US3085849A - Process for dyeing and printing cellulose-containing fibres and composition for same - Google Patents

Description

United States Patent No Drawing. Filed Mar. 10, 1961, Ser. No. 94,704 Claims priority, application Switzerland Mar. 11, 1960 4 Claims. (Cl. 8-54.2)

The present invention concerns a process for the dyeing and printing of fibres containing cellulose with reactive dyestuffs, the dyes and printing pastes used accr-oding to thech invention and the material fast dyed or printed there- 'Wl It is known that when dyeing fibres containing cellulose, in particular when dyeing regenerated cellulose in the presence of alkali at a raised temperature, the shade and colour strength of certain substantive dyestuffs is disadvantageously influenced. This phenomenon is known in the trade as boil fading. This boil fading, which is principally due to a reduction process, is caused either by the textiles themselves or by impurities adhering to them or also present in the dyebath. This phenomenon can be prevented or at least minimised by the addition of salts of nitrated aromatic sulphonic acids to the dye bath or to the printing paste.

Such boil fading phenomena also very often occur with reactive dyestuffs, i.e. dyestuffs which react chemically with the cellulose and which are, for this purpose, fixed generally at a raised temperature and in the presence of acid binding agents such as sodium carbonate, sodium hydroxide or other agents which react alkaline. When attempts are made to correct this by the addition of salts of nitrated aromatic sulphonic acids, in spite of this very often a clouding and/ or weakening of the dyeing occurs.

It has now been found that on dyeing and printing fibres containing cellulose with reactive dyestuffs, the boil fading phenomena can be eifectively prevented if the dyeing or printing is performed in an alkaline medium in the presence of salts of nitrated aromatic sulphonic acids and of small amounts of soluble salts of vanadium oxygen acids.

In dyeing processes, principally the water soluble ammonium and alkali metal salts, but in printing also the less soluble earth alkaline, copper, manganese salts of sulphated monoand di-nitro compounds of the benzene, naphthalene and anthracene series are used as salts of nitrated aromatic sulphonic acids. Advantageously, alkali metal and ammonium salts of mononitrobenzene sulphonic acid, especially m-nitrobenzene sulphonic acid, and dinitrobenzcne sulphonic acid as well as mixtures of same are suitable.

The vanadates usual as contact substances in oxidationreduction processes are used as salts of vanadium oxygen acids. As they are used in the present process in very small amounts, in order to attain a good distribution they should be Water soluble in the dyeing or printing agent. Aduantageously soluble salts as ammonium vanadates, alkali metal vanadates and mixtures of same are applicable. 'lhe alkali vanadates are preferred but also ammonium and amine salts of vanadic acids can be used. It has been found that simple salts, double salts and also complex salts of meta-, orthoand pyro-vanadates can be used; preferred compounds are the ammonium, sodium, potassium and lithium metavanadates.

The reactive dyestuffs, with which dyeings and prints without boil fading effects are obtained according to the 3,085,849 Patented Apr. 16, 1963 invention on fibres containing cellulose such as cotton, viscose rayon, staple fibre, jute, ramie and hemp by the new process, can belong to the most various classes of dyestuffs, for example, the azo, anthraquinone or phthalocyanine series. In particular they can also contain heavy metal bound in complex linkage. The reactive egroups of these dyestuffs can be any substituent which reacts with alkalies while splitting off as anion at temperatures such as are usual in dyeing and printing processes with reactive dyestuffs. For example, the reactive substituent can be the radical of a fl-halogen fatty acid or the radical of a cyclic carbimide halide which contains at least one halogen atom at a ring carbon atom adjacent to a tertiary ring nitrogen atom. In particular, this substituent can consist of an azine ring of aromatic character which contains at least two tertiary ring nitro-' gen atoms and at least one halogen of the atomic numbers 17 to 35 at ring carbon atoms adjacent thereto, that is, for example, a mono-, dior tri-halogen diazinyl radical and, in particular, a trichloropyrimidyl radical.

The protecting agents used according to the invention are either mixed with the dyestufis or added to the dye baths or printing inks. In two-bath processes it is also possible to add them only to the development bath. The salts of the nitrated aromatic sulphonic acids are added in amounts of about 1 to 20 parts by weight per 1000 parts of dyestufi or printing paste. The advantageous amount depends on the sensitivity of the dyestuffs used and is about 5-10 parts per parts of colouring agent. The amount of the salt of vanadic acid depends chiefly on that of the nitroaryl sulphonate added. In dyeing, generally amounts of only about are suflicient and in printing even amounts of about of the weight of the nitroaryl sulphonate are sufi'icient.

In other respects the fibres containing cellulose are dyed and printed with reactive dyestuffs with the addition of protecting agents according to the present process, by the methods usual for this class of dyestuffs. The advantageous effect of the protecting agents used according to this invention is apparent particularly in the Wet development processes such as e.g. the so-called pad-steam process and the single bath-steam process; but also the use of the protecting agents according to the invention is often indicated in dry development process, i.e. in the so-called thermofix process. Their effect is particularly striking in the dyeing and printing of synthetic silks such as viscose and cuprammonimn rayon and staple fibre.

The use of the protecting agents as defined in the dyeing and printing of fibres containing cellulose with reactive dyestuffs does not cause any disadvantageous side effects, for example it does not prejudice the fastness of the dyeings and prints. Often, even an easier fixation of the dyestuffs onto the fibre is noticeable in that stronger dyeings are obtained than when there are no protecting agents present.

Further details can be seen from the following examples which serve to illustrate the invention. It is also pointed out that reactive dyestuffs having a polyhalogenpyrimidine group as reactive substituent are isomeric mixtures as on being reacted with trior tetra-halogen pyrimidines it is ditficult to determine which halogen atom reacts with the amino group of the dyestuff. In such reactions, the pyrimidine radical can be bound in the 2- or 4-position. In the formulae given in the following examples the bond is shown in the 2-position of the pyrimidine ring. Thus these formulae illustrate only the one component of the isomeric mixture but they should be read to embrace the other component also.

Where not otherwise stated, parts are given in the examples as parts by weight. The relationship of parts by weight to parts by volume is as that of grammes to cubic centimetres. The temperatures are in degrees centigrade.

EXAMPLE 1 50 parts of urea, 20 parts of sodium carbonate, 10 parts of the sodium salt of 3-nitrobenzene sulphonic acid and 1 minutes. The goods so treated are rinsed hot and soaped at the boil for 30 minutes with a solution which contains 1 part of grain soap per 1000 parts of water. A strong, vivid yellow dyeing is obtained. If the same procedure is followed but no sodium metavanadate is used, then a considerably weaker and more cloudy dyeing is obtained. The same brilliant dyeing is obtained if, instead of the 10 parts of the sodium salt of S-nitrobenzene sulphonic acid, the same amount of an alkali metal salt of 2-nitrobenzene sulphonic acid, 4-nitrobenzene sulphonic acid, 2,4-dinitrobenzene sulphonic acid or of 3,5- dinitrobenzene sulphonic acid is used.

In addition, a similarly good result is obtained if, instead of the sodium metavanadate, the same amount of potassium metavanadate, ammonium metavanadate, sodium ortho-vanadate, potassium ortho-vanadate, sodium pyrovanadate or potassium pyrovanadate is used.

Deep brilliant dyeings are obtained if, in the above example under otherwise the same conditions, the dyestuffs given in the following table are used.

Table 1 Shade on cellu- SO H H0 8 ITIH:

Blue.

0 Cu-O l l Violet.

Brilllant red.

part of sodium metavanadate per 1000 parts. The impregnated goods are then dried and steamed for 4 to solution which contains 20 parts of the dyestuif of the 2,4-dinitrobenzene sulphofic' acid or of 3,5-dinitroben formula zene sulphonic acid is used.

5033 N31 5033 Similar dyeings are also obtained if, instead of the 01 I I sodium metavanadate, the same amount of potassium" L QN=N 5 metavanadate, ammonium metavanadate, sodium ortho vanadate, potassium orthovanadate, sodium pyrovanadate /C NH or potassium pyrovanadate is used.

803E If the dyestuffs given in the following table are used 01 under the same conditions, then deep, brilliant dyeings 10 parts of the sodium salt of 3-nitrobenzene sulphonic 10 are also obtained.

Table 2 No. Dyestufi Shade on cellulose fibres N oqmOswi CH N N- -SO3H Scarlet. NH;

01 S 311 H 0 NH- N=N- NH-O COl Brilliant red. I

N=O SOaH HOaS- J CH3 4} N 11038 s opera-om-o O--NHC SOaH g I /N Yellow.

0 4..... H033 N=NCH\ N Reddish yellow. (:1 HOOO- I (I NH-CO-GH: OH; 30311 5...- Condensation product from 1 mol of copper phthaloeyanine disulphonie acid Turquoise blue.

disulphoehloride and 1 mol of ammonia, 1 mol of 2,4-diaminobenzene-1-sulphonic acid and 1 mol of 2,4,5,6-tetrachloropyrimidine.

acid and 1 part of ammonium metavanadate in 1000 EXAMPLE 3 parts. The impregnated material is then dried at 100- Cotton, taple iibre 0r viscose is printed by one of the 120. The goods so prepared are then treated in the usual methods wlth the followmg Punting Ink! foulard with a solution which contains parts of caustic 40 parts of the dyestufi of the formula soda lye (36 B.) and 300 parts of sodium chloride in 1 1.000 parts of water after which the goods are steamed for 15 to 60 seconds at 100102. To remove non-fixed NEE-O dyestuff, the goods are first rinsed cold and then soaped C for 3 minutes at the boil with a solution of 1 part of I 51 grain soap in 1000 parts of water. A pure, level orange H038 HOgS- S03H dyeing is obtained. If dyeing is performed under the 100 parts of urea same conditlons but without sodium metavanadate then 200 parts of water a considerably weaker and more cloudy dyeing is ob- 10 Parts Of the Sodium Sa Of -nitr0benZene sultained 7O phonicacid An equally brilliant dyeing is obtained if, instead of the 630 Paris of Sodlum algmate (5% aqueous Solu' 10 parts of the sodium salt of 3-n1trobenzene sulphonic 3 parts f Sodium carbonate acid, the same amount of an alkali metal salt of Z-nitro- 0.01 part of ammonium metavanadate benzene sulphonic acid, 4-nitrobenzene sulphonic acid, =10l0.0l parts of printing ink The printed textile is dried and steamed for 7-10 minutes or is given a dry heat treatment at 150-180" for 4-6 minutes. The goods so treated are rinsed, first cold and then hot, whereupon they are soaped at the boil for 30 minutes with a solution of 2 parts of grain soap in 1000 parts of water. A deep, pure red print is obtained.

Under otherwise the same conditions but without the use of ammonium metavanada-te, considerably more blue and cloudy prints.

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

The same pure, full prints are also obtained if, instead of the ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate, potassium orthovanadate, sodium pyrovanadate or potassium pyrovanadate is used.

Deep, pure prints are also obtained if under otherwise the same conditions, one of the dyestuffs given in the following table is used in the above example.

in which 1.0 part of sodium metavanadate per 99 parts have been mixed, 200 parts of urea, 20 parts of sodium carbonate and 5 parts of the sodium salt of 3-nitrobenzene sulphonic acid per 1000 parts of water. The impregnated goods are dried and fixed for 4-8 minutes at 140-160". To remove non-fixed dyestuff, the dyed textile is rinsed, first cold and then hot whereupon it is soaped at the boil for 30 minutes with a solution of 2 parts of grain soap Table 3 No. Dyestufl Shade on cellulose fibres H0 NHC\ /N N=N d; 1 O O CH3 Brilliant re SO H HO S $03K N 2- no ONH- SO3H no S0311 Scarlet.

C=N I (I3 :N-

| so r:

(l) NH: A son: 3...- H018 (31 Blue.

I Y N-C l l 0 NH- NH--O C-Cl so H N=O (I) Cu-O 4 HO S N=i-I Ruby.

| son; HO3S- NHCOGH2-CH1C1 Cl NJ; s HoasON=N N=N, NH-O N Orangebrown.

N=C SOsH H:

NHz

EXAMPLE 4 in 1000 parts of water.

l A strong, brilliant blue dyeing Viscose 15 treated in the foulard with a solution which 7 is obtained. If the dyeing is performed under otherwise 10 are are treated with an aqueous solution which, in 1000 parts of water, contains 2.0 parts of caustic soda lye (36 B.), 300 parts of sodium chloride, parts of the sodium salt of 3-nitrobenzene sulphonic acid and 0.5 parts ofv sodium metavanadate after which they are steamed for 15 to 60 seconds at 100-107. To remove non-fixed dyestuif the goods are rinsed, first cold and then they are soaped for minutes at the boil with a solution of 1 part of grain soap in 1000 parts of Water. A pure, deep violet dyeing is obtained. Under otherwise the same con- Table 4 N o. Dyestufi Shade on cellulose fibres N g SOaH 1a.- N\ C-NH -SO;H l Yellow.

C=N l l N N- H=O -HN 1 01 A} 0 Cu0 SOaH 2 O1C O-HN N=N- Reddish blue.

No 01 I z c r HOaS- NHG\ o-o1 N=O 3..-- HO3S- N=N 51 Greenish black,

H0 NH-CO-CH=O-CH3 1 4.--. N=N- Brilliant red.

SO3H H0 8- EXAMPLE 5 ditions but without using sodium metavanadate, a con- Staple fibre is treated at -60 in the foulard with a 2% solution of the dyestufi of the formula siderably Weaker dyeing is obtained.

The same strong dyeings are attained if, instead of the 20 parts of the sodium salt of 3-nitrobenzene sulphonic acid, the same amount of an alkali metal or ammonium salt of 2-nitrobenzene sulphonic acid, 4-nitrobenzene sulphonic acid, 2,4-dinitrobenzene sulphonic acid or 3,5- dinitrobenzene sulphonic acid is used.

The same results are also obtained if, instead of the sodium metavanadate, the same amount of potassium metavanadate or ammonium metavanadate, sodium orthovanadate, potassium orthovanadate, 'sodium pyrovanadate or potassium pyrovanadate is used.

Pure deep dyeings are also obtained if, in the above example, one of the dyestuffs given in the following table and is then dried at 100102. The goods so prepared is used.

Table Shade on cellu- Dyestufl lose fibres 0 1, 1.... N= NCH C1 Redfilsh e ow. N- i; y HOOC :N

NH-O 0-01 80:13

2-... CO-NHQSO3H on Red.

HOxS- NHO N C O 3-... HOaS- N=N Reddish black.

I NH: O l I 4.... Condensation product from 1 mol of copper phthaloeyanine sulphonic acid trisulpho- Turquoise blue.

chloride and 2 mols of ammonia, 1 mol of m-phenylenediamine sulphonic acid and the condensation product from 1 mol of cyanuric chloride and 1 moi of 2-aminobenzene-l-sulphonic acid.

EXAMPLE 6 3 parts of the dyestuff obtained by condensing 1 mol of copper phthalocyanine disulphonic acid disulphochloride with 2 mols of 4,4'-diaminodiphenyl-2,2-disulphonic acid and then with 2 mols of fl-chlorocrotonic acid chloride, are dissolved in 2000 parts of water and 10 parts of the sodium salt of 3-nitrobenzenersulphonic acid, 0.3 part of sodium metavanadate and 5 parts of trisodium phosphate are added. 100 parts of cotton are entered at -25 and the bath is heated to 80-85 while gradually adding 100 g. of sodium chloride per litre in portions. Dyeing is continued for 60 minutes at this temperature,

finally they are soaped at the boil for minutes with a solution of 2 parts of grain soap in 1000 parts of water.

A strong, pure blue dyeing is obtained. Under the same ammonium metavanadate or potassium metavanadate, so-

dium orthovanadate, potassium orthovanadate, sodium pyrovanadate or potassium pyrovanadate is used.

Other deep, pure dyeings are obtained if the dyestuffs given in the following table are used in the above examthe goods are then rinsed, first cold and then hot, and ple.

Table 6 No. Dyestufl Shade on cellulose fibres N.. 1 -N= NH-O OH Reddish yellow.

$0311 2 HO3SON=N N= -NH-o0-orrl-o11r-oi Brown.

sozn

Table 6Continued No. Dyestufl Shade on cellulose fibres N. ll\ HO OGH3 HO NHC\ /N N=O 3 N=N I I OO Ha Red. H0 8 HO:S SO:H

O C u-- 0 if H: 4 H035 ar-NtiJ-som Reddish blue.

I 1TH S 0 3H f i Cl0 /OCI What We claim is:

1. Process for the dyeing and printing of cellulosecontaining fibre which comprises treating in alkaline medium, said fibre with a composition containing a reactive dyestuif and, as protective agents against boil fading phenomena, salts of nitrated aromatic sulphonic acids and small amounts of soluble salts of vanadium oxygen acids.

2. Process according to claim 1 wherein the soluble salt of vanadium oxygen acid is a member selected from the group consisting of ammonium vanadates and alkali metal vanadates.

3. A dyeing and printing composition for cellulosecontaining fibres comprising, in alkaline medium, a reactive dyestuif and, as protective agents against boil fad- Refet'ences Cited in the file of this patent UNITED STATES PATENTS 2,205,887 Kern June 25, 1940 2,278,540 Ellis et a1. Apr. 7, 1942 2,880,052 Conciatori et al. Mar. 31, 1959 2,891,941 Fasciati et al. June 23, 1959

Claims (1)

1. PROCESS FOR THE DYEING AND PRINTING OF CELLULOSECONTAINING FIBRE WHICH COMPRISES TREATING IN ALKALINE MEDIUM, SAID FIBRE WITH A COMPOSITION CONTAINING A REACTIVE DYESTUFF AND, AS PROTECTIVE AGENTS AGAINST BOIL FADING PHENOMENA, SALTS OF NITRATED AROMATIC SULPHONIC ACIDS AND SMALL AMOUNTS OF SOLUBLE SALTS OF VANADIUM OXYGEN ACIDS.