DE2409727A1 - METHOD OF DYING SYNTHESIS FIBER - Google Patents

Description

FARBWERKE KOECiIST AG before «j al J, K ^ i iit er * LucHus ά Brüning ¹ \ ^s *.

File number;

EOE 74 / F 063

Date: February 27, 1974.

Dr.CZ/Hü _;; ....-; -:

Process for dyeing synthetic fibers ; ^

Processes for dyeing synthetic fibers after exhaust processes under high temperature (HT) conditions with development black marks based on the diazo and oxidation technique are well known in numerous variants. The very long dyeing time (kl / 2 hours) is criticized as a major disadvantage of all conventional working methods of this type.

It has now been found that on bobbins made of synthetic fibers or from mixtures containing such synthetic fibers with water-insoluble ones Development black marks based on the diazo and oxidation dyeing technique especially after a high pressure pull-out process level dyes can be achieved with a significant reduction in dyeing time can if you can

the wound fiber material in a pressure-tight Bringing the dye container and by displacing the air as well as filling the autoclave with saturated steam or superheated steam Steam to temperatures between 105 and 135 heated, in a separate, but also dx-uck-tight caustic container connected to it by pipes the entire dye liquor prepared and also at temperatures between 105 and 135 C. heated,

being by special control of the temperature within the said Limit values and the vapor pressure in the two gas-closed systems ensure that there is a relative overpressure from 5 to 10 at (= 4.9 to 9 »S1 bar) comes into the preparation vessel, or one generated by applying external pressure, then the hot dye liquor by the differential pressure within 3 to 60 seconds at the same time from the inside as well as from the outside in the dry or wet Pressing the bobbin and finally the coloring leads in the usual way 3Ü end. <

;. <- 'S09836 / 0574 ''';'.

ORlGtNAL INSPECTED

* · » Fa —m

The principle of the present invention is to. that in an HT container with a dye liquor applied to the selected pressure and temperature conditions and from there by means of pressure (pressurized steam, compressed air, Purapdruck ")" into another, steam-filled as well as with the bobbins made of synthetic fibers, e.g. spooled threads or piece windings on dye trees, charged autoclave is transferred. This is done in such a way that one is appropriately large dimensioned pipelines, pumps and a distribution valve the liquor at the same time both from the inside as well as from the outside into the yoke body. on this way it is possible, even with textured synthetic threads, without deformation of the winding and threads · to distribute the liquor evenly in the material to be dyed in an extremely short time. There will be for this in general Times of more than 60 seconds, mostly even less than 30 seconds, are used. This rapid "shooting in" of the dye liquor is achieved by applying high pressure on the sixth of the preparation tank (pressure difference 5-10 at). Of the The dye container is vented beforehand by means of pressure steam and the goods are preheated at the same time. The textile Material can be dry or pre-washed, which can be done in the dye container itself.

The staining tank is pressure tight, well insulated and equipped with a high capacity heat exchanger provided in order to be able to keep the dyeing temperature constant. The liquor itself is in the preparation tank heated to about 135 ° C ", and then in the steam-filled Pressed in dye container. As part of this process, the dye container, if the appropriate There is diflerential pressure, even when it is developed Valve completely filled v / earth, ca 'with increasing pressure the previously existing Da.rr.pf condensed. 509836/0574

—3—

A modification of this method according to the present invention is that the dye container filled with pressurized steam is connected to a lockable condensation system. is connected. As a result, a relative pressure difference is also formed, as a result of which it. it is again possible to fill the dye container completely with the dye preparation when the vent valve is closed. It is also possible, by means of a partial vacuum in the dyeing container after the steam _{T has been} vented, to produce a relative negative pressure from a vacuum line that can be shut off. There are therefore several method options for generating the pressure gradient according to the invention. A complete evacuation of the dye container is not necessary in the method according to the invention.

After the entire dye liquor is in the dye container is located, i.e. after the sighting-in has been completed the dyebath alternately with the help of a circulation pump from the inside to the outside and from the outside to the inside chirch the material roll is pumped, with already the starting of the circulation pump during the filling phase can begin. The selected dyeing temperature is maintained. Now takes place in the final fixation of the dye in a short time. It is an advantage under these temperature conditions to work with sufficiently high delivery rates of the dex pump. Above 60.l / kg. min. result good staining results.

Due to the fact that the entire dye liquor is fed into the dye vessel at high speed on and in da.s more or less dry material in the form of coils the process differs from the previously carried out HT dyeing processes, including their procedural

509836 ⁴ / "0574 ■ ·

Variants have been discussed extensively in the literature. So it is not about according to the invention only part of the dye liquor or a concentrated one Dye dispersion introduced into the dye container, but almost the entire dye liquor abruptly pressed in. It is not foreseeable that level colorations can be achieved under these conditions since bispersion diazo seliwarz brands have a high drawability at these temperatures.

In addition, it could not be expected that the dye dispersions at such high temperatures, pressure differences, and possible turbulence are still suitable for penetration into Y / ickel bodies. Furthermore it is Surprisingly that the dye dispersions among these difficult apparatus conditions remain stable and do not tend to agglomerate.

The claimed one acts as a major advantage Process from the fact that at the high temperatures used, the drawability of the Dispersion diazo black marks can be used to the full can.

According to the process, the usual dyes are used as dyes Trademarks in a liquid setting for use. Such dyes are in the Color Index, 2nd edition (1971) listed under the name "Azoic Dyes".

For carrying out the claimed method fiber types syn the table 'origin are suitable in every form of processing that is after the HT dyeing method can be colored. However, the new method is preferred for textured threads made of polyester as well as threads and fibers made of triacetate are used.

509836/0574

- 5 -

When dyeing are in addition to dispersants and the No further chemicals for pH adjustment or for diazotizing or cleaning the fiber material Additions required. A pil constancy of the Dye bath of pH 6 enables the reproducibility of the dyeings; which by known suitable Buffer stone is reached. Both dry and wet material can be treated.

For level dyeing it is important that the liquor circulation is not interrupted when switching over, which, as is well known, is achieved by a four-way circuit or "flap control".

Windings made of linear, textured polyester threads are placed in a dye container, suitable for high temperatures (HT -) stains, incorporated; this

2 container is then made by Sattclarapf of 2 kp / cm vented and preheated with the tiare. Equilateral the whole for the staining is put in a container necessary amount of liquor prepared, which is 10 times the areneweight and - based on the dry weight of goods - one dispersed in water Mixture of the components

3,6 ¹ Jo Dispex-se Black 1, CINr. II365, 2.1 fi Azoic Coupling Comp. 20, C. 1. No. 37530, 1 g / l of a Sondensatiohsprodaktes from cresal / formaldehyde and a set acidic buffer based on polymeric phosphates and acetic acid 60 follow (to pH 6)

contains. A compressed air pressure is applied above the Plotiemii level set at 5.5 kp / cfii.

- 6 509836/05 74

The pressurized liquor approach is now heated to 135 ° C. By opening a shut-off valve The ex'heated liquor is allowed to enter the dyeing container within a suitable distribution line Enter the winding body from the inside as well as from the outside for 7-10 seconds. It then adjusts itself • at the beginning of the liquor circulation - a ice temperature around 125 ° C. With alternate liquor circulation, the bath temperature is now increased to 135 ° C and the goods are dyed at this temperature for 20 minutes. The dyeing apparatus is emptied by means of KT (high temperature) drain,

In the meantime been eiixe in Druclcansatzgefäß if fleet

2 cm ^ / l sodium hydroxide solution 38 ⁰ Be (32.5 ig)

Of5 g / l of the reaction product of 1 hol Nönylphenol with 10 moles Ätlsylenoxid

prepared and heated ^{to 90 0 C.} The liquor is then introduced, as well as from the inside from the outside by applying a Preßluftdruckes in the dyeing vessel, there arises a Mischtercperatur a 10G of about ⁰ C. The treatment time concerns with reciprocal; ^? lotten circulation and a temperature of 10O ⁰ C 10 Γύχηιι-th. By continuous overflow rinsing the temperature to 6O ⁰ C is lowered, and then discharged the Behandlungsfcaö. It closes them; steaming of the material at a saturated steam pressure of 1.5 kp / cia "'for 5 minutes. In the meantime, an aqueous bath is added to the pressure vessel

6 cm / 1 acetic acid (60 7ds) and 4 g / l sodium nitrate

at 110 ⁰ C and introduced after superimposition with compressed air under the known conditions in the dyeing kettle. Ss is a Mischtemporatur of 110 ⁰ C and the Vl is & terikl 15 minutes at

509836/0574

11O ° C treated with alternating liquor circulation. After the usual completion, you get a level and very real black color.

509836/0574

Example 2

Twine body made of polyester fibers and cotton in a mixing ratio of 65:35 is achieved according to Example 1 placed in a Färfcefoehälters and pre-steamed. The further treatment for dyeing the goods then takes place as described in Example 1, however with "*" one dispersed in water

Mixture of the components (from the weight of the goods ^ 2.35 / o Disperse Black 1 , CI. 11365 and 1.4 ^{c for} Azoic Coupling Comp.20, C.1.1fr. 3? '53O »until the end of the intermediate cleaning Continuous overflow rinsing, the bath temperature is lowered to 30 ° C and the bath is then drained.

The subsequent overdyeing of the cotton portion takes place with an aqueous liquor containing (of siaren weight)

0.6 ⁰ Jo of the dye sol, Vat Οχ-ane 1,

CINr. 59IO6,
1 g / l soda kaJz; and
10 g / l sodium sulphate calc.

for 20 minutes at a temperature of 30 C. Thereafter the dye bath is drained.

In the meantime, a liquor was prepared in the pressure preparation vessel containing 6 cm / l of acetic acid (60 / tig) and h g / l of sodium nitrite on an aqueous basis

and which, after overlaying, is heated to 135 ° C. with compressed air. By opening a shut-off valve in a distribution line, the liquor set is brought into the dye container with the material both from the inside and from the outside and after switching on the liquor circulation pump, a mixing temperature of 85 ° C. is set. In the case of mutual fleet

5.09836 / 0574

circulation, the treatment temperature is increased ^{to Ilö c} C and the Yiare treated for 15 minutes.

The usual way of doing this results in a level dyeing, whereby the polyester fiber is black and the cotton portion is yellow ^! are colored.

KO f: - & er a »^ j = ύ JS 5 ύ t /> .J i *

Example 3

Garmd-ckslkörper - made of polyester fibers and jBaunrvolle in a mixing ratio of ^ Ot ^ Q are introduced into a Fäx ^ bebeliäiter according to Example 1 and pre-steamed (from ¥ arengewioht)

of the dispersed Parbsίοff component mixture analogous to example 2,

until the end of the HT stage when dyeing the polyester component . This is followed by draining the dye liquor under high-temperature conditions (HT drainage).

In the meantime, a liquor is prepared in the pressure vessel, which in an aqueous medium contains 7 ⁶ / of the dye

Vat Black 9 ₉ CI ₄ Ir, 6523Ο

contains and which? heated to 65 C / ird. To. Creation a compressed air pressure on the liquor approach is the Both the inside and the outside of the liquid in the dye container transferred with the textile material and after switching on the liquor circulation pump it arises a mixed temperature of SO C ,. With reciprocal Plotting circle will occur after 10 minutes

40 cm ^ / l sodium hydroxide solution 3 &"Be (32.5 / oig) and 10 g / l sodium carbonate (as a solution in water) are added via the open circulation and the fare JQ Min, colored at SO *""G Rinse r / ir-d the pE ¥ ert of the textile material "adjusted to pH S & steeply then drained the rinsing bath. The textile goods are

c
closing 5 minutes I) si 120 C steamed,

Until z's / i. s olienzelzli.cn. Prepared ice cream and slide-in saucepan heated to 110 ° C, aged in Yasser

8 enrVl acetic acid (60 % 1 &) 4 g / l sodium nitrite,

is overlaid with compressed air of 5.5 kp / cm in the pressure vessel and introduced into the dyeing container by opening a distribution line, both from the inside and from the outside. After switching on the liquor circulation, a mixed temperature of HO ⁰ C occurs and the textile material is treated with alternating liquor circulation for 15 minutes.

After the usual finishing, a uniform, true black coloration is obtained on both fiber parts.

.-12-

509836/0574

-12- Example 4

Knitted fabrics made from triacetate fibers are dyed in an IIT piece tree introduced in the wound state. This container is then vented with saturated steam of 0.4 kp / cm and preheated with the goods. Simultaneously· the entire amount of liquor required for dyeing is prepared in a batch container, which the 10 times the weight of the goods and - based on the dry Tf ar close weight - one dispersed in barrels Mixture · of the components

3.0 ^c ß> Disperse Black 1, CINr. 11365, - 1.75 # Azoic Coupling Comp. 20, CINr. 37530,

1 g / l of the condensation product from cresol / Formaldehyde as well

1 g / l of the buffer mentioned in Example 1

Base pol} ^r mer phosphates and acetic acid

60 follow (to pH 6)

contains. A compressed air pressure of 5 » 5 kp / cm ~ is set above the liquor level.

The pressurized fleet approach is now heated to 110 ⁰ C. By opening a shut-off valve in a suitable distribution line, the heated liquor is allowed to enter the winding body from both the inside and the outside within 7-10 seconds. ^{A mixed temperature of 110 °} C. is then established after the liquor has started to flow. In the case of alternate liquor circulation, the Y / are treated for 30 minutes. The dye liquor is then cooled to 85 ° C. This is followed by continuous rinsing at 60 ^° C. for 10 minutes.

For the purpose of intermediate cleaning this -aqueous bath are over the open circulation

2 cirr / l sodium hydroxide solution 38 ° Be (32.5 ig) and 0.5 g / l of the urase purification product of 1 mole

Nonylphenol with 10 moles of ethylene oxide,

509836/0574
- 13 -

added and fabric IO minutes at 7O ⁰ C treated. This is followed by a rinsing process at 60 ⁰ C
at. Thereafter, the diazotization is carried out for 15 minutes at 6O ⁰ C with an aqueous liquor containing

2.5. cnrVl. Sulfuric acid (96 <Us)

2 g / l sodium nitrite

The additions are made via open circulation.

After the usual completion, you get even Blackening.

-14-

509836/0574

»14-

Example 5

Windings made from linear, textured polyester threads are introduced into a dyeing container according to Example 1 and pre-steamed. Further treatment for
The textile material is then dyed as described in Example 1, but with a mixture of components dispersed in water

3.0 % Solvent Brown, 3, CIMr. 11360,

1.75% Azoic Coupling Comp. 20, C.I.Nr. 37530,

1 cm ³ / l sodium hydroxide solution 38 ° Be (32.5% Lg)

• 1 g / 1 of the condensation product cresol /
Formaldehyde "and

2 g / l Katriui III ionochloroacetate.

After the establishment -close, as in the example 1, intermediate cleaning and diazotization.

A level black coloration is obtained.

-15-

509836/0574

■ "Xü ™

Example 6

Yarn bobbins made of polyester fibers and cotton in a mixture ratio of 65:35 are made according to Example 1 placed in a dye container and pre-steamed. The further treatment for coloring the tex tilmaterials then takes place as described in Example 1, but with one dispersed in water Mixture of the components (from Weireneewicl

2.1 % Disperse Black 1, CINr. 11365 and

1.2 % Azoic Coupling Comp. 20, CIKr.37530, up to the completion of the ΠΤ stage when dyeing the polyester component. This is followed by draining the dye liquor under high-temperature conditions (HT drainage). ■. «

In the meantime, a liquor containing 6% of a dye on an aqueous basis is prepared in the pressure vessel

Sol.Sulphur Black 1, C.I.Kr. 53186 and

5. g / l soda kaiz.

contains. After application of a Preßluftdruckes to the fleet approach and heating to 115 ⁰ C, the liquor is also transferred from the inside than from the outside into the Färfoebehälter with the textile material. "After activation of the liquor circulation arises a mixing temperature a 110 ⁰ C. In mutual liquor circulation becomes after 10 minutes

12 cm / 1 sodium hydrogen sulfide solution (21 % ± g)

3 cm / 1 ammonium polysulfide solution (15 % ± s) was added via the open circulation, followed by an addition of 20 g / l calcium sulfate in the same way.

-16-

509836/0574

With alternate circulation of the liquor, the goods then stained at 95 ° C. for 30 minutes. Then a continuous rinsing for 10 minutes. After draining the rinsing bath, the dye is for 10 minutes at * ίθ ° C with an aqueous bath of 1 cm / l ¥ Hydrogen superoxide (35%) oxidizes, the oxidation bath drained, the dyeing rinsed briefly and the textile material Steamed for 5 minutes at 120 ° C.

The z-rfischen time prepared in the pressure vessel and diazotization float heated to 110 ° C., on an aqueous basis

8 cm / 1 acetic acid (GO % ) and 4 g / l Katriiwmitrite

containing, is superimposed with compressed air of 5.5 kp / cn and hastily by opening a distribution line both from the inside and from the outside into the dye container. brings. After activation eggs Flcttenzirkulation a mixing temperature occurs from 110 ⁰ C and is treated, the textile material at mutual liquor circulation for 15 minutes.

After the usual completion, both parts of the fiber are colored slightly black.

-17-

509836/0 5 74

Claims (5)

Patent claims : Process for dyeing textile materials made from synthetic fibers or from mixtures containing such synthetic fibers, in the form of wrappers with water-insoluble development black marks based on the Diazq _T and Oxydcitionsfärfoeteclmilr. according to the Ausziehine method, characterized in that one 1 the wound fiber material in a pressure-tight Bringing the dye container and by displacing the air and filling the autoclave heated to temperatures between 105 ° and 135 ° C by means of saturated steam or superheated steam, in one of them separate, but connected thereto by piping, as the pressure-tight container approach prepared the entire dyeing liquor and also sv / regard heated to temperatures 105 ° and 135 ⁰ C, v / obei through special control of the temperature within the specified limits and the vapor pressure in the two closed systems ensures that there is a relative overpressure from the 5-10 at (= 4.9 to 9.81 bar) comes into the batch ventilator or one can do so by applying external pressure generated, then the hot dye liquor by the differential pressure within 3 to 50 seconds at the same time presses into the dry or wet bobbins from the inside as well as from the outside and finally the coloring leads to the end in the usual way. 2) The method according to claim 1, characterized in that the differential pressure for transferring the liquor from the batch reservoir into the dyeing container is generated by compressed air (i. -18- 5 0 9 8 3 6/0574 3) Method according to claim 1, characterized in that the dyeing vessel däß vented with Sattdanpf and is filled and subsequent for generating a relative pressure drop of a closable line condensation closed is. f: Z η ι J '