JP2003504532A - Coloring method with sulfur dye - Google Patents

Abstract

  (57) [Summary] A method for coloring a polyamide or polyamide-containing substrate with a sulfur dye comprises carrying out said coloring with a suitable reducing agent in a pH range of 8-11, 90-120 ° C. and under these conditioners. . Substrates colored using this method have also been claimed.

Description

Detailed Description of the Invention

The present invention colors a polyamide substrate or a polyamide-containing substrate with a sulfur dye (
and a substrate colored with such a dye.

Sulfur dyes are an important class of pigments. This class is a Vencatamaran (
Venkatamaran) "The Chemistry of Synthetic Dyes" II
It is described extensively in Volumes (Chapter XXXV and XXXVI) (1952) and Volumes VII and VII (1974) and in the Color Index. In essence, they are dyes that are capable of reducing to thiol groups and that contain aromatically linked oligo-sulfur bonds, which may be of oligomeric or polymeric structure. They form their respective intermediates mainly in the temperature range of elevated temperatures, eg> 100 ° C., in particular 110 to 300 ° C. (eg by melting or baking in the presence of water and / or inert organic solvents). Obtained by vulcanization (thionation). Even if the starting material is known, for example, the number or position of oligo-sulfur bonds, the number of sulfur atoms in the oligo-sulfur bond, the number of heterocycles and / or NH bonds and / or the structural structure of the sulfur dye molecule. The exact structure of sulfur dyes is generally unknown or incompletely known, as the number of repeating units can vary depending on the starting materials and synthetic conditions.

In cellulose coloring, sulfur dyes are most notably used. The most widely used sulfur dyes in this category are C.I. I. It is Sulfur Black 1.

[0004]

[Chemical 1]

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

As mentioned above, sulfur dyes are used in particular for coloring cellulose or cellulose-containing fabrics. The most widely used methods for coloring these materials are exhaust and continuous methods.

The sulfur dyes are preferably used in the aqueous form, in particular in the form of an aqueous paste. Aqueous forms can be produced, for example, by commercially available sulfur dyes, or by suspending sulfur dyes prepared by baking or in the melt in water.

The sulfur dye is applied to the substrate in reduced (leuco) form and then oxidized.
That is, the sulfur dye can be added to the colored liquor in reduced or oxidized form, which is then reduced with a suitable reducing agent.

[0009] For example, it is customary to use excess reducing agent to ensure that the dye is truly present in its reduced form, since atmospheric oxygen can oxidize sulfurized dyes.

Useful reducing agents are all reducing agents known to be suitable in the prior art, in particular sodium hydrosulfite, sodium formaldehyde sulfoxylate, potassium formaldehyde sulfoxylate, zinc formaldehyde sulfoxylate, Includes thiourea, polysulfide (Na _x S _y ), sodium sulfide, hydroxyacetone, and glucose.

Useful oxidizing agents are all oxidizing agents known to be suitable in the prior art, in particular dichromates (K ₂ CrO ₇ , Na ₂ CrO ₇ ), bromates (NaBrO ₃ , N 2
AIO _3), Buromaito (NaBrO _2), perborate (NaBO _3), persulfate _{(K 2 S 2 O 8,} Na 2 S 2 O 8), including hydrogen peroxide, and chlorates the (NaCIO _3).

[0012] Polyamide substrates and polyamide-containing substrates have hitherto not been satisfactorily pigmentable with certain sulfur dyes (for example CI Sulfur Black 1 or CI Sulfur Black 2). For example, it was not possible to color on-tone with positive dyes for polyamide / cotton blends.

The present invention relates to a polyamide substrate or a polyamide-containing substrate, for example polyamide / Lycra®, polyamide / cotton, polyamide / cotton /
Lycra ("Lycra" is a trademark of DuPont), polyamide / cotton and the like can be colored with Sulfa Black 1, Sulfa Black 2 or Sulfa Green 16 with good fastness. Polyamide microfibers such as Meryl® (“Merryl” ® is Nylst®)
are trademarks of the company ar)) are likewise suitable for coloring according to the invention.

A further advantage of the method according to the invention is that its good tonal coloration is obtained with exactly one dyestuff, for example on a cotton / polyamide substrate, in a one-step coloring process, which was previously It was not obtained by the known method.

In the prior art, polyamides and polyamide-containing substrates are pigmented with individual sulfur dyes up to 95 ° C. and at a pH of 12-14.

The present invention is a method for coloring a polyamide or a polyamide-containing substrate with a sulfur dye and / or a blend thereof, at a pH range of 7.5-11, especially 8-11, at 60-120 ° C. In particular, it includes performing the coloring at 90 to 120 ° C.

[0017]   The sulfur dye used can be used not only in the reduced form but also in the oxidized form.

C. I. Sulfa Black 1, C.I. I. Sulfa Black 2, C.I. I. Preference is given to the process according to the invention in which Sulfa Green 16 and / or their blends are used as sulfur dyes.

C. I. Particular preference is given to the process according to the invention in which Sulfa Black 1 is used as the sulfur dye.

Preference is likewise given to the process according to the invention in which the coloring is carried out at 60 to 110 ° C., in particular 90 to 110 ° C., more preferably 95 ° C.

[0021]   Preference is given to the method according to the invention in which the coloring takes place at a pH of 9.5-11.

Preference is given to the process according to the invention in which sodium formaldehyde sulfoxylate, potassium formaldehyde sulfoxylate, zinc formaldehyde sulfoxylate and / or their blends are used as reducing agents.

The invention likewise applies humectants, lubricants, sequestrants and / or
Alternatively, a method is provided in which an antifoaming agent is added.

The invention further provides a polyamide or a polyamide-containing substrate that has been colored by the method according to the invention.

The method of the present invention is particularly suitably carried out with the dye of Diresul® (Diresul® is a trademark of Clariant).

The invention is illustrated by the following example. Percentages are by weight unless otherwise stated. The temperature is in degrees Celsius.

[0027]   The liquor ratio used in the following examples is, unless otherwise stated, It is always 10: 1.

Example 1 15% Diresul® Black EV-4G (CI Sulfur Black 1) (Clariant), 5 g / l sodium formaldehyde sulfoxylate, 3 g / l calcination Make an aqueous colored liquor with sodium carbonate and 1 ml / l wetting agent. Polyamide microfibers (Merrill®) are introduced into the colored liquor at 60 ° C. The colored liquor is then 1 at 2 ° C./min.
Heat to 10 ° C. Coloring is continued for 30 minutes at 110 ° C., pH 9-10.5 and the bath is then cooled down to 70 ° C. at 2 ° C./min. The substrate is then rinsed with hot and cold water.

The dye is oxidized on the substrate for 30 minutes at 70 ° C. with a 4 g / l sodium bromate solution adjusted to pH 4 with acetic acid. The substrate is then rinsed with cold water.

[0030]   The substrate has very good fastness.

Example 2 : 15% Diresul® Black EV-4G (CI Sulfur Black 1) (Clariant), 5 g / l sodium formaldehyde sulfoxylate, 1 g / l calcination Make an aqueous colored liquor with sodium carbonate and 1 ml / l wetting agent. Polyamide microfibers (Merrill®) are introduced into the colored liquor at 60 ° C. The colored liquor is then 1 at 2 ° C./min.
Heat to 10 ° C. Coloring is continued for 30 minutes at 110 ° C., pH 9-10.5 and the bath is then cooled down to 70 ° C. at 2 ° C./min. The substrate is then rinsed with hot and cold water.

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

[0033]   The substrate has good fastness.

Example 3 : 15% Diresle® Black EV-4G (CI Sulfa Black 1) (Clariant), 3 g / l calcined sodium carbonate, 1 ml / l
An aqueous pigmented liquor is made with the wetting agent of and the sodium formaldehyde sulfoxylate of 5 g / l. Polyamide substrate (PA 6.6 Nyls
uisse) Art. 2044) is introduced into the colored liquor at 60 ° C. The colored liquor is then heated to 95 ° C at 2 ° C / min. Continue coloring at 95 ° C for 60 minutes, then cool down the bath at 2 ° C / min to 70 ° C. PH is 9-1 during the coloring process
It is 0.5. The substrate is then rinsed with hot and cold water.

The dye is oxidized on the substrate for 30 minutes at 70 ° C. with a sodium bromate solution (4 g / l) adjusted to pH 3-4 with acetic acid. The substrate is then rinsed with hot and cold water.

[0036]   The substrate has good fastness.

Example 4 : 15% Diresle® Black EV-4G (CI Sulfur Black 1) (Clariant), 1 g / l calcined sodium carbonate, 1 ml / l
An aqueous pigmented liquor is made with the wetting agent of and the sodium formaldehyde sulfoxylate of 5 g / l. Polyamide substrate (PA6.6, Nilsse Art.
2044) is introduced into the colored liquor at 60 ° C. The colored liquor is then 2 ° C.
Heat to 95 ° C./min. Continue coloring at 95 ° C for 60 minutes, then cool down the bath at 2 ° C / min to 70 ° C. The pH is between 9 and 10.5 during the coloring process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate for 30 minutes at 70 ° C. with a sodium bromate solution (4 g / l) adjusted to pH 3-4 with acetic acid. The substrate is then rinsed with hot and cold water.

[0038]   The substrate has good fastness.

Example 5 : 15% Diresul (registered trademark) Olive RDT-B solution (liq.) (CI Sulfa Green 16) (Clariant), 3 g / l calcined sodium carbonate, 1 ml / l An aqueous pigmented liquor is made with the wetting agent of and the sodium formaldehyde sulfoxylate of 5 g / l. A polyamide substrate (Nielsse Art. 2044, PA 6.6) is introduced into the colored liquor at 60 ° C. The colored liquor is then heated to 95 ° C at 2 ° C / min. Continue coloring at 95 ° C for 60 minutes, then cool down the bath at 2 ° C / min to 70 ° C. During the coloring process, the pH is 9-10.
It is between 5. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate for 30 minutes at 70 ° C. with a sodium bromate solution (4 g / l) adjusted to pH 3-4 with acetic acid. The substrate is then rinsed with hot and cold water.

[0040]   The substrate has good fastness.

Example 6 : 20% Diresur (registered trademark) Black EV-PL (CI Sulfur Black 2) (manufactured by Clariant), 3 g / l calcined sodium carbonate, 1 ml / l
An aqueous pigmented liquor is made with the wetting agent of and the sodium formaldehyde sulfoxylate of 5 g / l. Polyamide / Lycra® blend (80
: 20) introduce the substrate into the colored liquor at 60 ° C. The colored liquor then 2
Heat to 110 ° C at ° C / min. Continue coloring at 110 ° C for 30 minutes, then bath at 2 ° C
Cool down to 70 ° C in minutes. The pH is between 9 and 10.5 during the coloring process. The substrate is then rinsed with hot and cold water. P with acetic acid at 70 ° C
The dye is oxidized on the substrate for 30 minutes with a sodium bromate solution adjusted to H3-4 (4 g / l). The substrate is then rinsed with hot and cold water.

[0042]   The substrate has good fastness.

Example 7 : 15% Diresur® Black EV-4G (CI Sulfur Black 1) (Clariant), 3 g / l calcined sodium carbonate, 1 ml / l
An aqueous pigmented liquor is made with the wetting agent of and the sodium formaldehyde sulfoxylate of 5 g / l. Polyamide / Lycra® blend (80
: 20) introduce the substrate into the colored liquor at 60 ° C. The colored liquor then 2
Heat to 95 ° C at ° C / min. Continue coloring at 95 ° C for 60 minutes, then cool down the bath at 2 ° C / min to 70 ° C. The pH is between 9 and 10.5 during the coloring process. The substrate is then rinsed with hot and cold water. PH 3 with acetic acid at 70 ° C
The dye was applied on the substrate using a sodium bromate solution adjusted to ~ 4 (4 g / l)
Oxidize for 0 minutes. The substrate is then rinsed with hot and cold water.

[0044]   The substrate has good fastness.

Example 8 : 15% Diresur® Black EV-4G (CI Sulfur Black 1) (Clariant), 20 g / l calcined Glauber salt, 3 g / l calcined sodium carbonate. An aqueous colored liquor is made with 1 ml / l wetting agent and 5 g / l sodium formaldehyde sulfoxylate. A polyamide / cotton / Lycra® blend (30:60:10) substrate is introduced into the colored liquor at 60 ° C. The colored liquor is then heated to 95 ° C at 2 ° C / min.
Continue coloring at 95 ° C for 60 minutes, then cool down the bath at 2 ° C / min to 70 ° C. The pH is between 9 and 10.5 during the coloring process. The substrate is then rinsed with hot and cold water. The dye is oxidized on the substrate for 30 minutes at 70 ° C. with a sodium bromate solution (4 g / l) adjusted to pH 3-4 with acetic acid. The substrate is then rinsed with hot and cold water. The substrate shows excellent comparability in color strength and hue between cotton and polyamide and has a commercially acceptable fastness.

Example 9 : 15% Diresur® Black EV-4G (CI Sulfur Black 1) (Clariant), 20 g / l calcined Glauber salt, 3 g / l calcined sodium carbonate, An aqueous colored liquor is made with 1 ml / l wetting agent and 5 g / l sodium formaldehyde sulfoxylate. A polyamide / cotton / Lycra® blend (30:60:10) substrate is introduced into the colored liquor at 60 ° C. The colored liquor is then heated at 2 ° C / min to 110 ° C. Continue coloring at 110 ° C. for 60 minutes, then cool down the bath at 2 ° C./min to 70 ° C. The pH is between 9 and 10.5 during the coloring process. The substrate is then rinsed with hot and cold water.

The dye is oxidized on the substrate for 30 minutes at 70 ° C. with sodium bromate solution (4 g / l) adjusted to pH 3-4 with acetic acid. The substrate is then rinsed with hot and cold water.

The substrate exhibits excellent equalization in color strength and hue between cotton and polyamide and has a commercially acceptable fastness.

Example 10 : 15% Diresul® Black EV-4G (CI Sulfur Black 1) (Clariant), 3 g / l calcined sodium carbonate, 1 ml / l
An aqueous pigmented liquor is made with the wetting agent of and the sodium formaldehyde sulfoxylate of 5 g / l. Polyamide / Lycra® blend (80
: 20) introduce the substrate into the colored liquor at 60 ° C. The colored liquor then 2
Heat to 95 ° C at ° C / min. Continue coloring at 95 ° C for 60 minutes, then cool down the bath at 2 ° C / min to 70 ° C. The pH is between 9 and 10.5 during the coloring process. The substrate is then rinsed with hot and cold water. PH 3 with acetic acid at 70 ° C
The dye was applied on the substrate using a sodium bromate solution adjusted to ~ 4 (4 g / l)
Oxidize for 0 minutes. The substrate is then rinsed with hot and cold water.

[0050]   The substrate has good fastness.

[Procedure Amendment] Patent Cooperation Treaty Article 19 Amendment Translation Form

[Submission date] November 24, 2000 (2000.11.24)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Contents of correction]

[Claims]

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Claims (10)

[Claims] 1. A method for coloring a polyamide or a polyamide-containing substrate with a sulfur dye and / or a blend thereof, comprising: 7.5-1
A method comprising performing the coloring at 60 to 120 ° C. in a pH range of 1. 2. A process according to claim 1, wherein the sulfur dye used is an oxidized sulfur dye which is reduced in a coloring solution by a reducing agent suitable under the conditions given in claim 1. . 3. The method according to claim 1, wherein a reduced sulfur dye is used. 4. A C.I. I. Sulfa Black 1, C.I. I. Sulfa Black 2, C.I. I. Process according to any of claims 1 to 3, wherein Sulfa Green 16 and / or blends thereof are used as sulfur dyes. 5. C.I. I. Process according to any of claims 1 to 3, wherein Sulfa Black 1 is used as a sulfur dye. 6. The method according to claim 1, wherein the coloring is performed at 90 to 110 ° C. 7. The method according to claim 1, wherein the coloring is carried out at a pH of 9.5-11. 8. Sodium formaldehyde sulfoxylate, potassium formaldehyde sulfoxylate, zinc formaldehyde sulfoxylate and / or blends thereof are used as reducing agents.
And a method according to any of 7. 9. The method according to claim 1, wherein wetting agents, lubricants, sequestering agents and / or defoamers are added. 10. A polyamide or polyamide-containing substrate colored by the method according to any of claims 1-9.