SU42887A1 - A method of making colored yarns and other regenerated cellulose articles - Google Patents

Description

Jfs 4166 describes the salts of the acid esters of leuco compounds. These are water soluble and persistent substances from which dyes can be easily obtained by oxidation in an acidic medium and which have already been proposed for dyeing (French Patent No. 571264, its additions, and others).

The subject of the present invention is a dyeing method, which makes it possible to directly regenerate regenerated cellulose in different forms (in the form of a ntk, film, tape, hair, etc.) based on the use of the mentioned esters.

As is well known, one method of making regenerated cellulose, for example rayon, known as viscose, is that cellulose is converted to soda cellulose xanthate, soluble in caustic soda, and cellulose treated with caustic soda and carbon disulfide. This solution, after adding the necessary substances to it, is passed through dies or other suitable equipment into a coagulating bath, i.e. into an acidic bath in which the fully or partially hydrated cellulose takes the form of filament, film, tape, etc.

Another method of making regenerated cellulose, for example, rayon, known as copper-ammonia, is that the cellulose is dissolved in an ammonia solution of copper oxide or copper hydroxide. The viscous mass thus obtained crosses through the spinnerets or through another suitable apparatus, semi (113)

The resulting product is coagulated in an acid or alkaline bath, in which cellulose, fully or partially hydrated, is regenerated.

The author has found that, in order to obtain colored yarns, films, tapes, etc., from regenerated cellulose can be added in any phase of the production process, for example, to aqueous alkaline solutions of the sodium salt of cellulose xanthate or solutions of copper-ammonium cellulose, solutions of salts of acid esters of leuco compounds of bottom dyes and, having moved the mixture well, produce staining of regenerated cellulose by oxidation in an acidic medium after or during coagulation. The dyeing process can be performed in various ways:

1. Cellulose solution (cellulose xanthate or copper-ammonia cellulose) contains the salt of the acid ester of the leuco compound of any cubic dye. Cellulose is regenerated in a coagulating bath and staining is produced by oxidation in an acidic medium, which is created in the second bath.

2. It is possible to combine the coagulation process with the staining process in one operation, adding an acid or an oxidizing agent to the coagulating bath. In this case, coagulation and staining occur simultaneously.

In the case of copper-ammonium cellulose, the conditions necessary for dyeing with coagulation simultaneously are already combined when using an acidic coagulating bath. At the time of coagulation, i.e.

Copper-ammonia cellulose in more or less hydrated cellulose forms a copper salt, for example, sulfuric acid, acting in an excess of acid as an oxidizing agent and giving staining (see French Patent No. 571264).

3. To solutions of cellulose (cellulose xanthate or copper-ammonium cellulose) is added not only the salt of the acid ester of leuco compounds. but also a suitable oxidizing reagent, which is not effective in alkaline conditions, but becomes effective in an acidic environment, for example, sodium nitrite. In this case, staining occurs in the coagulating bath simultaneously with coagulation.

In a similar way, instead of salts of acid esters of leuco compounds of bottoms dyes, salts of esters of any other substances, which give dyes during oxidation, can be used.

It is also possible to use, for example, the salt of the ether described in French patent no. 726168. This salt is also easily soluble in the oxidation in chi. a layer of the medium gives N-dihydroanthraquinone-azine (indanthrene).

French Patent No. 689583 describes salts of enol ethers, easily soluble, obtained from azo compounds of anthraquinone and easily converted into the latter by oxidation in an acidic medium. These substances can also be used for coloring according to the invention.

The salts of the esters mentioned here, and many others, can be applied according to the invention for the production of colored cellulosic products. The yarns, ribbons, etc., thus obtained, of the regenerated cellulose are then subjected to all finishing operations.

Already, it was proposed to obtain cellulosic products in a colored form by adding dyes to the viscose mass. However, all these methods are not practical. Dyes are not able to withstand a high content of scabs in the viscose mass, or the treatment (sometimes at elevated temperatures) in a coagulating bath with a high content of acid. The same applies to copper-ammonia cellulose. The release during the coagulation of this mass in the acid bath of the copper salt and its oxidizing effect, the use in some cases of a strongly alkaline coagulating bath (sometimes at elevated temperatures) can adversely affect most dyes. However, most of the dyestuff dyes do not have the strength of modern vat dyes.

On the other hand, the introduction of vat dyes in the form of their leuco compounds into the viscose mass is associated with many inconveniences. The premature oxidation of the leucos compounds of vat dyes in the alkaline mass of viscose can be very harmful. On the other hand, an excess of a reducing agent, such as hydrosulfite, aimed at eliminating premature oxidation, may cause unexpected effects during coagulation.

effects that can slow down the normal course of the process.

The present invention eliminates all of these tools. Salts of esters withstand the treatment with strong alkalis, acids, etc., and the resulting products, painted with vat dyes, retain their shades with the strength that distinguishes vat dyes.

The proposed method also makes it possible to obtain special splicing effects. When spinning artificial silk, usually several thin threads are collected into one thicker one. These different threads can be dyed with different dyes from different salts of the esters. Dyed yarns can also be combined with uncut ones. In this way, you can create various effects.

Since the salts are dissolved in water, by more or less prolonged treatment, the salts of the esters contained in it can be easily removed from the pulp material. With further processing, curious effects are obtained: for example, cellulose appears to be more intensely colored in the middle than from the surface, or even not colored at all from the surface, but only inside. Such effects cannot be obtained by conventional means.

All salts of the esters from the cellulose containing them can be completely removed by appropriate washing. Other effects can be obtained, a combination of the proposed method and other methods used for impregnation, preservation, etc., and used for salts of leachate esters of vat dyes or other substances, provided that the colored material can be regenerated with acidification in an acidic medium.

It is also possible to obtain interesting effects on the fabric by coating it in a certain way with a solution of copper-ammonium cellulose or further with a solution of cellulose xanthate containing the main salt of the ether, causing it to coagulate in a pattern and show coloring by oxidation in an acidic medium. Thus, on the fabric get painted reliefs of perfectly uniform nuances, with the strength of vat dyes.

Example 1. To obtain a completely homogeneous mass, a certain amount of sodium salt of cellulose xanthate, corresponding to 1 kg of dried viscose yarn or yarn, is mixed with a solution containing some amount of leuco indigo ether, corresponding to 20 g of indigo. This mass is passed through the spinnerets into a coagulating bath containing 18 ° Ve sulfuric acid at a temperature of 40-50 °. The viscose yarns thus obtained are dried and processed in the course of V4-Vs minutes with an ordinary TeMnepaTj pe in a bath containing 35 g of sulfuric acid 66 ° We and 4 g of crystalline sodium nitrite in 1 liter of water. Thus staining is performed. The dyed fiber is rinsed, treated in an alkaline bath, rinsed again and dried.

Example 2. To the viscose mass was added, as in Example 1, a solution of the ester salt of leukosomal compound 6: 6, lithoxythioindigo. The mass is passed through spinnerets into vanilla containing 18 ° Be sulfuric acid and 4 g of crystalline sodium nitrite and heated to 40 °. At the same time, viscose is coagulated and orange colored. The fiber is washed, treated in an alkaline bath, rinsed and separated.

Example 3. To the mass of viscose, a solution of a leucoinligo ester salt was added, as in Example 1. The mass is caused to coagulate to form a thick filament or ball. By vigorous washing with water, all the salts of the ether are removed to a known depth, which can be preset on the samples. Subsequent treatment in an acidic oxidizing bath gives the internal color of the mass under an unpainted and transparent outer layer.

Example 4. 1 g of the leucodimethoxydibenzontron (powder) ester salt is dissolved in 50 ml of warm veda with the addition of 20 cm of 25% ammonia, 20 c.tfl of this solution is mixed with 20 cm of a thick solution of copper-ammonium cellulose. The mixture is passed through filters, and the threads coagulate in a 40% sulphate bath at 30 °. During this operation, the ammonium copper cellulose disintegrates to form hydrated cellulose and copper salt, which in an excess of acid acts as an oxidizing agent to the compound. The fiber is then subjected to conventional finishing operations. In this case, coagulation and staining occur simultaneously,

EXAMPLE 5 1 g of the salt of leucodirenine pyrenequinone ester ether is dissolved in 50 drops of warm water. After cooling, 20 cm of 25% ammonia was added to this solution. 20 cm of this solution is mixed into a 20 cm thick solution of copper-ammonium cellulose. The well-stirred mass is passed, as usual, through dies, and the filaments are coagulated at a temperature of 40 ° in a bath containing 40% caustic soda and sometimes some sugar, glucose, glycerol, and similar impurities. The coagulating bath does not clog with this treatment. Then the fiber is washed well with water and treated in an acid bath containing, for example, 20 g of sulfuric acid 60 ° Be per 1 liter. Coloring is completed either by treatment in a bath containing, for example, 36 g of sulfuric acid 66 ° Be, 3 g of crystalline sodium nitrite and 10 g of ammonium vanadate solution (1/1000) ha 1 l of water at a temperature of 20-40 °, or by treatment in a bath containing 0.5 g of sodium or cadium dichromate, 36 g of sulfuric acid 66 ° Be, 20 g of ammonium vanadate (1/1000) and 2 g of oxalic acid per 1 / g of water.

Example 6. The 5th paste containing 18% of the salt of the enryl ester of leuco-compound 3, 8-dichloro-1: 2: 2: 1 - Dianthraquinone-azine (French patent No. 726168) is dissolved by S ZO l viscose mass, mass, as usual , are passed through spinnerets, and the filaments are coagulated. During coagulation, the filaments are stained red-violet. Then complete the staining, skipping

fiber through a bath containing a weak solution of sodium bichromate or sodium nitrate.

a) When dyed in a bichromatic bath, the composition of the WENMA may be as follows: 0; 5 g of sodium bichromate

36 g of sulfuric acid 66 ° Be

20 g ammonium vanadate (1; 1000) 2 g crystalline oxalic acid

on 1 l of water.

The threads are treated in a bath for one minute at 35-40 °. The coloration unfolds completely; a vibrant blue color is obtained.

The dye can sometimes be slightly over-oxidized, which acts in a known manner on the nuance. However, this over-oxidation is eliminated by the latest operations necessary for the finishing of the product, for example, desulfurization, which can be carried out in a bath, which also has the properties of a weak rejuvenate. a fresh and bright blue hue is thus obtained.

In this example, the leucosilane 33-dichloro 1: 2: 2 salt of dianthraquinonazine can be replaced with the 1: 2: 2: 1 ester salt of dianthraquinone azine, and the strands of cel ... ose will get a shade of indanthrene.

Example 7. 2 kg of the salt of S-aminoanthraquinone ester is dissolved in 5 liters of warm water. This solution is mixed with 30 liters of viscose mass. A well-mixed mass is passed through the dies and allowed to coagulate.

a) When dyeing with copper sulfate, the threads are treated for 25 seconds at 95 in the next bath:

40 g of crystalline blue vitriol 200 g of table salt 24 g of hydrochloric acid with a strength of 19 ° Be. The product is washed and then treated in the cold in a weak reducing solution, for example, 1 g of hydrosulfite, sodium (in powder) and 2-3 cm of sodium hydroxide 38 ° le for 1 -. Washed again, washed and separated.

b) When dyed with dichromate, the threads are treated for 20 seconds at 60 ° in the following bath:

0.5 g of sodium bichromate S6 g of sulfuric acid 60 ° Be 20 g of ammonium vanadate solution (1/1000) 2 g of oxalic acid

on 1 l. Further processing is carried out in a recovery bath according to paragraph a.

c) Ferric chloride staining is performed for 1 minute at 40 ° in the next bath;

15 2 crystalline ferric chloride

18 g of hydrochloric acid 19 ° Be per 1 liter of water. Then, the treatment is carried out in a recovery bath, as described in paragraph a.

In all cases, intense blue pulp is obtained.

Instead of the reduced ester salt of amyoanthraquinone, n |) salts of the esters of E-aminoanthraquinone derivatives, such as 2-amino-3-chloroanthraquinone, which give the same effect, can also be mentioned.

Example 8. 2 cl liquid paste from ester azoprodukt from diazotized 2-amino-3-chloroanthrahydroquinone and anilide

A: 8-hydroxynaphthoic acid containing 5.6% of the dye is dissolved in 30 liters of viscose mass. The solution has a violet-brown color. The filaments are obtained in the usual way and are coagulated. In this phase of production, the product has a deep blue tone. The final color is obtained later on after a 30-second treatment at 70 ° in a bath containing 30 cm of a 30% solution of sodium nitrite and 20 cm of sulfuric acid 66 ° We. The product is washed and finished. The viscose is bright red.

Similarly, cellulose yarns dyed with salts of esters of other azo compounds of anthraquinone, for example, diazotized p-aminoanthraquinone with; 3-naphthol or with various anilides (-oxynaphthoic acid, can be obtained.

Example 9. To 30 l of finished viscose mass is added:

300 cm solution of 1/1000 ammonium vanadate

600 cm aluminum chlorate 25 ° In

5 g salt of acid ester of leuco-dimethoxydibenzontron.

The whole mixture is well mixed and passed through dies in the usual way. The filaments are coagulated in an acid bath.

Leaving the material to lie for some time in the chambers at normal temperature, it is allowed to develop a green tone. This extremely simple staining ends in approximately two hours.

After that, the thread is subjected to a conventional, final finish.

Instead of aluminum chlorate, it is also possible to use a solution containing soluble chlorate, for example, sodium chlorate, and soluble aluminum salt, sodium, aluminum sulphate.

The subject of the patent. The method of obtaining dyed yarns and other products from regenerated cellulose by introducing coloring substances into solutions of cellulose or its derivatives .. serving for the manufacture of these products, is distinguished by the fact that in a solution of cellulose xanthate or in a copper-ammonium cellulose solution intended for artificial silk yarns for the manufacture of other products from regenerated cellulose, salts of the acid esters of vat dye leuco compounds (for example, the so-called indigozols or solazols) are introduced or compounds which, upon oxidation, are capable of forming insoluble dyes, for example, the 3-amino-anhydroxyquinone acid sulphate salt, then form a thread of artificial silk or another product by coagulation by conventional means, combined with or accompanied by acidification in an acidic medium to form an insoluble dye in the mass of the resulting product.