DE738763C - Process for dyeing molded structures made of superpolyamides - Google Patents

Description

Bur. lud, Eigeiidoi ^
12 JAN -1944

Molded structures made from superpolyamides can be mixed with almost all types of dyes be dyed, preferably with acidic dyes, basic dyes, acetate artificial silk dyes, certain sulfur and vat dyes.

In general, however, dyeing takes a long time if done vigorously Wants to receive colorations.

It has now been found that superpolyamides can dye in uninterrupted work in a very short time. This process consists in that the products from super polyamides at a temperature above 100 "with solutions or dispersions of dyes or dye intermediates in organic solvents, the over 100 'boil, be treated.

With this procedure it is possible

ao dyeings of deep hue and, if one chooses suitable dyes, of excellent To preserve authenticity. The process is particularly valuable for the production of dyeings in which tissue parts are un-dyed be left; because the colored parts of the material to be dyed can after cooling before washing out and finishing on the uncolored parts or on those in other Color-dyed parts of the material to be dyed can be applied without the uncolored parts being soiled.

All dyes that are stable at temperatures above 100 ° and the dyes to be used or Intermediate dye-dissolving organic solvents can be used to run of the present procedure can be used. In particular, those organic solvents come into consideration, which at higher temperatures over 100 'have a certain swelling effect on superpolyamides exercise. The following solvents can be mentioned in particular: Ethylene, diethylene, triethylene glycol and the esters, ethers and ester ethers of the

various glycols; Mono-, di- and tiiethanolamine; Furfuryl or tetrahydrofurfuryl alcohols; higher aliphatic alcohols; Benzyl alcohol; Formamide; Hexamethylenediamine, Aniline, pyridine and other aliphatic, cyclic or heterocyclic organic bases; Cyclohexanol, cyclohexanone or other cyclic alcohols or ketones; Phenols, cresols and their esters; Mineral oils or oils of vegetable origin; Fats, waxes, higher fatty acids and alcohols.

Mixtures of two or more of the solvents can also be used.

Any dyes or dye intermediates can be used in the practice of the invention use that in the organic solvent or solvents used the temperature in question are soluble. The solution obtained can also the shape of a hemikoUoidal ^ or colloidal Dispersion, as is often the case with color. substances occurs. It can be in certain In cases it may be useful to use dye baths in which some of the dye is in true colloidal solution and the other part is in dispersion. The last one This part then serves to keep the solution at its saturation point at all times.

As a result of the fact that the temperature in question only goes up through the need to avoid melting or dissolving of the dyed material is limited is, you can choose the temperature so high that the dyes in any case. the organic solvents used are dissolved. There are z. B. fatty dyes, Dyes for lacquers, sulfur and vat dyes, which dissolve in the hot organic liquid without reduction, are used for carrying out the process. These The last-mentioned dyes can also be used in a reduced state, such as it z. B. by adding a little sodium sulphide to the dye bath, which the unreduced Contains dye at which high temperatures are readily reached. When applied fiber blends of superpolyamides and cellulose fibers can be used in this way to be colored. Alan can too reduced stabilized compounds, e.g. B. the salts of the sulfuric acid esters of leuco vat dyes, use. For coloring the superpolyamides, acidic dyes, basic dyes and substantive dyes can also be used Dyes, acetate rayon dyes or ice color preparations can be used.

After passing through the dyebath, the material to be dyed must start from the excess Dyebath can be freed by rinsing, either with water or with volatile Solvents that are miscible with the solvent for the dye, because you have the Do not achieve removal of the solvent for the dye by evaporation can. Spirit or methyl alcohol is expediently chosen as the volatile solvent. But also other common volatile solvents that are easily recovered let can be used.

Example ι

A tissue consisting in weft and warp of filaments of polyhexamethylene adipamide is immersed at 120 ⁰ in a 20 / o solution of the 1,4,5,8-TetraminoanthrachinonsinÄthylenglykol, immediately washed with running water and then soaped off easily, these three operations are carried out automatically one after the other in uninterrupted work processes. The fabric is then dried on the sizing frame. A strong blue color is obtained.

Example 2

Polyhexamethylene adipamide threads. one pass at intervals through the same solution as indicated in Example 1, at 130 ^0, washed, soaped and dried as indicated in Example. 1 Threads _e with alternating blue and white areas are obtained.

Example 3 'gg

Polydekamethylene adipamide horsehair is continuously fed through a 3U. ' _o ige solution of i-amino-4-oxyanthraquinone in tricresyl phosphate at a temperature of 2oo °. Then it is rinsed with alcohol 10c and dried. A strong, violet-red color is obtained.

Example 4

A braid of threads of superpolyamides is continuously through a 40 / oige Solution of naphthalene green V (Schultz, Farbstofftabellen, 7th edition, No. 777.1 in Tetrahydrofurfuryl alcohol at a temperature of 150 'out, then with flowing i " rinsed in water and lightly soaped. A vivid and strong green coloration is obtained of good authenticity.

Example _1X ,

A thin sheet of polydekamethyl bisacic acid amide is continuously replaced by a 40% solution of the nigrosine base (Schultz, a. a. Ü., No. 9S5) in tetrahydrofurfuryl alcohol led at 150 and, as indicated in Example 4, rinsed and soaped. Man acquires a purple-black color.

Example 6

Horsehair made from super polyamides, which through. Condensation of adipic acid, hexamethylene diamine and a glycol are obtained is carried continuously, a 0.5 o / o solution • the sulfur dye Pyrogenindigo in ethylene glycol (Schultz, supra, no. Πιο] hindurchgefüihrt. The solution temperature is maintained at 130 ⁰ No reducing agent is added. The horsehair is then rinsed and lightly soaped to give a beautiful blue color.

Example 7

A fabric made from threads of polyhexa

methylenadipitnsäureamid is at 130 ⁰ in

A '0.3 o / _o solution of thioindigo immersed in ethylene glycol, then, as described in Example 1, rinsed with water and soaped off. This gives a pink coloration of excellent sea water and light fastness.

A modification of the procedure of Examples 6 and 7 is that 0.50 / 0 Sulfur sodium can be added to the dye bath. This addition is enough to turn the dye on the fiber into the leuco compound to convict. This working method is chosen when fabrics are to be dyed, which contain cellulose fibers.

Example 8

A fabric made of superpolyamides is at 200 ° in a suspension of 2 parts 1, 4, 5, 8-tetraminoanthraquinone immersed in 100 parts of petroleum jelly. Part of the dye is dissolved in the oil and part merely suspended in the oil. After immersion and cooling, the tissue will be with Benzene rinsed, then lightly soaped, these processes in uninterrupted work be performed. The fabric is dyed deep blue, in a considerable way uniform way. The oil is recovered by distilling the benzene and used for the continuation of the working process. An equivalent result will be obtained when you add "peanut oil" to the petroleum jelly replaced

Example 9

A cloth made of threads of polyhexamethylene ^{adipamide in weft and warp is immersed at 130 J} in a solution containing 6 g of the sulfuric acid ester of leuco-5, 7, 5 ', 7'-tetrabromoindigo in ethylene glycol per liter. ~~

After leaving the bath the fabric runs continuously between two nip rolls, and then passing in a developing bath, which is maintained at 6 NC ° and 66 liters of sulfuric acid 20g ⁰ Be, ig contains sodium nitrite.

The passage of the tissue through the development bath is regulated in such a way that it Takes 5 minutes. After exiting the bath, it is rinsed and put on a Finishing frame dried. A blue color is obtained. ,

Example 10

The same fabric as in Example 9 is ^{treated in the same device at 130 °} with a solution of the following composition:

Ethylene glycol 100 parts,

i-Amino-2-chlorobenzene hydro-

chloride 0.3 -, _gQ

2- (2 ', 3'-oxynaphthoylamino) naphthalene 0.2

The "development bath consisting of a solution, the ζ-im'Liter g of formic acid containing 2 g of sodium nitrite. The mixture is kept at 45 ^0th The fabric obtained has a nice, lively and strong orange in color.

Example 11

In the same device, the same tissue is dissolved in a solution of the leuco vat dye immersed by reducing 60 g indigo (in 200 / oigem dough) in ι 1 ethylene glycol with ι ο g formaldehyde sodium sulfoxylate is obtained at 135 °. This temperature is used during dyeing maintain.

The development bath, which is kept at 60 °, consists of a solution of 5 g Hydrogen peroxide and 1 g commercial ammonia solution in 1 water. One receives a Fabric that has the blue color of indigo.

Example 12

The same cloth is in the same device in a solution of 60 g of the Ice color preparation, consisting of a mixture of the alkali salt of the diazoamino compound from 1-diazo-5-ethoxybenzene-3-s1.1lfonsäurediethylamid and sarcosine and the corresponding amount of i- (2 ', 3'-oxynaphthoylamino) -4-chloro-2-methylbenzene immersed in one liter of ethylene glycol at a temperature of 130 '.

The developing bath consists of an aqueous solution of "the following composition: 60/0 ο formic acid, i2 ° / o ο acetic acid, 2.50 / 0 sodium sulfate. The temperature is maintained at 90 ". One obtains a Pink color.

In addition to the products made of superpolyamides colored according to the examples Threads, fibers, cuticles, burin hair, tubes, hollow or solid, shaped or cast Objects and finished products made of super polyamides are colored. The used Dye solutions can be mixed with plasticizers or softeners.

Claims (2)

Patent claims: i. Process for dyeing shaped structures made of superpolyamides, if appropriate in the presence of cellulose fibers, characterized in that the structures are mixed with organic solvents which boil over iob ° and contain dyes or intermediate dyestuff compounds or in finely divided form, at temperatures above 100 ° for a short time brings into contact, ¹ with water or volatile solvents, which do not dissolve the structure and are miscible with water or the solvents used, rinses, soaps if necessary and dye-substance compounds, as usual, developed into the dye. 2. Embodiment of the method according to claim 1, "characterized in that that dyeing in a uniform or alternating manner, by non-dyed or otherwise dyed Leaves gaps, is carried out in uninterrupted operation.