DE1258821B - Method of dyeing wool - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

D 06p

German class: 8 m - 1/03

Number: 1 258 821

File number: C19562IV c / 8 m

Filing date: August 5, 1959

Opening day: January 18, 1968

The subject of the main patent 1 039 992 is a process for dyeing wool with sulfonated wool Copper phthalocyanines in an aqueous bath. It is characterized in that in the presence of Colored compounds that have at least one basic nitrogen atom to which at least one a polyglycol ether chain-containing radical is bonded, the molecule at least four

C - C - O groups

contains.

It has now been found that these dyeings, which are carried out in an aqueous and appropriately acetic acid bath have been produced, can advantageously be completed if the pH of the dyebath increased over 6 after the material to be dyed has absorbed the desired amount of dye.

In principle, all water-soluble, alkaline-reacting substances are suitable for increasing the pH value Links. However, in order to avoid fiber damage, especially in the case of wool dyeing, is recommended it is advisable to add such alkaline substances, of which a certain excess is the The pH value cannot be increased to more than about 9, and it is advantageous to increase the pH value to 6.5 to 9. You can use nitrogen-containing bases here, z. B. amines such as ethanolamines. In some cases, ammonia does a good job and proves to be particularly well suited also hexamethylenetetramine. Also alkali salts of phosphoric acids, especially di- or trialkali orthophosphates or polyphosphates are beneficial. There can also be two or more alkaline agents Substances are added, e.g. B. ammonia and hexamethylenetetramine.

The aftertreatment at increased pH requires only a relatively short time, e.g. B. about 10 to 30 minutes. It is expediently carried out at approximately the same temperature at which the dyeing was carried out. For example, the dyebath can be kept at the boiling point during the aftertreatment or let the temperature drop slightly, e.g. B. by not having any after increasing the pH adds more heat. Finally, the dyeing can be done as usual with warm and / or cold water rinsed and dried. A certain amount goes through the post-treatment at an increased pH value Part of the dye on the fiber is returned to the dye bath. But it is here to not or not properly fixed on the fiber process for dyeing wool

Addendum to the patent: 1039 992

Applicant:

CIBA Aktiengesellschaft, Basel (Switzerland)

Representative:

Dr.-Ing. Dr. jur. F. Redies,

Dr. rer. nat. B. Redies, Dr. rer. nat. D. Turk

and Dipl.-Ing. Ch. Gille, patent attorneys,

4000 Düsseldorf-Benrath 3,

Erich-Ollenhauer-Str. 7th

Named as inventor:

Dr. Richard Casty, Kaiseraugst;

Heinz Abel, Reinach (Switzerland)

Claimed priority:
Switzerland from August 6, 1958

Dye, so that the The dyeings obtained show better wet fastness properties than the corresponding ones without subsequent increase in the pH-value produced dyeings.

In the following examples, unless otherwise noted, parts are parts by weight, percentages are percentages by weight, and temperatures are given in degrees Celsius.

example 1

In a dyeing bath of 3000 parts water, 1 part Kupferphthalocyanintrisulfonsäure, 5 parts of 40 ^u / cent of acetic acid and 0.5 parts of the adduct described below from oleylamine and ethylene oxide is entered at 40 ° with 100 parts of wool yarn, the temperature increased to 20 minutes 90 ° and dyes at this temperature for about 30 minutes until the dyebath is practically exhausted. Then it is brought to the boil and dyeing continues for 1 hour at the boiling point. For the removal of insufficiently fixed and only superficially deposited

709 719/401

Dyestuff is then added to the dyebath 2.5 parts of 25% strength aqueous ammonia solution and 1 part of hexamethylenetetramine to. The treatment is continued for 15 minutes in the boiling bath and the woolen yarn is then rinsed. A uniform, turquoise-blue color is obtained Dye of an extremely pure shade and good wet fastness properties.

Without the addition of the nitrogen-containing auxiliary, you get a much weaker, very flaky and therefore practically useless coloring. By adding the alkaline substances towards the end of the During the dyeing process, the wet fastness properties (wash, milled, water and perspiration fastness) are significantly increased.

The ethylene oxide addition product is produced as follows:

100 parts techn. 1 part of finely divided sodium is added to oleylamine and heated to 140 °, whereupon ethylene oxide is introduced at 135 to 140 °.

As soon as the ethylene oxide is absorbed quickly, the reaction temperature is lowered to 120 to 125 ° and continues with the introduction of the ethylene oxide until 113 parts of ethylene oxide have been taken up. That The reaction product obtainable in this way is practically clearly soluble in water.

Example 2

You dye wool yarn according to the procedure of Example 1 instead of copper phthalocyanine trisulfonic acid with copper phthalocyanine-3,3 ', 3 ", 3'" - tetrasulfonic acid or copper phthalocyanine-3,4 ', 4 ", 4'" - tetrasulfonic acid, at the end of the dyeing process, also by adding ammonia, the pH value is increased, blue dyeings with good wet fastness properties are also obtained.

Green colorations are obtained if a mixture of copper phthalocyanine tri- or tetrasulfonic acid is used and the dye of the formula

HO, S

SO ₃ H

= N-C

OH

; C -N

SO, H

CH,

used.

Example 3

Wool yarn is dyed in the manner indicated in Example 1. Instead of the conversion product but one of the following products is used from oleylamine and ethylene oxide:

a) N-alkyl-propylenediamine, the alkyl radicals of which denote the Residues of tallow fatty acids correspond to + 8 moles of ethylene oxide,

b) N-alkyl-propylenediamine, the alkyl radicals of which are unbranched and saturated and have 16 to 18 carbon atoms contain, + 6 moles of ethylene oxide,

c) mixture of behenylamine and arachidylamine + 8 or 12 moles of ethylene oxide,

d) Mixture of the amines obtainable by reducing the tallow fatty acid amides + 6 to 8 moles of ethylene oxide,

e) N-dodecyl-propylenediamine + 6 moles of ethylene oxide.

f) The sulfuric acid ester obtained according to the following manufacturing instructions:

79 parts of a fatty amine mixture ( ³ / io mol) consisting of 30% hexadecylamine, 25% octadecylamine and 45% octadecenylamine are allowed to react with ethylene oxide in the presence of 0.8 part of sodium until 106 parts ( ²⁴ Iw mol) of ethylene oxide have been absorbed . The reaction temperature is initially 140 to 150 ° and can be gradually lowered to 120 to 125 °. 30.75 parts ( ¹ ^ o mol) of the ethylene oxide adduct obtained are in a stirrer-CH,

flask at 60 ° in 15 minutes with 5.4 parts of urea and then in 30 minutes with 5.4 parts Sulfamic acid (V20 mol and 10%) are added and the mixture boils in a stream of nitrogen for 5 to 6 hours Water bath held. The product obtained (41 parts) is readily soluble in water and reacts neutral.

As indicated in Example 1, the addition of ammonia and hexamethylenetetramine The pH of the dyebath increased for 15 minutes treated further in boiling bath and then rinsed with cold water. Uniform, turquoise-blue ones are also obtained Dyeings of a pure shade and good wet fastness properties.

Example 4

The procedure is as in the previous examples, but the dyebath is used to increase the pH value instead of ammonia and hexamethylenetetramine ammonia only sodium bicarbonate, Trisodium phosphate or triethanolamine too. The dyeings post-treated in this way are also characterized by good wet fastness properties.

Example5

A mixed fabric or mixed yarn, consisting of half wool and half polyamide fibers, is used according to colored according to the instructions of one of Examples 1 to 3, the pH also increasing in the manner indicated will. Uniform colorations are obtained.

Claims (4)

Patent claims: 1. Further development of the process for dyeing wool with sulfonated copper phthalocyanines according to patent 1039 992, characterized in that the dyeings, after the dyed material has absorbed the desired amount of dye, by increasing it the pH of the dyebath is above 6. 2. The method according to claim 1, characterized in that the pH of the dye bath increased to 6.5 to 9. IO 3. The method according to any one of claims 1 and 2, characterized in that the dye bath Adds nitrogen-containing compounds that are capable of increasing the pH value. 4. The method according to claim 3, characterized in that the dyebath is hexamethylenetetramine clogs. Considered publications: British Patent No. 762 510;
Australian Patent No. 211 019. 709 719/401 1.68 © Bundesdruckerei Berlin