DE2360632A1 - METHOD OF COLORING POLYAMIDE TEXTILE PRODUCTS - Google Patents

Description

"concerning:
Process for dyeing polyamide textile products.

The invention relates to a new method for dyeing Polyamide textile products in aqueous medium. She concerns especially the manufacture of dyed Poryaraid textile products, which are completely homogeneous and evenly colored and do not show any streaking.

The main aim of the method according to the invention is to To significantly improve the productivity of the known coloring material; namely, it allows a considerable increase in the amount of fabric to be dyed, one in particular noticeable reduction in the dyeing time and a lowering of the dyeing temperature usually used.

The person skilled in the art is aware of the difficulties involved in dyeing polyamide textile products such as fibers in the form of flakes, filaments, fiber webs, fabrics, jerseys or made-up th products in general. Difficulties _

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express themselves by the appearance of streaks or uneven tints, which make the product unsuitable as a commercial product do.

For a long time, numerous methods of dyeing in aqueous sand have been sanded Medium has been developed aimed at polyamide textile products reduce the annoying banding or even make it disappear completely.

In order to achieve homogeneous dyeings on polyamide textiles, an attempt was first made to dye the polyamide material with acidic dyes, chrome dyes or other metal-containing dyes in the presence of an anionic leveling agent. The purpose recommended temperature of the liquor should be 90 to 130 ⁰ C, can be colored both so.daß boiling point under atmospheric pressure or in 'an autoclave under any suitable pressure. Although this somewhat improved the very annoying streaking, the effectiveness of such a process remained unsatisfactory.

Attempts have also been made to use polyamide fibers at temperatures to dye that are below the absorption temperature for the dyes. This procedure uses an aqueous bath used, the low Jo content of a mixture of aliphatic monocarboxamides as a carrier for the dyes and contains at least one lower hydroxyalkyl group-containing primary or secondary amines. One such Mixture also contains anionic dispersants and a swelling agent for the fiber. True, Iiei3.siah a lot Observe a uniform or homogeneous color tone, but the risk of annoying streaking was still latent, v / eil the banding was only weakened, but not really eliminated (FR-PS 1 522 041).

There are other proposals in the field which represent novel combinations of known agents. Example

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wise, raan textile products based on polyamides at a temperature of at least 10O ⁰ C in an acidic bath can dye one or more suitable dyes -. ,, an anionic leveling agent and a weak ionic complexing agent, which in the presence of the other anionic components in the liquor does not precipitate, contains (FR-PS 1 185 750) .. With the help of these conditions ; durable and homogeneous colorations are achieved and the streaking error is largely masked, but not. ensures the complete disappearance of stripes.

This last-described procedure has been further developed in such a way that the recipe is replaced by a sulfur-containing Reducing agent was added, which caused the yellowing the polyamides counteracts or limits it; dp-s Yellowing is known to be a sign of oxidation that caused by-the-aqueous treatment at high temperature will. .This also avoids eh ·, -. That the. coloring becomes blind as a result of yellowing or loses its luster and the colored material decomposes (FR-PS-I 313'937).

With the help of this improvement in the process of dyeing Po ^ amides are achieved considerably better results as before; But even with these procedures, the hand part remains the formation of streaks, albeit greatly weakened, still exist. ■ ■ -. .

The object of the invention is to overcome this known main disadvantage all dyeing processes for polyamide textile products, according to which, it is practically impossible to produce colored products without streaking to get, fix. :

With the inventive method for dyeing polyamide. Textile products will have an excellent homogeneous dyeing reached, the bad part of the banding irrevocably, eliminates and, to a very important extent, the. productivity or Increased efficiency of the coloring material.

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According to the invention, the textile products are based on Polyamides at an appropriate temperature and suitable Acid.itüt in an aqueous bath, colored, which in addition contains the following components for the desired colorants:

a. a group of anionic leveling agents

b. a weak cationic complexing agent

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

d. a detergent and dispersant that prevents the liquor from separating or flocculating favors better circulation of the liquor in the textile material,

In a series of tests that led to the subject of the invention, and which combine known and unknown agents in a novel way, a synergistic effect was surprisingly found, due to which the polyamide textile products with an extremely homogeneous hue, suitable hue and without even after dyeing noticeable streaky defects at a temperature below ¹ 100 ° C obtained rden \ e, which was not previously possible.

The group of anionic leveling agents used according to the invention contains at least two components with the property of provisionally attaching to the active dyeing sites to fix the textile material, so that the dyes are prevented from too quickly to the specific areas occupy. · "

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

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can and in which A is one of the groups CII ₀ , SO ₀ or IiH and η is an integer from 0 to 4 i.st. Under this form

- I.

mel falls example, the preferred · used. <** ⁰ ^ Di-naphthylmethane-ß ,. ß'-disodium sulfonate.

2 The second anionic leveling agent B is · a salt one organic acid, namely an alkylarylsulfoiic acid or a polyalkylarylsulfonic acid, in which the Arj ^ lrest - a benzene- or naphthalene nucleus and is the neutralizing ion o'der cation from the group of alkali metals or amines and ΝΗλ_ is chosen; these include, for example, dodecylbenzene ammonium sulfonate or tetrapropylbenzene sodium sulfonate. -

The weak cationic complexing agent is usually a condensation product of ethylene oxide and an aromatic one Amine or a long-chain fatty amine, for example " Stearylamine oxyäthyliert with 8 mol Äthylenoxii This Means has the task ^ to immediately convert the dyes in the liquor into a complex! the .balance of this Complex is destroyed when the temperature of the liquor increases is so that the released dyes in this way can slowly replace the anionic leveling agents at the dye-technically active parts of the textile material,

The sulfur-containing organic compound that is an active Reducing agent is used in the treatment of polyamide textile products " is thiourea or one of its M-alkyl substituted Derivatives such as W-monomethyl thiourea.

As a detergent and dispersant which has the property to keep the dye bath or the liquor homogeneous and that

■ ■ ■

To facilitate the penetration and circulation of the bath inside the textile materials during the treatment, a mixture of oxy.athylated and sulfated Cn to C ₀₀ fatty alcohols, for example ethoxylated and sulfated steallyl alcohol, is suitable. "_ 6 -

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The different ones mentioned above in the process according to the invention Agents used are introduced into the dyebath or the liquor in Kengenanteilen, each as a solid Bath or liquor indicated. The anionic leveling

1
medium of the group B is / l is added in an amount of 0.10 to 1.50 g, so that this agent from 1.5 to 2 Ge \ -r.- ^c in the bath in a Mengenan- · part; i, based is present on the material to be dyed.

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

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

The εchulfölhaltige organic compound is in very low Amounts added, namely 0.0045 to 0.06 g / l.

The proportion of detergents and dispersants makes 0.25 to 1 g / l from ..

The Färbetenperatur is at least 8O ⁰ C and at most 130 ⁰ C. Preferably, is dyed at a temperature of from s5 to 100 ⁰ C, i.e. at a Teniperatur, which in practice is substantially below the temperature range of recommended for the known methods and applied will. Apart from the fact that, according to the invention, dyeing is carried out at a low temperature, the rate of temperature rise can also be accelerated, v / ob with dyeings of one quality and. Preserve quality in a way that it has never been achieved before.

The acidity or acidity of the liquor is also important because of the novel combination according to the invention known means. It was found that the acidity conditions depending on the various levels of temperature

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rose the. Fleet can be controlled extremely easily can: the pH value is 7 to 8, as long as the temperature stays below 80 ° C and drops to 3 to 7 as soon as the Temperature which reaches the threshold which is essential for the dyeing process, that is, as soon as the temperature is preferably SO up to 100 ° C.

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

First, at room temperature the various above agents listed in the specified proportions dissolved in water; this liquor is placed in the dye tub - in which the 'textile products have previously been placed. Of the

The pH is then adjusted to neutral or slightly basic, either by adding a customary one organic acid such as acetic acid or one in the field used alkaline agent.

The treatment of the toxic material begins at R.aumteniperatur; thereafter, the liquor is heated gradually in correspondence einem- temperature rise of preferably 0.5 to 4 ° C per min up to the selected or desired temperature, for example 40 ⁰ C under Kormaldruck ,. During this first stage of the process, the anionic leveling agents are temporarily fixed to the sites of the textile material that are active in the dyeing process.

At the end of this first stage, the separately produced added aqueous solution of the dyes in the impregnation bath for the textile material. The dyes are then used by the intercepted weak cationic complexing agents' and thus prevented from reacting too quickly and irregularly to the Wind up textile material.

When the addition of the "dye solution" is complete, the liquor

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gradually to 85 to ⁰ C QO erliitzt with a temperature rise of 0.5 to 4 ⁰ C per min, preferably from 0.8 to 1.2 ° C per minute and then held at about the final reaching temperature for 15 minutes.

As a result of the increase in temperature, the one that retains the dyes becomes The complex is destroyed and the released dyes "now occupy the areas of the textile material that are active in terms of dyeing instead of the anionic ones initially bound there. Leveling agent. ■

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

Unlike the known methods, where the required If the amount of acid is added at the beginning of the dyeing process, according to the invention, the addition takes place gradually in the course of the dyeing process.

Finally, the dye liquor is allowed to circulate for 15 to 60 minutes or rotate; then it is cooled and peeled off; afterward v / the dyed fabrics are rinsed.

The total duration of the dyeing process depends on the degree of exhaustion or absorption of the dyes from the liquor; this The 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 the help of systematically Samples taken during the coloring process, the coloring of which is then evaluated in the colorimeter.

The liquor ratio should advantageously 1 s 4 to 1:50

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(Volume).

The inventive dyeing process is applicable to continuous or discontinuous fibers based on polyamide, which are known as flakes, ribbons, mats, cards, bobbins, Docking, etc. may be present. The "procedure is -alike applicable to woven, knitted or non-woven products, which are wound on a perforated Ifarenbaum that allows the circulation of the liquor through the textile material permitted; the material can also be in the form of packets either in a circulating dye vat or in a perforated one Rotary drum are used. .

The process according to the invention can usually be used in all used dyeing containers, provided with the necessary heating and cooling devices and with control and regulating, carry out facilities. These known dyeing machines include drum machines, paddle machines, barges or runners for fabrics or webs, special machines for dyeing textured! Jersey, autoclaves and more.

The simple acid dyes and the * soluble or dispersible metal-containing dyes.

The following examples serve to explain the Invention. . ■ "- .. ·." "'

example 1

To the synergy occurring in the process according to the invention various dyeing tests with polyamide textile products were demonstrated carried out.

A fabric was used for this., Weight 350 kg, length 350Oa, a continuous polyamide 66 thread for the warp and weft had been used, which was used during dyeing according to

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- 10 driving caused banding.

The following staining conditions were observed in each experiment:

It was dyed according to the three-color print and the amount of dye given in Ge \ r, - "/ o, based on the polyamide textile product:

CI. Acid Orange 5 1> j ".

.CI. Acid Red .57 0.6 # CI. Acid blue 72 1 %

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

The dyeing process began at 20 ^° C. in the presence of the various agents according to the invention. ; it, the 2ad was gradually warmed over 10 min to 4O ⁰ C and added to the FarbstoffIosung at this temperature, while the PLL was UERT of the bath. 7 Finally, the temperature was brought over a period of 60 min at 9O ⁰ C, 45 min and held at this height the 3ad during this time quickly .iert 4 by the addition of increasing amounts of acetic acid to pH ^T. This was followed by cooling and the cooled bath was allowed to rotate or circulate for a further 15 minutes and finally withdrawn. the fabric was rinsed and then dried.

These conditions were systematically observed in all tests, the results of which are listed below.

1-1 dyeing at temperatures below 100 C with a single anionic leveling agent, a weak cationic one komple;: forming agent and a sulphurous

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1Λ-43 648.-11-organic Compound in the following quantities:

anionic leveling agent ■ "

Sodium salt of diiiaphthyl .- ■. methanedisulfonic acid 0.22 to 1.25 g / l

weak cationic complexing agent. ._ ■ "'" Stearylamine ox3 "ethylated with
8 moles of ethylene oxide .. 0.20 to 1.25 g / l

sulfur-containing organic
Link .
- "Thiourea 0. -01 to 0.05 g / 1.

Although the proportion of various funds has been increased the fabric appeared on the basis of polyamide-66. Badly uni-colored in warp and weft and showed Banding while the hue was satisfactory. ·

• 1-2 Colored was below 100 ⁰ C with two anionic leveling agents, a weak cationic complex-forming agent and a sulfur-containing organic compound, wherein the amounts of the various agents were in the liquor in the following Fourth "

■ 1. Anionic leveling agent. Sodium salt of dinaphthyliriethandisulfonic acid 0.20 to 1.25 g / l

2. Anionic leveling agent. 'Ammonium salt of' dodecylbenzene • sulfonic acid 0.20 to 1.80 g / l

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weak cationic complexing agent stearylamine oxyethylated with Moles of ethylene oxide. 0.20 to 1.25 g / l

sulfur-containing organic compound.
'Thiourea δ 0.01 to 0.05 g / l.

The product woven in warp and weft with polyamide-66 still showed a certain lack of uniformity with stripes still visible, but the height or the I level of hue was satisfactory.

1-3 Colored was below 100 ⁰ C with a single anionic leveling agent, a weak cationic kompleinbildenden means an organic compound and a detergent and dispersant in the following amounts:

anionic leveling agent sodium salt of dinaphthylmethanedisulphonic acid 0.120 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

Detergents and dispersants
Mixture of oxyethylated

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with sulfated G _Q Ms G _or>

α 20

Fatty alcohols 0.25 to 1 g / 1. . -

- The products made entirely from polyamide-66 showed a marked color tone, a very satisfactory color tone height (niveau de la iiuance); established . but there were numerous and distinct stripes.

1-4 Colored below 10O ⁰ C with two anionic Bgali-. detergents, a Sch-Viachen cationic coraplex-forming agent, a sulfur-containing organic compound and a detergent and dispersant in the following amounts:;

1. Anionic leveling agent, sodium salt of dinaplithylmethanedisulphonic acid .

0.20 to 1.25 g / l

2. Anionic leveling agent, ammonium salt of dodecyl beiizolsulfonic acid .

0.20 to 1.80 g / l

some cationic complexing agent
Stearylamine oxy-ethereal with S -: mol ethylene oxide '

sulphurous organic matter, blinding.
Thiourea

0.20 to 1.25 g / l 0.01 to 0.05 g / l

Detergent and dispersing agent Mixture of oxyäthyllerten and sulfatlerteii Cg up to € ₂₀ fatty alcohols ■.

0.25 to 1.25 g / l

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Those consisting of polyamide-66 in warp and weft
Products showed an excellent color tone,
were completely uniformly colored and surprisingly showed no streaking at all.

Example 2

A fabric made of polyaniia-6 without twisting in the warp was made and Schu / 3, weight 180 kg, length 2000 m, colored.

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

The liquor ratio was 1: 3 in contrast to the usual procedure for liquor ratios of 1:10 bis
1: 15.

The following combination of dyes was used for dyeing:

-O

Braun Telon BST (Bayer) 2.5 %
CI. Acid Orange 67 O, 36O? 4
CI. Cäure-Orange 51 0.085? O.

The dye liquor also contained the following according to the invention provided funds in the following amounts:

"Sodium salt of Dinaphthylmethe.nsulfonsäure 0.95 g / l

Ammonium salt of dodecybenzenesulfonic acid 0 * 25 g / l

Stearylamine / jxyethylated with 8 mol of ethylene oxide 0.95 g / l

Thiourea 0.02 g / l

Mixture of oiled and sulfated

C ₈ to C ₂₀ fatty alcohols 0.5 g / l.

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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 liquor was then brought to 90 ^° C. in the course of about 60 minutes and kept at this temperature for about 15 minutes.

Then the dye bath was acidified by every 5 min cnr first 200 ^ acetic acid, to 400% CNI 1000 cm ^/. and finally 1000 cm "'of acetic acid was added.'

The dyebath is turned for another 15 minutes and then set then normal exhaustion of the bath of dye stuck.

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

A sample of the same fabric, length 1500 m, was im same autoclave under otherwise identical conditions nedocli oline second anionic leveling agent and without detergent and dispersant colored. The dyed goods showed the desired hue but was not colored uniformly and showed severe streaking.

Patent claims:

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Claims (13)

Patent claims - 1. Process for dyeing polyamide textile productsii elevated temperature from an acidic aqueous medium which, in addition to the dyes, is an anionic leveling agent contains weak cationic complexing agent and a sulfur-containing organic reducing compound, thereby characterized by dyeing from a liquor, which additionally contains at least a second anionic leveling agent and a detergent and dispersant. 2. The method according to claim 1, characterized in that a compound of the general formula R (A) R 'is used as the first anionic leveling agent, in which R and R ^{1 are the} same or different sulfonated benzene or naphthalene nuclei *, A is one of the groups Is CH ₂ , SO ₂ or NH and η is an integer from 0 to 4. - 3. The method according to claim 1 or 2, characterized in that that disodium-oc, oo'-dinaphthylmethane-ß, ß-disulfonate is used as the first anionic leveling agent . 4. The method according to claim 1 or 2, characterized in that the second anionic leveling agent an alkali, ammonium or ara salt of an organic acid from the group consisting of alkylarylsulfonic acids and polyalkylerylsulfonic acids used. 409827/0960 1A-43 848 5. The method according to claim 1 to 4, characterized g e. k e η η - indicates "that ammonium dodecylbenzenesulfonate and / or sodium tetrapropylbenzenesulfonate are used as the second anionic leveling agent. 6. The method according to claim 1, characterized in that g e k e η η ζ. e i c hn e t that a weak cationic complex-forming Means the condensation product of Äth} ^ lenoxid and an aromatic Arain and / or a long-chain fatty amine used. - 7. The method according to claim 1 to 6, characterized in that g e k e η η, that the weak cationic complexing agent stearylamine is oxyethylated with 8 moles of ethylene oxide used. . . 8. The method according to claim 1, characterized in that I- " n e t that thiourea is used as a sulfur-containing organic compound or its H-alkyl derivatives are incorrect. 9. A method according to claim 1, characterized ge k s η z ^ eic et hn in that, as detergent and dispersant is a mixture of sulfated äthoxylierteh and C ₀ to C _"o fatty alcohols used; . 10. The method according to claim 1 to 9, characterized · that the dye bath 0.10 to 1.5 g / l first anionic leveling agent, 0.15 to 2 g / l, preferably 0.25 to 0.50 g / l second anionic leveling agent, 0.10 to 1> 50 g / l schv / aches cationic complexing agent, 0.0045 to 0.06 g / l- sulfur-containing organic compound and 0.25 to 1 g / l detergent and dispersant added. ' 11. The method according to claim 1 to 10, characterized ge ke η-η that dyeing is carried out at temperatures from 80 to 130 ⁰ C, preferably from 85 to 100 ⁰ C. 4 09827/0960 1-43 848 12. The method according to claim 1Ms 11, characterized in that the temperature is increased at a speed under normal pressure from 0.5 to 4 ° C / min up to 40 ° C and from 0.5 to 4 ° C, preferably from 0.3 to 2 ° C / min to dyeing temperature elevated. 13. The method according to claim 1 to 12, characterized in that the pH of the bath 7 to 8
at temperatures below 80 ⁰ C and from 3 to 7 at Färbetemperätur. 409827/0960