CA1091866A - Process for dyeing textile material - Google Patents

Abstract

PROCESS FOR DYEING TEXTILE MATERIAL

Abstract of the Disclosure Process for dyeing textile materials by the customary methods using aqueous dye liquors containing water-soluble dyestuffs, the residual liquor being removed after dyeing is completed and the dyed goods being washed, wherein the coloured washing liquor is continuously re-moved and brought into contact with a cationically modified cellulose-containing material in order to effect decolor-ation and the decolorised washing liquor is then recycled to the dyed goods for further washing; this process achieves quite considerable savings in respect of water, energy, time and chemicals and gives, brilliant dyeings having a good depth of colour.

Description

1~91866 The subject of the invention is a process for dyeing textile materials by the customary methods using aqueous dye liquors containing water-soluble dyestuffs, the residual li~uor being removed after dyeing is completed and the dyed goods being washed, characterised in that the coloured washing liquor is continuously removed and brought into contact with a cationic, modified cellulose-containing material in order to effect decoloration and the decolorised washlng liquor is then recycled to the dyed goods for further washing.
In customary dyeing processes, for example in cheese dyeing or beam dyeing apparatuses, winch vats, jets or drum dyeing machines, paddles or jiggers, numerous, for example 4 to 8, washing and rinsing operations in a corres-pondingly large number of baths are always necessary i~ order to finish the dyeings, so that the dyed goods are as free as possible from dyestuff which has not been fixed or has not been taken up. These washing processes not only require large ~ amounts of water but als~ involve a considerable expenditure ; of energy since the ~resh washing liquors always have to bew~rmed S
e~tlme ~d,moreover, the time required is relatively long, compared with the time for the actual dyeing process.
~;j Furthermore, the washhg wa~ers containing dyestuffs frequently 7 give rise to ecological problems.
` With the process according to the invention with which t relatively small amounts of washing water suffice, since this is continuously purified and recirculated, it is now possible to achieve quite considerable saving~ in respect of water, ''. . ~.
.7.~ - 2 -.~- S

. .
.~.~.. , , . ~
' - - , ..

1~1866 energy, time and chemicals. ~n addition, a significant ecological advance is achieved. However, the process according to the invention is not only distinguished by these ecological and economic advantages but, in addition, the dyeings Gbtained have an even greater depth of colour and are more brilliant than those obtained from the former processes.
Decolorising of the washing waters with the adsorbents can be carried out, according to the invention, by different process variants, process variant c) being preferred: a) the so-called stirring process in which the washing waters to be purified stirred with the adsorbent in a vessel or a series of vessels and then separated off; b) the so-called fluidised bed process in which the adsorbent is kept in a suspended ~tate by the flow o~ the washing waters t~e purified; and c) the so-called fixed bed process in which the washing waters to be purified are fed through adsorbent materi.al arranged in a filter-like manner.
The purification of the washing liquor is appropriately carried out at lO to 150C. Preferably, however, it is carried out at between ~0 and 100C, or especially at 45 to 65C. If desired, the purification of the washing water can be carried out under pressure or under vacuum.
The pH value of the washing liquors is preferably 3 to g, or especially 5 to 8. The pH value i9 adjusted by adding dilute, strong acids ? such as, for example, sulphuric acid, hydrochloric acid or phosphoric acid, or bases, such as, for example, sodium hydroxide solution or potassium hydroxide , ~ . .
`:
, , .' .
.
'~
- .
; ' ' ~ ' .' lV9~866 solution, a single addition being made prior to the actual washing process and further additions being made continuously during washin~.
The washing process is preferably so controlled that the washing liquor is circulated at least 5 times, and in particular 10 to 20 times, in the course of one hour. As a rule, the total washing opera~ takes 0.3, and especially 1 to 3, hours.
- In some cases it can be advantageous to carry out brief pre-rinsing, that is to say for 1 to 5 minutes, of the dyed goods with a small amount, that is to say, for example, ; with an amount which is 4 to 7 times smaller than the subse-.
quent amount of washing liquor, of water, at, for example, 15 .',''!" to 25C prior to the continuous washing process.
-~ Natural and synthetic fibres can be used as the textile fibre material which can be dyed according to the invention.
Natural fibres which may be mentioned are, for example:
; cotton, flax, jute, wool or silk and synthetic fibres which may , ............................................ .
be mentioned are regenerated cellulose, such as viscose, poly-amide fibres, for example those made of poly-~-caprolactam ~ ,. . .
;j~ (polyamide 6), polyhexamethylenediamine adipate (polyamide 6,6), poly-~-amino-undecanoic acid (polyamide 7) or aromatic poly-~ amide fibres, polyurethane or polyacrylonitrile fibres or acid-;~ modified polyester or polyamide fibres.
However, the textile material is preferably made of ` cellulose-containing materials, especially cotton.
, ~ , ~ These fibre materials can also be used as mixed fabrics "s, ~,., .

., ,;,~ , : .:

, ~ ., . - . ... .
-. .

with one another or with other fibres, for example mixtures of polyacrylonitrile/polyester, polyamide/polyester, polyester/
viscose, polyester/wool and, above all, polyester/cotton.
The textile material can be in very diverse stages of processing, for example in the form of flocks, tops, yarn, textured filaments, woven fabrics, knitted fabrics, fibre fleeces or textile floor coverings.
Possible water-soluble dyestuffs which can be used for dyeing, and removed from the washing waters,according to the invention are anionic or cationic dyestuffs or optical brighteners. ~ Anionic dyestuffs or optical brighteners are preferred.
The anionic dyestuffs are dyestu~fs in which the anionic cha~acter is due to the formation of a metal complex alone and/
or to acid substituents conferring solubility in water.
Possible acid substituents of this type which confer solubility in water are carboxylic acid groups, phosphoric acid groups, acylated sulphonic acid imide groups, such as alkyl- or aryl-disulphimide groups or alkyl- or aryl-carbonylsulphimide groups, alkyl- or aryl-imide groups, sulphuric acid ester groups and, above all, sulphonic acid groups.
The anionic dyestuffs can belong to very diverse cate-gories of dyestuff. Examples which may be mentioned are oxazine, triphenylmethane, xanthene, nitro, acridone, stil-bene, perinone, naphthoquinonimine, phthalocyanine, anthra-quinone and azo dyestuffs. The latter can be metal-free, metallisable or metal-containing monoazo, disazo and polyazo .
~i 5 - .
, . '~ ' .
.~ .

dyestuffs, including the formazane dyestuffs,wherein the metal atom forms a l:l-complex or 1:2-complex, especially 1:2-chromium or 1:2-cobalt compl~xes, which contain two identical, or two different, molecules of azo dyestuff bonded as a com-plex to a chromium atom or cobalt atom. These dyestuffs can also contain, in the molecule, so-called reactive groupings which enter into a covalent bond with the fibre material to be dyed. Reactive dyestuffs of this type are particularly suitable.
The cationic dyestuffs which can be removed from the washing liquors with the aid of the cationically modified cellulose material are, quite generally, the customary salts :~.
and metal halide double salts, for example zinc chloride double salts, of the known cationic dyestuffs, in which the cationic character emanates from a carbonium, oxonium or sulphonium group ~nd, above all, from an ammonium group. Examples of ; such chromophoric systems are: methine, azomethine, azo, : ,) ' hydrazone, azine, oxazine, thiazine, diazine, xanthene, ;~ acridine and polyarylmethane, such as diphenylmethane or tri-phenylmethane, dyestuffs as well as coumarin dyestuffs and azo . ,~. .
dyestuffs which contain an indolinium, pyrazolium, triazolium, v tetrazolium, oxadiazolium, thiodiazolium, oxazolium, thiazolium, pyridiniumj pyrimidinium or pyrazinium ring. They can also be arylazo, phthalocyanine and anthraquinone dyestuffs which carry an external ammonium group, for example an external cyclammonium or alkylammonium group.
The process according to the invention is suitable not . .,.; ~
, ., .' ,.
.~., .
~ - 6 -.. ~;; .
, ... .

i:.
: . , - ~.
, , ~ , ':
. ~, . ... .. . . ..
. : - -., - ~ :

only for actual dyeing but also for optical brightening of textile materials since the residues of anionic or cationic optical brighteners can also be removed from the washing liquors. Particularly advantageous results are obtained with anionic optical brighteners.
The optical brighteners can belong to any category of brightener The anionic brighteners are, in particular, stilbene compounds, pyrazolines, dibenzoxazolyl or dibenz-imidazolyl compounds or naphthalic acid imides, which contain, in the molecule, at least one acid group, such as a carboxylic acid group or, preferably, a sulphonic acid group, and can be fibre-reactive. In the case of the cationic brighteners, these are, above al1, optical brighteners of the methine, azamethine, benzofurane, benzimidazolyl, coumarin, naphthal-imidc or pyrazoline serie~.
The process according to the invention enables anionic and cationic surface-active agents and textile auxiliaries and dyeing auxiliaries, as well as phosphates, also to be removed, at least partially, from the aqueous washing liquors, in addition to the dyestuffs. Such auxiliaries are described in more detail in the book "Tenside-Textilhilfsmittel-Waschrohstoffe" ("Surface-active Agents - Textile Auxiliaries -,.
'~' Detergent Raw Materials") by'Dr. Kurt Lindner (published by ;'; Wissenschaftlicher Verlagsgesellschaft Stuttgart, 1964).
Anionic compounds of the alkylarylsulphonic acid type are of - particular interest in practice.
According to the invention, cellulose-containing ~ ` , ~' - 7 -.,. ., - , , , . -.,. ~ . .

textile materials are preferably dyed with fibre-reactive dye-stuffs.
The cationic character of the modified cellulose materials which can be used according to the invention is due to the presence o~ basic substituents. The cellulose materials contain, as substituents of this type, for example amino groups, imino groups, quaternary ammonium groups, immonium groups, tertiary phosphino groups, quaternary phos-phonium or sulphonium groups and also thiuronium or guanidinium groups. ~
Preferred basic substituents are amino groups, for example primary, secondary or, above all, tertiary amino groups, as well as quaternary ammonium groups. These con-"
~ain, as N-substituents, aliphatic, cycloaliphatic or arali-phatic groups and the N-substituents can also form 5-membered to 8-membered, and especially 6-membered, rings. The N-..... . .
substituents are advantageously lower alkyl groups with, in each case, 1 to 5 carbon atoms, which are optionally substitu-., ~ ted by hydroxyl or cyano-groups.
- Suitable cationically modified cellulose materials which can be employed according to the inv~ntion are described, for example, in German Offenlegungsschriften 1,942,742 and ;~ 2,309,079. These materials, which are capable of adsorp-~i tion, are cationically modified cellulose in which the hydroxyl , ~ ~ groups have been at least partially replaced by quaternary ? ammonium groups of the formula :
.. ...
`';

. . .

.. ..... . . . .
.
, ' ':

.

109~866 (l, r ~ - CH2 - ~H - CH2 - N (Alk)31 An ~
L OH J
, wherein Alk denotes identical or different lower alkyl radi-cals and An ~ denotes the anion of an inorganic or organic acid, especially a sulphate, sulphonate or halide ion, by reaction with a corresponding epoxypropylammonium salt.
The cationic constituent of the cationically modified cellulose materials is pre~erably bonded to the cellulose part via a grouping of the formula

(2) - O - CH2 - N -v in which the nitrogen belongs to.an amide group of the cationic : part and the oxygen is bonded to the cellulose part.
Advantageous cationically modified cellulose materials . are characterised in that their cationic constituent is bonded '~"i4 to the cellulose part via the grouping of the ~ormula ,. .
.;~ ,, .
.~` (3) - O - CH2 - N - X -.", .-. R
. . .
~,:
in which X denotes the divalent bridge -CO-, -CO-O-, -CS-, ~C--NH, ~P~~O)q. 1 or -S02- or a carbon atom whlch is a con-OR' stituent of a nitrogen heterocyclic structure and ad~acent to ~ ,, : - the ring nitrogen, R and R' each denote hydrogen or an organic radical and q and q' in each case denote 1 or 2.
,'" - :., .
~, _ g _ , .. ,:, .
. .,. - , ,, : . ~ ~ . .. .

,' ,' . , ,' : , ' ~ ' ' . .: .' , ,' , ~ ' .~ , .
'~ ' ' , , ' , . , ' . ' ' ' ' ,, ' ' . `

In formula (3), X above all denotes the -CO- bridge.
R is preferably hydrogen or alkyl with l to 5 carbon atoms, which is optionally substituted by halogen, cyano, hydroxyl or alkoxy with 1 to 5 carbon atoms. The substituent R can also be a constituent of a nitrogen hetero-ring, in which the groupings -CO-, -CS- and -C=NH can also be included, as in derivatives of 5-pyrazolone, 5-aminopyrazole, barbituric acid or cyanuric acid. R can also optionally represent a ~ur-.~.
ther grouping -CH2-0-(H), which is optionally also bonded to the cellulose. Amongst these radicals, R is appropriately -CH20(H) or preferably hydrogen. R' is preferably alkyl with l to 5 carbon atoms.
Depending on the nature of the starting components used to manufacture the cationically modified cellulose materials, the basic sub~tituent can be bonded to the grouping of the formula (2) or (3)v~ any desired bridge members. Possible bridge members are, for example, divalent hydrocarbon radi-cals, for example lower, straight-chain or branched alkylene radicals, such as the methylene, 1,2-ethylene or 1,2- or 1,3-propylene group, the 1,4-cyclohexylene group or lower alkeny-lene radicals, such as the vinylene group, and also acid radicals which can be derived from an inorganic or organic polybasic acid, as well as ureido, thioureido, guanidine or , ~ , , ; triazone groupings.
The basic groupings required for the cationic modifi-cation of the cellulose materials can also be constituents of polymeric compounds, such as polycondensates, polymers or ~, _ :.;
,. -- 10 --~' ' ; .
~. , ~ - , - ~ ,- .

~091866 .
polyadducts.
Polymeric compounds of this type can correspond to the general forrnula (4) T-Bm wherein T denotes a basic, polymeric parent substance, B
denotes an amide grouping, especially a carboxylic acid amide group, and m denotes a number of at least 1, for exarnple 1 to 200,000, and at least one amide group is methylolated and optionally also etherified or reacted with glyoxal. These polymeric compounds can be derived from homopolymers, copolymers, graft polymers or block polymers.
` The basic groupings present in the parent substance T
:~, can be amino groups, such as, for example, primary, secondary or tertiary amino groups, and/or onium groups, such as, for - example quaternary amrnonium, sulphoniurn or phosphoniurn groups~
Cationic polymers containing methylol groups can be obtained, for sxarnple, by reacting basic, nitrogen-containing, polymeric compounds which contain ~ ngs w~ch can be methylol-ated, such as, for example, carboxylic acid amide groups, sulphonic acid amide groups, phosphonic acid amide groups or aminotriazine groups, with formaldehyde or formaldehyde donors, : ~
or also with glyoxal.
Suitable basic, nitrogen-containing, polymeric com-pounds in the abovementioned sense are, in principle, polymers which contain basic nitrogen atoms, ~hich are capable of , - forming a salt, and amide groupings.
:, .. ...
". -- 11 --... .

. . ' '. : ~ ' : '-: . . - : .
, ~. . . . .: .... .
, ~

lO9i86~;

Suitable polymers are basic aminoplasts which are soluble in water or can be dispersed in water, such as, for example, formaldehyde-dicyandiamide condensation products.
Appropria~ely, the reaction is carried out with condensation products of formaldehyde, di.cyandiamide and one or more of the following components: urea, ammonium chloride and an alkylene-polyamine with, for example, a total of 2 to 18, and preferably with 2 to 8, carbon atoms and 2 to 5 amino groups.
The alkylenepolyamines are, for example, ethylenedi-amine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, 1,2-propylenediamine, dipropylenetriamine, tripropylenetetra-mine, dihydroxydipropylenetriamine, dibutylenetriamine, tri-butylenetetramine, tetrabutylenepentamine, dipentylenetri-amine, tripentylenetetramine, tetrapentylenepentamine, dihexa-methylenetriamine, trihexamethylenetetramine and tetrahexa-methylenepentamine.
Particularly suitable basic aminoplasts are, above all, , formaldehyde-dicyandiamide, formaldehyde-dicyandiamide-ethylene-diamine or formaldehyde-urea-dicyandiamide condensation pro-ducts. Preferred products are obtained, for example, by a condensation reaction of formaldehyde, dicyandiamide and ammonium chloride or of formaldehyde wi~h the reaction product of dicyandiamide and ethylenediamine or the correspondin~ acid salt, such as the hydrochloride, or ammonium.chloride, and are described, for examplç, in Swiss Patent Specification 456,475, German Offenlegungsschrift 2,321,627 and French Patent , . ~
, .. .,, . ~

...

Specification 2,189,327. Further ~asic aminoplasts are manufactured by a condensation reaction of urea, dicyandiamide and formaldehyde in the presence of an acid, such as hydro-chloric acid, or by a condensation reaction of dicyandiamide with formaldehyde and the tetrahydrochloride of triethylene-tetramine.
Reaction products, containing N-methylolamide groups, of halogenohydrins or dihalogenohydrins with alkylene- or polyalkylene-polyamines or -imines, such as, for example, re-action products of epichlorohydrin with diethylenetriamine, dipropylenetriamine or triethylenetetramine, or with poly-.
ethyleneimines, can likewise be employed as basic polymers.
Basic reaction products of this type are described, for ~ example, in German Auslegeschrift 1,010,736. Further ~ basic epoxide resins are epoxidised precondensates of ali-phatic polyamines with polyepoxides, which are described, for example, in U.S. Patent Specification 3,346,519.
Basic polyamides which are manufactured by a conden-sation reaction of dibasic carboxylic acids containing 2 to 10 carbon atoms, for example adipic acid or its functional deriva-.............. tives, such as, for example, esters, amides or anhydrides, with polyamines, especially polyalkylenepolyamines, such as :. those polyamides described, for example, in U.S. Patent Spec-." -ification 2,882,185, are also suitable as basic, nitrogen-:.
:~ containing polymers.
The polyamidepolyamines which are obtained by reacting . polymerised, preferably dimerised to trimerised, fatty acids .
"
.:
'"

,: ' ' ' ' ",'~ ,'- ' ~ ' ~ ' '' ~ ' . ' ~ , . : . .
. .

with polyamines, appropriately in a ratio such that the poly-amide resin formed has an amine value in the range of approxi-mately 200 to 650 mg of potassium hydroxide per gram of poly-amidepolyamine, are also of interest as basic polymers.
Basic polyamides which can be methylolated can also be condensation products of polymeric fatty acids with polyamines, such as those described in British Patent Specifications No.
726,570 and No. 847,028 and it is possible to react these pro-.
ducts with epoxide resins which are formed by reacting poly-hydric phenols with poly~unctional halogenohydrins and/or glyceroldichlorohydrin and are described in U.S. Patent Speci-fications 2,585,115 and 2,589,245.
Further basic polyamide resins which can be methylol-ated are, for example, the products obtained by reacting halo-genohydrins, for example epichlorohydrin, with aminopolyamides obtained ~rom polyalkyleneamines and aliphatic dicarboxylic acids with 2 to 10 carbon atoms, such as the products des-cribed, for example, in U.S. Patent Speci~ication 3,311,594.
Suitable polyamide resins which can be used to manu-, facture the cationically modified cellulose materials are also : described, for example, in British Patent Specifications Nos.
` 726,570, 810,348, 811,797, 847,028, 865,656 and 1,108, 558.
.). .
. Basic polyamides obtained from a reaction mixture which contains polymeric fatty acids (manufactured in accord-" .
~I ance with British Patent Specifications No. 878,985 and No.
:.............. 841,544), monomeric fatty acids and lower polyalkylenepoly-. ., ~ amines by condensation polymerisation at high temperatures can .....
. - 14 -~ . .
;: .
.

~ ~ .
. .

also be used for the manufacture of the cationically modified cellulose materials.
Further basic polymers are the polymers of an alkylene-imine with 2 to 4 carbon atoms which have an average molecular weight (MW) of 500 to 200,000, and preferably 10,000 to 40,000, and contain at least one methylolamide group.
These polymers as a rule possess a Brookfield viscosity at 20C
of 500 to 20,000 centipoise (cp). Suitable alkyleneimines are, in particular, ethyleneimine, propyleneimine, 1,2-butyl-eneimine and 2,3-butyleneimine. Of all the alkylene-imines, ethyleneimine is preferably used. The methylol-amide group can be introduced, for example, by reacting the ,~:
polyalkyleneimine with chloracetamide and subsequently methyl-olating the reaction product.
~ ationic polymers containing 2-vinyl-1-cycloamidine-propionamide groupings which have been methylolated or glycol-` ated with glyoxal are also advantageous polymers which can be employed to modify the cellulose. Such polymers are des-, ~ .
cribed, for example, in U.S. Patent Specification 3,772,259.
N-Methylolamide group-containing addition polymers and ,,-~, ~ copolymers, such as, for example, optionally quaternised co-f polymers of base-substituted maleimides, acrylic acid esters and acrylamides as well as vinylpyridine and ethylenically unsaturated comonomers are also suitable as basic polymers.
,, Examples of suitable comonomers which may be mentioned are:
alk~rl acrylates or methacrylates with 1 to 12 carbon atoms in the alkyl radical, which can optiGnally also be further sub-,., ~ ..

~. .

.

. .
.. . . . .
. , , ~ .
- . ~ : . , - , .- . . , . :, .
. - . . . . ..

:

~191866 stituted, especially by hydroxyl gr~ups, such as methyl acryl-ate or methacrylate, ethyl acrylate or methacrylate, ~-hydroxy-ethyl acrylate or methacrylate, n-butyl acrylate or meth-acrylate and dodecyl acrylate or methacrylate; (meth)-acrylic acid, (meth)-acrylamide and (meth)-acrylonitrile; vinyl esters of aliphatic carboxylic acids containing 1 to 12 carbon atoms, or mixtures of such carboxylic acids, such as vinyl acetate, vinyl formate and vinyl butyrate or vinyl esters of a mixture o~ carbox~lic acids with 9 to 11 carbon atoms; vinylbenzenes, :
such as styrene, chlorostyrene and methylstyrene; and maleic acid monoalkyl esters and monoalkylamides.
N-Methylolamide group-containing polymeric reaction -; products of a,~-dihalogenoalkanes or bis-chloromethyl-aromatic ; compounds with amino compounds, such as, for example, dialkyl-amines or peralkylated polyamines, especially diamines, are also suitable.
Moreover, basic polymers which contain N-methylolated , '~ urea, urethane, amidine or guanidine groupings can also be employed to modify the cellulose materials.
Acyclic and cyclic monoamines or polyamines, mono-imines or polyimines, or quaternary ammonium salts of these i:, amines and imines, each o~ which contain at least one N-methylolamide group, are advantageously suitable for the cat-,~, ~ ionic modification of the cellulose materials. The : ., methylolamide group is capable of reacting with the hydroxyl groups in the cellulose, so that the basic compound is bonded to the cellulose part via the grouping of the formula (2) or , :~ , ` - 16 -., .

.
-~ .
' . . . .
.,.~ ~ . -

(3)-It is particularly advantageous when the cellulose materials are cationically modified with an amino compound which contains at least one amino group and at least one N-methylolamide group, especially a N-methylolcarboxamide group, which is optionally etherified by Cl-C4-alkoxy. Amino com-pounds of this type can advantageously be derived ~rom ali-phatic monoamines or polyamines or from hydrogenated nitrogen-heterocyclic compounds, for example pyrrolidine, piperidine, pipecolines, morpholine or piperazines, but especially from a monoamino compound which contains a single methylolamide group.
Monoamino compounds containing an optionally etherified N-methylolcarboxamide group which are particularly suitable according to the invention are the compounds of the general formula (5) / N - Q - CO - IN - CH2 - OR"
, D
. ''2 . Y
in which R" denotes Cl-C4-alkyl or, preferably, hydrogen, R
;~ and R2 independently of one another denote hydrogen, lower .~ alkyl which is optionally substituted by halogen, hydroxyl, . lower alkoxy or cyano, or cycloalkyl, benzyl or the group of - .
. the formula . , (6) - Q - CO - N - CH2 - OR"
,............. . .
."
: - 17 -: : .
: .

. .. .
" . . . . ..

.. . . . , ~
.'' , ' ' ' . ' .
. .

or Rl and R2, together with the nitrogen atom which links them, denote a 5-membered or 6-membered heterocyclic radical, such as, for example, pyrrolidinyl, piperidino, morpholino or piperazinyl, Q denotes an alkylene- or alkyl-substituted alky-lene chain with up to 8 carbon atoms, pre~erably Cl-C3-alkylene, and Y denotes hydrogen, lower alkyl or -CH20R". Methylol compounds of the formula (5) which contain only a single grouping of the formula (6) are particularly preferred.
i~ In these methylol compounds, Rl and R2 are appropriately both lower alkyl or lower alkoxy-lower alkyl or form, together with the common nitrogen atom, a morpholino radical. Rl and R2 are, however, preferably lower alkyl, Y is preferably hydrogen , . . .
and R" is especially hydrogen.
Such methylol compounds of the formula (5) can be obtained by reacting an amino compound with an amide of a 1,2-unsaturated, aliphatic carboxylic acid or with a halogeno-acetamide and methylolating the reaction product with formalde-hyde or a formaldehyde donor, such as, for example, paraform-aldehyde or trioxane. Suitable monoamines are, in particu-ilar, monoalkylamines or dialkylamines with 1 to 4 carbon atoms in each alkyl radical or optionally alkoxylated C2-C4-alkanol-amines with 1 to 4 carbon atoms in any alkoxy radical which may be present and suitable amides are acrylamide, maleic acid diamide or chloracetamide.

Preferred cationically modified cellulose materials can be obtained when the modification is carried out with poly-amino compounds which contain at least one N-methylolcarbox-. ~ .

. .

. .

~ ,, - . .:

. .

.

: . , . -.

10~1866 amide group and which are derived, for example, from alkylene-polyamines or hydrogenated diazines, especially from a N,N-dialkyl-ethylenediamine or a N,N-dialkyl-propylenediamine or piperazine. Polyamino compounds of the general formula (7) ~ N ¦ Ql ~ Nl ~ R6 in which Ql denotes an alkylene- or alkyl-substituted alkylene chain with up to 8 carbon atoms, preferably C2-C3-alkylene, R~, R4, R5 and R6 independently of one another deno-te hydrogen, lower alkyl which is optionally substituted by hydroxyl, cyano, - halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula (6), or R3 and R4, together with the nitrogen atom ; which link~ ~hem, denote a 5-membered or 6-membered hetero-,,:
:~ cyclic radical, for example of the type mentioned above for ''A~'' Rl and R2, or, if n is 1, R4 and R5, together with the group-ing ~N-Ql-N which links them, also denote a divalent hetero-cyclic radical, especially a piperazino ring, and n denotes 1 to 1,000, preferably 1 to 4 and especially 1, and at least one ~. .
; of R3, R4, R5 and R6 represents the group of the formula (6) ~` and, if~n denotes more than 1, each R5,independently of the :: .
others,can represent hydrogen, lower al~yl which is optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or , -` cycloalkyl, benzyl or the group of the formula (6), or each R5, or individual R5s, together with the adjacent R5 and with the ,. -- 19 --., . I

. . . :: : .
,..
~, , : ~ . . .
- ; .,.. -,. , .. ~ . . . . . . ..
- ~. -10918~6 grouping - N-Ql-N = which links them, can also represent a divalent heterocyclic radical, especially a piperazino ring, are especially suitable.
Amongst the polyamino compounds of the formula (7), those wherein n is 1 and which correspond to the diamino com-pounds given below, of the formula R~
(8) R ~ Ql ~ I - Q - C0 - I - CH20R"

.
wherein R3, R4, R5, Rn, Q~ Ql and Y have the indicated meaning, are preferred.
Diamino compounds of the formula (8) in which R3 and R4 both denote lower alkyl and R5 denotes the group of the formula (6), or R4 and R5, together with the grouping ~N-Ql-N C which links them, dénote a piperazino ring and R~
denotes the group of the formula (6), Q denotes Cl-C3-alkylene, Ql denotes ethylene or propylene and Y denotes hydrogen, are particularly preferred.
Methylolamide compounds which contain at least one onium group, especially a quaternary ammonium group, are of particular practical interest for modification of the cellulose materials. Advantageously, ammonium salts of this type correspond to the following formulae (9), (10) and (11):
-; .
, .
... .
, .,, .-,: . .
. ., ~ - 20 -, , ... - -: "
. ~,, ... , .-. -' ~ "' `- .
.
., _ _ ~) ,, (g)l~ N - Q - CO - N - CH20R" An ~3 Vl . Y , _ . _ .,~ . . _ ' ' 1~9 (10)L ~ ~ I {Ql ~ N! R6~ An

4 V2 { ~ ~

~','' , . . . .
: .
: wherein Vl, V2 and V3 independently of one another denote ;.
hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula (6), Rl, R2 and Vl, or R~, R4 and V2, together with the nitrogen atom which links them, denote a pyridine ring which is optionally substituted by lower alkyl and An Q denotes the anion of an organic or inorganic acid, and Rl, R2,. R3, R4, R5, R6, R", Q, Ql~ Y and n have the meaning ~ndicated for formulae (7) and (8) and at least one of R3, R4, R5, R6, V2 and V3 represents the group of the formula (6) and, if n denotes more than 1, each R5 or each V3,independently of ~' .

:
. .:, :.,- . . .. . . - -. . ,. - . - -: ' ' . . .. .
, . . .

lOgl866 the others, can represent hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula (6), or each R5, or individual R5s, together with the adjacent R5 and with the common grouping ~ -Ql-N , can also represent a divalent heterocyclic radical, especially a piperazino ring. The -~ compounds of the formula (11) can also be only partially quaternised with V3 in the recurring units of the formula -Ql N -~ ~ Amongst the quaternary ammonium compounds of the form-ulae (g), (10) and (11), the quaternary ammonium salts of the formula (12) ,, , 12) ~ > I ~Ql IN ) O - CO - N - CH20R An ch Rl, R2, R3, R', Vl, Q, Ql~ Y, An ~ and q have the ,~- , . indicated meaning, are preferred.
,r." Ammonium salts of the formula , (13) ~1 >N _ Q ' - CO - NH - CH20U ]

. ~ .
or of the formula ,: .
.

.

... .

.~ .
"-,, .. . . .

. . ' ' ' ' , ~ , ' ' ,. .

~3 Vl ' R3 ' ~ An (3 wherein Rl', R2', Vl', Rl" and^R2" each denote lower alkyl, or Rl' and R2', together with the nitrogen atom which links them, denote a morpholino ring, R3' denotes hydrogen or the group of the formula -Q"-CO-NH-CH20H, Q' represents methylene or propylene, Ql' represents ethylene or propylene, Ql' denotes Cl-C3-alkylene and An ~has the indicated meaning, are par-ticularly preferred.
Quaternised polymeric compounds of the formula (15) or block copolymers of the formula (16) "

(15) ~ Q2 - ~ ~ Q3-W2-C~ -A-~4 C~

or . . , . ~". . . .. . . ....
~;
.
',"'~ .

~.

, .
., .
.

, ' .
'' ' :` : ': " .'' : : .
-.. . .. .

~ Q2 ~ ~33Q -~2-CO-~3-~-W4-CO- 1 (16) R7 n An ~ r l~ ' {Q2~ 43~-W2 -co-w3 -A U

~: ' , '- ' ': ' which can also be only partially quaternised, can also be employed to modify the cellulose materials, ~n the formulae (15) and (16), Q2' Q3' Q2' and Q3' in-dependently of one another denote an alkylene- or alkyl-sub-~tituted ~lkylene chain with 2 to 8 carbon atoms, and prefer-ably with 2 to 4 carbon atoms, V3, R7, V3' and R7' independent-ly of one another denote hydrogen, lower alkyl which is option-.
ally substituted by halogen, hydroxyl, cyano or lower alkoxy, - or benzyl or the group of the formula (6a) -Q'-CO-N-CH2-OR", ~: Q' denotes methylene or propylene, Wl, W2, Wl' and ~ W2' independently of one another each denote a direct bond, . ~
~ oxygen or the group - N-Y; W3, W4, W3' and W4' independently of one another each denote a direct bond or -NH-; -CO-A-CO-and -CO-A'-CO- each denote the radical of a polybasic car-- boxylic acid, especially the radical of a saturated or unsat-urated aliphatic dicarboxylic acid, or the radical of an :. : -~' ' ... ~ .
, 1~91866 aromatic dicarboxylic acid, such as of terephthalic acid or isophthalic acid or of naphthalene-2,6-dicarboxylic acid, r and p each denote 1 to 10,000 and s denotes 1 to 10 and n, An~, R" and Y have the indicated meaning and at least one of V3, R7, V3', R7' and Y represents the group of the formula (6a) and, if n is more than 1, each R7 or V3 and each R7' or V3', independently of the others, can represent hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the form-ula (6a), or each R7 and R7' or individual R7s and R7's, together with an adjacent R7 or R7' respectivel.y and with the grouping -N-Q2-N= and -N-Q2~-N- which link them, can represent a divalent heterocyclic radical, especially a piperazino ring.
Amongst the quaternised pol~meric compounds of the formula (15), those which correspond to the formula (17) ,, .

(17) ~' NH - Q4 - N~33 05 - NH - CO - Al - CO

:` CH2- CO~H - CH20R" ' .,,. . , rl - ~herein Q4 and Q5 each denote C2-C4-alkylene, R"' denotes . hydrogen or methyl, V4 denotes lower alkyl and Al denotes the . radical of an aliphatic C2-C4-dicarboxylic acid, especially C2-C4-alkylene, and rl denotes 2 to 100 and An~ has the . indicated meaning, are particularly preferred.
. ,.~, .
~ Addition polymers and copolymers such as, for example, .,~
. .

; .
., .
. ~ .

-..
.,...... , ~ .. . . .
.
~;, . ,, - , . ~ : ' - .

optionally quaternised polym~rs of N-substituted maleamides or maleimides or copolymers of N-substituted maleimides and ethylenically unsaturated monomers, for example styrene, are also suitable as basic polymers for the cationic modification of the cellulose materials. Polymers and copolymers of this type have, in the molecule, for example, recurring units of the formulae (18) and (19) (18) ~ An .: Z2q-lCO CO R
.; R"OCH2 - N ~ Ql ~ N - R2 '~' Y , Vl or _ _ . .

~ 3 ~4 -: (19) Z2q~lco / o, . Q~ -.N - Q-co-N-cll2oR
,~ _ ' "' ' ' Vl Y ' , , ;.; in which one of Zl and Z2 denotes hydrogen and the other de-. notes hydrogen, lower alkyl, cyano, carboxyl or carbamoyl, Z3 and Z4 independently of one another denote hydrogen or lower alkyl and q denotes 1 or, preferably 2, and Rl, R~, R", Vl, ~, .

~; :
,.
:

Ql' Y and An~ have the indicated meaning.
Advantageous other polymers of ethylenically unsatura-ted monomers have recurring units of the formulae (20) and (21) Z . - - ' (20) 2 ~ ll ~; W5 ~ Ql - N - Q - CO - N - CH20R"

and . . z .

" - CH2- C - ~1 ' .
(21) L W5 ~ Ql ~ I ~ - CO - N - CH20R" ~ An ~,, , , , ' , ' wherein W5 denotes oxygen, -COO- or -CON- and Z and Z' each denote hydrogen or lower alkyl, such asZ for example, methyl, and Q, Ql' Rl, R", Vl, Y and An~ have the indicated meaning.
The recurring units of the formula (20) and (21) can ~' also be incorporated in copolymers with other copolymerisable .,~,. , ;il vinyl compounds, for example the abovementioned ethylenically unsaturated comonomers.
;~ In the definition of the radicals of the compounds of ~ the formulae (5) to (17), which can be used to modify the ,~r~ ~ , cellulose materials, and of the recurring units of the formulae ,. ~
(18) to (21), lower alkyl and lower alkoxy as a rule represent s ~ those groups which contain 1 to 5, and especially 1 to 3, car-bon atoms, such as, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl or amyl, or methoxy, ethoxy or ., ,~, , ~,:
.

: - . . - .

: . . . . : :~ . , ` . - ' ' , . .

~ - , .. , - . - , . ~ , .

10~1866 isopropoxy. Halogen, in connec~ion with all of the above substituents, denotes, for example, fluorine, bromine or, preferably, c~.lorine.
The cationic modification is as a rule effected by treating, for example, impregnating, the cellulose materials with the cationic methylol compound, or mixtures which form it, in an acid medium, for example at a pH value of 2 to 6, and heat-setting the treated cellulose materials, appropriately at temperatures of between 20 and 200C, and preferably between 50 and 150C, heat-setting being carried out until the product is dry. Mixtures of the basic methylol compounds can also ` be employed to modify the cellulose. A catalyst can option-ally be used for setting. Suitable catalysts are, for e~ample, ammonium thiocyanate, ammonium chloride, ammonium hydrogen orthophosphate, magnesium chloride, zinc nitrate, maleic acid, tartaric acid or citric acid.
:, , The cationic methylol compounds can also be etherified with an alkanol containing at most 4 carbon atoms, for example with ethanol, propanol, butanol or, especially, methanol.
The cationically modified cellulose materials as a ,.~!, rule contain at least 0.4% by weight, and preferably 0.7 to 1.5% by weight, of basic nitrogen. The total nitrogen con-tent, which also includes the amide nitrogen, appropriately is at least o.6% by weight and preferably 0.8 to 3% by weight.
Aminoplast precondensates which do not contain any basic groups, such as, for example, primary, secondary or tertiary amino groups or quaternary ammonium groups, can . .

.

,',' ,, ~ . , , ~ ' . - ' - -optionally also be used as reactants.
Aminoplast precondensates are understood as addition products of formaldehyde and nitrogen compounds which can be methylolated, such as, for example, urea compounds or thiourea compounds or 1,3,5-aminotriazines.
Suitable urea compounds and thiourea compounds are, for example, urea, thiourea, substituted ureas, such as alkyl- or aryl-ureas, alkyleneureas and alkylenediureas, such as ethyleneurea, propyleneurea, dihydroxyethyleneurea, hydroxy-propyleneurea and acetylenediurea, and also dicyandiamide, dicyandiamidine, urones and hexahydropyrimidones.
Examples of 1,~,5-aminotriazines which may be mentioned are: melamine and N-substituted melamines, such as N-butyl-melamine, N-trihalogenomethylmelamines, triazones, ammeline, guanamines, such as, for example, benzoguanamine, acetoguana-min~s and diguanamines, as well as guanidines which can be brought into a water-soluble form by conversion into corres-ponding ammonium salts.
Aminoplast precondensates which can be used are, preferably, the methylol compounds of the said ureas and 1,~,5-aminotriazines. Amongst these compounds, those to be singled out in particular are, above all, N-methylolureas and N-methylolmelamines. Partial ethers of such methylol com-. -pounds, for example with alkanols with 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol or n-butanol, can also - be used.
-~ The cellulose-containing materials to be used for : ,"
.,;., , :
, ............................ .
.. :. .
., - .
. . ,. . : .:
.. . . .
;,..... ~ , -.
.
. , - -;, . ~ .

1~)9~866 cationic modification are bleached or unbleached pine sulphite cellulose, kraft sulphate cellulose, paper, cardboard products, wasteFaper, ~e ~br~ made ~ o~n,raycn s~ple, ~,ramie, hemp, linen or viscose and also peat, mechanical wood pulp, sawdust, wood fibres, wood flour, cork flour, bark or cereal waste.
These cellulose mat0rials are appropriately converted into a form suitable for treatment with the methylol compound, for example into a fibre suspension. The cellulose can also be in the form of granules, filter paper, absorbent paper or paper pulp.
If desired, the adsorbent to be used according to the invention can be mixed with activated carbon powder and/or other known filtration aids, such as, for example, peat, kieselguhr or diatomaceous earth. In this case the activated carbon i8 added to the adsorbent materials in ~mount~ o~ 2 to 95% by weight, and preferably of 10 to 70%
by weight, calculated relative to the total weight of the adsorbent material.
In the manufacturing instructions and examples which follow, percentages are always percentages by weight.
^ Manufacturin~ instructions A. a) 115 g of an adduct obtained by an addition reac-tion of 2 mols of acrylamide with 1 mol of N,N-dimethyl--~ ethylenediamine are dissolved in 93 ml of water and the solu-'f`'' tion is allowed to react, at a temperature o~ 0-10C, with 85 ml of a ~5.1% strength solution of formaldehyde until the '.:
~; content of free formaldehyde is 0.7%. 293 g of a 50/0 ....
,~x, ~ - 30 -. . .. . . . . . ... . . .
. ,. - .~ . .
,`~' ` ' ' . . "~' ' -,- ., -" ; - ~
~ . ~., . -~' .: :',. . .
- .
- .. . ~ :. .... ,: ..
. .. . .. .. .
. : : , . . : - . . ;: : - . :

lV9186~;

strength aqueous solution of the dimethylol compound of the formula (101) (CH3)2N-CH2-CH2-N(CH2CH2-CONH-CH20H)2 are obtained.
The solution is then diluted with 1,172 g of water and the pH is adjusted to 3 with concentrated hydrochloric acid.
b) 9.1 g of filter paper (weight per unit area 100 g/

m ) are so saturated with the acid solution prepared according to a) that 25.7 g of the acid solution are taken up by the , paper. The impregnated paper is condensed for 10 minutes at 105-110C, and washed with water. The nitrogen content , - of this adsorbent is 2.15%.
,,, B. a) 43.2 g of an adduct obtained by an addition reac-tion of 1 mol of diethylamine with 1 mol of acrylamide are . .
; dissolved in 35.4 g of water and methylolated with 25.8 g of a 35% strength formaldehyde solution, with the addition of 0.1 g of sodium hydroxide, for 5 hours at 50-60C. A 50~0 . ~;
~i; strength, yellowish solution of a methylol compound of the ;~. formula , ~ (102) (C2H5)2N-CH2CH2-CONH-CH20H
. ~ .
. . .
-- is obtained.
.':
This solution is then diluted with 417.5 g of water and the pH is adjusted to 3 with concentrated hydrochloric ; acid.
~:",.
s b) 9.5 g of filter paper are so saturated with the ..... .
.; , .-:, ..
: -- 31 --: . ~ .
, ., : . , ,. . , . , . . . , .. -. .

:, . .. .. .

~091866 acid solution prepared according to a) that 30.4 g of the acid solution are taken up by the paper. The impregnated paper iæ condensed for 10 minutes at 110C and washed with water.
The nitrogen content of this adsorbent material is 2.07%.
C. a) 63.2 g of an adduct obtained by an addition reaction of acrylamide with morpholine are introduced into a suspension of 18 g of paraformaldehyde and 0.2 g of sodium hydroxide in 80 ml of ethanol. The reaction mixture is then heated up to 50C and allowed to react for 5 hours, whilst stirring, until a clear colourless solution forms.
The solution is diluted with 550 ml of ethanol and cooled to -50C using solid carbon dioxide. 29 g of a crystalline methylol compound of the formula ' , .

; - (103) ~ N-CH2C~I~C0`,~-C1120H

,~ which has a melting point of 92-93C are obtained.
b) 9.3 g of filter paper are so saturated with a 10/o strength aqueous solution of the methylol compound of the formula (103) which has been ad~usted to a pH of 3 that 33.3 g , of the acid solution are taken up by the paper. The paper is condensed for 10 minutes at 110C and washed with water.
:~ .
The nitrogen content of this adsorbent material is 1.6%.
~; D. a) 68.5 g of an adduct (melting point: 236-237C) obtained by an addition reaction of 2 mols of acrylamide with 1 mol of piperazine are dissolved in 313 ml of water and . s ~ methylolated with 51.3 g of a 35.1% strength solution of , . . .

:.
. ............................................. .
-. :::. , formaldehyde, with the addition of 0.1 g o~ sodium hydroxide, for 5 hours at 50-60C. A clear solution which has a form-aldehyde content of O.Og~O forms. This solution is then completely evaporated and the residue is recrystallised from a mixture of ethanol and methanol (1:1).
27 g of a methylol compound of the formula ,; ~ .
,, CH Cl~ -CO NllCIl OH
` (104) N

N J
~ I .
CH2 -C1~2 -co-M~

... . .
~ which has a melting point of 151-153C are obtained.
:.:~i . , ~ b) 9.6 g of filter paper are so saturated with a l~/o ,i',, .
~trength aqueous solution of the methylol compound of the ; formula (104), which has been ad~usted to a pH of 3 with con-, ~ centrated hydrochloric acid, that 34.6 g of the acid solution ,, .
are taken up by the paper. The treated paper is condensed for 10 minutes at 110C and waæhed with water. The nitro-gen content of the resulting adsorbent material is 2.5Z%.
. .
E. a) 50 g of the product tmelting point: 278-282C
with decomposition) obtained by reacting piperazine and chlor-.
acetamide are dissolved in 315 ml of water and methylolated with 42.8 g of a 35.1% strength solution of formaldehyde, with the addition of 0.1 g of sodium hydroxide. The resulting solution, which contains the methylol compound of the formula .
''", :

, ................. .
~..

.. ~ .. ......... ....
~, , .

.~ -- : : , ,, , . . . . .

`
. fll2-co~ cH2oH

(105) ~ N
N
, C~12 - CO -hl~l -CH201~ `
is diluted with 242 ml of water and the pH value is adjusted to 3 with concentrated hydrochloric acid.
b) 9.4 g of filter paper are so saturated with the acid solution, prepared according to a), of the methylol com-pound of the formula (105) that ~3.7 g of this solution are taken up by the paper. The impregnated paper is condensed ~or 10 minutes at 120C and washed with water. The nitro-gen content of the adsorbent material is 2.4%.
F. a) Z2.6 g of the morpholinium compound of the formula . , ~ CH2-c~-NH2 Cl ,.,r, ' ' , CH3 . i. - - - , , .
- are dissolved in 110 ml of water and methylolated with 9.6 g of a 36.5% strength solution of formaldehyde, with the addition of 0.05 g of sodium hydroxide, for 5 hours at 50-55C to give a methylol compound of the formula . " , .

(106) 0 ~ CH2-cO-~H~-cH2oH C1 , ~ . , .
The resulting solution is then diluted with 118 ml of water ,. .

' ... .

... . .

.. . . .

and the pH is adjusted to 3 with concentrated hydrochloric acid.
b) 9.4 g of filter paper are so saturated with the acid solution, prepared according to a), of the methylol com-pound of the formula (106) that 34.9 g of this solution are taken up by the paper. The impregnated paper is condensed at 140C for 10 minutes and washed with water. The nitro-gen content of the resulting adsorbent material is 0.8%.
, .
-, G. a) 27.2 g of the adduct obtained by an addition re-., .
action of 2 mols of acrylamide with 1 mol of N,N-diethylamino-propylamine are dissolved in 150 ml of ethanol and quaternised with ll g of ethyl bromide for 5 hours at 60-70C. The resulting solution is then evaporated at 50C, after which 35.9 g of the partially quaternised ammonium compound are obtained in the form o~ a viscous oil. The ammonium com-pound is dissolved in 185 ml of water and methylolated with 16~4 g of a 36.5% strength solution of formaldehyde, with the addition of 0.05 g of sodium hydroxide, for 5 hours at 50-60C
., .
~ to give a methylol compound of the formula A,. .
~ (107) (C ~5)3N-CH2CH2CH2N(CH2CH2CONHCH20H)2 Br ~
. ,~ .
The resulting solution of the methylol compound is diluted with 182 ml of water and the pH is adjusted to 3 with concen-., .
: trated hydrochloric acid.
.
~- b) 9.6 g of filter paper are so saturated with the acid solution prepared according to a) that 36.2 g of this ... .
~ solution are taken up by the paper. The impregnated paper ,, .
.... . .

, , .

.. . . . .
, . . . . .
,~ - , ' , ~ .
, ' ' .' ~ ~; ~' ' - '' 1(~91866 is condensed for 10 minutes at 130C and washed with water.
The nitrogen content of the adsorbent material is 2.0%.
H. a) 22.5 g of a 36.9% strength solution of hydro-chloric acid are added to a solution of 34.9 g of 2-dimethyl-aminopropionamide in 22.5 ml of water, whilst cooling.
30.4 g of a 35.1% strength solution of formaldehyde and 20 ml of water are then added at room temperature, whilst stirring.
After a reaction time of 2 days at 25C, the conversion of formaldehyde is 98% of theory. A 35% strength aqueous solution of a methylol compound of the formula (108) (CH3)2N - CH2CH2 - CONH - CH20H

approximately 80% of which is in the form of the hydrochloride, is obtained.
The pH of 46 g of this solution is ad~usted to 4 with 18% strength hydrochloric acid and the mixture is diluted with 30 ml of water b) 7.7 g of filter paper are so saturated with the acid solution prepared according to a) that 25.5 g of the acid solution are taken up by the paper. The impregnated paper is condensed for 10 minutes at 140C and then washed with . ,i.
water. 8.3 g of an adsorbent are obtained. The nitro-gen content of this adsorbent material is 2.0%.
I. a) 69.7 g of an addition product of bis-(2-ethoxy-ethyl)-amine and acrylamide are dissolved in 22,5 ml of water and 22.5 g Of 36.5% strength hydrochloric acid are added, whilst cooling. 15 ml of water, 30.4 g of a ~5.5% strength ~ .

. .
,~ .

~ .
` . . ' . :- ~ ' , . ' ' 109~866 solution of formaldehyde, 15 ml of water and 30 ml of a 2 N
sodium hydroxide solution are then added at 25C, whilst stirring. After a reaction time of 14 days at 25C, the conversion of formaldehyde is 96% of theory. 207 g of a ~, 38% strength aqueous solution of the methylol compound of the formula ; (109) (C2H50CH2CH2)2N - CH2CH2 - CONH - CH20H

- approximately 80% of which is in the form of the hydrochloride, are obtained.
The pH of this solution is adjusted to 4 with dilute ~; hydrochloric acid and the mixture is diluted with water to give a 20% strength solution.
, ....
b~ Using the acid solution prepared according to a), filter paper is so saturated, and condensed, as described in .
~ Instruction H.b), that 8~3 g of an adsorbent are obtained.
;
A~ter washing with water, the nitrogen content of this adsorb-ent material is 1.6%.
"i:~
s J. a) 144 g of 2-diethylaminopropionamide, 90 g of para-,, formaldehyde and 0.6 g of magnesium oxide are allowed to react ~ for 40 minutes at 96-98C, whilst stirring. The reaction - product is then cooled to 40C and water is then added.
430 g of a 47% strength solution of the dimethylol compound of the ~ormula ; ~
, ,, "", ( 110 ) ( 2H5 ) 2N - CH2CH2 - CoN ( cH2oH ) 2 ~` are obtained. The pH of 33.4 g of this solution i~ adjusted ~` . , ' .
~ - 37 -`';
,. ' ",, '~
.~, , ~ .

109:1866 to 4 with 5 N hydrochloric acid and the solution is diluted with water to a weight of 80 g.
b) Using the acid solution prepared according to a), filter paper is so saturated, and condensed, as described in Instruction H. b),that 9.0 g of an adsorbent are obtained.
After washing with water, the nitrogen content of this adsorb-ent material is 2.5%.
K. a) 144 g of 2-diethylaminopropionamide are dissolved in 300 ml of benzene and 31.2 g of paraformaldehyde and 0.2 g of sodium methylate are added. The mixture is allowed to ; react for 10 hours at 45C, whilst stirring. 91.4 g of a 36.~/o strength solution of hydrochloric acid and 92 g of methanol are then added at room temperature. The emulsion formed is slowly heated to the boil and the water is distilled off as an azeotrope. The residue is then evaporated, after which 198 g of a compound of the formula ~, (111) (C H )2N - CH2CH2 - CONH - CH20C 3 :
are obtained.
b) Using a 20/ strength aqueous solution of the com-pound prepared according to a), filter paper is so saturated, and condensed, as described in Instruction H.b), that 8.7 g of ~ an adsorbent are obtained. After washing with water, the `- nitrogen content of this adsorbent material is 2.6%.
L. a~ 56 g of pyridine ar~ added to a solution of 75.2 g of 2-chloropropionamide in 750 ml of dioxane at 50C, whilst stirring. This mixture is stirred at a temperature of .-:
,..

"
\

.:"
`' : ', ~:
. . . , ~. ..

.. , 100C for 18 hours. The precipitate which has ~ormed on cooling is filtered off and recrystallised from ethanol.
65 g of a compound of the formula .
~ ' ~3 , ~ N - CH2CH2 - CONH2 Cl ~

are obtained. 28.9 g of this compound are dissolved in 60 ml of water, 15.8 g of a 35.5% strength solution of formal-dehyde are added and the mixture is stirred for 14 days at room temperature. The pH value of the reaction mixture is kept at 8 by adding a 1 N sodium hydroxide solution. The conversion of formald~hyde is 67% of theory. 115 g of a 29~o strength solution of the methylol compound of the formula , .

(112) L ~ N - Cl~2CH2 - C0~ - CH20U~ C1 , ~ ..

, .~ are obtained. The pH of this solution is adjusted to 4 with , "
hydrochloric acid and the mixture is diluted with water to give a lOyo strength solution.
~ b) Using the acid solution prepared according to a), filter paper is so saturated, and condensed, as described in Instruction H.b)t that 9.0 g of an adsorbent are obtained.
;.
x~ After washing with water, the nitrogen content of this .. . .

~.

:, ' : .
....

adsorbent material is l.~/o.
M. a) 25 g of a 36% strength solution of formaldehyde are added to a solution of 45.7 g of carbamoylcholine chloride in 150 ml of water. This mixture is stirred at a tempera-ture of 25C for 3 days and the pH value i~ kept at 8.5 by adding a 0.1 N sodium hydroxide solution. The conversion of formaldehyde is 95% of theory. A 24% strength solution of a methylol compound of the formula (113) ~(CH3)3~ _ CH2CH2 ~ - C0 - NH -~cH2oH] C1 . . .

.
is obtained. The pH of this solution is adJùsted to 4 with hydrochloric acid and the mixture is diluted with water to give a 10~/o strength solution.
b) 7.7 g of paper are so saturated with the acid solution prepared according to a) that 23 g of the solution are taken up by the paper. The impregnated paper is con-densed for 5 minutes at 170C and then washed with water.
... .
The nitrogen content of this adsorbent material is 0.9%.
N. a) 20 g of a copolymer of the formula - CH - CH2 - CH - fH-1~ c~o CH2CH2CH2 - I(CH3)2 C1 imately _ CH2 - CO~H2 400 , .
,~

''. , .
;.
. - . - . : .. ,. , . . - . -. , . - . . . .
- . - - . , .. . .
. . - . : .

-~ :

10918~6 are dissolved in 80 g of water and 8.9 g of a 35.5% strength ; solution of formaldehyde are added. The reaction solution is then heated to 55C and the pH value is kept at between 8 and 8 5 by adding 1 N sodium hydroxide solution. After a reaction time of 17 hours, the conversion of formaldehyde reaches 96% of theory. 113 g of a 20% strength clear solu-tiOll of the methylolated polymer of the formula ~: ... ' . . :.. . . .

(114) ~ N approx-CH2CH2CH2 - l(CH3)2 mately - CH2 - C0NH ~ C~20n . . _' ,........... ..

~re obtained. The pH of this solution is then adjusted to ' 4 with concentrated hydrochloric acid and the mixture is dilu-; ted with water to give a l~/o strength solution.
b) Using the acid solution prepared ac~ording to a), - 7.7 g o filter paper are so saturated, and condensed, as des-cribed in Instruction H. b),that 10.0 g of an adsorbent are obtained. After washing with water, the nitrogen content : ~
of this adsorbent material is 2.1%.
O. a) 25.5 g of a polymer of the formula C0 - (CH2)4 ~ C0~ - (CH2)3 ~ N - (CH2)3NH -~

.. . ..
., - 41 _ . ' : '' - - - - -- -. , ' : , :
.. ,, , ~

. , , lOgl86~ .

which has been obtained by a condensation reaction of diethyl adipate with 4-aza-4-methylheptamethylenediamine, are dissolved in 18 ml of dimethylformamide. 12.3 g of N-methoxymethyl-a-chloracetamide are added to this solution at 70C, whilst stirring. The reaction mixture is stirred for a further 18 hours at 80-85C and is finally evaporated. The residue is dissolved in 147 ml o~ water. A 2~/o strength solution of a polymer of the formula "

: r CH3 - Cl ~ ~ -(115) L C0 - (CH2~4 - C0~ (cl~2)3 l 2 3 ~ 30 ', . CH2 -- CONH - CH20CH3 is obtained.
The pH of this solution is then adjusted to 4 with concentrated hydrochloric acid and the mixture is diluted with water to give a l~/o solution.
b) Using the acid solution prepared according to a), 7.7 g of filter paper are so saturated, and condensed, as des-cribed in Instruction H. b),that 8.4 g of an adsorbent are obtained. After washing with water, the nitrogen content of this adsorbent material is 1.8%.
P. 7~7 g of filter paper are so saturated with a solution which comprises 20 parts of -the methylol compound of the for-mula (102), 4 parts of dimethylolmelamine and 76 parts of ; water/5 N hydrochloric acid and has been adjusted to a pH of 4 that 24.3 g o~ this solution are taken up by the paper.
: :.
..
~; - 42 -. .
. , .
~ . ~, .. . . . . . . .. . . .... . . .
;:. . .' - .', , :, -. .,.... : - . . . , - .
-, , "
.: , . . .
-The impregnated paper is dried for 10 hours at 140C iand then worked up as described in Instruction A.b). 9.4 g of an adsorbent material with a nitrogen content of 6% are obtained.
Example 1 325 g of a cotton tricot fabric are dyed, in a winch vat, for 10 minutes at 100C in 13 1 of an aqueous liquor which contains, relative to the fabric, ~% of the blue reac-tive dyestuff C.I. No. 61,211 as well as 80 g/l of sodium chloride and 2 g/l of sodium 3-nitrobenzene-1-sulphonate.
The temperature is lowered to 75C in the course of 30 minutes and 20 g/l of sodium carbonate and ~ ml/l of a 4~/0 strength solution of sodium hydroxide are added. Dyeing is then carried out for 60 minutes at 75C and the blue coloured residual liquor is then run off.
The winch vat is now filled with 13 1 of deionised water, the pH value of which has been adjusted to 6 with 1 N
sulphuric acid, and the liquor is warmed to 55C.
The washing liquor is passed through a filter device, which is incorporated in a cycle with the winch vat, for 60 . .
; minutes at a throughput rate of 3 l/minute.
The filter consists of an adsorption column which is ` 13 cm in diameter and contains 30 g of the adsorbent according to Instruction A. b) in a shredded form.
, The pH value of the circulating wash liquor is kept at between 5.5 and 6.5 by adding 1 ~ sodium hydroxide solution or 1 N sulphuric acid.
In respect of fastness to rubbing (dry and wet), .

~ .. . . . . ...
- . ~ -.
: ., , , , . . :
, ~ ' ', .
.. . .

.

1~91866 fastness to wet hot pressing, fastness to washing, fastness to Xenon light and shade, the dyeing finished in this way is equal to a dyeing finished in the conventional manner, that is to say washed in 5 separate washing and rinsing baths.
However, according to the process, large amounts of water and energy and considerable time have been saved.
Example 2 Using a liquor ratio of 1:20, 100 kg of cotton tricot are dyed, in a winch vat, for 45 minutes at 75C with a dye liquor which contains 3 kg of a dyestuf~ of the formula :'. , , :
Cl ~ao3s~~ llll n=N ~I -Q
C~3 Cl S03Na S03~a S03Na ( 201 ) . , , and 70 g/l o~ sodium chloride. The dyestuff is then fixed for one hour at 75-80C by adding 20 g/l of sodium carbonate and 3 ml/l of 40% strength sodium hydroxide solution.
All of the dye liquor is then run off and the dyed goods are rinsed once cold.
The dyeing is finished by circulating the next washing liquor which is at 80C and has a pH of 5-6 maintained by means of sulphuric acid, this liquor being circulated through 6 kg of an adsorbent materia~ manufactured in accordance with ;. .

: , - , ,~, " -" ' , , Instruction K. b), which is in the form of chips (2mm x 13mm) and is arranged in a filter-like manner.
The filter part of the apparatus used for this purpose consists of two 65 cm high, perforated sheet metal cylinders 'which have diameters of 30 and 20 cm and are arranged co-axially.
:
The bath is circulated at a frequency of 14 per hour.
After 45 minutes the washing liquor'which was initially deeply coloured is virtually colourless.
With regard to the fastness properties, such as fast-ness to washing, fastness to water, fastness to perspiration (alkaline or acid), fastness to rubbing (dry and wet) and fastness ~o Xenon light, the dyeing finished in this way is equal to a dyeing washed in the conventional manner, that is to say with 7 separate alternately cold and hot washing and rinsing bath~, but this dyeing appears to have a greater depth of colour and to be more brilliant'.
Example 3 ,25 g of a cotton tricot fabric are dyed,'in a winch vat, for 10 minutes at 100C in 1~ 1 of an aqueous liquor which contains, relative to the fabric, 3% of the blue reac-tive dyestuff C.I. No. 61,211 as well as 80 g/l of sodium , chloride and 2 g/l of sodium 3-nitrobenzene~l-sulphonate.
The temperature is lowered to 75C in the course of 30 minutes and 20 g/l of sodium carbonate and ~ ml/l of a 4~/0 strength ~ , solution of sodium hydroxide are added. Dyeing is then carried out for 60 minutes at 75C and the blue coloured "' , :, ,. . : ~:
.: ~ :-- .
., .. ~, . , . : , -.
,, ... :

~09~66 residual liquor is then run off.
The winch vat is now filled with 13 1 of water, the pH value of which has been adjusted to 6 with 1 N
sulphuric acid, and the liquor is warmed to 80C.
The washing liquor is passed through an adsorption apparatus, which is incorporated in a cycle with the winch vat, for 60 minutes at a throughput rate of approximately 3 l/minute. This apparatus contains 30 g of the adsorbent material prepared according to Instruction B. b) (in the form o~ 2 x 13 mm chips).
The pH value of the circulating washing liquor is kept at between 5.5 and 6.5 by adding 1 N sodium hydroxide solution . .
or 1 N sulphuric acid. The liquor is virtually colourless a~ter one hour.
In resp~ct of fastness to rubbing (dry and wet), fastness to wet hot pressing, fastness to washing, fastness to Xenon light and shade, the dyeing finished in this way is equal to a dyelng finished in the conventional manner, that is to say washed in 6 separate washing and rinsing baths.
,, However, according to the process, large amounts of water and energy and considerable time have been saved.
Similar results in respect of dyeing and fastness ...
properties are obtained when the adsorbent material described in Example 3 is replaced by tne adsorbents listed in column 2 of the table which follows. The amounts and the forms of , , the adsorbents used are indicated in the third and fourth columns of the table.

... .

:...... .
~ ..... .
, ,.... ,. , .. - , - .- ~

:. ,, ~:
,, . ~ . . : , - .
, . . . . . . . . ... .

Table , . ..
ExampleAdsorbent material Amount Form/dimension prepared according to (g) (mm) Instructions, or of the structure ___ 4 . A. b) 80 2hlpl3 C. b) 100 c2hipl3 ~ 6 D. b) 80 2hxP13 : 7 E. b) 80 1hip6 8 F. b) 100 clhxp6 9 G. b) 60 C2hxPl3 H, b) 80 c2hip~

11 I. b) 80 c2hipl3 12 J. b) 25 C2hxPl3 . 13 K. b) 20 2 x 13 ;`............ . 14 K. b) 20 pulp L. b) . 40 C2hxPl3 16 M. b) 80 C2hxPl3 17 N. b) 80 C2hxPl3 :. 18 0. b) 80 ch ps .: .
,. ..

. - 47 -. - , . .

: . . . .
.. . . .
. .
. :

Table (Continuation) ,:
ExampleAdsorbent material Amount Form/dimension prepared according to (g) (mm) Instructions, ; or of the structure 19Cell[ocH2cHcH2N(cH3)3cl ] 80 2 x 13 20Cell[OC2H4N(c2H5)2] _ chips Example 21 2 kg o~ non-mercerised cotton yarn are dyed in the customary manner, using a liquor ratio of 1:10, in a circula-tion apparatus with 40 g o~ a dyestuf~ of the formula OH
(202) ) - N=N ~ NH-CO ~ ~
2 ~ ~ 3 ~ Cl ,COONa H3 $
,.
.
The dye lLquor is then run o~f and the dyed goods are rinsed with 20 1 of cold water. The dyestuff which has not been fixed is then removed in a bath at 80 - 95C and a pH value ... .
o~ 6 by continuously passing part of the liquor through a fixed bed arrangement (diameter 15 cm, packing density 0.2 g/
cm3) in which there are 100 g of the adsorbent material pre-pared according to Instruction K. b) in the form of chips (2 mm x 13 mm). The washing process is ended after one hour, during which time the liquor is circulated 12 times.
.,~ .
... .

'; - _ 48 -"
, .
~ .
,... . . , ~ - , . . .:.

, ~ . .. - ... . . .
, ~ -, ~..... :, ~. : -.: .

With regard to the properties listed in Example 2, the dyeing thus obtained is equal to a dyeing produced in the conventional manner and washed with 7 separate cold and hot rinsing and washing liquors.
~ 1hen the dyeing process is repeated with the aid of adsorbent material regenerated with 5 1 of a 0.05 N sodium hydroxide solution, yarn dyed to an equal standard is again obtained.
Example 22 80 kg of cotton tricot are dyed in the customary manner, using a liquor ratio of 1:8, in a Jet dyeing apparatus with 600 g of the blue reactive dyestuff C.I. No. 61,211.
After the dye liquor has been run off, the dyed goods are rinsed twice with cold water. The d~eing i8 then finished in the next bath at 80 - 90C and a pH of 5-6 by contirluously passing a partial stream of the washing liquor through a fixed bed arrangement in which there are 2 kg of the adsorbent material prepared according to Instruction K. b) in the form of chips (2 mm x 13 mm) between 2 40 cm high perforated sheet metal cylinders which have diameters of 20 cm and 10 cm and ,. ~
-~ are arranged coaxially. The process is ended after one hour, during which time the bath is circulated about 11 times.
In respect of the criteria listed in Example 1, the dyed goods thus obtained are of equal quality, compared with a dyeing i:
; washed in the conventional manner.
, . .
....
' .

. .
:, , .~ .
... .. .

.

Claims (41)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Process for dyeing textile materials by the customary methods using aqueous dye liquors containing water-soluble dye-stuffs, the residual liquor being removed after dyeing is completed and the dyed goods being washed, wherein the coloured washing liquor is continuously removed and brought into contact with a cationically modified cellulose-containing material in order to effect decoloration and the decolorised washing liquor is then re-cycled to the dyed goods for further washing.

2. Process according to claim 1 wherein the temperature of the washing liquor is 30 to 100 C.

3. Process according to one of claims 1 and 2 wherein the pH value of the washing liquor is 3 to 9.

4. Process according to claim 1 wherein the washing liquor is circulated at least 5 times in the course of one hour.

5. Process according to claim 1 wherein the washing operation takes 0.3 to 3 hours.

6. Process according to claim 1 wherein brief preliminary rinsing with water is carried out prior to continuous washing.

7. Process according to claim 1 wherein the purification of the washing liquor is carried out by the fluidised bed or fixed bed process.

8. Process according to claim 1, wherein the modified cellulose material contains amino groups or quaternary ammonium groups as cationic substituents.

9. Process according to claim 1, wherein a cationically modified, cellulose-containing material in which the cationic constituent is bonded to the cellulose via a bridge of the formula ( 2 ) in which the nitrogen belongs to an amide group of the cationic radical and the oxygen is bonded to the cellulose is used.

10. Process according to claim 9, wherein the cationic constituent of the modified cellulose material is bonded to the cellulose part via a radical of the formula - O - CH2 - ? - X - (3) in which X denotes the divalent bridge -CO-, -CO-O-, -CS-, , or -SO2- or a carbon atom which is a constituent of a nitrogen heterocyclic structure and adjacent to the ring nitrogen, R and R' each denote hydrogen or an organic radical and q and q' in each case denote 1 or 2.

11. Process according to claim 10, wherein the cationic constituent of the modified cellulose material is bonded to the cellulose part via the grouping of the formula (3), in which R denotes hydrogen or CH2-O(H) and R' denotes C1-C5-alkyl.

12. Process according to claim 10, wherein the cationic constituent of the modified cellulose material is bonded to the cellulose part via the grouping of the formula (3) in which X denotes the -CO- group.

13. Process according to claim 1, wherein the cationic constituent of the modified cellulose material is derived from an amino compound which contains at least one amino group and at least one N-methylolcarboxamide group.

14. Process according to claim 1, wherein the cationic constituent of the modified cellulose material is derived from an amino compound which contains at least one amino group and at least one N-methylolcarboxamide group which is etherified by C1-C4-alkoxy.

15. Process according to claim 13, wherein the cationic constituent of the modified cellulose material is derived from an aliphatic monoamine or polyamine or hydrogenated nitrogen heterocyclic compound which contains at least one N-methylolcarboxamide group.

16. Process according to claim 13, wherein the cationic constituent of the modified cellulose material is derived from an optionally etherified methylol compound of the general formula (5) in which R" denotes hydrogen or C1-C4-alkyl, R1 and R2 in-dependently of one another denote hydrogen, lower alkyl which is optionally substituted by halogen, hydroxyl, lower alkoxy or cyano, or cycloalkyl, benzyl or the group of the formula - Q - CO - ? - CH2 - OR" (6) or R1 and R2, together with the nitrogen atom which links them, denote a 5-membered or 6-membered heterocyclic radical, Q denotes an alkylene- or alkyl-substituted alkylene chain with up to 8 carbon atoms and Y denotes hydrogen, lower alkyl or -CH2OR".

17. Process according to claim 16, wherein the cationic constituent of the modified cellulose material is derived from a compound of the formula (5) in which R1 and R2 both denote lower alkyl or lower alkoxy-lower alkyl, or R1 and R2, together with the common nitrogen atom, denote a morpholino radical, Q denotes C1-C3-alkylene and Y and R" denote hydrogen.

18. Process according to claim 15, wherein the cationic constituent is derived from an alkylenepolyamine or hydrogen-ated diazine which contains at least one N-methylolcarboxamide group.

19. Process according to claim 18, wherein the cationic constituent of the modified cellulose material is derived from a polyamino compound of the general formula (7) in which Q1 denotes an alkylene- or alkyl-substituted alkylene chain with up to 8 carbon atoms, R3, R4, R5 and R6 independently of one another denote hydrogen, lower alkyl which is optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cyclo-alkyl, benzyl or the group of the formula (6) -Q-CO-?-CH2-OR" or R3 and R4, together with the nitrogen atom which links them, de-note a 5-membered or 6-membered heterocyclic radical, or, if n is 1, R4 and R5, together with the grouping which links them, also denote a divalent heterocyclic radical, and n denotes 1 to 1,000, Q represents an alkylene chain or alkyl-substituted alkyl-ene chain with up to 8 carbon atoms, Y represents hydrogen, lower alkyl or -CH2OR" and R" represents hydrogen or C1-C4-alkyl, and at least one of R3, R4, R5 and R6 represents the group of the formula (6) and, if n denotes more than 1, each R5 independently of the others can represent hydrogen, lower alkyl which is option-ally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula (6), or each R5, or individual R5s, together with the adjacent R5 and with the grouping which links them, can also represent a divalent heterocyclic radical.

20. Process according to claim 19 wherein the cationic constituent of the modified cellulose material is derived from a diamino compound of the formula (8) in which R3, R4, R5, R", Q, Q1 and Y have the meaning indicated in claim 19.

21. Process according to claim 20, wherein the cationic constituent of the modified cellulose material is derived from a diamino compound of the formula (8) in which R3 and R4 both denote lower alkyl and R5 denotes the group of the formula (6), or R4 and R5, together with the grouping which links them, denote a piperazino ring and R3 denotes the group of the formula (6), Q denotes C1-C3-alkylene, Q1 denotes ethylene or propylene and Y denotes hydrogen.

22. Process according to claim 1, wherein the cationic constituent of the modified cellulose material is derived from a quaternary ammonium compound of the formula (9) (10) or (11) in which V1, V2 and V3 independently of one another denote hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula (6) -Q-CO-?-CH2-OR", R1, R2 and V1, or R3, R4 and V2, together with the nitrogen atom which links them, denote a pyridine ring which is optionally substituted by lower alkyl, An? denotes the anion of an organic or inorganic acld, R1 and R2 independently of one another represent hydrogen, lower alkyl which is optionally substituted by halogen, hydroxyl, lower alkoxy or cyano, or cycloalkyl or benzyl, or the group of the formula (6) -Q-CO-?-CH2-OR"

or R1 and R2, together with the nitrogen which links them, represent a 5-membered or 6-membered heterocyclic radical, R3, R4, R5 and R6 independently of one another represent hydrogen, lower alkyl which is unsubstituted or substituted by hydroxyl, cyano, halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula (6), or R3 and R4, together with the nitrogen atom which links them, represent a 5-mem-bered or 6-membered heterocyclic radical, Q and Q1' each represents an alkylene or alkyl-substituted alkylene chain with up to 8 carbon atoms, Y represents hydrogen, lower alkyl or -CH2OR", R" represents hydrogen or C1-C4-alkyl and n is 1 to 4 and at least one of R3, R4, R5, R6, V2 and V3 represents the group of the formula (6) and, if n denotes more than 1, each R5 or each V3 independently of the others can represent hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula (6), or each R5, or individual R5s, together with the adjacent R5 and with the common grouping , can also represent a divalent heterocyclic radical.

23. Process according to claim 22 wherein the cationic constituent of the modified cellulose material is derived from a quaternary ammonium compound of the formula (12) which R1, R2, R3, R", V1, Q, Q1 and Y have the meanings indi-cated in claim 22; An ? denotes the anion of an organic or inor-ganic acid and q is 1 or 2.

24. Process according to claim 23 wherein the cationic constituent of the modified cellulose material is derived from a quaternary ammonium compound of the formula (13) or of the formula (14) in which R?, R?, V?, R? and R? each denote lower alkyl, or R? and R?, together with the nitrogen atom which links them, denote a morpholino ring, R? denotes hydrogen or the group of the formula -Q"-CO-NH-CH2 OH , Q' denotes methylene or propylene, Q? denotes ethylene or propylene, Q" denotes C1-C3-alkylene and An ? has-the meaning indicated in claim 23.

25. Process according to claim 1, wherein the cationic constituent is derived from a polymeric compound of the general formulae (15) or (15) in which Q2, Q3, Q? and Q? independently of one another denote an alkylene- or alkyl-substituted alkylene chain with 2 to 8 carbon atoms, V3, R7, V? and R? independently of one another denote hydrogen, lower alkyl which is optionally substituted by halogen, hydroxyl, cyano or lower alkoxy, or benzyl or the group of the formula (6a) -Q'-CO-?-CH2OR", Q' denotes methylene or propylene, W1, W2, W? and W? indepen-dently of one another each denote a direct bond, oxygen or the group ; W3, W4, W? and W? independently of one another each denote a direct bond or -NH-; -CO-A-CO- and -CO-A'-CO-each denote the radical of a polybasic carboxylic acid, r and p each denote 1 to 10,000 and s denotes 1 to 10 and Y repre-sents hydrogen, lower alkyl or CH2OR", R" represents hydrogen or C1-C4-alkyl, A? represents the anion of an organic or in-organic acid and n is 1 to 4 and at least one of V3, R7, V?, R? and Y represents the group of the formula (6a) -Q'-CO-?-CH2OR" and, if n is more than 1, each R7 or V3 and each R? or V? independently of the others can represent hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula (6a), or each R7 and R? or individual R7s and R?s, together with an adjacent R7 or R? respectively and with the grouping and which link them, can represent a divalent heterocyclic radical.

26. Process according to claim 25, wherein the cationic constituent is derived from a polymeric compound of the formula ( 17 ) in whlch R"' denotes hydrogen or methyl, Q4 and Q5 each denote C2-C4-alkylene, A1 denotes the radical of an aliphatic C2-C4-dicarboxylic acid and r1 denotes 2 to 100 and An ? has the meaning indicated in claim 22.

27. Process according to claim 1, wherein the cationic constituent is derived from a polymeric or copolymeric compound which contains, in the molecule, recurring units of the formulae (18) or (19) in which one of Z1 and Z2 denotes hydrogen and the other denotes hydrogen, lower alkyl, phenyl, cyano, carboxyl or carbamoyl, Z3 and Z4 independently of one another denote hydrogen or lower alkyl and q denotes 1 or 2, R1 and R2 in-dependently of one another represent hydrogen, lower alkyl which is unsubstituted or substituted by halogen, hydroxyl, lower alkoxy or cyano, or cycloalkyl or benzyl or the group of the formula (6) -Q-CO-?-CH2-OR", or R1 and R2, together with the nitrogen atom which links them represent a 5-membered or 6-membered heterocyclic radical, V1 represents hydrogen, lower alkyl which is unsubstituted or substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula (6), R1, R2 and V1 together with the nitrogen atom which links them denote a pyridine ring which is option-ally substituted by lower alkyl, Q and Q1 each represents an alkylene or alkyl-substituted alkylene chain with up to 8 carbon atoms, and R", Y and An ? have the meaning indicated in claim 22.

28. Process according to claim 1, wherein a cationically modified cellulose material in which the hydroxyl groups have been replaced by quaternary ammonium groups of the formula (1) in which Alk denotes identical or different lower radical and An ? has the meaning indicated in claim 22, is used.

29. Process according to claim 1, wherein the cationic, modified cellulose material has been obtained with the addi-tional use of an aminoplast precondensate which is free from basic groups.

30. Process according to claim 17, wherein the cationic constituent is derived from a compound of the formula (5) in whlch R1 and R2 both denote methyl or ethyl, Q denotes ethylene and Y and R" denote hydrogen.

31. Process according to claim 16, wherein the cationic constituent is derived from a compound of the formula (5) in which R1 and R2 both denote ethyl, Q denotes ethylene, Y
denotes hydrogen and R" denotes methyl.

32. Process according to claim 16, wherein the cationic constituent is derived from a compound of the formula (5) in which R1 and R2 both denote ethyl, Q denotes ethylene, Y
denotes -CH20H and R" denotes hydrogen.

33. Process according to claim 17, wherein the cationic constituent is derived from a compound of the formula (5) in which R1 and R2, together with the nitrogen atom which links them, denote morpholino, Q denotes ethylene and Y and R"
denote hydrogen.

34. Process according to claim 21, wherein the cationic constituent is derived from a compound of the formula (8) in which R3 and R4 denote methyl, R5 denotes the group -Q-CO-?-CH2OH, Q and Q1 each denote ethylene and Y denotes hydrogen.

35. Process according to claim 21, wherein the cationic constituent is derived from a compound of the formula (8) in which R3 denotes the group -Q-CO-?-CH2OH, R4 and R5, together with the grouping which links them, denote piperazino, Q denotes methylene or ethylene and Y denotes hydrogen.

36. Process according to claim 24, wherein the cationic constltuent is derived from a compound of the formula (13) in which R?, R? and V?, together with the nitrogen atom which links them, denote a pyridine ring, Q' denotes ethylene and An ? denotes a chloride ion.

37. Process according to claim 24, wherein the cationic constituent is derived from a compound of the formula (13) in which R1, and R2, together with the nitrogen atom which links them, denote morpholino, V? denotes methyl, Q' denotes methylene and An ? denotes a chloride ion.

38. Process according to claim 24, wherein the cationic constituent is derived from a compound of the formula (14) in which R1, R2 and V? each denote ethyl, R? denotes the group -Q'-CO-NH-CH2OH, Q' and Q" denote ethylene, Q? denotes propylene and An ? denotes a bromide ion or chloride ion.

39. Process according to claim 10, wherein the cationic constituent is derived from a compound of the formula (CH3)3 ? CH2CH2-O-CONH-CH2OH Cl? .

40. Process according to claim 8, wherein the cationic constituent is derived from a compound of the formula (H5C2)2N-CH2CH2-Cl .

41. Process according to claim 1, wherein cellulose-con-taining textile material is dyed with fibre-reactive dyestuffs.