DE2112878A1 - Solutions containing fixing aids - Google Patents

Description

Pafentanwälto

Dr. W. Schalk, DipUng. P. Wirth

Dipl.-Inn. G. Nuremberg

D ;. V .: - '! ^ Ad-Kowarzik

Dr. P. Wei.ihold, Dr. D. Gudel

6 Fronkfurl / M., Size. Eschenheimer Sh-. 39

SAHDOZ AG
Basel, Switzerland

Case

l
Fixing aid-containing solutions

The German patent specification No. 855,001 describes "in procedures

for the production of water-soluble, organic, nitrogen-containing condensation products from polyalkylene polyamines and cyanamides and its derivatives. The condensation products are basic, syrupy, almost colorless liquids or solid substances that with Can be converted into salts using mono- or polybasic organic or inorganic acids. The basic products or their water-soluble salts are suitable as such or together with water-soluble compounds of the polyvalent metals, like copper, to improve the fastness properties of dyeings with nouns dyes on cellulose. In For example, condensation products from polyethylene polyamines come into question and dicyandiamide, for example those from triethyllentetramine and dicyandiamide, tetraethylene pentamine and dicyan

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diamide and especially those made from diethylenetriamine and dicyandiamide. Surprisingly, it has been shown that the condensate! ons ^ roducts are not uniform with regard to the fixing effect for direct dyes; 7 to 20 % of the condensation products present in the solution are little or no effective as fixing aids for direct dyes. By suitable measures, fractions can be obtained in which practically the entire fixing effect is contained, while fractions with little or no fixing effect are also present. The invention relates to a process for the preparation of solutions which are suitable as fixing aids for anionic dyes, characterized in that the water-insoluble constituents are obtained from the aqueous solutions which contain the condensation products (A) of polyalkylenepolyamines and cyanamides or water-soluble salts of these condensation products separates and separates. According to the invention, the solutions obtained in this way contain a maximum of 15 percent by weight (based on the total dry matter content) of the water-insoluble by-products (building materials) formed during the production of the condensation products A, which are little or no effective as fixing aids for anionic dyes and especially for direct dyes .

The aqueous solution from which the precipitated solids are separated can be prepared in different ways, e.g. the raw condensation product can be prepared at increased Temperature can be dissolved in water, whereby a clear solution is formed. The water-soluble salts of the condensate

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on products are dissolved in water or the condensation products are dissolved in acid. The solutions are then left to stand, advantageously at temperatures not exceeding 30 °, if necessary for several days, until solids have separated out from them. If necessary, the excretion can be accelerated by germs. The excreted pesticides consist of the little or ineffective parts as fixing agents. It is also possible, for example, to stir the condensation products present in pieces with water at room temperature for, for example, 5-20 hours. The initially in finer (i form precipitating solids are thereby converted into a coarser and filterable form. Accordance with the process they will be separated by known methods, for example by filtration, decantation or by centrifugation or by the combined use of such separation methods, there remains.

a clear, by-product depleted aqueous solution.

The amount of condensation occurring in the inoperative by-products of the condensation conditions in the manufacturing% position of the base dependent. They amount to approx. 7-20 percent by weight of the raw base.

Solutions such as 10-70 # contain dry matter, especially those with j5O-6o;. $ Dry matter content.

The solutions obtained have an improved storage stability compared to the solutions of the crude condensation products.

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The solutions according to the invention are very suitable for fixing ionic dyes and, in particular, direct dyes, for example on fiber materials or natural fibers
or regenerated cellulose and especially in the production of colored paper. They are also, for example, alone or together with water-soluble compounds of polyvalent metals such as copper, for improving the fastness properties of dyeings with substantive dyes, for the production of fibers. They also have the property of precipitating acidic dyes from their aqueous solutions.

The dyeings obtained have improved fastness to alcohol compared to those obtained with the aid of the crude condensation products
colorations obtained. '.

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In the following examples, the parts mean parts by weight and the percentage by weight; the temperatures are given in degrees Celsius.

Example 1 "·".

500 parts of the condensation product of dicyandiamide and Diäthylentriasiin, h according to Example ¹ of German patent 855 OOl are pulverized and added to 500 parts of water at Zimmertamperatur .. The whole while. Stirred for 5 hours at 15-20 ° and then left to stand for 72 hours at room temperature. A sediment separates out and is separated off by filtration. After drying it is ^ 7 parts.

Example 2 ,

450 parts of diethylenetriamine and 378 parts of dicyandiamide are made up in a stirred flask with a reflux condenser. The whole is kept at a temperature of 107-157 ° for 6-8 hours, cooled and ground.

135 parts of the resulting product are dissolved in 600 parts of water. It is then neutralized with about 8 l parts of 26.5% hydrochloric acid and adjusted to 1000 parts with water. The solution is filled into a pointed funnel, in which one

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leaves it at zero degrees for 10 days. This is followed by a filter decanted. A clear solution is obtained in addition to a white residue, which is powdery after drying, which is discarded.

Example 3 ;

1000 parts of the according to Example 4 of the German patent No. 855OOI produced condensation product from dicyandiamide and diethyl ethyltriamine are added to 860 parts of water within 60-90 minutes with stirring. The temperature is kept below 30 °. A cloudy solution has formed 4-5 hours after the addition.

With strong cooling, YjJO parts now become 30% hydrochloric acid Allow the temperature to be adjusted in such a way that the temperature is always kept below 50 °. The pH is adjusted to 7.0 by further adding 60 parts of 50% hydrochloric acid (the pH value was measured in a 10-fold dilution with a pH meter).

When the neutralization is complete, 20 parts are grounded. Diatomaceous earth was added and the mixture continued to stir for 15 hours. It is then heated to 70 + 5 ° and kept at this temperature for 60-90 minutes and then filtered through a spiral filter ohm cooling. The optimal Piltriertemperatur is 5O-7O ^0th The filter residue is 70 parts, 20 parts are diatomaceous earth. -

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example

600 parts of the getnäss Example 11 of German patent ¹ 855 v OOl condensation product available / ground with

55O parts of water kept together with stirring at 60-70 ° until the condensation product is dissolved. It is left to stand at 30 ° for 5 days and then filtered.

Example 5

A with 2.% solar violet BL [Schultz, Farbstofftabellen, 7th Ed. Erp. Vol. IS. 123 (193 ^ 3 dyed cotton piece was removed for 20 minutes in a bath with a liquor length of 1:40, which, based on the cellulose weight, contains J & a solution according to Example 3. This is followed by rinsing and drying - ter staining significantly improved.

example 6th

1000 parts of paper pulp (bleached spruce sulfite cellulose ), which is present in a vat with a consistency of h% and a freeness of 20 ° SR , are 20 parts of the anionic dye of the formula

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CO-CH,

added.

After a mixing time of 10 minutes, 20 parts of the solution prepared according to Example 5 are added. The mixture produced in this way is processed into paper.

The 2 # dyeing obtained has improved wet fastness and in particular improved alcohol fastness.

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Claims (1)

Claims 1 »'· Process for the preparation of solutions used as fixing aids are suitable for anionic dyes, characterized in that from the aqueous solutions, the condensation products (A) of polyalkylenepolyamines - 'and cyanamides or water-soluble salts of these condensation products contain, which excretes and separates water-insoluble components. 2. The method according to claim 1, characterized in that the water-insoluble constituents from solutions containing the condensation products of polyethylene-polyamines and dicyandiamide are separated out. ' 5. The method according to claim 2., Characterized in that the water-insoluble constituents from solutions which contain the condensation products of (a) diethylenetriamine, triethylenetetramine or tetraethylene pentamine and (b) dicyanamide are separated. h .. Aqueous solutions according to the method according to one of claims-1. until _3 - have been obtained. 5. Using the solutions as an aid to fixing anionic dyes on cellulose-containing fiber material, characterized in that they contain a maximum of 15 percent by weight (based on the total amount of condensation products (A)) of water-insoluble products. 109842/1825 . \ 6 / Use of the solutions according to claim 5, characterized in that that they have a dry matter content of 10 to 70 Jo, preferably 30 to 60 · <£, contain. 7t '-Use of the solutions according to claim 5 as an aid for fixing direct dyes on paper » 8. That using the solutions according to claim 7 stained paper. . · 1 0 9 8 A 2/1 8 2-S-