DE2360632B2 - PROCESS FOR DYING POLYAMIDE TEXTILE PRODUCTS - Google Patents

Description

The invention relates to a new process for dyeing polyamide textile products in water Medium. It mainly concerns the manufacture of dyed polyamide textile products that are completely are homogeneously and evenly colored and have no streaking whatsoever.

The main aim of the process according to the invention is to significantly improve productivity; namely, it allows a considerable increase in the amount of fabric to be dyed a particularly noticeable reduction in the dyeing time and a lowering of the dyeing temperature usually used.

Those skilled in the art are aware of the difficulties involved in dyeing polyamide fabrics such as fibers in In the form of flakes, filaments, spun fibers, woven fabrics, jerseys or made-up products well known. The difficulties are expressed by a mixture of aliphatic monocarboxamides and primary or secondary amines containing at least one lower hydroxyalkyl group contains, such a mixture additionally contains anionic dispersants and a swelling agent for the fiber. It is true that a much more even or homogeneous color tone could be observed, the risk of troublesome streaking was still latent because the streaking was only weakened, but was not actually turned off (French patent 1522041).

There are other proposals in the field which represent novel combinations of known agents. For example, textile product aiii dye the base of polyamides in an acidic bath at a temperature of at least 100 ° C, the one or more suitable dyes, an anionic leveling agent and a weak cationic Complexing agent that is present in the liquor in the presence of the other anionic components does not fail, contains (French patent specification 1185 750). With the help of these conditions though durable and homogeneous coloring is achieved and the defect of the stripe formation is largely masked, but not the complete disappearance of stripes ensured.

This last-described procedure was further developed to the effect that the recipe was supplemented by a sulfur-containing reducing agent, which counteracts the yellowing of the polyamides or restricts it; yellowing is known to be a phenomenon of oxidation caused by the aqueous treatment at high temperature is caused. This also prevents the Coloring becomes blind or loses its luster as a result of yellowing and the colored material is decomposed (French patent specification 1313 937).

With the help of this improvement, the process for dyeing polyamides will be considerably better Results achieved than before; But even with this method, the disadvantage of the strip formation remains, even if greatly weakened, still exist. The object of the invention is this known Main disadvantage of all dyeing processes for polyamide

55

60

by the appearance of stripes or uneven- _t -.,

tints that make the product as a commercial product 65 textile products, according to which it is practically impossible

make unsuitable. to obtain colored products without stripes

For a long time there have been numerous methods of dyeing, remedying,
has been developed in an aqueous medium, which then With the method according to the invention for dyeing

Ben of polyamide textile products, an extremely homogeneous dyeing is achieved, the disadvantage the banding is irrevocably eliminated and, to a very important extent, productivity or efficiency of the dyeing process increased.

According to the invention, the textile products are based on polyamides at a corresponding temperature and appropriate acidity colored in an aqueous bath, which in addition to the desired Colorants contains the following components:

a) a group of anionic leveling agents,

b) a weak cationic complexing agent,

c) an organic sulfur-containing reducing compound, which changes the textile products in the course of treatment prevents changes that result in a decrease mechanical properties, yellowing and / or hardening of the product manifest,

d) a detergent and dispersant, which separates or flocculates the liquor prevents and favors a better circulation of the liquor in the textile material.

In test series that have led to the subject of the invention, and the known in a novel way and combining unknown agents with each other, surprisingly became a synergisther Effect found, due to which the polyamide fabrics with extremely homogeneous Shade, suitable shade height and without streaky blemishes that are still perceptible after dyeing a temperature below 100 ° C can be obtained, which was previously not possible.

The group of anionic leveling agents used in the present invention contains at least two Components with the property of being temporarily attached to the active dyeing areas of the textile material to fix, so that the dyes are prevented from too quickly the specific places to them can replace siermittel at the dye-technically active points of the textile material

The sulfur-containing organic compound that is an active reducing agent in the treatments of polyamide fabrics, is thiourea or one of its N-alkyl substituted derivatives such as N-monomethyl thiourea.

_{A mixture of oxyethylated and sulfated C 8} to C ₂₀ fatty alcohols is used as a detergent and dispersant, which has the property of keeping the dyebath or the liquor homogeneous and facilitating the penetration and circulation of the bath inside the textile materials during treatment,

lfi Stll

y _{8 20}

for example ethoxylated and sulfated stearyl alcohol suitable.

The various aforementioned agents used in the process according to the invention are introduced into the dyebath or liquor in proportions which are given as solids per liter of bath or liquor. The anionic leveling ^{agent of group B 1} is added in an amount of 0.10 to 1.50 g / l, so that this agent is present in the bath in an amount of 1.5 to 2 percent by weight, based on the material to be dyed.

The proportion of anionic leveling agent of group B ² is advantageously 0.15 to 2 g / l, preferably 0.25 to 0.50 g / l.

The proportion of weak cationic complexing agent is 0.10 to 1.50 g / l.

The sulfur-containing organic compound is added in very small amounts, namely from 0.0045 to 0.06 g / l.

The proportion of detergent and dispersant is 0.25 to 1 g / l.

The dyeing temperature is at least «0 ° C and at most 130 ° C Colored at a temperature of 85 to 100 ° C, that is to say at a temperature which in practice is significantly below the temperature range that is recommended and used for the known processes. Apart from the fact that dyeing is carried out at a low temperature according to the invention, the speed can also the rise in temperature can be accelerated, with colorations obtained in a quality and quality d i i bih iht iht dn

occupy.

The first anionic leveling agent B ¹ corresponds to the general formula R (A) _n R ', in which R and R' stand for sulfonated benzene or naphthalene nuclei which

can be dike or different and become a ₄₅ in the A, as it has not yet been achieved.

of the groups CH ₂ , SO ₂ or HH and η is a The acidity or acidity of the liquor: st

is an integer from 0 to 4. This formula is also important due to the novel

for example the preferred α, α-di-like combination of known agents used. It was fixed-

naphthyl methane / 3, / J'-di-sodium sulfonate. put that the acidity conditions depending on the

The second anionic leveling agent B ² is a salt of ₅₀ different levels of temperature rise

an organic acid, namely an alkylarylsul liquor, can be controlled extremely easily.

acid or a polyalkylarylsulfonic acid, in which: the pH value is 7 to 8, as long as the temperature

the aryl radical is a benzene or naphthalene nucleus and the temperature remains below 80 ° C and drops to 3 to 7

Remove the neutralizing ion or cation from the group as soon as the temperature is appropriate for the dyeing process

of the alkali metals or the \ mines and NH ₄ selected _{55 reached the} substantial threshold, that is, as soon as the

If this includes, for example, dodecylbenzene, the temperature is preferably 80 to 100.degree

^we '? - - - · ·· · ■ · Subject matter of the invention is therefore that in claim 1

will; g p

ammonium sulfonate or tetrapropylbenzene sodium sulfonate.

The weak cationic complexing agent is usually a condensation product of Ethylene oxide and an aromatic amine or a long-chain fatty amine, for example stearylamine oxyethylated with 8 moles of ethylene oxide. This agent's job is to immediately remove the dyes in the liquor to convert into a complex; the equilibrium di Kls is destroyed when the temperature called procedure.

The method according to the invention is expediently carried out as follows:

First, the various agents listed above are given in the specified at room temperature Proportions dissolved in water; this liquor is added to the dye vat previously G,. the textile products have been inserted. The pH will then change to a neutral or slightly basic one

this complex is destroyed when the temperature is then oasiicucn to a neutral oaer ieicnt the liquor is increased so that the released color value is set, either by adding a substance In this way slowly the anionic leveling common organic acid such as acetic acid or

an alkaline agent used in this field.

The treatment of the textile material begins at Room temperature; then the liquor is gradually heated, in accordance with an increase in temperature from preferably 0.5 to 4 ° C. per minute, up to the selected or desired temperature, for example 40 ° C under normal pressure. The provisional stage takes place during this first stage of the procedure Fixing of the anionic leveling agents to the active areas of the textile material in the dyeing process.

At the end of this first stage, the separately prepared aqueous solution of the dyes is placed in the impregnation bath given for the textile material. The dyes are then weakly cationic Complex-forming agents intercepted and thereby prevented from reaching the textile material too quickly and irregularly take off.

After the addition of the dye solution is complete, the liquor is gradually heated to 85 to 90 ° C with a Temperature rise from 0.5 to 4 ° C per minute, preferably from 0.8 to 1.2 ° C per minute and then at the reached end temperature held for about 15 minutes.

As a result of the increase in temperature, the complex that retains the dyes is destroyed and the ones released Dyes now occupy the areas of the textile material that are active in terms of dyeing technology instead of the areas there initially bound anionic leveling agent.

The pH of the liquor is then reduced to a value of 3 to 7 by adding an acid, preferably an organic acid, the addition either all at once or in several stages during a period of 15 to 60 minutes, depending on the chosen Dyes takes place.

In contrast to the known processes, in which the required amount of acid; at the beginning of the dyeing process is added, according to the invention, the addition takes place gradually and proportionally in the course of the dyeing process.

Finally, the dye liquor is allowed to circulate or rotate for 15 to 60 minutes; then it is cooled and peeled off: then the dyed textile products are removed flushed.

The total duration of the staining process depends on the degree of exhaustion or absorption of the dyes from the fleet; this degree of exhaustion is determined by means of a test stain.

In the same way, the speed of the temperature rise of the liquor can be determined with With the help of samples taken systematically during the coloring process, which are then colored in the colorimeter Is evaluated.

The liquor ratio should advantageously be 1: 4 up to 1:50 (volume).

The dyeing method η according to the invention can be used on continuous or discontinuous fibers based on polyamide, which are available as flakes, tapes, mats, Cards, bobbins, docks, etc. can be present. The method is equally applicable to woven, Knitted products or non-woven products that are wound onto a perforated fabric tree, which allows the liquor to circulate through the textile material; the material can also be in shape of packages either placed in a circulating dye vat or in a perforated rotating drum will.

The process according to the invention can be provided in all dyeing containers that are customarily used with the necessary heating and cooling devices and with control and regulating devices. These known dyeing machines include drum machines, paddle machines, barges or Skids for fabrics or webs, special machines for dyeing textured jersey, autoclaves and more.

The simple acid dyes and the soluble or dispersible metal-

to containing dyes chosen.

The following examples serve to explain the invention in more detail.

example 1

In order to demonstrate the synergy occurring in the process according to the invention, various Dyeing tests carried out with polyamide textile products.

For this purpose, a fabric, weight 350 kg, length 3500 m, was used for the one in warp and weft continuous polyaraid 66 thread has been used which caused streaking when dyed by conventional methods.

The following dyeing conditions were observed in each experiment:

It was colored according to the three-color print and the amount of dye in percent by weight, based on the polyamide textile product:

CI. Acid-Orange 3 C.I.-No. 10385 1% CI. Acid-Red 85 C.I.-No. 22 245 0.6% CI. Acid blue 40 C.I.-No. 62125 1%

An autoclave with a liquor circulating by means of a pump was used as the dyeing apparatus. The usage differential pressure was about 2 bar and measures the pressure loss during the passage of the liquor through the textile material at a liquor ratio 1:15 (volume).

The dyeing process began at 20 ° C in the presence of the various agents; after that the bath gradually became heated to 40 ° C in the course of 10 min and the dye solution added at this temperature, while the pH of the bath was 7. Finally, the temperature over the course of 60 min brought to 90 ° C, held 45 min at this height and the bath quickly brought to pH 4 by adding increasing amounts over this time Amounts of acetic acid. This was followed by cooling and turning the cooled bath for about 15 minutes or more let animals and finally withdrawn; the fabric was rinsed and then dried.

These conditions were systematically adhered to in all experiments, the results of which are given below are listed.

1-1 dyeing at temperature below 100 ° C with a single anionic leveling agent, a weak cationic complexing agent and a sulfur-containing organic compound in the following amounts:
Anionic leveling agent

Sodium salt or dinaphthylmethanedisulfonic acid

0.20 to 1.25 g / l

Weak cationic complexing agent stearylamine oxyethylated with 8 moles of ethylene oxide 0.20 to 1.25 g / l sulfur-containing organic compound
Thiourea 0.01 to 0.05 g / l

Although the share of the versrhiprlpnpn funds prhriht

the nylon-66-based fabric appeared poorly solid-colored in the warp and weft and showed banding while the hue was satisfactory.

1-2 Dyed below 100 ° C with two anionic leveling agents, one weakly cationic complexing agents and a sulfur-containing organic compound, the proportions of the various means in the fleet were as follows:

1. Anionic leveling agent

Sodium salt of dinaphthylmethanedisulphonic acid

0.20 to 1.25 g / l

2. Anionic leveling agent, ammonium salt of dodecylbenzenesulfonic acid

0.20 to 1.80 g / l

Weak cationic complexing agent stearylamine oxyethylated with 8 moles of ethylene oxide

0.20 to 1.25 g / l

Sulfur-containing organic compound thiourea 0.01 to 0.05 g / l

The product, woven in warp and weft with polyamide-66, still showed a certain defect Uniformity with streaks still visible, but the height or level of the hue was satisfactory.

1-3 Dyeing was done below 100 ° C with a single anionic leveling agent, a weak one cationic complexing agents, a sulfur-containing organic compound and a Detergents and dispersants in the following quantities:

Anionic leveling agent
Sodium salt of dinaphthylmethanedisulphonic acid

0.20 to 1.25 g / l

Weak cationic complexing agent stearylamine oxyethylated with 8 moles of ethylene oxide

0.20 to 1.25 g / l

Sulfur-containing organic compound thiourea 0.01 to 0.05 g / l

Detergent and dispersant mixture of oxyethylated and sulfated C ₈ to C ₂₀

Fatty alcohols 0.25 to 1 g / l

The products, woven entirely from polyamide-66, showed an excellent hue, a very satisfactory hue (niveau de la nuance); however, numerous and clear ones were found Stripes.

1-4 Dyeing took place below 100 ° C with two anionic Leveling agents, a weak cationic complexing agent, a sulfur-containing one organic compound and a detergent and dispersant in the following amounts:

1. Anionic leveling agent

Sodium salt of dinaphthylmethanedisulphonic acid

0.20 to 1.25 g / l

2. Anionic leveling agent, ammonium salt of dodecylbenzenesulfonic acid

0.20 to 1.80 g / l

Weak cationic complexing agent stearylamine oxyethylated with 8 moles of ethylene oxide

0.20 to 1.25 g / l sulfur-containing organic compound
Thiourea 0.01 to 0.05 g / l

Detergent and dispersant, mixture of oxyethylated and sulfated C ₈ to C ₂₀ fatty alcohols 0.25 to 1.25 g / l

The warp and weft made of polyamide-66 products showed an excellent color tone, were completely uniformly colored and surprisingly showed no streaking at all.

Example 2

A fabric made of polyamide-6 without twisting in warp and weft, weight 180 kg. length 2000 m, colored.

A Durand autoclave, volume 900 l, with a circulation pump was used as the dyeing apparatus 17 hp used. The fabric was rolled up on a tree of goods.

ao The liquor ratio was 1: 5 in contrast to the usual way of working with liquor ratios of 1:10 to 1:15.

The following combination of dyes was used for dyeing:

a ₅ acid brown 2 Cl no. 17 605 2.5%

CI. Acid yellow 25 CL no. 18 835 0.360% CI. Acid Orange 51 CL No. 26 550 0.085% The dye liquor also contained the following agents provided according to the invention in the following amounts:

Sodium salt of dinaphthyl methanesulfonic acid

0.95 g / l ammonium salt of dodecylbenzenesulfonic acid

0.25 g / l

Stearylamine oxyethylated with 8 moles of ethylene oxide

0.95 g / l

Thiourea 0.02 g / l

Mixture of oxyethylated and sulfated C ₈ to C ₂₀ fatty alcohols 0.5 g / l

The temperature of the liquor was quickly brought from room temperature to 40 ° C. in the course of 10 minutes; the dyes were then added to the bath at this temperature. The fleet was then brought to 90 ° C in the course of about 60 minutes and held at this temperature for about 15 minutes.

The dyebath was then acidified by first adding 200 cm ^{3 of} acetic acid, then 400 cm \ 1000 cm ³ and finally 1000 cm ^{3 of} acetic acid every 5 minutes.

The dyebath was allowed to spin for about 15 minutes and then normal exhaustion of the bath was turned on Dye solid.

The liquor was then allowed to run off, the textile material was rinsed with water and then dried. The finished fabric showed an excellent color tone, was dyed completely uniformly and free from adverse streaks.

A test piece of the same fabric, length 1500 m, was placed in the same autoclave under otherwise same conditions, but without a second anionic leveling agent and without detergents and dispersants colored. Although the dyed goods showed the desired shade, they were not uniform colored and showed severe streaking.

Claims (3)

Patent claims: 1. A process for dyeing polyamide textile products at elevated temperature from acidified aqueous liquor which, in addition to the dyes, contains 0.10 to 1.5 g / l of an anionic leveling agent of the general formula R (A) _n R ', in which R and R 'are identical or different sulfonated benzene or naphthalene nuclei, A is one of the groups CH ₂ , SO ₂ or NH and η is a number from 0 to 4, 0.10 to 1.50 g / l condensation product of ethylene oxide and an aromatic amine and / or a long-chain fatty amine as a weak cationic complexing agent and 0.0045 to 0.06 g / l thiourea or an N-alkyl derivative thereof as a reducing compound, characterized in that the liquor is additionally 0.15 to 2 g / l alkali Aiming at ammo, in polyamide textile products, the very annoying Sfreüenbildung to weaken or even to make it disappear completely. In order to achieve homogeneous dyeing on polyamide textiles, an attempt was first made to use the polyamide material with acidic dyes, chrome dyes or other metal-containing dyes in the presence to dye an anionic leveler. The recommended temperature of the liquor should be 90 to ίο 130 ° C, so that both boiling under atmospheric pressure as well as in the autoclave can be colored under any suitable pressure. True was this somewhat improves the very annoying banding, the effectiveness of such a procedure but remained unsatisfactory. Further, it was attempted to dye polyamide fibers at temperatures which are below the Aufziehtemperatur for the dyes. In this process, an aqueous bath is used, which is used as a carrier nium or amine salt of an alkylarylsulfonic acid _ao ger for the dyes a low percentage or polyalkylarylsulfonic acid as a second anionic leveling agent and 0.25 to 1 g / l mixture of ethoxylated and sulfated C ₁₁ to C ₂₀ fatty alcohols as detergents and dispersants, colors at temperatures of 80 to 130 ° C and a pH of the bath of 7 to 8 at temperatures below 80 ° C and from 3 to 7 at dyeing temperature. 2. The method according to claim 1, characterized in that the second anionic Leveling agents ammonium dodecylbenzenesulfonate and / or sodium tetrapropylbenzenesulfonate are used. 3. The method according to claim 1 or 2, characterized in that the liquor at one speed heated under normal pressure of 0.5 to 4 ° C./min to 40 ° C., the dye solution is added and the liquor continues at one speed brings from 0.5 to 4 ° C, in particular from 0.8 to 2 ° C / min to dyeing temperature.