US2004476A

US2004476A - Dyeing of textiles

Info

Publication number: US2004476A
Application number: US568870A
Authority: US
Inventors: Barz Fritz; Landolt Albert; Geigy Wilhelm; Kaegi Hans; Graenacher Charles
Original assignee: Gesellschaft fuer Chemische Industrie in Basel CIBA
Current assignee: BASF Schweiz AG
Priority date: 1930-10-16
Filing date: 1931-10-14
Publication date: 1935-06-11
Anticipated expiration: 1952-06-11
Also published as: GB366918A; NL30888C; FR725637A; BE390553A; DE582101C

Description

"Patented June 11,1935

PATENT OFFICE DYEING OF TEXTILES Fritz Barz, Albert Landolt, Wilhelm Geigy,'Hans Kaeg-i, and Charles Graenacher, Basel, Switzerland, assignors to Society of Chemical Industry in Basle, Basel, Switzerland No Drawing. Application October 14, 1931, Serial No. 568,870. In Switzerland October 16, 1930 11 Claims.

It is known that dyeings produced by means of so-called direct dyestufl's on fibres of vegetable origin, such as cotton or artificial silk from regenerated cellulose, have at best but little fastness to water. This is a difliculty in the way of their use for many purposes, and indeed may exclude their use.

According to thisinvention the fastness to water and to wet ironing, of dyeings obtained with such dyestuffs, and in many cases the fastness to top dyeing with such dyestuffs, is quite generally improved by an after-treatment with water-soluble salts of organic bases which are characterized by their containing, on the one part, at least one basic nitrogen-containing residue x, and, on the other part, at least one aliphatic residue R consisting of ,at least 10 carbon atoms.

This property of the water-soluble salts is quite generally inherent in the just defined bases. It is in a particularly high measure existing with those bases in which thealiphatic residue R consists of 12 or more carbon atoms. It is also indifierent whether the residues R and a: are directly bound to each other, or whether they are indirectly linked by a bridge consisting of an oxygen or nitrogen atom.

Such products in which the residues R an a: are directly bound to each other, thus corresponding to the general formula anion-:t-R

in which a; and B have the above identified significations, are the salts of higher aliphatic amines,

such as diethylcetylamine hydrochloride fa s 0 ZHPN" 0 a:

(cf. Reychler, chemisches Zentralblatt, [1913], "II, page 1376) tie OOH;

, dimethyloctodecenylamino hydrochloride i CHrN- CB 35 H 01 Such products correspond for example to the general formula wherein at stands for the residue of an organic base, 0 means a bridge consisting of an oxygen atom, and R stands for an aliphatic residue consisting of at least 10 carbon atoms. Such compounds are for example the mixed ethers from cetylalcohol and N-hydroxymethylpyridinium chloride of the formula oi-n-onr-o-cnnn I no or: at tin the stearic acid dimethyl or diethylaminoethanolester hydrochloride of the formula H (;JH|

NCH:OH:-0-fi 11 u C] H;

the stearoylcholine chloride of the formula on. on,

N-onr-oH'ro- -om Cl H: 0

(cf. Fourneau, Bull. Soc. Chim. France [4], 15, page 549) the corresponding benzyl derivative of the formula 2 the palmitic acid ester of the I- -hydroxyphenyI-S trimethyl-ammonium chloride of the formula on. cm

the stearic acid ester of the hydroxyethylpyridinium chloride 01' the formula I ct-N-oH,nr-o-c c,1m.

no on the hydrochloride of the diethylaminoethyloctodecyl carbonate of the formula 11 can n-om-cm-o-o-o onnu I the stearyl ester of the addition product of the glycerinemono-chlorhydrine or of the and-glycerinedichlorhydrine to pyridine of the formulas.

In such compounds the stearoyl or the palmitoyl residue may be replaced by the residues of other acids such as oleicacid, capric acid, lauric acid, myristic acid or ricinoleic acid. Further the alcoholic residue, such as the residue of the cetyl alcohol, may be replaced by the alcoholic residues which correspond to the above named acids, such as oleic alcohol etc.

Further compounds in which the two residues R and a: are not directly bound to each other are for example the salts of such partially acylated polamines which have been acylated with such acids which themselves contain the above defined residue B, it being indifferent whether the nonacylated amino groups of the polyamine are present in the form of a primary, secondary or tertiary base or in the form of a quaternary ammonium compound. Such partially acylated polyamines are inter alia disclosed in the U. S. Patents 1,534,525 and 1,737,458. Other partially acylated polyamines are for example such which derive from diamines containing OH-groups, for example the hydrochloride of oleoyl-p-hydroxy- 'y-diethylamino-propyl-amide of the formula (cf. Patent 1,805,355, Example 1) and the ammonium compounds thereof, such as I 1 1 Ocm-n-cr'a-on-cm-rm-o o-c a CK 6,11. tn

as also such'which derive from cyclic dlamines,

hydrochloride of the formula as the addition product of dimethyl-sulfate to such as the stearoyl-para-amino-dlmethyl-aniline (cf. German Patent 559,500, Example and the ammonium compounds deriving therefrom, such the above compound of the formula cm on:

cnPo-s-o H,

the 4-oleoyl-amino-(diethyl-amino-ethyl-methyl) -aniline hydrochloride of the formula (cf. Patent 1,894,375, Example 4) suitable monoacyl-piperazine salts (cf. Fourneau, Bull. Soc. Chim. France [4], 45, Pages 1172-1189), further basic urethanes', such as, for example, the dimethyl sulfate addition product to m-dimethylamino-phenyl-cetylurethane of the formula on, 011, om No-s-o-om NH-C-O-UggHg or to diethylamino-ethyl-cetylurethane of the formula and the like. Such acylated polyamines may further be produced by .partially acylating compounds, such as diethyl'enetriamine, triethylenetetramine, NHzCH2-CH2NH-CH2CH2 NHa, NH2-CHrCHzNH-CH2CH2NH- CH2-CH2NH2, etc., and other similar compounds, and their .alkylation or varalkylation products, or the ammonium compounds thereof.

Among these products those are particularly valuable whichderive from high molecular acids. Among these there may be mentioned capric acid, palmitic acid, stearic acid, and oleic acid, lauric acid, and the like (of. Patent 1,947,951).

The improvement in the fastness to water is not limited to direct dyeings, but it is to ,be observed also in the case or dyeings which are subsequently developed, for instance by after-treatment with formaldehyde, or by diazotization and coupling on the fibre. I

The invention opens the door for the use'of direct dyestufls for dyeing hat bands, umbrella silks, batique goods, half-wool goods or half-' silk goods which must be dyed by the two-bath process, namely first with the direct dyestufl' and then as a top dyeing with an acid dyestufl in an acid bath, and also to other applications of such dyestuffs, the improvement constituting a considerable industrial advance.

Not only can the fastness towards water of dyeings on cellulosic textile materials, this expression comprising'textiles from natural cellulose, such as cotton, ramie, linen, iute etc., or from regenerated cellulose, such as so-called viscose silk or cuprammonium silk, be improved by this invention, but similar effects can be produced on other materials, such as-paper or wood. More or less pronounced eifects can also be obtained on other textiles or other materials, such as wool and acetate silk, even ifthey have been dyed with dyestufls other than direct dyeing dyestuffs, for example acid dyestufls. The aftertreatment of the dyed material may occur during any of the operations which follow dyeing, for example, in the finishing operation, the watersoluble salts of the bases containing the above mentioned residues 2: and B being added to the appropriate treatment bath.

' The following examples illustrate the invention:-

. Example 1 100 kilos of cotton yarn are dyed with 2 kilos of Cotton yellow CH (Schultz 1923,

No. 304) and 20 kilos of crystallized Glaubers salt.

kilos of viscose tricot are dyed in the usual manner at boiling temperature with 0.2 kilo of Chlorantine red 8BN (Schultz 1923,

in a bath containing Glaubers salt. After rinsing the material is after-treated for 20 minutes in a cold solution of 100 grams of the cethylether of the N-hydroxymethylpyridinium chloride in 200 liters of water, hydroextracted and dried. The fastness towards water of the knitted fabric has become essentially better.

Example 3 Cotton piece goods which have been dyed as usual with 2 per cent. ofDirect sky blue green shade (Schultz 1923, No. 424) are after-treated in a fresh bath with a solution of 1 per cent. (calculated on the weight of the goods) of the -oleic acid ester of the hydroxy-ethylpyridinium chloride and dried, the operation being as indicated in Example 2. The dyed material is fas towards water.

Example 4 50 kilos of cotton yarn are dyed with 1.5 kilos of Direct Saframine RW (Color Index Supplement 1928, P e 39) 1000 litres of water,

0.5 kilo of crystallized sodium carbonate and kilos of crystallized sodium sulfate,

for one hour at boiling temperature, then rinsed and treated in abath consisting of 1000 litres of water and 0.5 kilo of the trimethylammoniummethylsulfate of monostearoyl-para-phenylenediamine for -30 minutes at 4550 C., and finally rinsed for a short time and dried. The dyeing thus after-treated has an essentially improved fastness to water.

Example 5 Bleached cotton material is dyed in a neutral rinsed and dried.

bath containing Glaubers salt for one hour at boiling temperature with 3 per cent. of direct fast violet BL (a dyestui'f comparable with No. 325

of the Color Index) and then rinsed. The dyed,

Example 6 A mixed fabric of viscose artificial silk and cotton is dyed in the usual manner in a bath containing Glauber's salt with 2.5 per cent. of Rigan blue (3- (Melliands Textil-Berichte 1930, page 642) for one hour at 70-80 C. andis then after-treated in a further bath with 1 per cent. of the acetate of oleoyl-p-hydroxy-y-diethylamino-propylam'lde (cf. specification 1,805,355, Example 1), as

inExample 4. In this case also there is an essentially improved fastness to water.

Example 7 100 kilos of viscose thread are dyed for one hour at 80 C. with 6 kilos of Melantherine BH (Color Index No. 401), 1 kilo of crystallized sodium car-- bonate and 40 kilos of crystallized sodium sulfate.

After rinsing well the material is treated with a solution of 0.6 kilo of trimethylammonium-methyl sulfate of mono-oleoylethylenediamine in 2000 litres of water for minutes at 45 C. It is then Example 8 10 kilos ofhalf-silk ribbon (cotton and silk) are dyed with 0.25 kilo of Chlorantine fast brown BBL (Color Index Supplement, pa e 31), 0.150 kilo of Chlorantine fast blue 8GL (Color Index Supplement, page 31) 0.100 kilo of Diamine fast orange R (Color Index, page 349) 0.2 kilo of marseilles soap and 4 kilos of crystallized sodium sulfate in 400 litres of water atapproximately boiling point for one hour. After thorough rinsing the goods are after-treated as described in Example 4 in a liquor which contains 0.06 kilo of the acetate of mono-oleoyl-diethyl-ethylenediamine (cf. specification 1,534,525, Example 9) in 200 litres of 4 water. In this case also there isan essential improvement in the fastness to water.

Example 9 In half-wool the cotton is dyed as usual with 3 per cent. of Chlorantine fast blue GLN (Color Index Supplement, page 31), then rinsed and Example 10 nan-won material is first dyed in an acid bath in the usual manner with l per cent. of Tartrazine (Color Index No. 640). It is then well rinsed, and

the cotton is dyed at 55 C. with 3 per cent. of Direct sky blue green shade (Color Index No. 518) with or without addition of a reserving agent,

such as the material known by the registered name Katanol W.

The half-wool material which has thus been dyed in a two-color effect is rinsed and then water.

Example 1.1

Difilculties exist in obtaining pure white or colored discharges on material dyed with substan tive dyestuifs, in the washing operation which follows steaming. If on the other hand the goods are passed after steaming through a solution containing for example 0.3 gram of the trimethyl-ammonium-methylsulfate of mono -oleoyl ethylenediamine per litre, the dyeing becomes vfast to water, so that it can be washed thor oughly with water. For example, if cotton velvet dyed with 3 per cent. of Direct Safranine B (Color Index, page 351) is discharged in the known manner by means of sodium sulfoxylate, and then passed through the aforesaid trimethylammonium-methylsulfate solution, the velvet may be allowed to remain overnight in luke warm water without fear that the color will run.

A likeresult is obtained if the treatment with the trimethylanunonium methylsulfate of monooleoylethylenediamine is interposed between the dyeing and printing operations.

7 Example 12 Cotton'fabric is printed with printing color having for example the following composition:-

10 grams of Chlorantine fast blue RL (Color Index, page 345) 670 grams of water 300 grams of solid British gum 20 grams of sodium phosphate 7 1000 grams The material is steamed twice in a quick steamer or for half an hour in a vessel at ordinary pressure. It is then passed through a bath containing per litre 0.3 gram of oleoylaminoethyl-diethylmethylammoniumsulfomethylate (of. Patent 1,737,458, Example 2), rinsed and dried. There is obtained a blue print of good fastness to water.

Similar effects are also attained if the acylated diamines used in the foregoing example are replaced by others, such as the trimethylammonium-methyl sulfate of monostearoyl metaphenylenediamine (of. German Patent 559,500); the addition product of dimethyl sulfate and ortho-, meta or para-dimethylaminophenylcarbamic acid hexadecyl or octodecyl ester; the hydrochloride of diethylaminoethylimino-dicarboxylic acid dimenthyl ester (cf. Patent 1,527,868, Example 4) or the corresponding addition product with dimethyl sulfate; and the .like.

Similar efiects are also attained if the watersoluble salts of the bases containing the residues R and a: mentioned in the introduction, and used 1 introduction.

Example 13 Silk paper is dyed by the immersion process by padding with a dyestufi solution containing 10 grams of Direct Sairanine B (Golor Index, page 351) per litre. It is then treated, either after drying or without drying, in a bath containing 1 gram of ole-oylaminoethyl-diethylmethylammoniumsulfomethylate (of. Patent 1,737,458, Example 2) per litre. The material is thus dyed a red shade which is fast to water. If instead of Direct $afranine B there is used in the process of this example Kiton blue A (Color Index Supplement, page 44) there is obtained a blue dyeing fast to water.

Example 14 Loaded silk piece goods are dyed for hour at C. with 215 per cent of Alizarin Fast blue BB (Color Index Supplement, page 26) and 4 per cent of acetic acid. They are then rinsed in cold water and after-treated for 20 minutes at ill-45 C. with l per cent of the trimethylammoniummethylsulfate of mono-oleoylethylenediamine. The blue dyeing is rendered essentially faster towards water by the after-treatment.

What we claim is:---

1. A process for improving the fastness of dyeings produced onmaterials by means of watersoluble dyestuffs, which consists in subjecting the dyed material to an after-treatment with watersoluble salts of organic bases which bases are characterized by containing at least one basic nitrogen-containing residue and an aliphatic residue consisting ofat least 10 carbon atoms.

2. A process for improving. the fastness of dyeings produed on textile materials by means of water-soluble dyestuifs, which consists in subjecting the dyed material to an after-treatment with water-soluble salts of organic bases'which bases are characterized by containing at least one basic nitrogen-containing residue and an aliphatic residue consisting of at least 10 carbon atoms.

3. A process for improving the fastness of dyeings produced on textile materials by means of water-soluble dyestuffs, which consists in subjecting the textile material dyed with direct dyeing dyestufis to an after-treatment with watersoluble salts of organic bases which bases are characterized by containing at least one basic nitrogen-containing residue and'an aliphatic residue consisting of at least 10 carbon atoms.

4. A process for improving the fastness of dyeings produced on textile materials by means oi? water-soluble. dyestuffs, which consists in subjecting the textile material dyed with direct dyeing dyestuiis to an after-treatment with waterso-luble salts of organic bases which bases are characterized by containing at least one basic nitrogen-containing residue and an aliphatic residue consisting of at least 12 carbon atoms,

5. A process for improving the fastness of dyeings produced on cellulosic textile materials selected from the group consisting of native and,

regenerated cellulose by means of water-soluble direct dyeing dyestuffs, which consists in subjecting the cellulosic textile material dyed with direct dyeing dyestuffs to an after-treatment with water-soluble salts of organic bases which bases are characterized by containing at least one 6. A process for improving the iastnessof dyeings produced on cellulosic textile materials selected from the group consisting of native and regenerated cellulose by means 01' water-soluble dyestufls, which consists in subjecting the cellulosic textile materials dyed with direct dyeing dyestufis to an after-treatment with a watersoluble salt of the formula in which .1: stands for a basic nitrogen-containing residue, and R for an aliphatic residue consisting of at least 12 carbon atoms.

'1. A process for improving the iastness o! dyeings produced on cellulosic textile materials selected from the group consisting oi native and regenerated cellulose by means of water-soluble dyestuffs, which consists in subjecting the cellulosic textile materials dyed with direct dyeing dyestufis to an after-treatment with a watersoluble salt of the formula 8. A process for improving the fastness of dyeings produced on cellulosic textile materials' selected from the group consisting of native and regenerated cellulose by means of water-soluble dyestuffs, which consists in subjecting the cellulosic textile materials dyed with direct dyeing dyestuffs to an after-treatment with a water-soluble salt of the general formula in which 2: stands for the residue of an organic base, constitutes a bridge consisting of an oxygen atom, and R stands for an aliphatic residue containing at least 12 carbon atoms.

9. A process for improving the fastness of dyeings produced on cellulosic textile materials selected from the group consisting of native and regenerated cellulose by means of water-soluble dyestufls, which consists in subjecting the cellu- 10. A process for improving the tastness ct dyeings produced on cellulosic textile materials selected from the group consisting of native and regenerated cellulose by means of water-soluble dyestuffs, which consists in subjecting the cellulosic textile materials dyed with direct dyeing dyestuffs to an after-treatment with a watersoluble salt of such partially acylated polyamines which have been acylated with such acids which contain an aliphatic residue consisting of at least 12 carbon atoms.

11. A process 'for improving the fastness oi dyeings produced on cellulosic textile materials selected from the group consisting of native and regenerated cellulose by means of water-soluble dyestuffs, which consists in subjecting the cellulosic textile materials dyed with direct dyeing dyestufis to an after-treatment with a water-soluble salt of the formula HANS KAEGI. CHARLES GRAENACI-IER.