KR20020027484A - Dyeing process with sulfur dyes - Google Patents

Abstract

Processes for dyeing polyamides or polyamide containing substrates with sulfur dyes include those carried out with suitable reducing agents under these conditions at temperatures of pH 8-11, and 90-120 ° C. The present invention also relates to substrates dyed using this method.

Description

Dyeing process with sulfur dyes {DYEING PROCESS WITH SULFUR DYES}

Sulfur dyes are an important class of dyes. This class is extensively described in Venkatamaran, "The Chemistry of Synthetic Dyes", volume II (chapters XXXV and XXXVI) (1952) and volume VII (1974) and in the Color Index. In essence they are dyes which comprise oligo sulfur bonds (reducible with thiol groups) linked by aromatic compounds and which may be of oligomeric structure or polymer structure. They are obtained mainly by thiation of the individual intermediates (eg baking in the presence of water and / or inert organic solvents or in the melt) at temperatures above 100 ° C., in particular from 110 to 300 ° C. For example, the number or position of oligo sulfur bonds, the number of sulfur atoms of oligo sulfur bonds, the number of heterocycles and / or NH bonds in the sulfur dye molecule, and / or the number of structural repeat units can be determined from the starting materials and the synthesis. As the conditions vary, the starting material is known, although the exact structure of the sulfur dye is generally unknown or incompletely known.

Sulfur dyes are most frequently used in cellulose dyeing. The most widely used sulfur dyes of this class are C.I. Sulfur Black 1:

Other sulfur dyes include C.I. Sulfur Black 2, C.I. Sulfur Black 11, C.I. Sulfur Black 18, C.I. Sulfur green 35 etc. are mentioned. A detailed list can be found in the color index.

As mentioned above, sulfur dyes are used to dye cellulose or cellulose containing fabrics. The most commonly used method of dyeing these materials is the exhaust and continuous process.

Sulfur dyes are preferably used in the form of aqueous solutions, in particular in the form of aqueous pastes. Aqueous forms can be prepared, for example, by commercially available sulfur dyes or by baking or suspending sulfur dyes in molten state in water.

Sulfur dyes are applied to the substrate in reduced (luco) form and then oxidized. That is, the sulfur dye is added to the dyeing liquid in a reduced form or is added in an oxidized form and then reduced using a suitable reducing agent. For example, because atmospheric oxygen can oxidize sulfur dyes, it is common to use excess reducing agent to ensure that the dye is present in reduced form.

Useful reducing agents are all reducing agents conventionally known to be suitable, in particular sodium hydrosulfide, sodium formaldehyde sulfoxylate, potassium formaldehyde sulfoxylate, zinc formaldehyde sulfoxylate, thiourea, polysulfide (Na _x S _y ) Sodium sulfide, hydroxyacetone and glucose.

Useful oxidants include all oxidants known to be suitable in the art, specifically biclomate (K ₂ CrO ₇ , Na ₂ CrO ₇ ), bromate (NaBrO ₃ , NaIO ₃ ), bromite (NaBrO ₂ ), perborate ( NaBO ₃ ), persulfate (K ₂ S ₂ O ₈ , Na ₂ S ₂ O ₈ ), hydrogen peroxide and chlorate (NaClO ₃ ).

Polyamide substrates and polyamide-containing substrates have, to date, been identified with certain sulfur dyes, such as C.I. Sulfur Black 1 or C.I. It was not satisfactorily stained by Sulfur Black 2. For example, polyamide / cotton blends were not dyeable in uniform shades by only one dyeing.

The present invention relates to a process for dyeing polyamide substrates or polyamide-containing substrates with sulfur dyes and substrates dyed with such dyes.

Accordingly, the present invention relates to polyamide-based or polyamide-containing substrates, for example polyamide / lycra (registered trademark of Ducrat), polyamide / cotton, polyamide / cotton / lycra, polyamide / Cotton and the like are dyed with Sulfur Black 1, Sulfur Black 2 or Sulfur Green 16 with good fastness. Polyamide microfibers, for example Meryl (registered trademark of Nylstar), are likewise suitable for dyeing according to the invention.

A further advantage of the process according to the invention is that it is dyed in a good uniform color tone, for example by only one dyeing and one step dyeing process on cotton / polyamide substrates, which the previously known methods do not provide. .

Conventionally, polyamides and polyamide-containing substrates are dyed with individual sulfur dyes at 95 ° C. or lower and at pH 12-14.

The present invention provides dyeing of polyamides or polyamide-containing substrates with sulfur dyes and / or mixtures thereof, carried out at temperatures of 7.5 to 11, specifically 8 to 11 and 60 to 120 ° C., in particular 90 to 120 ° C. Provide a method.

The sulfur dyes used can be used not only in reduced form but also in oxidized form.

The method of the present invention, C.I. Sulfur Black 1, C.I. Sulfur Black 2, C.I. Sulfur Green 16 and mixtures thereof are preferred in that they can be used as sulfur dyes.

The method of the present invention, C.I. Sulfur black 1 is particularly preferred in that it is used as a sulfur dye.

The process of the invention is particularly preferred in that the dyeing is carried out at 60 to 110 ° C, in particular at 90 to 110 ° C, more preferably at 95 ° C, even more preferably at 110 ° C.

The method of the invention is preferred in that the dyeing is carried out at pH 9.5 to 11.

The method of the present invention is preferred in that sodium formaldehyde sulfoxylate, potassium formaldehyde sulfoxylate, zinc formaldehyde sulfoxylate and / or mixtures thereof are used as the reducing agent.

The present invention also provides a method in which wetting agents, lubricants, sequestrants and / or antifoams are added.

In addition, the present invention provides polyamide or polyamide-containing substrates dyed by the process according to the invention.

The method of the present invention is particularly suitably carried out using a dyeing method of Diresul (registered trademark of Clariant) EV type.

The following examples illustrate the invention. Percentages are by weight unless otherwise indicated. The temperature is in degrees Celsius.

The proportion of solution used in the examples below is 10: 1, unless stated otherwise.

Example 1

The aqueous solution for dyeing is 15% of Diresul black EV-4G (CI Sulfur Black 1, prepared by Clariant), 5 g / l sodium formaldehyde sulfoxylate, 3 g / l calcined sodium carbonate and 1 ml / l It consists of a humectant. Polyamide microfibers (meryl) are introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 110 ° C. at a rate of 2 ° C./min. Staining is continued for 30 minutes at 110 ° C. and pH 9-10.5, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. The substrate is then washed with hot and cold water.

The dye was oxidized on the substrate for 30 minutes using sodium bromate solution (4 g / l) at 70 ° C. and pH 4 adjusted with acetic acid. The substrate was then washed with hot and cold water.

The substrate has very good fastnesses.

Example 2

The aqueous solution for dyeing was 15% of Diresul black EV-4G (CI Sulfur Black 1, prepared by Clariant), 5 g / l sodium formaldehyde sulfoxylate, 1 g / l calcined sodium carbonate and 1 ml / l It consists of a humectant. Polyamide microfibers (meryl) are introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 110 ° C. at a rate of 2 ° C./min. Staining is continued for 30 minutes at 110 ° C. and pH 9-10.5, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. The substrate is then washed with hot and cold water.

The dye was oxidized for 30 minutes using sodium bromate solution (4 g / l) at 70 ° C. and pH 4 adjusted with acetic acid. The substrate was then washed with hot and cold water.

The substrate has very good fastnesses.

Example 3

The aqueous solution for dyeing is 15% of Diresul black EV-4G (CI Sulfur Black 1, prepared by Clariant), 3 g / l calcined sodium carbonate, 1 ml / l wetting agent and 5 g / l sodium formaldehyde sulfoxyl Consists of rate. Polyamide substrate (PA 6.6 Nylsuisse Art. 2044) is introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 95 ° C. at a rate of 2 ° C./min. Dyeing continues at 95 ° C. for 60 minutes, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. During the dyeing process, the pH is 9 to 10.5. The substrate is then washed with hot and cold water. The dye was oxidized on the substrate for 30 minutes using sodium bromate solution (4 g / L) at 70 ° C. and pH 3-4 adjusted to acetic acid. The substrate is then washed with hot and cold water.

The substrate has very good fastnesses.

Example 4

The aqueous solution for dyeing is 15% of Diresul black EV-4G (CI Sulfur Black 1, prepared by Clariant), 1 g / l calcined sodium carbonate, 1 ml / l wetting agent and 5 g / l sodium formaldehyde sulfoxyl Consists of rate. Polyamide substrate (PA 6.6 Niles Ice 2044) is introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 95 ° C. at a rate of 2 ° C./min. Dyeing continues at 95 ° C. for 60 minutes, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. During the dyeing process, the pH is 9 to 10.5. The substrate is then washed with hot and cold water. The dye was oxidized in the substrate for 30 minutes using sodium bromate solution (4 g / l) at 70 ° C. and pH 3-4 adjusted to acetic acid. The substrate is then washed with hot and cold water.

The substrate has very good fastnesses.

Example 5

Aqueous solutions for dyeing were 15% Diresul olive RDT-B solution (CI Sulfur Green 16, prepared by Clariant), 3 g / l calcined sodium carbonate, 1 ml / l wetting agent and 5 g / l sodium formaldehyde It consists of a foxylate. Polyamide substrate (PA 6.6 Niles Ice 2044) is introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 95 ° C. at a rate of 2 ° C./min. Dyeing continues at 95 ° C. for 60 minutes, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. During the dyeing process, the pH is 9 to 10.5. The substrate is then washed with hot and cold water. The dye was oxidized on the substrate for 30 minutes using sodium bromate solution (4 g / L) at 70 ° C. and pH 3-4 adjusted to acetic acid. The substrate is then washed with hot and cold water.

The substrate has very good fastnesses.

Example 6

Aqueous solutions for dyeing include 20% of Diresul black EV-PL (CI Sulfur Black 2, prepared by Clariant), 3 g / l calcined sodium carbonate, 1 ml / l wetting agent and 5 g / l sodium formaldehyde sulfoxyl Consists of rate. The polyamide / lycra (80:20) blend substrate is introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 110 ° C. at a rate of 2 ° C./min. Dyeing continues at 110 ° C. for 30 minutes, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. During the dyeing process, the pH is 9 to 10.5. The substrate is then washed with hot and cold water. The dye was oxidized on the substrate for 30 minutes using sodium bromate solution (4 g / L) at 70 ° C. and pH 3-4 adjusted to acetic acid. The substrate is then washed with hot and cold water.

The substrate has very good fastnesses.

Example 7

The aqueous solution for dyeing is 15% of Diresul black EV-4G (CI Sulfur Black 1, prepared by Clariant), 3 g / l calcined sodium carbonate, 1 ml / l wetting agent and 5 g / l sodium formaldehyde sulfoxyl Consists of rate. The polyamide / lycra (80:20) blend substrate is introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 95 ° C. at a rate of 2 ° C./min. Dyeing continues at 95 ° C. for 60 minutes, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. During the dyeing process, the pH is 9 to 10.5. The substrate is then washed with hot and cold water. The dye was oxidized in the substrate for 30 minutes using sodium bromate solution (4 g / l) at 70 ° C. and pH 3-4 adjusted to acetic acid. The substrate is then washed with hot and cold water.

The substrate has very good fastnesses.

Example 8

The aqueous solution for dyeing is 15% of Diresul black EV-4G (CI Sulfur Black 1, prepared by Clariant), 20 g / l calcined Glauber salt, 3 g / l calcined sodium carbonate, 1 ml / l wetting agent and 5g / l sodium formaldehyde sulfoxylate. Polyamide / cotton / lycra (30:60:10) blend substrates are introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 95 ° C. at a rate of 2 ° C./min. Dyeing continues at 95 ° C. for 60 minutes, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. During the dyeing process, the pH is 9 to 10.5. The substrate is then washed with hot and cold water. The dye was oxidized on the substrate for 30 minutes using sodium bromate solution (4 g / L) at 70 ° C. and pH 3-4 adjusted to acetic acid. The substrate is then washed with hot and cold water. The substrate exhibited a good balance between color intensity and color between cotton and polyamide and exhibited commercially acceptable fastnesses.

Example 9

The aqueous solution for dyeing is 15% of Diresul black EV-4G (CI Sulfur Black 1, prepared by Clariant), 20 g / l calcined glauber salt, 3 g / l calcined sodium carbonate, 1 ml / l wetting agent And 5 g / l sodium formaldehyde sulfoxylate. Polyamide / cotton / lycra (30:60:10) blend substrates are introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 110 ° C. at a rate of 2 ° C./min. Dyeing continues at 110 ° C. for 60 minutes, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. During the dyeing process, the pH is 9 to 10.5. The substrate is then washed with hot and cold water. The dye was oxidized in the substrate for 30 minutes using sodium bromate solution (4 g / l) at 70 ° C. and pH 3-4 adjusted to acetic acid. The substrate is then washed with hot and cold water.

The substrate exhibited a good balance between color intensity and color between cotton and polyamide and exhibited commercially acceptable fastnesses.

Example 10

The aqueous solution for dyeing is 15% of Diresul black EV-4G (CI Sulfur Black 1, prepared by Clariant), 3 g / l calcined sodium carbonate, 1 ml / l wetting agent and 5 g / l sodium formaldehyde sulfoxyl Consists of rate. The polyamide / lycra (80:20) blend substrate is introduced into the dyeing solution at 60 ° C. The dyeing solution is then heated to 95 ° C. at a rate of 2 ° C./min. Dyeing continues at 95 ° C. for 60 minutes, then the bath is cooled to 70 ° C. at a rate of 2 ° C./min. During the dyeing process, the pH is 9 to 10.5. The substrate is then washed with hot and cold water. The dye was oxidized in the substrate for 30 minutes using sodium bromate solution (4 g / l) at 70 ° C. and pH 3-4 adjusted to acetic acid. The substrate is then washed with hot and cold water.

The substrate has very good fastnesses.

Claims (10)

A process for dyeing polyamide or polyamide-containing substrates with sulfur dyes and / or mixtures thereof, comprising performing at pH 7.5 to 11, and 60 to 120 ° C. The method of claim 1, The sulfur dye used is an oxidized sulfur dye, which is reduced in the dyeing solution with a suitable reducing agent under the conditions of claim 1. The method of claim 1, Reduced sulfur dye is used. The method according to any one of claims 1 to 3, As a sulfur dye, C.I. Sulfur Black 1, C.I. Sulfur Black 2, C.I. Sulfur Green 16 and / or mixtures thereof are used. The method according to any one of claims 1 to 3, As a sulfur dye, C.I. How Sulfur Black 1 is used. The method according to any one of claims 1 to 5, The dyeing is carried out at 90 to 110 ℃. The method according to any one of claims 1 to 8, The dyeing is carried out at pH 9.5-11. The method according to any one of claims 2 and 4 to 7, Sodium formaldehyde sulfoxylate, potassium formaldehyde sulfoxylate, zinc formaldehyde sulfoxylate and / or mixtures thereof are used as reducing agents. The method according to any one of claims 1 to 8, A humectant, lubricant, sequestrant and / or antifoam. 10. A polyamide or polyamide-containing substrate dyed by the process according to any of claims 1-9.