DE1032211B - Process for dyeing polyamide fiber material - Google Patents

Description

GERMAN

It is known that polyamide fibers can be damaged by acids and oxidizing agents by partial or total degradation takes place on exposure to these agents. On the other hand Processes have already been mentioned, according to which the action of acids has certain refining effects to be achieved on polyamide fiber material, but due to the use of relatively high Acid concentrations and vigorous exposure conditions each not only have limited effects Frames are available, but also not all types of polyamide fibers can be treated. So they are not generally applicable procedures.

Surprisingly, it has been shown that there is a very intensely increased dye affinity for everyone Dye classes on polyamide fiber textile material can be obtained by using the polyamide fiber material with an inorganic acid or an aliphatic carboxylic acid or their acidic salts in one concentration treated from 2 to 60% at temperatures of 20 to 100 ° C for about 5 to 60 seconds, thoroughly washes and then dyes. Such conditions with regard to concentration and duration of exposure should be used and temperature applied, which is little above the exposure limit for the subject Polyamide lie, so that the surface change of the fiber that may arise in the process there are no significant disadvantages for the mechanical properties of the textile material.

Such conditions are for

concentration ίη% temperature 80 n ° C in Time until 50 ι 70 until 100 5 Seconds Lactic acid 15th "50 20th "100 5 up to 60 Oxalic acid 10 "60 60 "100 5 "60 Formic acid 10 "45 20th "100 5 ,, 60 acetic acid 10 "13 " 100 5 "60 Hydrochloric acid .. 2.5 20th "60 sulfur "30 20th "100 5 acid .... 8th "20th "100 5 "60 nitric acid 2 20th "60 phosphorus "50 "100 5 acid .... 25th 60 "60 hydrogen "40 "100 5 peroxide .. 5 "60

In the case of polybasic, strong acids, their acidic salts can also be used in place of the free acid if correspondingly more energetic conditions are applied, e.g. B. ammonium bisulfate in concentrations of 30 to 60% at temperatures of 70 to 100 ° C with exposure times of 5 to 60 Se process
for dyeing polyamide fiber material

Applicant:
Raduner & Co. A.-G., Horn (Switzerland)

Representative: Dr. W. Schalk and Dipl.-Ing. P. Wirth,

Patent attorneys,
Frankfurt / M., Große 'Eschenheimer Str. 39

Claimed priority:
Switzerland from May 8, 1961

announce. By adding oxidizing agents, preferably Hydrogen peroxide, to acids can have the same or often even increased effects with lower levels Acid concentration can be achieved. For such mixtures, of course, there are no limits as in Specify the case of acid alone or oxidizing agent alone, since not only the temperature and the reaction time, but also the concentration of both components can be varied.

The action of the finishing agent is determined by post-treatment in suitable media, e.g. B. by Washing out and / or neutralizing, interrupted.

The range of the limit of action is quite wide because the reactivity is different Surprisingly, polyamide types were found to be different. For every single polyamide a number of conditions can be determined within the ranges listed above under which the effect according to the invention occurs to an optimum extent. This results in being the most unpredictable, most valuable technical progress the possibility by simple variations of the conditions in the application of the degrading reagents to achieve a variation in the change in color absorption capacity.

While the known finishing processes for polyamide fiber material (in most cases polyhexamethylene diamine adipate) expressly claim conditions and concentrations that are already hard on the upper for the respective polyamide fiber types

809 557/444

Limit, d. H. hub on the area of damage and z. B. for caprolactam due to great damage or even complete destruction are no longer practically applicable at all according to the method of the present invention polyamide fiber material of any kind and chemical Texture can be refined. In addition, it is surprisingly found that by a slight change the conditions within the above-mentioned limits produced specific, deliberate effect variations can be. The method according to the invention thus enables various types to achieve different effects from synthetic polyamides, in such a way that at the same time The presence of differently reactive polyamides does not seriously damage the more sensitive component will.

In the case of polyamide fiber material that has been pretreated in accordance with the process, one is consistently provided increased dye affinity for all dye classes, and fibers treated in this way can surprisingly using the simplest dyeing methods, i.e. without the special processes otherwise usual for polyamide fibers, be colored using the z. B. usual dyeing methods for cellulose material or wool. The fastness properties achieved in this way correspond at least to those of dyeings which are achieved using special processes on polyamide fibers. The advantage here is among other things in the fact that it is possible to work with neutral fleets in contrast to those otherwise used with certain Processes used high acid dye baths. ■

The method can be applied to yarns, i.e. endlessly spun yarns or staple fibers of any kind Woven and knitted and on blended and blended fabrics of any quality and any other Kind of mixed fiber material made of polyamides are used. Furthermore, already fixed, d. H. stabilized polyamide yarns and fabrics are used. Through suitable Use of fixed and unfixed components or by using different types of components Differentiated color effects can be achieved with polyamide fibers (tone-on-tone effects).

The process can be applied over the entire surface on smooth goods by means of impregnation as well as topically by printing soluble and / or insoluble, against the finishing agents (acids and / or oxidizing agents) inert reserves with or without pigments, metal powder, fillers or the like, whereby, depending on the process according to the finishing treatment, a different colorability (with Coloring tone-on-tone or multi-color effects). On the other hand, you get similar effects if you the finishing agent according to the process is printed on in a pattern and / or sprayed on, if necessary together with white or colored pigments and similar illuminants. . ■

The fact that polyamide fibers are used in staple or yarn form (long-spun or as a stack material) according to the process, which not only increases the affinity is achieved, but also a new way of producing fancy yarns that are in conjunction result in color effects with untreated yarns.

Of course, the diversity of possible effects can be achieved by including all of them Types of other fancy yarns, e.g. B. immunized, passivated, animalized yarns increase.

Effective degrading agents are inorganic acids and aliphatic carboxylic acids as well their acid salts have been called. In addition, oxidizing agents, preferably hydrogen peroxide, be used. Nitric acid acts both as an acid and as an oxidizing agent. The conditions, such as concentration, temperature and exposure time, vary depending on the one desired Effect by preferably having a shorter exposure time and a significantly reduced concentration is used for the same effect. This is opposite the known processes that work at low temperatures, longer exposure times and higher Concentrations work, an advantage not to be underestimated, e.g. B. especially with regard to the technical application of the process.

It is known that to achieve more even ' Color depths on stockings with water-insoluble disperse dyes in the presence of Tanrain and optionally in the presence of acetic or formic acid can be colored. This well-known However, the method differs fundamentally from the present method, in which by a pretreatment changes the affinity of the material and only after the pretreatment has been completed is colored. It is also known to treat polyamide fiber material with an oxidizing agent, e.g. B. hydrogen peroxide, to treat fibers of different origins and different production approaches can be stained with direct dyes.

The aim of the process, however, is not to achieve better equality, but to increase it of affinity. The color depths made possible by the present process on polyamide fiber material are considerably superior to the depth of color that is effected according to the known method.

It is also known that poly * hexamethylene diamine adipate can be improved in affinity by treatment with aromatic acids such as salicylic acid can. However, the use of the relatively sparingly soluble aromatic acids requires one Set of precautionary measures to keep the finishing agent from being applied to the goods fails. Furthermore, the known acids are often very difficult to remove from the polyamides, which is noticeable disadvantageously in further dyeing, and moreover, f as these acids not completely removed from the product, easily causes skin irritation.

.Example!

A taffeta fabric made of polycaprolactam fibers is unfixed without prior desizing Condition treated for 10 seconds at 80 ° C with a solution containing 8% hydrogen peroxide and Contains 20% acetic acid. The action is interrupted by immediately subsequent cold washing and neutralize.

The mixture is then dyed by the following procedure with a direct dye: 2% Chlorantinlichtrot 6 BLL (Schultz, dye tables, VII edition, .Ergänzungsband, S. 79th!), Of dyeing at 6O ⁰ C, bring within one hour to boiling temperature and g 1 / l Color table salt as the temperature drops. Then rinse and dry as usual.

The taffeta fabric treated in this way shows a deep red color in contrast to that which is not in accordance with the process pretreated goods that are only slightly colored. The fastness properties of the deeply deepened dyeing, in particular the lightfastness are partly equivalent to that of the untreated samples, but in some cases even better.

Example 2

A fabric pretreated as in Example 1 is coated with a diazotizable or re-copperable dye colored, with also a very considerable deepening of nuances compared to the non-pretreated Enter well.

Example 3

A fabric made of polycaprolactam fibers is desized, washed out and then as usual Subjected to treatment: 18% nitric acid is allowed to act at 20 ° C. for 15 seconds and interrupt the reaction by immediately rinsing it thoroughly with cold water. It is stained with 4% indanthrene navy blue BF PIv. fine (Schultz, color tables, VII edition, volume 2, P. 131) according to the IN method with 14 ecm sodium hydroxide solution (38 ° Be) and 4 g / l hydrosulfite at an initial temperature of 20 ° C, within 30 to 40 minutes Bring to 60 ° C and color after adding 2 g / l of table salt for another 30 minutes. The subsequent Oxidation and subsequent soaping are carried out as usual.

The fabric treated according to the procedure is dyed deep navy blue, while an untreated, but pattern colored in the same way shows a light blue-gray.

Example 4

A knitted fabric made of polycaprolactam fibers is treated as in Example 1 with a solution which Contains hydrogen peroxide and acetic acid, and then with 2 <Vo indigosol green JGG (Color Index No. 1269/70) and 1 g sodium nitrite and 5 g Glauber's salt per liter colored at 45 ° C for one hour. Afterward is developed with 5 ecm sulfuric acid of 66 ° Be per liter at 50 ° C for 20 minutes. To washing and neutralizing are soaped at the boiling temperature.

Due to the pretreatment, the nuance is quite considerable compared to a knitted fabric that has not been pretreated deepened. After the pretreatment and neutralization, the tissue can optionally be stored still to be dried. After wetting and dyeing, the same deepening of nuances results as in the case of not interdried knitted fabric, which proves that the increase in affinity is due to the fiber finishing is achieved and not by one currently caused by the finishing agent Swelling phenomenon.

Example 5

A lining material made Polyhexamethylendiaminadipat is treated with 4O ° / cent acetic acid at 95 ⁰ C for 8 seconds then immediately washed as in the earlier examples. It is then dyed with a sulfur dye 2% pyrogen green 2 G (Color Index No. 1115, Supplementary Volume 2, p. 61), 4 g of sodium sulphide, 1 g of soda calc. and 0.2 g triethanolamine per liter. These agents are used for staining for one hour at the boiling temperature and then for another 30 minutes at a falling temperature. Reoxidation takes place in the usual way using perborate or superoxide.

The comparison with a sample that was not pretreated but colored in the same way shows that the pretreatment according to the method brings about a strong increase in the affinity for sulfur dyes.

Example 6

A heavy polyhexamethylenediamine adipate cretone fabric with a weight per square meter of 300 g is with 50% lactic acid for 30 seconds treated at 95 ° C. After washing, the naphthol dye Naphthol AS ITR (Schultz, op. Cit., Supplementary volume !, p.174) (10g / l) dyed at 45 ° C on the jigger. After intermediate drying, ITR is developed with the fast red base (Schultz, op. Cit., P. 93) and soaps in the usual way for cellulose material. The color depth is considerably reinforced compared to cretonne that has not been pretreated.

Example 7

A polyhexamethylene diamine adipate muslin is made with 20% formic acid at 95 ° C during Treated for 20 seconds. After washing out, it is dyed with the acetate dye celliton scarlet B. (Schult z, op. Cit., Supplementary volume 2, p. 144) (2%) and 1 g of soap / 1 at 90 ° C for IVa hours. Man receives a much deeper gray than the one colored in the same way, but not in accordance with the process pre-treated samples.

Example 8

Polycaprolactam yarn is treated with 9% hydrochloric acid at 80 ° C. for 5 seconds, then washed out and with the acid dye cloth brilliant red 4 BN (Schultz, op. cit., p. 270) (2%) without Addition of acid for 1 hour at 80 to 100 ° C colored.

The color nuance achieved in this way in a neutral bath is considerable deeper than that of yarn that has not been pretreated in accordance with the process, which, as was customary up to now, was made in acidic Dyebath has been dyed.

Claims (5)

Claims 1. Method of dyeing polyamide fiber material using acids for enhancement the affinity of the fiber materials, characterized in that the polyamide ^ fiber material with an inorganic acid or an aliphatic carboxylic acid or their acidic Salts in a concentration of 2 to 60% at temperatures of 20 to 100 ° C for about 5 to 60 seconds treated, washed thoroughly and then colored. 2. The method according to claim 1, characterized in that in addition to the acids, oxidizing agents, preferably hydrogen peroxide, in a concentration of about 5 to 40% at temperatures act on the polyamide fiber material for about 5 to 60 seconds from about 60 to 100 ° C leaves. 3. The method according to claim 1 and 2, characterized in that the acidic treatment agent Hydrochloric acid, sulfuric acid, acetic acid, formic acid or oxalic acid is used. 4. The method according to claim 1 to 3, characterized in that for dyeing an acid dye, Direct dye, azo dye, vat dye, acetate dye or a sulfur dye is used. 5. Further embodiment of the method according to claim 1 for the production of differentiated Effects on polyamide-containing blended fabrics, which on the one hand contain fibers made of polymeric Aminocarboxylic acids, in particular polymeric ε-aminocaproic acid, exist, and on the other hand Contain fibers that are made from polymeric reaction products of diamines with dicarboxylic acids, in particular of hexamethylenediamine and adipic acid, characterized in that ίο this mixed fabric at temperatures of 20 to 100 ° C for 5 to 60 seconds with an inorganic Acid or aliphatic carboxylic acid an equivalent weight of not more than 60 treated at such a concentration that the relationship Number of the equivalent weight of the acid in 11 liquor Equivalent weight of acid is in the range of 0.05 to 0.10, washes thoroughly and then stains. Considered publications:
British Patent Nos. 614,009, 557,939;
U.S. Patent No. 2,480,775. When the application was announced, 6 coloring tables and 2 explanations were laid out. © 809 557/444 6.58