugar solutions in water-alkaline environment;

Fig. 4: graphical representation of the kinetics of recovery of sugar mixtures of isomaltulose, trehalose, as well as other sugars, such as glucose, isomaltulose and glucose.

Example 1:

The dyeing of textile materials sulfur dye

Baptiste (washed and boiled in lye) cotton was dyed in a laboratory dyeing machine Turbomat company Anida 10% immedialely black CBR, liquid. The dye during application to the textile material was recovered reducing agent to water-soluble forms. The process complies with commonly used technologies (heated in a strongly alkaline medium at the initial temperature 40oC to 100oC, duration of reaction at 100oC is 1 Chan aqueous solution of glucose (10 g/l). Experience 1 (trehalose, isomaltulose) was carried out with a reducing agent of the following composition: 17.5 weight. % fructose, 14.9 weight. % glucose, 19,5 weight. % isomaltulose, 41.5 weight. % trehalose, 3,1 weight. % isomaltose, 3.2 weight. % of higher oligomers (including inverse products), 0.3 weight. % unidentified residue (calculated on the dry matter) (the concentration of the reductant: 14 g/l aqueous solution).

Experience 2 (trehalose, isomaltulose, sucrose) was carried out with a reducing agent of the following composition: 12.3 weight. % fructose, 9.7 weight. % glucose, 10.4 weight. % sucrose, 19,5 weight. % isomaltulose, 41.5 weight. % trehalose, 3,1 weight. % isomaltose, 3.2 weight. % of higher oligomers (including inverse products), 0.3 weight. % unidentified residue (calculated on the dry matter) (the concentration of the reductant: 14 g/l aqueous solution). This reductant hydrolysis can obtain the reducing agent used in experiment 1.

A. the Measurement of color differences (lab. CIE) on the painted textile substrates

Table 1 and table 2 shows the results of measurements of the color differences according to DIN 5033/part 1 and DIN 6174. Designation: DC - difference between purity or changing color, DH is the difference in color shades, DE - total color difference (DE > 2 the difference is - hasniza in color against the yellow-blue shades. From table 1 and table 2 shows that the values of DE as in the measurement of color differences of experience 1/comparison with glucose and experience 2/comparison with glucose is less than 2, so that color differences dyed textile materials can not be seen visually.

Century Reflected light colours

The measurement light reflected from the dyed textile materials led to the results presented in Fig. I (Iso: isomaltulose, Tre: trehalose). The progress curve values of the reflection light detected by the restorations, according to the invention correspond to those of comparative examples; and, however, was slightly higher value of the reflection of light.

C. color fastness

Table 3 presents the results of determination of the resistance to washing, resistance to sweat and resistance to friction.

1. Determination of resistance to washing (60oC) according to DIN EN 20105, part CO3.

2. Determination of resistance to washing (95oC) according to DIN EN 20105, part A.

3. Determination of resistance to sweat according DIN 54020.

4. ) Determination of resistance to abrasion according to DIN EN ISO 105-X 12.

From table 3 it can be seen that dostigashti, achieved with the use of glucose.

D. Determining the color of the transparency index of dye bath after a complete dyeing

Table 4 presents the results that were achieved when determining the color of the transparency index of dye bath finished dyeing. It also presents data on application of the method according to the invention correspond to the data of comparative experience.

Example 2:

The dyeing of textile materials kovovymi dyes

Materials used:

Textile material - Fabric 100% CO (cotton, raw white, pre-prepared for dyeing)

The weight of the sample is 8.5 grams

Dye - Indigo clean (BASF)

The content of the dye - 5 ml/l

Adjuvant 5 ml/l NaOH 3 g/l dithionite sodium (reducing agent)

The composition of the concentrated solution recovered cube - 80 ml of soft water, 4 g of Indigo clean (BASF) and 5 ml of NaOH 3 g/l dithionite sodium

Topped with soft water To 100 ml.

Conducting experience:

The Indigo powder suspended in 50 ml of water. To 30 ml of water was first added sodium lye and then dithionite sodium as a reducing agent. As the dye, and the mixture is supporting rivali 30 min at 50oC for maturation of the cube.

Dyeing cube:

In the glass (volume 1500 ml) was heated to 800 ml of water to 50oC, was treated with soda lye and dithionite sodium, was added a concentrated solution of restorative cube and filled up to 1000 ml Staining produced in two to 10 minutes.

A. Dyeing without reductant:

The dyeing was carried out as described above, and was not added reducing agent. This experience serves as a control experiment.

It was noted that the tub has acquired a dark blue color. When placing the textile material in the dye bath, it was possible to observe the absence of staining. It was noted only slight pollution of the textile material.

Century Dyeing with dithionite natra as the reductant:

The dyeing was carried out as described above, however, and as a reducing agent was added dithionite sodium. This experience serves as a comparison with the method according to the invention.

It was noted that bath after 15 minutes of ripening cube acquired a yellowish color, and its surface has a weakly metallic blue color. Used textile material after oxidation at ogasim isomaltulose and trehalose (Experiment 1):

The dyeing was carried out according to the above method. Instead of dithionite sodium was added restorer of 17.5 weight. %) fructose, 14.9 weight. % glucose, 19,5 weight. % isomaltulose, 41.5 weight. % trehalose, 3,1 weight. % isomaltose, 3.2 weight. % the higher oligomer (including inverse products), 0.3 weight. % unidentified residue (calculated on dry substance). The reducing agent was introduced at concentrations of 10 g/l, 20 g/l and 30 g/L.

It was noted that bath after addition of the reducing agent according to the invention and subsequent maturation acquired a blue-green color. Placed in a bath of textile material after oxidation in air acquired a blue color, which, however, was much lighter than when using dithionite sodium. When increased amounts of reducing the color depth is reduced.

D. Dyeing with a reducing agent according to the invention containing isomaltulose and trehalose and sucrose (Experiment 2):

Conditions of experience consistent with the above experimental conditions. Instead of dithionite sodium was added reductant from 12.3 weight. % fructose, 9.7 weight. % glucose, 10.4 weight. % sucrose, 19,5 weight. % isomaltulose, 41.5 weight. % trehalose, 3,1 weight. % isomaltose, 3.2 weight. % the highest oligotrichia 10 g/l, 20 g/l and 30 g/L.

It was noted that the bath after the addition of the reducing agent according to the invention and subsequent maturation of the cube has acquired a blue-green color. Placed in a bath of textile material after oxidation in air acquired a blue color, which, however, was much lighter than when using dithionite sodium. When increased amounts of reducing the color depth is reduced.

That is, the Dyeing with a reducing agent according to the invention containing trehalose, isomaltulose and sucrose by the action of ultrasound:

Conditions of experience and the structure of experience are as described under D). Was additionally applied ultrasound. It was noted that the bath after the addition of the reducing agent according to the invention and subsequent maturation of the cube has acquired a blue-green color. Placed in a bath of textile material after oxidation in air acquired a blue color, which was much darker than when dyeing without the use of ultrasound. With the increased number of recovery tools the color depth is reduced.

Table 5 reflects the experimental data:

The experiments conducted and marked in accordance with table 5, yielded results which made the obreteniyu, superior to those that were obtained through dithionite sodium.

Test resistance

The test of stability shows the ability of the paint to resist the impact of textile production (resistance to technological influences) and during operation (operational stability).

The results of strength tests are shown in table 6.

As resistance to abrasion, and resistance to washing in the case of the use of reducing agents according to the invention looks good and comparable to that achievable with dithionite sodium.

Example 3:

Determination of the redox potential E

Example 3 shows that isomaltulose or mixtures containing isomaltulose, establish the equilibrium redox potential faster than other sugars, such as glucose.

It was studied the equilibrium redox potential E at a pH of 12.2 (KOH 25%) and a temperature of 20oC a 1.5 molar solution with respect to Ag/AgCl/KCl (3 M, E*= 210 mV SHE, 20oC). Investigated a 1.5 molar solution contained (a) isomaltulose, and b) containing isomaltulose mixture of sugars (soma ukcosa, e) oxidized isomaltulose and f) trehalose.

In Fig. 3 one can notice that the equilibrium redox potential with isomaltulose and a mixture containing isomaltulose, installed in a few minutes, while the establishment of redox potential with the control of substances is much slower, i.e. within a few hours. Oxidized isomaltulose detects compared with other control substances faster equilibrium redox potential.

Example 4:

Recovery of sulphur black

This example shows that isomaltulose or mixture containing isomaltulose (isomaltulose, trehalose, glucose, fructose, isomaltose) capable of significantly faster recovery of sulfur dyes, than taken as a reference substance is glucose.

In Fig. 4 shows the intervals during which achieved full recovery of the dye, depending on the relationship being restored carbonyl groups of reducing agent to the amount of dye.

In Fig. 4 shows that the full vosstanovlenie 50oC is much faster than using as the reducing glucose. Initially soluble dye Diresul Black Liquid RDT before the study was transferred to absolutely free of sulfide and insoluble form. This is taken to study the dye in strongly alkaline and not containing a reducing agent aqueous medium at 50oC is completely insoluble.

In Fig. 3 and 4 show that the dyes according to the invention is capable of more rapid establishment of equilibrium redox potential and at the same time provide accelerated recovery of the dye.

1. Method of recovering dye from the group consisting of sulfur dyes, VAT dyes, characterized in that the recovery is carried out in an aqueous-alkaline medium with isomaltulose or a mixture containing isomaltulose and trehalose, as a reducing agent, at a concentration of reducing agent is from 1 to 50 g/l

2. The method according to p. 1, characterized in that the reducing agent is used in a concentration of from 10 to 30 g/L.

3. The method according to p. 1 or 2, characterized in that the reducing agent further comprises isomaltose, sucrose, glucose, fructose and the weight. % trehalose, from 10 to 90 weight. % isomaltulose, from 0 to 15 weight. % sucrose, from 0 to 20 weight. % fructose, from 0 to 20 weight. % glucose, 0 to 5 weight. % isomaltose and from 0 to 5 weight. % of oligomers of carbohydrate (calculated on dry substance).

5. The method according to one of paragraphs. 1-3, characterized in that the reducing agent contains 42 weight. % trehalose, 20 weight. % isomaltulose, 10 weight. % sucrose, 12 weight. % fructose, 10 weight. % glucose, 3 weight. % isomaltose and 3 weight. % of oligomers of carbohydrate (calculated on dry substance).

6. The method according to one of paragraphs. 1-3, characterized in that the reducing agent contains 42 weight. % trehalose, 20 weight. % isomaltulose, 17 weight. % fructose, 15 weight. % glucose, 3 weight. % isomaltose and 3 weight. % of oligomer carbohydrate (calculated on dry substance).

7. The method according to one of paragraphs. 1-5, characterized in that aqueous alkaline medium has a pH > 11.

8. The method according to one of paragraphs. 1-6, characterized in that the recovery is carried out at at least 50oC, preferably at 80 - 100oC.

9. The method according to one of paragraphs. 1-7, characterized in that the recovery is realized under the action of ultrasound.

10. Method of dyeing or printing cellulose-containing textile dyes from the group consisting of sulfur KRA is tel, then the dye to restore one of the ways to restore dyes on PP. 1-8, then oxidize.

11. Method of dyeing or printing cellulose-containing textile dyes from the group consisting of sulfur dyes or VAT dyes, in which the first water-insoluble dye restore one way on PP. 1-8, and then applied to the material and then oxidize.

12. Method of dyeing or printing cellulose-containing textile dyes from the group consisting of sulfur dyes or VAT dyes, in which the first water-insoluble dye restore one way on PP. 1-8 and simultaneously applied to the material, and then oxidize.

13. The method according to one of paragraphs. 9-11, characterized in that the dyeing or printing is carried out under the action of ultrasound.

 

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