DE740909C - Process for coloring artificial structures made of chloroform-soluble cellulose acetate - Google Patents

Description

Process for dyeing artificial structures made from chloroform-soluble Cellulose acetate fibers, tapes, films and the like Experience has shown that cellulose acetate can also be used with dyes, which in themselves lead to Dyeing of cellulose acetate are suitable, dye poorly. The same goes for in the event that such structures can also be used for other classes of dyestuff due to special treatment have been made dyeable, e.g. B. for animalized structures made with acidic wool dyes to be colored. This is poor or even lacking in colorability presumably due to the fact that the mentioned cellulose derivatives have a peculiar, have little hydrophilic, keratinized surface that is practically pore-free and hence the penetration of the mostly high molecular weight dyes into the interior of the structures not allowed.

It is now known that dyeing of acetate silk d. H. of structures made from acetone-soluble cellulose acetates, thereby facilitating that one - the dye baths or - printing pastes add swelling agents. Artificial Buildings made of chloroform-soluble gellulose acetate can be stained if you use them subject to a very strong swelling and to color it in the swollen state brings. In order to achieve this success, the swelling must be carried out with strong swelling agents, for example: e q.0% acetic acid, if necessary at higher temperatures, for example temperatures above 5o °, are carried out, conditions under which the usual acetate rayon completely dissolved or already largely destroyed will. Surprisingly, the properties of the chloroform-soluble structures suffer Gelulose acetate, e.g. B. strength, elongation and the like., In such a treatment practically not.

After the treatment with the swelling agent, the structures can be used directly in depths and full shades with good fastness properties. In particular, it is then also possible to create structures which an animalizing agent incorporates -has been dyed with acidic wool dyes.

The structures can also be completely washed with water before dyeing be freed from the swelling agent without the dyeability noticeably suffering. Will but structures treated in this way are dried so. that they can no longer be dyed well.

However, ways have been found, the dyeability of the structures too to be preserved after drying. If one treats namely highly swollen structures, -which can be freed from the swelling agent by washing, with a swelling fixer Medium, so they remain easy to dye even after drying. As such, the swelling Fixing agents come into consideration, for example, solutions of organic salts or inorganic acids and / or wetting agents free of sulfonic acid groups. By this treatment is evidently the state of swelling responsible for the good dyeability more or less stabilized. Wash before dyeing or during dyeing the fixing means out of the formations again, they ground through them Dyes deeply stained. If the dyeings obtained in this way are dried, they swell out the structures are irreversible, the dyes are firmly bound in the structures and therefore show excellent fastness properties. Such colorations on animalized material are, for example, in all cases significantly more true than corresponding colors on wool. So has z. B. a dye made according to the invention with amido yellow E the flexing fastness q. to 5 (standards of the German Authenticity Commission), while a corresponding coloring to '' great only has the authenticity i to 2. The same thing applies to a number of dyes whose coloration on wool is poor or have moderate wash and fulling fastness properties.

As already mentioned several times, the method according to the invention is from of particular importance for the dyeing of animalized structures made of chloroform-soluble Oellulose acetate, d. H. Forms, which -during their production, for example by adding to the spinning solution, a basic compound has been incorporated and which therefore have an affinity for acidic wool dyes. It succeeds after Procedure according to the invention, for example, fibers made from chloroform-soluble cellulose acetate manufacture that can be used both alone and together with wool in the same tones can be dyed with acidic wool dyes. One spins z. B. Triacetcicellulose Fibers with the addition of a resinous body containing nitrogen, treated so obtained fibers with a swelling agent and a swelling-fixing center according to of the invention and dyes with acidic wool dyes. This fiber is on it interwoven or forfeited with wool; the finished blended fabric or knitted fabric can then be dyed with acidic wool dyes in the same shades. Of course two-color effects can also be achieved in this way. You can also do that animalized acetyl cellulose fibers together with wool, e.g. B. to tops, yarns. Process woven or knitted fabrics and apply a swelling agent to them before dyeing treat that does not attack the wool. This mixed product can be mixed with acidic Dye wool dyes the same shade. As mentioned above, they surpass the Synthetic fibers produced dyeings, the dyeings on wool -wide on washing and Flexing fastness.

Of course, the process can also be applied analogously to printed articles Find application. You can z. B. a fabric made of Ce11ulosetriacetatfaschen or animalized Print Ccllulose triacetate fibers in places with a swelling agent of the type mentioned and then staining with a suitable dye with intermediate treatment with a the means to fix the position. Colored patterns on -veil_ @ em Reason or vice versa. Example i From chloroform-soluble cellulose acetate (Acetic acid content: 59 to 61t! `` Fiber produced using your wet spinning process is continuously passed through a bath which contains 600,000 acetic acid. The fiber swells very strongly. The fiber bundle is then washed with Deacidified water, cut into stacks and then divided into io parts of a bath of io% Bring table salt. After the swollen fibers have been treated in a salt bath for 5 to 10 minutes is spun off and dried. After a short wash, gelatin dyes, z. B. Cellitonechtblati B (S c h u 1 t z, color tables, i. Erg.-Volume, 1934, S.; 5), colored as usual. The colors show in contrast to the starting material deep and rich tones. The same material, dried after swelling without salt treatment, only takes on a very faint coloring.

Instead of table salt you can also use iobis 300, the above solutions from someone else inorganic or organic salt can be applied. As salts, for example -be used, so -of their solubility admits the chlorides, Bromides, iodides, sulfates, nitrates, borates, phosphates, sulfites, thiosulfates, rhodanides of the alkalis and alkaline earths, furthermore the alkali and alkaline earth salts of the lower ones Fatty acids and mixtures of the salts mentioned.

The salt baths can be used to improve the grip of the fibers in ' known white preparation and softening agents are added.

EXAMPLE 2 The procedure is as in Example 1, but instead of the common salt bath, a solution of 5 g per liter of a wetting agent or emulsifying agent which is free of acid groups is used to stabilize the swelling; z. B. the action products of reactive tertiary amines on substituted succinic, acid anhydrides according to patent 726 670 or of reaction products of oleyl alcohol or castor oil with an excess of ethylene oxide.

Example 3 Fibers swollen according to example i are treated with a bath, which contains 5% sodium chloride and 0.1% of a sulfo group-free wetting agent, after-treated. The results obtained correspond to those described in Examples 1 and 2.

EXAMPLE 4 A celluloseaoetate artificial silk with 590.70 acetic acid content obtained by the dry spinning process is treated in strand form for 30 seconds at 30 ° in 50% acetic acid and aftertreated as in Example 3. The washed-out silk is stained deep black with Gellitonechtsch`varz BTN (Schultz, Farbstofftabellen, i. Erg: Band, 1934 p. 75), while 'untreated silk produces a dirty brownish black.

Example 5 'To a crude solution of cellulose triacetate is added, as described in French patent 83o 8oo, 5 to 15010 (calculated on cellulose acetate) of a reaction product of starch benzenesulfonate with an amine and spun into fibers. Despite the presence of the nitrogenous bodies, these fibers are only stained in traces with acidic wool dyes. The fibers are now drawn continuously through a bath of 600% acetic acid at 20 ° 20 to 30 seconds, washed out and treated according to Example 1 with a 20% saline solution. After drying, the fibers are dyed with Amidogelb E (Schultz, Farbstofftahelllen, Volume I, 1934 No. 16). The deep coloration obtained shows remarkable authenticity. She has z. B. the mill fastness 4 to 5 (standards of the German Authenticity Commission z935), while a corresponding dyeing on wool only has the mill fastness i to 2. A number of other acidic wool dyes behave in the same way, e.g. B. Quinoline Yellow (Schu1 tz, Dye Tables, Volume I, 293i, No. gi8), Brillantcrocein B (Schultz; Dye Tables, i. Erg.-Volume, 1934, No. 539), Alizarinrubinol R (Schultz, Dye Tables , Volume I, 1931, No. 1210), woolly violet B (Schultz, Dye tables, Volume I, 1931, No. # Dye tables, 974), Alizarindirektblau Volume II, 1932, A (Schultz, p.9), Azos.äureschwarz 3 BL extra (Schultz, Farbstofftabellien, r: Erg.-Band, 1934, p. 70) and others. Example 6 With an animalizing agent, e.g. B. a reaction product of hard chlorinated paraffin with ethylenediamine mixed crude solution of cellulose triacetate in glacial acetic acid is spun after the wet spinning process; the fibers obtained are swollen in 60% acetic acid at 60 ° for 15 seconds, washed with water and in a salt bath (containing 5% sodium acetate, 2% ammonium thiocyanate, 2% of a common preparation agent and 0.5% isododecenylsuccinic acid diethylaminomethyl ester) for 5 minutes treated (liquor ratio i: 2o). The hurled and dried fiber is colored perfectly with acidic wool dyes.

Example 7 Produced according to Example 5 with the addition of an animalizing agent Triacetate fiber is swollen for 30 seconds at 10 ° in 650 ° acetic acid, which is about 20o of a chromium compound, e.g. B. sodium dichromate or chromium acetate, and optionally a reducing agent such as formaldehyde or glucose is added in amounts of 1% is. The fiber bath is deacidified and cut into stacks. The ones in a salt bath (containing 8% sodium acetate, 1% of a sulfonic acid group-free wetting agent and 2% of a customary preparation agent, calculated on the liquor) of aftertreated fibers are dried and processed with wool into a yarn or fabric. The mixed goods is colored with acidic wool dyes in uniform tones. Particularly suitable are chromium enh @ 2cklungs-, Nachchromierungs- or Metachrome dyes.-The colorations on the artificial fibers - not only achieve the same wash, flex and perspiration fastness, rather, the dyeings produced on pure wool also relate to lightfastness equal.-, Example 8 Triacetate rayon is woven which contains an animalizing agent, with wool in the ratio i: i. The tissue is in a bath, containing 6o% acetic acid and 2 o'o glucose, treated for 15 seconds at 2o °, off, spun, washed and with a salt; bathe analogously to Example 7 in the liquor ratio 1:15 post-treated, dried and can then be treated with anthralan blue B (Schultz, color tables, i. Erg.-Band ', 1934, p.68). Uniform colorations are obtained both types of fiber. Especially: real colorations can be achieved through use of salts of the acidic leuco-sulfuric acid esters of vat dyes, which also dye both types of fiber in the same shade and with the same fastness properties.

Example 9 A fiber produced according to Example 17 is dyed with a water-insoluble dispersing dye, e.g. B. a cellitone-fast dye. By the presence of the animalizing agent becomes the drawability of the cellulose triacetate compared to such dyes, it is surprisingly not canceled out significantly increased, so that z. B. the dye baths are largely drawn out and the The dyeings obtained are deeper than those on aectate artificial silk with an acetic acid content from, 54 to 55%.

Example 11o Prepared by the dry or wet spinning process Fibers made from chloroform-soluble cellulose acetate are treated with 6oo'o acetic acid, optionally in the presence of a thickener, printed in places,, one Subjected to salt treatment according to Example i and, after drying, with cellite dyes colored at 7o to 8o '. Fibers are created, which have interesting two-tone effects show that the untreated areas only a little, but the treated areas are very strong accept the dye.

Example 11i Triacetate fibers are spun with the addition of an animalizing agent and proceed with the fibers as described in example io. It can both with Cellite dyes such as flamed with acidic wool dyes, chrome dyes, etc. Fibers are obtained.

Example 12 A fabric made from cellulose triacetate is, with a printing paste which contains 650, 'o acetic acid, in any Patterns printed, washed out, subjected to a salt treatment according to Example16 and dried. With suitable dyes, e.g. B. Cellitechtblau B, colored result dark patterns on a light background.

Example 13 A fabric made from an animalizing agent Triacetate rayon is printed as described in Example 1: 2. One colors now with cellulose dyes, effects similar to those described in Example 12 result. On the other hand, it is dyed with acidic wool dyes or chromizing dyes, which If you reserve acetate silk, colored patterns on a white background can be achieved.

Claims (2)

PATENT CLAIMS: i. Process for dyeing fibers, ribbons and Films made from cellulose acetates with an acetic acid content of over 59011ö, thereby characterized that the structures with at least 3o0; öiger acetic acid or a equally strong swelling agent and then with a solution of a salt and or or a sulfonic acid group-free wetting agent treated and, optionally after intermediate drying, stains. 2. The method according to claim i, characterized in that that animalized structures are dyed with acidic wool dyes. For demarcation of the subject of the application from the state of the art are in the grant procedure in Considered: Research booklet 13, published by the German Research Institute for the textile industry in Dresden, inscribed »The gloss clouding of the acetate artificial silk in hot baths «by Stahl, 1931, p.34; German patent specification No. 6o9 293, 638 303; British Patent No. 448 816, 448 817, 448917-