DE2155143B2 - METHOD OF COLORING CELLULOSETEXTILE MATERIALS - Google Patents

Description

There exist a number of physical forms of cellulosic textile materials that are difficult to level out Shades to be colored due to the obvious fact that the dye is not diffused evenly through the material to be colored. Typical of such shapes are materials, which comprise several layers of a tightly woven fabric, wraps of spun yarn, such as e.g. B. three-strand mercerized sewing thread or seven-strand mercerized embroidery thread, heavy packing canvas, Drell, belts, belt fabrics, tapes with reinforced Edges, "ladder tapes", and tapes with drawstrings for curtains, spider cakes made of viscose and all thick packs of non-spun cellulose fibers.

It has now been found that such cellulose textile materials can be dyed by certain selected classes of reactive dyes in well-penetrated and leveled dyeings, if the material in a neutral or weakly acidic aqueous medium containing an electrolyte, with the dye at a temperature above 100 ⁰ C brings in contact for a sufficient time until the desired penetration and exhaustion is achieved, and when the dye is then fixed on the material by treating the colored material with an acid-binding agent.

The essential new feature of the novel method is the unexpected finding that the vast majority of the water-soluble reactive dyes acidic in weak or neutral aqueous dye baths at temperatures of 100- 140 ⁰ C are nearly as stable against hydrolysis than at the lower temperatures 75-85 ° C, which has so far been recommended as the maximum temperature for such dye baths. The only exception of remarkable importance is the class which has a dichloro-s-triazine group as a group reactive with cellulose.

Reactive dyes which have been found to be useful in the new process are dyes,

Di- and tri-chloropyrimidine, sulfatoethyl sulfone,

Sulfatoethylsulfonyl-amino-,

5-chloro-6-methyl-2-methylsulfonylpyrimid-4-yl-,
/ J- (4,5-dichloropyridaz-6-on-l-yl) propionyl-, acryloyl-.ß-phenylsulfonylpropionylamino-, 2,4-dichloropyrimid-5-yl-,

2-chlorobenzothiazol-6-yl-,

1,4-dichlorophthalazin-6-yl, dichloroquinoxaline, ίο / i-chloroethylaminosulfonyl and in particular Mono-chloro-s-triazine groups, which are amino, etherified hydroxy or anilino or

have substituted anilino groups contain. The dyes include members of the phthalocyanine, Anthraquinone and azo series including monoazo, disazo and metal complex azo dyes.

Aptitude test

To determine suitability for use in the new method, the following becomes simple Test indicated.

There will be two dyeings on cotton strands

carried out using equal amounts of the dye. In either case, the dye bath also contains 80 g / l table salt and 5 g / l sodium m-nitrobenzene sulfonate.

(a) The dyeing is for 45 minutes at 120 ⁰ C and at a pH of 5.0-5.5 (0.15 g / l acetic acid), then the dye bath is cooled to 8O ⁰ C, finally is sodium carbonate ( 20 g / l) are added, and then dyeing is continued for 45 minutes.

(b) The dyeing is carried out for 45 minutes at 8O ⁰ C under neutral conditions, then

Sodium carbonate (20 g / l) is added and the dyeing is continued for 45 minutes. Both strands are then rinsed in water and boiled for 15 min with 0.3% detergent ■ »ο remove loose dye.

In many cases it is found that the two colorations have the same depth of shade. However, if the coloration obtained by method (a) is weaker than that produced by method (b), then the difference can be determined using a geometric gray scale map such as are used for performing wash tests on colorations ( BS2663: 1961). A dye is considered suitable if the difference in shade depth is no greater than 4 ratings on this card. However, even at 80 ⁰ C is a reactive dye containing the dichloro- or dibromo-s-triazine, so unstable that it can not be used with the new process.

The following cellulose-reactive dyes, which are identified by their Color Index reference numbers (reactive) have successfully passed this test, for example:

black 8

brown 2,7,9,17 and 19

blue 2,3,5,19,21,25,26,40,46,49,53,

64 and 7 i

b5 green 5 and 8

orange 2,7,12,13,23,25,32,35 and 43

red 3,13,19,56 and 58

yellow 3,6,15,18 and 33

/ i

tape

2 poly / 18's cotton

Cord

4 χ 4 ply.

4 ply.

Single / 14's.

20 turns / 25 mm

4.1 turns / 25mm
8.8 turns / 25 mm
28 turns / 25 mm

IO

15th

The new process can be carried out in a wide variety of dyeing devices that are used for Dyeing at temperatures above 100 ° C are suitable, such. B. Pack dyeing container for cylinder rolls, cone rolls, Cops, trees, torpedoes, strands, packed I. n, ribbons, narrow woven fabrics, or all of them of piece goods wound up on perforated holders containers for bulk goods, print jiggers, reels and jet dyeing machines.

The new process may conveniently be carried out by reacting the immersed material to be dyed in the dye liquor, which can already be warm and may comprise, for example, about 40 ⁰ C, the material then to the dyeing temperature, preferably 120-125 ° C heated, and then maintains that temperature until the desired penetration and exhaustion is achieved. This usually takes 30 minutes to 1 hour, but shorter or longer times may be advisable in special cases. Thereafter, the acid-binding agent used to fix the dye on the fiber of dye liquor added in the preferred mode of operation, after the latter has been preferably cooled to 80-90 ⁰ C. Alternatively, the material can be transferred to a separate container for treatment with a solution of the acid binding agent, or the staining liquid can be drained and replaced with a solution of an acid binding agent.

The coloring liquid can contain the usual additives, of which a neutral or weakly acidic salt is generally essential in order to achieve sufficient exhaustion. In this regard, sodium chloride or sodium sulfate can be used in concentrations of 10 to 100 g / l, namely γ, optionally with small amounts of acidic salts, such as e.g. B. sodium dihydrogen phosphate to bring the pH of the dye liquid in a range of 6.0 to 7.0. Other customary additives can also be present. In particular, it is desirable that a mild oxidizing agent, such as. B. sodium nitrobenzenesulfonate is present.

The invention is further illustrated by the following example, in which the parts are expressed by weight.

example

The material to be dyed consisted of a cotton ribbon with a width of approximately 34.9 mm, which had been wrapped around a piece of cord and sewn through in the middle. The cotton ribbon had the following characteristics:

30th

40

45

50 color inside and outside achieved by the following process:

A piece of tape was wrapped around a spring holder for a cylinder wrap, until a cylinder wrap of 700 g in weight was obtained, and then the package was placed in a laboratory pack dyeing machine used and dyed after cleaning and acid rinsing in 7 kg of a dye liquid that contained the following:

It consisted of a dense cotton mass with a weight of 12.0 g per 0.9 m Manufacture of zippers are used.

When dyeing in the usual way at 80 ° C, it was found that the penetration of the dye in the centrally sewn part was insufficient. Not just the cord, but also the cotton ribbon itself was colored a much paler color than the outer surface. In contrast, a completely even

Dye No. I. 4 g / l Dye # 2 3 g / l Dye # 3 1.5 g / l Sodium nitrobenzene sulfonate 5 g / l Table salt 100 g / l

The dye liquor was placed for 20 min at 120 ⁰ C and 30 maintained at 120-125 ⁰ C min and then cooled to 90 ⁰ C. Then, sodium carbonate was added in an amount of 20 g / l, and the dye liquid was circulated at 90 ° C for an additional 60 minutes.

The material was then rinsed in cold water and in hot water, in a 0.1% detergent solution Cleaned for 15 min at the boil, rinsed again in hot and cold water and then drained left and dried.

The following was used:

Dye 1:

The 1: 2 chromium complex of the monoazo compound

Cyanuric chloride, 4-nitro-4'-aminostilbene-2,2-disulfonic acid and 6-amino-2- (o-carboxyphenylazo) -1-naphthol-3-sulfonic acid (equ'molecular proportions).

Dye 2:

2- [4 '- (2 "-Chloro-4" -amino-s-triazine-6 "-ylamino) 2'-ureidophenylazo] naphthalene- 3,6,8-trisulfonic acid.

Dye 3:

The copper complex of 6- (2'-chloro-4'-amino-s-triazine-6'-y!) - N-methylamino- 2- [4 "- (2 '", 5' "- disulfophenylazo) -5" -methyl-2 "-hydroxyphenylazo] -1-naphthol-3-sulfonic acid.

A very dark brown color was obtained.

The following table is a list of more Dyes indicated that were found to be suitable for use in the new process suitable. Column I gives the Color Index designation or the trade name if the dye is not in the Color The index appears and column II shows the respective cellulose-reactive group.

55

60 Color Index
black 8
brown 2
brown 7
brown 9
brown 17
brown 19
blue 2
blue 3
blue 5
blue 19
blue 21
blue 25

Monochloro-s-triazine

Monochloro-s-triazine

Monochloro-s-triazine

Monochloro-s-triazine

Monochloro-s-triazine

2,3-dichloroquinoxaline

Monochloro-s-triazine

«-Chloroäthylaminosulfony!

Monochloro-s-triazine

/ S-sulfatoethylsulfonyl

/ 3-sulfatoethylsulfonyl

/ J-chloroethylaminosulfonyl

blue 26 blue 40 blue 46 blue 49 blue 53

blue 64 blue 71 green 5 green 8 orange orange orange orange orange orange orange

orange

Monochloro-s-triazine orange 43 Monoehloro-s-triazine Monochloro-s-triazine red 3 Monochloro-s-triazine red 9 3,6-dichloropyridazin-4-yl- 5 red 13 carbonylamino red 56 Monochloro-s-iriazir. red 58 Monochloro-s-triazine yellow 3 Monochloro-s-triaziri yellow 6 Monochloro-s-triazine 10 leaf 15 Monochloro-s-triazine yellow 18 2-sulfatoethylsulfony] yellow 33 Monochloro-s-triazine Monochloro-s-triazine Reatex ß-sulfatoethylsulfonylamino 15 Brilliant Yellow 4RL Acryloylamide jJ-phenylsulfonylpropionyl- Elisiane amino Brilliantrol B Monochloro-s-triazine

5-chloro-6-methyl-2-methylsulfonyl-pyrimid-4-ylamino Monoch'oro-s-triazine Monochloro-s-triazine Monochloro-s-triazine Trichloropyrimidine

Monochloro-s-triazine monochloro-s-triazine monochloro-s-triazine] 3-sulfatoethylsulfonyl Monochloro-s-triazine j3- (4,5-dichloropyridaz-6-onl-yl) propionyl

2-chlorobenzothiazol-6-yl carbonylamino

1 ^ -Dichlorophthalazin-ö-ylcarbonyiamino

Claims (2)

Patent claims: 1. Method of dyeing cellulosic textile materials, the physical form of which is a dye in makes equalized shades difficult, characterized in that the material is in a neutral or weakly acidic aqueous medium containing an electrolyte with a corresponding to the water-soluble reactive dye selected in the text given in the description at a temperature above 100 ° C until the desired penetration and Exhaustion are achieved, and that you then the dye on the material by treating the dyed material is fixed with an acid-binding agent. 2. The method according to claim 1, characterized in that the dye used as a reactive Group has a monochloro-s-triazine group which has an amino, etherified hydroxy, anilino or contains substituted anilino group.