DE933144C - Process for dyeing or printing cellulose-containing materials and dye preparations suitable for its implementation - Google Patents

Description

Process for dyeing or printing cellulosic materials and dye preparations suitable for carrying it out. It has been found that cellulosic materials can be dyed or printed in a valuable way, if you use neutral to alkaline dye baths or printing pastes which contain direct dyes, in which one of the metals from atomic numbers 27 to 29 complex to at least one o-Oxy-o'-carboxyazogrupp.ierung is bound, aliphatic a-aminocarboxylic acids and Phosphorus-containing anions, which differ from phosphoric acids with the composition Hm + 2Pm03m + 1 derive, in which m is an integer with a value of at least 2, contain. The dye baths can either be used directly in the concentration required for dyeing or advantageously by diluting so-called stock solutions, which of the above Composition correspond, however, the substances mentioned in higher, for the immediate Use to contain too strong a concentration. For the printing pastes In any case, solutions with high concentrations of dye are required.

The dyes to be used according to the invention are direct dyes which contain one of the metals with the atomic numbers 27 to 29, i.e. cobalt or in particular nickel or copper, especially the latter, in a complex bond to at least one o-oxy- o'-carboxyazo group. Direct dyes of this type are to be understood as meaning exclusively those which are inherently so readily water-soluble that they can be used in dyebaths of the usual concentration without additives to increase solubility. Experience has shown that this is the case with a solubility of at least around ro g of dye in hot water.

The dyes also contain at least one o-oxy-o'-carboxyazo group bonded in a complex manner to one of the metals mentioned. These complex atom groupings are here partly defined by the formulas shown, in which the complex-bonded metal atom present, namely Co, Ni or Cu, is used for Me. The formulas undoubtedly give the correct stoichiometric amounts of metal and the correct position of the metal atoms in the complex, but the distribution of major and minor valences in the complex bond between the metals and the dye is not yet clearly established.

There are mainly dyes with at least two azo groups into consideration. The azo groups of a dye can be completely or partially present as metallized o-oxy-o'-carboxyazo groups. Furthermore, the Dyes also have other metal complex-forming groups than those mentioned, e.g. B. o, ö -dioxyazo groups or salicyl groups, the former preferably also in the form of heavy metal complexes and the latter is expedient do not exist as metal complexes.

It is also useful if those present in the dyes ionic acidic groups, d. H. especially the sulfonic acid and carboxylic acid groups (if the latter are not in the form of the o-oxy-o'-carboxyazo metal complexes), are present as alkali metal salts.

As aliphatic a-aminocarboxylic acids in the present process preferably the simply built and easily accessible acids, such as. B. a-aminopropionic acid (Alanine), methylaminoacetic acid (sarcosine), ß-oxyethylaminoacetic acid and especially aminoacetic acid (Gly'kokoll) is used.

In addition to the dye and the α-aminocarboxylic acid, the dyebaths also contain phosphorus anions which are derived from phosphoric acids with the composition Hm + 2Pm03rn + 1, where my whole number is at least 2. For example, alkali salts of the polyphosphoric acids H, P4 O13 or H5 P3 01o, but in particular of pyrophosphoric acid (H4 P2 07), are suitable.

With regard to the quantitative ratio of the substances described above, which are present in the solutions or printing pastes or are used for their production the following should be noted: Of the a-aminocarboxylic acids, z-, vecklike about one tenth to half the amount of dye (as: such, i.e. without substantial amounts of salts such as sodium sulfate or other diluents calculated). More than this amount of α-aminocarboxylic acids can be found in some Cases tend to have a detrimental effect. The amount of phosphati'onen is advantageous one-fifth to double the amount of dye. Deliver good results in the in most cases approximately equal amounts of dye and crystallized tetraalkali pyrophosphate, while even larger excesses of phosphorus-containing anions generally do not . have an adverse effect.

The order in which the necessary substances are added to the water Preparation of the stock solutions and dyebaths is quite arbitrary and usually has no influence on the result. On the other hand, the result is good often worsened when making higher concentration solutions In addition to the substances mentioned, other electrolytes were added in significant quantities and it is therefore advantageous to avoid such an addition. For this reason it is also generally indicated that the metal-containing dyes are not in one Form adjusted to a certain strength by means of sodium sulfate or sodium chloride to be used, but in the form in which they are usually used during manufacture are deposited and in which they no longer contain such quantities of these salts, that an adverse effect occurs. This adverse effect is essentially the same in a disruption of the solution process, which although in greater dilution, z. B. at the concentration usually found in dyebaths, hardly any entry, at high concentration, as in the stock solutions, especially for printing pastes or is partly required for the apparatus dyeing, can lead to the Dyes cannot be completely dissolved. _ The according to this procedure too The dye baths or printing pastes used must be neutral or preferably alkaline react. If the alkaline reaction does not readily occur -z. B. by -the Presence of tetrasodium pyrophosphate - if it occurs, it can be prevented by adding suitable, alkaline-reacting substances such as alkali hydroxides, trisodium orthophosphate, ammonia or ethanolamine. For the reasons given above, however, it is in some cases less advisable, for this purpose alkali carbonates or -Bicarbonate to use. Instead of the dye baths, stock solutions or printing pastes in such a way that one has the substances required for this Solving individually and one after the other in water, it is generally advisable to use the relevant To process substances into dry preparations.

Valuable preparations are z. B. those that have direct dyes of the composition described above and aliphatic a-aminocarboxylic acids or contain alkali metal phosphates of the type specified. These preparations can be used to manufacture the stock solutions, dyebaths and printing pastes are used, -which one is still used for the solution the compounds -which contain the phosphorus-containing anions, or the a-aminocarboxylic acids clogs.

As a rule, however, it is advisable to produce such preparations which apart from the direct dyes and the aliphatic a-aminocarboxylic acids too even the phosphorus anions, z. B. in the form of the alkali salts of the relevant Phosphoric acid.

If the preparations are to be adjusted to a certain color strength, it is recommended z. B., for this purpose the amount of alkali pyro- or polyphosphate to choose larger or smaller or non-electrolytes, such as urea, od, e.r water-soluble Mix in carbohydrates such as sucrose or dextrin. As already indicated, The commonly used diluents, such as sodium sulfate, can sometimes be used have an adverse effect. However, this only applies to some of the Considerable dyes to the extent that such additives are favorable Reduce the effect of the z-aminocarboxylic acid and the phosphorus compounds to a large extent would.

The dyeing is carried out with the solutions to be used according to the invention otherwise according to known, customary for substantive dyes Methods. Likewise, the printing pastes are also useful with the known, for Direct dyes suitable thickeners prepared in the usual way and used.

The present procedure makes it possible in those cases where this eligible dyes are more common for the preparation of stock solutions Concentration and coloring from diluted bath still sufficient in itself for production of stock solutions of higher concentrations, such as those for printing pastes as well as for the Apparatus dyeing are required, but are too insoluble, the solubility to increase so much that the products concerned are usually without difficulty can also be used for these purposes. Furthermore, according to the present method in some cases stronger and purer color tones achieved. In addition, the α-aminocarboxylic acids together with the phosphates, that some of the dyes are considerably faster and deeper penetrate the cellulose fiber, which is advantageous in various ways, so z. B. in that the production is particularly uniform or particularly strong and yet non-bronzing colorations are made possible, and this can be done within can be achieved in a relatively short time. It also shows that the procedure with continuous staining, e.g. B. when dyeing on a foulard, particularly good Provides service. Finally, in some cases the winding speed of the Dyes from dyebaths according to the present invention through the addition of fractionated salt better controlled than from dyebaths without the additives mentioned.

In certain cases it will be desirable to use this procedure available dyeings or prints still to be treated with agents that increase their wet fastness properties. Suitable products for this purpose can be mentioned are: the impact of formaldehyde on compounds such as cyanamide, Dicyandiamide, dicyandiamidine, melamine. There are also such aftertreatment agents into consideration, in the manufacture of which no formaldehyde is used, as well as with copper salts combined aftertreatment agents, especially those with those dyes produced colorations and prints are further improved, which are still free metallizable Have groups.

In the following examples, unless otherwise stated, parts are parts by weight and percentages are percentages by weight. Example i io parts of the dye of the formula are mixed with i part glycocoif and 9 parts crystallized sodium pyrophosphate. This mixture is dissolved in 100 parts of water by boiling.

0 parts of this stock solution are added to a dye bath of 2880 parts Water at 60 ° was added and another 30 parts of crystallized sodium sulfate were added.

100 parts of cotton are taken into this bath and this is increased Temperature in 1 / s hour on go up to g5 °. It is kept at this temperature for 1 hour and after rinsing and drying it takes on a yellowish brown color, which is purer and is stronger than one with the same amount of dye, but without glycocolla and sodium phosphate phosphate produced dye, wherein the dye to dissolve a much larger amount of water is required.

Even though the bath reacts alkaline, acetate silk effects remain pure white reserved, while in the - comparative bath, which by adding: sodium carbonate has been adjusted to the same pH value and contains neither glycocoll nor pyrophosphate, the acetate silk effects are soiled.

Wool effects are dyed in the same shade, while in the comparative bathroom -the portion of the dye that is absorbed by the wool is destroyed and wool effects colored dirty gray.

If you carry out the same staining as described above, but with the difference is that instead of 30 parts, crystallized sodium sulphate uses 120 parts the bath is practically completely drawn out, and a color is obtained which is significantly stronger than the comparison coloration without glycocolla and pyrophosphate. Without these additives, the dye cannot be completely exhausted if 6o or more parts of crystallized sodium sulfate in the dyebath are present begins to flocculate and the precipitated dye for coloring is lost. The difference in the purity of the shade is still in this case more important than the above dyeing with only 30 parts of sodium sulphate.

If the stated amount is increased from 2o parts of stock solution to q.o or 80 parts and otherwise colors as described, so in these cases too there is a the increase in color strength and considerably surpassing the comparison color of purity observed. The comparison color cannot be matched with a larger amount of salt be helped, the tendency for these higher dye concentrations of the dye to flocculate is much more pronounced. With glycocolla and pyrophosphate The product containing it, on the other hand, can also have a much stronger color here can be increased even more by adding more electrolytes.

Examples of 10 parts of the concentrated dye of the formula are marked with i, 5. Parts of glycocolla and 2 parts of crystallized sodium pyrophosphate are mixed. The mixture is soluble in 250 parts of boiling water, whereas without glycol, 1000 parts of water are required despite the presence of the pyrophosphate.

Dyesman; as in example i'described, 100 parts cotton or Viscose rayon with 3 parts of the mixture of dye, glycol and sodium pyrophosphate, so you get a clear yellow with extraordinary lightfastness and good waterfastness.

Will the rinsing bath. 1 ig each of a condensation product of formaldehyde and dicyandiamide added, so the coloration also shows very good fastness against Soap / soda cream on.

The dyeing has the same fastness properties as one without glycocall and phosphate produced comparative coloration, but surpasses this in purity of the Hues. It is easily possible with this dye, too to achieve very strong yellow tones on dyeing machines with a very short liquor ratio, which is not possible without glycocolla and pyrophosphate due to a lack of solubility is. For example, io parts of the with glycocolland and sodium pyrophosphate (see above) mixed dye dissolved in 40o parts of boiling water and in a Dye jigger to zoo parts poured water. To. Addition of 10 parts of crystallized Sodium sulfate goes into zoo parts of cotton, the temperature drives in 1/2 Hour to boil and stain i hour at this temperature. You get an extremely strong yellow from very good real books. For this staining method is the dye in itself, d. H. without glycocolla and pyrophosphate, not applicable at all, since he to dissolve it alone requires 1,000 parts of water and no addition of sodium sulfate tolerates without flaking.

If the nickel complex of the abovementioned dye is used instead of the copper complex, the improvement is even more pronounced, and even purer, yellow colorations with excellent fastness properties result. Example 3 10 parts of the dye of the formula are mixed with 1 part Glykokdll and 9 parts crystallized sodium pyrophosphate. This mixture dissolves clearly in 100 parts of water, while the dye mixed with 10 parts of crystallized sodium sulfate requires ten times the amount of water.

While the mixture with glycocolla and sodium pyrophosphate gives a pure yellowish brown, the dye mixed with sodium sulfate only gives a more cloudy, reddish brown. Example 4 10 parts of the dye of the formula are mixed with 1 part glycocolla and 9 parts crystallized sodium pyrophosphate, and the mixture is dissolved in zoo parts boiling water. One dilutes to 800 parts with water and padded a cellulose tissue with d'I'eser solution; it is then developed for 10 minutes in a boiling bath, each containing 150 g of sodium chloride. A strong, reddish brown with excellent color penetration is obtained. This procedure, which is particularly favorable for dyeing pimples through, can only be used for lighter shades without glycolcoll and pyrophosphate, since a corresponding amount of the dye made with sodium sulfate dissolves only in 1,000 parts of water at boiling temperature. In addition, this temperature can hardly be maintained during padding. Example 5 parts of the dye of the formula which should contain only a little salt, are mixed with 1 part sarcosine and 9 parts crystallized sodium pyrophosphate and dissolved in 3-0o parts boiling water (without the addition of sarcosine, 1000 parts of water are required). If the sarcosine is replaced by equal parts of alanine (α-aminopropionic acid), a preparation of similarly good solubility is obtained.

This mixture is used to dye vegetable matter as described in Example i Fibers, yellow dyeings of very good light and water fastness are obtained compared to the colorations of the just 'mixed with crystallized' sodium sulfate Dye of much greater purity.

After treatment in the rinsing bath for 10 minutes with: 2 g each 1 of a product consisting of 25 parts of copper acetate and 75 parts of a condensation product from 1 mole of dicyandiamide and 2.2 moles of formaldehyde, even greener colorations are obtained, which are significantly better when it comes to washing fastness.

If the tetrasodium pyrophosphate is replaced in the above-mentioned mixture by equal parts of hexasodium tetrapolyphosphate, one obtains similar; good results.

Example 6 15 parts of the dye mentioned in Example 13 are used with 2 parts of glycocolla, 13 parts of crystallized tetrasodium pyrophosphate and 150 parts of urea mixed and dissolved by boiling with 395 parts of water. This solution is poured with stirring. in 500 parts neutral tragacanth thickening, which has a content of 30 parts of dry matter, and still sets 5 parts of m-nitrobenzenesulfonic acid-s Sodium too.

This printing ink is used to print a cotton, a. Cellulose and a viscose fabric.

The prints are dried and then steamed for ¢ 5 minutes. Then; is rinsed thoroughly in cold water and dried. Yellow-brown, uniform prints of very good light and water fastness are obtained on all three fabrics. If you add 3 9 1 of a product to the rinsing bath. from 20 parts of sodium copper tartrate and 80 parts of a condensation product of dicyandiamide and formaldehyde, dissolved with half the amount of ammonia, and treated for 10 minutes, the prints also have good washfastness. Example 7 2o parts of the dye mentioned in Example 2 are given q. Parts of glycocolla and 8 parts of crystallized tetrasodium pyrophosphate mixed. Muri adds i so parts of urea and dissolves the whole thing in 295 parts of boiling water. This solution is stirred into 500 parts of neutral tragacanth thickener (containing 30 parts of dry substance) and another 20 parts of crystallized tetrasodium pyrophosphate and 5 parts of sodium m-nitrobenzenesulfonate are added.

A viscose fabric is printed, dried and steamed for 10 minutes and gets a good, regular, yellow print.

Claims (5)

PATENT CLAIMS: i. Process for dyeing or printing cellulosic materials, characterized in that neutral to alkaline dye baths or printing pastes are used, which direct dyes, in which one. of metals with atomic numbers 27 to 29 is complexly bonded to at least one o-oxy-o = carboxyazo group, aliphatic a-aminocarboxylic acids and phosphorus-containing anions, which are derived from phosphoric acids of the composition Hm + 2Pm03m + 1, where m is an integer of at least 2 means included. 2. The method according to claim i, characterized in that the dye baths or printing pastes anions of pyrophosphoric acid contain. 3. The method according to claim i or 2, characterized in that the Dye baths or printing pastes contain amino acetic acid. 4. Procedure according to one of claims i to 3, characterized in that the dye baths or Printing pastes contain complex copper compounds of the specified type. 5. For dyeing or printing cellulosic materials suitable neutral to alkaline solutions or printing pastes, which direct dyes in which one of the metals from atomic numbers a7 to 29 is complexed to at least one o-oxy-o'-carboxyazo group, aliphatic a-aminocarboxylic acids and: phosphorus-containing anions, which are derived from phosphoric acids of the composition Hm + 2 PM Ognc + 1 , preferably in the form of the alkali salts of the formula alkali, + 2 P "03" + 1, where m is an integer equal to at least a, contain. Cited publications: German Patent No. 684494; French patent specification No. 775 69o.