Process for the treatment of cellulose-fibres

Process for the treatment of cellulose fibres in the form of a doubled pre-drawn sliver, by impregnating with fixing agents of the formula ##STR1## IN WHICH: R.sub.1, R.sub.2 and R.sub.3 represent C.sub.1 -C.sub.4 -alkyl, or hydroxyl-substituted C.sub.2 -C.sub.4 -alkyl or PA1 R.sub.1 and R.sub.2 can be jointed to form a ring with N, PA1 R.sub.4 represents hydrogen or methyl, PA1 X.sup.n(-) represents an anion and PA1 n represents 1, 2 or 3, And with adhesives, and subsequently subjecting to a fixing process.

The subject of the invention is a process for the treatment of cellulose 
fibres with fixing agents before the manufacture of yarn. The process is 
characterised in that cellulose fibres or their mixtures with synthetic 
fibres, in the form of a doubled pre-drawn sliver, are impregnated with 
fixing agents of the general formula 
##STR2## 
in which R.sub.1, R.sub.2 and R.sub.3 represent a C.sub.1 -C.sub.4 -alkyl 
group, or a hydroxyl-substituted C.sub.2 -C.sub.4 -alkyl group or 
R.sub.1 and R.sub.2 can be joined to form a ring with N, 
R.sub.4 represents hydrogen or a methyl group, 
X.sup.n(-) represents an anion and 
n represents 1, 2 or 3, 
And with adhesives, and are subsequently subjected to a fixing process. 
In this process it is possible either simultaneously to apply anionic 
dyestuffs, preferably of the type of the direct dyestuffs, or to carry out 
the process subsequent to the impregnation and fixing and, if desired, 
after the cellulose has been further processed to give yarns, woven 
fabrics, knitted fabrics and non-wovens. 
Possible anions X.sup.n(-) are both anions of inorganic acids, for example, 
the chloride, bromide, sulphate or phosphate ion, and anions of organic 
acids, for example of aromatic or lower aliphatic sulphonic acids, such as 
the benzenesulphonate, p-toluenesulphonate, methanesulphonate or 
ethanesulphonate ion, and also the anions of acid alkyl esters of 
inorganic acids, such as the methosulphate and the ethosulphate ion. 
R.sub.1 and R.sub.2 together with N preferably form a 5-membered or 
6-membered ring, for example a pyrrolidine, piperidine, morpholine or 
thiamorpholine ring. 
As examples of representatives of the compounds of the formula (I) there 
may be mentioned: N-trimethyl-N-(2,3-epoxypropyl)-ammonium chloride, 
N-triethyl-N-(2,3-epoxypropyl)-ammonium chloride, 
N-tributyl-N-(2,3-epoxypropyl)-ammonium chloride, 
N-propyl-N-dimethyl-N-(2,3-epoxypropyl)-ammonium chloride, 
N-trimethyl-N-(2,3-epoxy-2-methyl-propyl)-ammonium methosulphate, 
N-methyl-N-(2,3-epoxypropyl)-morpholinium chloride, 
N-ethyl-N-(2,3-epoxy-2-methyl-propyl)-thiamorpholinium chloride, 
N-butyl-N-(2,3-epoxypropyl)-piperidinium bromide, 
N-methyl-N-(2,3-epoxypropyl)-pyrrolidinium chloride, 
N-methyl-n-(2,3-epoxypropyl)-morpholinium p-toluenesulphonate, 
N-2-hydroxyethyl-N-(2,3-epoxypropyl)-morpholinium chloride, 
N-methyl-N-(2,3-epoxypropyl)-morpholinium methosulphate and 
N-ethyl-N-(2,3-epoxy-2-methyl-propyl)-morpholinium ethosulphate. 
The preparation of the compounds of the formula (I) can be carried out in 
accordance with various processes which are in themselves known (see, for 
example, Houben-Weyl, "Methoden der Organischen Chemie" ("Methods of 
Organic Chemistry"), volume XI/2, page 611, 4th edition 1968; French 
Patent Specification 1,450,083, DOS (German Published Specification) 
2,056,002 and U.S. Pat. No. 3,737,406.) 
They are preferably prepared by quaternising amines of the formula 
##STR3## 
in which: R.sub.1 to R.sub.3 have the meaning indicated under formula (I), 
with epoxy compounds of the formula 
##STR4## 
in which: R.sub.4 has the meaning indicated under formula (I) and 
Hal represents a halogen atom, preferably a chlorine or bromine atom. 
Possible adhesives are those water-soluble compounds, free from hydroxyl 
groups, which are also known as sizes in textile chemistry. Preferentially 
usable adhesives are alginates, especially sodium alginate or ammonium 
alginate, polyacrylates or polymethacrylates and their copolymers, and 
polyvinyl acetates, which are described, for example, in K. Lindner 
"Tenside - Textilhilfsmittel - Waschrohstoffe" ("Surface-active agents - 
Textile assistants - Detergent raw materials"), volume II (1964), pages 
1726 and 1727. 
The cellulose fibre materials are both materials of natural cellulose, such 
as cotton and linen, or regenerated cellulose, such as rayon. Synthetic 
fibre materials which can be admixed to the cellulose are polyester, 
polyamide, polyacrylonitrile, modified acrylic or acetate fibres. 
Examples of direct dyestuffs are described in the Colour Index, 3rd edition 
(1971), volume 2, pages 2005 to 2478. 
The cellulose materials treated with the fixing agents of the formula (I) 
and adhesives can, after processing to yarns or textile sheet-like 
structures, be dyed from a dilute or concentrated liquor. 
Both the pretreatment and the simultaneous treatment with the direct 
dyestuffs are carried out by impregnating the cellulose fibre materials 
with aqueous liquors which contain the compounds of the formula (I), 
advantageously in an amount of 10 to 100 g, preferably 20 to 60 g, and the 
adhesives, advantageously in an amount of 5 to 50 g, preferably 10 to 20 
g, per liter of padding liquor, the alkali required for the fixing onto 
the fibres, for example sodium carbonate, sodium bicarbonate or, 
preferably, sodium hydroxide, and, where relevant, the direct dyestuff, as 
well as, where necessary, a solubilising, or solubilising and dispersing, 
product, for example based on a carboxylic acid amide, and subjecting the 
fibre materials to a fixing process after squeezing off to a certain 
liquor pick-up, for example 50%. 
The impregnation is carried out at 20.degree. to 80.degree. C, but 
preferably at 25.degree. to 30.degree. C. 
The fixing process can be effected by steaming for 1 to 10 minutes at 
100.degree. to 150.degree. C, preferably by steaming for 8 minutes at 
103.degree. C, or by steaming for 1 to 5 minutes at 130.degree. to 
170.degree. C, or by a dry treatment of 1 to 5 minutes at 100.degree. to 
220.degree. C, preferably a dry treatment for 3 minutes at 150.degree. C. 
The fixing can also be carried out in accordance with the cold pad batch 
process, by storing the padded material for 8 to 48 hours, preferably 12 - 
24 hours, at room temperature. 
The impregnation, fixing and further processing of the sliver are 
preferably carried out in the manner described in Swiss Patent 
Specification 428,514 and in "Textile Month," January 1973, page 30 et 
seq. 
In these publications, a doubled, pre-drawn sliver of cellulose fibres or 
their mixtures with synthetic fibres is treated with adhesives in a 
special impregnating apparatus and after a subsequent drying, thermofixing 
or steaming process a fixed sliver is obtained. This fixed sliver can be 
fed directly to the ring spinning machine, circumventing the flyer, or 
gives, after a further pass through a second unit, a processable yarn. 
However, hitherto satisfactory fixing, and hence adequate fastness 
properties of the direct dyestuffs on the cellulose fibre, were not 
achievable by means of these processes. 
With the aid of the new process it has now proved possible to achieve 
excellent fixing. It has been possible substantially to improve the 
fastness properties, especially the wet fastness properties of the dyeings 
achieved. 
In addition, a substantial increase in depth of colour was achievable at 
the same time. 
Because of the excellent fixing action it is also possible to dispense with 
the soaping, at the boil, of the dyed cellulose materials, which is 
customary in this process in order to achieve good fastness properties. 
Very good fastness properties are achieved merely by simple hot rinsing. 
In the case of mixtures of synthetic fibres with cellulose fibres, such as, 
for example, polyester/cellulose, it is possible also to add a disperse 
dyestuff, for dyeing the polyester fibre component, to the impregnated 
liquors alongside the direct dyestuff for the cellulose fibre constituent. 
The five-figure Colour Index numbers given in the examples which follow 
relate to the data in the Colour Index, 3rd edition (1971), volume 4; the 
other dyestuffs used are described in the Colour Index, 3rd edition 
(1971), volume 2.

EXAMPLE 1 
A doubled, pre-drawn cotton sliver is impregnated, in an impregnating 
apparatus such as that described in Swiss Patent Specification 428,514, 
with a liquor which contains the following compounds: 60 g/l of 
N-methyl-N-(2,3-epoxypropyl)morpholinium chloride, 20 g/l of the dyestuff 
of the formula 
##STR5## 
10 ml/l of sodium hydroxide solution of 38.degree. Be strength, 2g/l of 
di-(2-ethyl-hexyl) monosodium phosphate, 2g/l of ethylene glycol and 15 
g/l of Na alginate (neutral alginate thickener). The temperature of the 
treatment is 25.degree. C. After impregnation, the material is squeezed 
off to a liquor pick-up of 50% and is subjected to a dry heat treatment 
for 3 minutes at 150.degree. C. 
After the manufacture of a yarn or thread, or woven fabric, knitted fabric 
or other textile sheet-like structure, the material is rinsed in cold and 
hot water and soaped at the boil for a few minutes. 
A brilliant and fast blue dyeing having the following excellent wet 
fastness properties results. 
______________________________________ 
DIN 54,006 
Fastness to water, severe conditions 
5 
5 
DIN 54,020 
Fastness to perspiration, alkaline 
5 
5 
DIN 54,020 
Fastness to perspiration, acid 
5 
5 
DIN 54,010 
Washing at 60.degree. C 5 
5 
DIN 54,011 
Washing at 95.degree. C 4-5 
5 
______________________________________ 
The upper figure denotes the staining of cotton and the lower figure the 
staining of rayon or wool. 
Equally good results were achievable when using the dyestuffs C.I. 35,860 
and 23,160 or dyestuffs of the formulae 
##STR6## 
The N-methyl-N-(2,3-epoxypropyl)morpholinium chloride used is prepared as 
follows: 
8.325 g (90 mols) of epichlorohydrin are heated to 50.degree. C in a 10 l 
three-necked flask equipped with an internal thermometer, stirrer, 
dropping funnel, condenser and drying tube, and thereafter 1,822 g (18 
mols) of N-methylmorpholine are added continuously over the course of 1 
hour at this temperature, with intensive stirring and exclusion of 
atmospheric moisture. The reaction mixture is now stirred intensively for 
a further 24 hours under the same conditions, in the course of which the 
reaction product starts to crystallise out already about 1 hour after 
completion of the addition of the N-methylmorpholine. After the mixture 
has cooled to room temperature and stood overnight, the reaction product 
is filtered off, thoroughly washed repeatedly with ethyl acetate and 
finally dried at 50.degree. C (ultimately under 13 mm Hg) in a vacuum 
drying cabinet. 
Yield: 3,310 g of N-methyl-N-(2,3-epoxypropyl)morpholinium chloride (95% of 
theory); grey-white hygroscopic salt; melting point 160.degree. to 
161.degree. C (with decomposition); C.sub.8 H.sub.16 ClNO.sub.2 (molecular 
weight 193.5), calculated: 18.33% Cl; found: 18.20% Cl. 
EXAMPLE 2 
A doubled pre-drawn cotton sliver is impregnated, in an impregnating 
apparatus such as that described in Swiss Patent Specification 428,514, 
with a liquor which contains the following compounds: 60 g/l of 
N-trimethyl-N-(2,3-epoxypropyl)-ammonium chloride, 10 ml/l of sodium 
hydroxide solution of 38.degree. Be strength, 1.5 g/l of 
di-(2-ethyl-hexyl) monosodium phosphate, 1.5 g/l of ethylene glycol and 10 
g/l of Na alginate (neutral alginate thickener). The temperature of the 
treatment bath is 25.degree. C. After impregnation, the material is 
squeezed off to a liquor pick-up of 40% and subjected to a thermofixing 
process for 3 minutes at 150.degree. C. 
EXAMPLE 3 
A doubled, pre-drawn sliver of polyester and cotton mixed in the ratio of 
67:33 is impregnated in an impregnating apparatus corresponding to Example 
1, with a liquor which contains the following compounds: 40 g/l of 
N-methyl-N-(2,3-epoxy-propyl)-morpholinium chloride, 10g/l of the dyestuff 
of example 1, 12 g/l of the disperse dyestuff of the formula 
##STR7## 
2 g/l of di-(2-ethyl-hexyl) monosodium phosphate, 2 g/l of ethylene 
glycol, 3 g/l of the sodium salt of trichloroacetic acid, 12 g/l of Na 
alginate and 100 g/l of urea or another carboxylic acid amide. 
The temperature of the treatment bath is 25.degree. C. After impregnation, 
the material is squeezed off to a liquor pick-up of 50% and subjected to a 
dry treatment for 1 minute at 200.degree. C. 
After a yarn or a textile sheet-like structure has been produced, the 
material is rinsed cold and warm and soaped for 5 minutes at the boil. 
The dyeing is distinguished by excellent wet fastness properties. 
Equally good results are obtained if, instead of the alginate thickener, 
another thickener, for example based on polyacrylates, is used as the 
adhesive.