DE1132539B - Process for dyeing and printing cellulose-containing fiber material with reactive dyes - Google Patents

Description

It is known that certain substantive dyes are used when dyeing cellulosic! Fiber material, in particular when dyeing regenerated cellulose in the presence of alkali at elevated temperature, a suffer unfavorable influences on hue and color strength. This phenomenon is called in the technical language as »overcooking«. This "boiling off" of the dyes, which is mainly due to a reduction process, is caused by the textiles itself or caused by impurities adhering to the same or also in the dyebath. By adding salts of nitrated aromatic sulfonic acids to the dye bath or printing paste the appearance can be prevented or at least weakened.

Reactive dyes, d. H. Dyes, which enter into a chemical bond with the cellulose and to for this purpose in the presence of acid-binding agents such as sodium carbonate, sodium hydroxide or other alkaline reacting agents, and mostly fixed at elevated temperature, also show a lot often such overcooking phenomena. If one wants them by adding salts nitrated aromatic If sulfonic acids correct, then very often a clouding and / or weakening of the color nevertheless occurs.

It has now been found that when dyeing and printing cellulose-containing! Fiber material with Reactive dyes can prevent overcooking phenomena very well if you dye or print or the fixation of the dyes in an alkaline medium in the presence of salts nitrated aromatic sulphonic acids and small quantities of soluble salts of the oxo acids of vanadium undertakes.

The salts of nitrated aromatic sulfonic acids used in dyeing processes are mainly water-soluble ones Ammonium and alkali salts, but also the less soluble alkaline earth, Copper and manganese salts of sulfated mono- and dinitro compounds of the benzene, naphthalene and Anthracene series into consideration. One uses primarily the salts of m-nitrobenzenesulfonic acid and the Dinitrobenzenesulfonic acids.

The salts of the oxo acids of vanadium used are as contact substances in oxidation-reduction processes known. Because they are used in very small quantities in the present process they should be water-soluble for the purpose of good dispersibility within the dye or printing medium. For this reason the ammonium and alkali vanadates are preferred; but also amine salts of vanadic acids may be considered. It can

of cellulosic! Fiber material

with reactive dyes

Applicant:
JRGeigy AG, Basel (Switzerland)

Representative: Dr. F. Zumstein,
ίο DipL-Chem. Dr. rer. nat. E. Assmann

and DipL-Chem. Dr. R. Koenigsberger,
Patent Attorneys, Munich 2, Bräuhausstr. 4th

Claimed priority:
Switzerland of March 11, 1960 (No. 2767)

Paul Dussy, St. Louis (France),

Hans Bosshard, Basel,

and Dr. Willy Leutenegger, Bottmingen (Switzerland), have been named as the inventor

simple salts, double salts and also complex salts of the meta-, ortho- and pyrovanadates are used; preferred compounds are the ammonium, sodium, potassium and lithium metavanadates.
The reactive dyes with which, according to the invention, on cellulose-containing! Fiber material, such as cotton, viscose rayon, rayon, jute, ramie and hemp, which receives dyeings and prints without boiling-up phenomena according to the new process, can belong to a wide variety of dye classes, for example the azo, anthraquinone or phthalocyanine series. In particular, they can also contain heavy metal bound in complexes. The reactive groups of these dyes can be any substituents which react with alkalis with entrainment of the pair of binding electrons at temperatures which are customary in dyeing and printing processes for reactive dyes. The reactive substituent can be, for example, the residue of a β-halogen fatty acid or the residue of a cyclic carbimide halide which contains at least one halogen atom on a ring carbon atom adjacent to a tertiary ring nitrogen. It can in particular consist of an azine ring of aromatic character which contains at least two tertiary ring nitrogen atoms and at least one halogen of atom numbers 17 to 35 on its adjacent ring carbon atoms, for example a mono-, di- or halogen

209 618/311

Trihalodiazinyl and especially a trichloropyrimidyl radical be.

The protective agents used according to the invention are either mixed with the dyes or added to the dye baths or printing inks. With two-bath procedures they can optionally also be added to the fixation bath first. The salts of the nitrated aromatic sulfonic acids are used in amounts of about 1 to 20 parts by weight per 1000 parts of colorant or printing ink used. The appropriate amount depends on the sensitivity of the one used Dyes and amounts to about 5 to 10 parts per 1000 parts of colorant. The amount of vanadic acid The salt depends primarily on that of the nitroarylsulfonate used. In general Quantities of about one twentieth are sufficient for dyeing and even for printing amounts of about a thousandth of the weight of the nitroarylsulfonate.

The dyeing and printing of cellulosic! Fiber material with reactive dyes with the addition of Protective agents in accordance with the present process are otherwise carried out according to those for this class of dyestuffs common methods. The beneficial effect of the protective agents used according to the invention is evident especially in the wet development process, such as the so-called pad steam and single bath steam process; but also in the dry development process, d. H. the so-called thermosetting process, the use of protective agents according to the invention is often indicated. Their effect is particularly striking when dyeing and printing rayon such as viscose and copper rayon and rayon.

HO ₃ S

The use of defined protective means

when dyeing and printing cellulose-containing!

Fiber material with reactive dyes does not impair the authenticity of the dyeings and Prints. Often even a facilitated fixation of the dyes on the fiber is noticeable by gets stronger colors than in the presence of the protective agent.

Further details are from the following

ίο Examples can be seen which the illustration serve the invention. It should also be noted that reactive dyes, which act as reactive substituents have a Polyhalogenpyrimidinmppe, isomer mixtures, since in the reaction with tri- or Tetrahalopyrimidines it is difficult to determine which halogen atom corresponds to the amino group of the Dye reacts. The pyrimidine residue can be bonded in the 2- or 4-position. With the formulas the following examples show the bond in the 2-position of the pyrimidine ring. These formulas therefore illustrate only one component of the isomer mixture, but are to be understood as meaning that they also include the other component.

Unless expressly stated otherwise, the parts in the examples are understood to be parts by weight. Parts by weight are related to parts by volume as grams are to cubic centimeters.

30th

example 1

Mercerized cotton is padded with an aqueous solution containing 20 parts of the per 1000 parts Dye of the formula

SO, H

Cl

Cl

50 parts of urea, 20 parts of sodium carbonate, 10 parts of sodium 3-nitrobenzenesulfonate and part of sodium metavanadate contains. The impregnated fabric is then dried and for 4 to 8 minutes muffled. The goods treated in this way are rinsed hot and soaped at the boil for 30 minutes with a Solution of 1 part curd soap per 1000 parts water. A strong, bright yellow color is obtained. If you proceed in the same way without using sodium metavanadate, you get a significant one weaker and more cloudy coloring. The same brilliant coloring can be achieved if one instead of 10 parts of sodium 3-nitrobenzenesulfonate, the same amount of an alkali metal salt 2-nitrobenzenesulfonic acid, 4-nitrobenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid or 3,5-dinitrobenzenesulfonic acid used.

An equally good result is also obtained if instead of sodium metavanadate the equal amount of potassium metavanadate, ammonium metavanadate, sodium orthovanadate, potassium orthovanadate, Sodium pyrovanadate or potassium pyrovanadate is used.

Example 2

Spun rayon is impregnated at 20 ° C. with an aqueous solution containing 20 parts of the dye in 1000 parts the formula

NH ₂ SO ₃ H

Cl,

Cl-C
Cl

N = N

: c -ν; c = ν '

C-NH

Contains 10 parts of sodium 3-nitrobenzenesulfonate and 1 part of ammonium metavanadate. The impregnated fabric is then dried at 100 to 120 ° C. The goods prepared in this way are padded with a solution containing 10 parts of sodium hydroxide solution (36 ° Be) and 300 parts of sodium chloride per 1000 parts of water and then steamed at 100 to 102 ° C. for 15 to 60 seconds. To remove unfixed dye, the material to be dyed is first rinsed with cold water and then soaped at the boil for 30 minutes with a solution of 1 part of curd soap in 1000 parts of water. A pure, uniform, orange color is obtained. If otherwise the same conditions are used without sodium metavanadate, the result is a significantly weaker and more cloudy color. An equally brilliant color is obtained, 15

if instead of the 10 parts 3-nitrobenzenesulfonic acids Sodium the same amount of an alkali salt of 2-nitrobenzenesulfonic acid, 4-nitrobenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid or 3,5-dinitrobenzenesulfonic acid used.

Similar colorations are also obtained if the sodium metavanadate is replaced by the same Amount of potassium metavanadate, ammonium metavanadate, sodium orthovanadate, potassium orthovanadate, sodium pyrovanadate or potassium pyrovanadate is used.

Example 3

Cotton, rayon or rayon rayon is made using one of the usual methods with the following Printing color:

40 parts of the dye of the formula

.N-C

OH NH- '

Cl

c — ei

N = N -V

JTl LJg O ν

HO, S n = c (

SO ₃ H

100 parts urea,
200 parts of water,

10 parts of the sodium salt of 3-nitrobenzenesulfonic acid, 630 parts of sodium alginate (5% aqueous solution), 30 parts of sodium carbonate,

0.01 part ammonium metavanadate.

1000 parts of printing ink.

The printed textile material is dried and steamed for 7 to 10 minutes or subjected to a dry heat treatment at 150 to 180 ° C. for 4 to 6 minutes. The goods treated in this way are first rinsed cold, then hot and then boiled for 30 minutes with a solution of 35

40

Soap 2 parts curd soap in 1000 parts water. A deep, pure red print is obtained.

Under otherwise identical conditions, but without the use of ammonium metavanadate, one obtains clearly bluer and cloudy prints.

A similar result is obtained if the printing ink is used instead of the 0.01 part of ammonium metavanadate Contains 0.1 part.

Example 4

Viscose rayon is padded with a solution that contains 30 parts of the dye in 1000 parts of water formula

HO, S

O NH ₂ SO ₃ H NH-C _x , N - C. Xl I.
i
/ \ / \
Γ "Χ > XH ! SO ₃ H ^ Cl 0 NH-

to which 1.0 part of sodium metavanadate has been admixed per 99 parts, 200 parts of urea, 20 parts Contains sodium carbonate and 5 parts of sodium 3-nitrobenzenesulfonate. The impregnated goods is dried and fixed at up to 160 ° C. for 4 to 8 minutes. For removing unfixed The dyed textile material is first rinsed cold, then hot and then with a solution of dye Parts of curd soap in 1000 parts of water soaped at the boil for minutes. You get a strong, brilliant blue color. Used without the use of sodium metavanadate, all other things being equal process, one obtains significantly weaker colorations.

Example 5

Spun rayon is made with a 2% solution of the dye of the formula

Cl

N-C.

> —NH-C

SO, H

HO ₃ S

padded at 50 to 60 ° C and then dried at 100 to 102 ° C. The goods prepared in this way will with an aqueous solution containing 20 parts of sodium hydroxide solution (36 ° Be), 300 parts of sodium chloride in 1000 parts, 10 parts of sodium 3-nitrobenzenesulfonate and Contains 0.5 parts of sodium metavanadate, treated and then for 15 to 60 seconds 100 to 107 ° C steamed. To remove unfixed dye, the material to be dyed is first rinsed with cold water and then soaped at the boil for 30 minutes with a solution of 1 part curd soap in 1000 parts of water. A pure, deep purple color is obtained. Without the use of sodium metavanadate a significantly weaker color is obtained under otherwise identical conditions.

Example 6

3 parts of the dye, obtained by condensation of 1 mol of copper phthalocyanine disulfonic acid disulfochloride with 2 moles of 4,4'-diamino-diphenyl-2,2'-disulfonic acid and then with 2 moles of ß-chlorocrotonic acid chloride, are dissolved in 2000 parts of water and treated with 10 parts of 3-nitrobenzenesulfonic acid Sodium, 0.3 part of sodium metavanadate and 5 parts of trisodium phosphate were added. You go up at 20

35

40

CH ₃

25 ° C with 100 parts of cotton and heated the bath while adding 100 g of sodium chloride in portions per liter to 80 to 85 ° C. The dyeing is carried out at this temperature for 60 minutes and then rinsed the dyed goods first cold, then hot and finally soaped with a solution of 2 parts curd soap in 1000 parts of water for 30 minutes at boiling temperature. A strong, pure blue is obtained Coloring. Without the addition of sodium metavanadate, one obtains one under otherwise identical conditions significantly weaker coloration.

Claims (2)

PATENT CLAIMS: 1. Process for dyeing and printing cellulosic! Fiber material with reactive dyes, characterized in that the dyeing or printing or the fixing of the dyes is carried out in an alkaline medium in the presence of salts of nitrated aromatic sulfonic acids and of small amounts of soluble salts of the oxygen acids of vanadium. 2. The method according to claim 1, characterized by the use of ammonium or Alkali Vanadata. © 209 618/311 6.62