IE44262B1 - Process for dyeing textile material and treating the wash liquor used therein. - Google Patents

Abstract

1521229 Treatment of wash liquors from dyeing processes CIBA-GEIGY AG 12 Nov 1976 [21 Nov 1975] 47306/76 Heading C1C [Also in Division D1] Cationically modified cellulose containing material is used to effect decolorization of wash liquors from dyeing processes containing watersoluble anionic dyes, the decolorized water then being recycled to the dyeing process. Preferably the washing liquor is at 30‹-100‹ C. at pH value of 3 to 9. Purification of the water being effected by fluidized bed or fixed bed processes. Anionic dyes and optical brighteners may be removed from the wash water by cationically modified cellulose materials in which the hydroxyl groups have been at least partially replaced by quaternary ammonium groups of formula in which Alk is a C 1-5 alkyl radical, An- is an anion by reaction with an epoxypropylammonium salt.

Description

. The present invention provides a process for dyeing textile materials by the customary methods using aqueous dye liquors containing water-soluble anionic dyestuffs, the residual liquor being removed after dye5 ing is completed and the dyed goods being washed with water, characterised in that the washing liquor containing the dye is continuously removed and brought into contact with a cationically modified (as hereinafter defined) cellulose-containing material in order to rem10 ove the dye and the purified washing liquor is then recycled to the dyed material for washing the latter. It is to be understood that the terms ''dyeing'1 and dyestuff as used herein cover not only dyeing and dyestuffs but also optical brightening and optical brighteners, respectively.

In customary dyeing processes, for example in cheese dyeing or beam dyeing apparatuses, winch vats, jets or drum dyeing machines or paddles or jiggers, numerous, for example 4 to 8, washing and rinsing oper20 ations in a correspondingly large number of baths are always necessary in order to finish the dyeing, 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 also involve a considerable expenditure of energy since the fresh washing liquors always have to be warmed each time and, moreover, the time required is relatively long, compared with the time for the actual dyeing process. Furthermore, the wash10 ing waters containing dyestuffs frequently give rise to ecological problems.

With the process according to the invention >»·’.th which relatively small amounts of washing water suffice, since the same water is continuously purified and re10 circulated, it is now possible to achieve quite considerable savings in respect of water, energy, time and chemicals. In addition, a significant ecological advance is achieved. However, the process according to the invention i.s not only distinguished by these ecologic15 al and economic advantages but, in addition, the dyeings obtained have an even greater depth (of colour) and are more brilliant than those obtained with previous processes .

Decolorising of the washing waters with the cellul20 osic 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 are 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 state by the flow of the washing waters to be purified and c) the so-called fixed bed process in which the washing waters to be purified are fed through adsorbent material arranged as a filter.

The purification of the washing liquor is appropriately carried out at 10 to 15θ°0· Preferably, however, it is carried out at 30 to 100°C, or espec5 ially at 45 to 6S°C. 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 9, especially 5 to 8. The pH value can be ad10 justed by adding dilute, strong acids, for example sulphuric acid, hydrochloric acid or phosphoric acid, or bases, for example sodium hydroxide solution or potassium hydroxide solution, a single addition being made prior to the actual washing process and further additions being made continuously as necessary during washing.

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 operation takes 0.3, and especially 1 to 3, hours.

In some cases it can be advantageous to carry out a 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 subsequent amount of washing liquor, of water, at, for example, 15 to 25°C prior to the continuous washing process.

Natural and synthetic fibres can he 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, polyamide fibres, for example those made of poly-e-caprolactam (polyamide 0), polyhexamethylenediamine adipate (polyamide 6,6), polyω-amino-undecanoic acid (polyamide 7) or aromatic polyamide 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 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, yarns, 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 arc anionic dyestuffs or optical brjghtuners.

Anionic dyestuffs arc dyestuffs in viich the anionic character 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. - 6 The anionic dyestuffs can belong to very diverse categories of dyestuff. Examples which may be mentioned are oxazine, triphenylmethane, xanthene, nitro, acridone, stilbene, perinone, naphthoquinonimine, phthalocyanine, anthx’aquinone and azo dyestuffs. The latter can be metal-free, metallisable or metal-containing monoazo, disazo and polyazo dyestuffs, including the formazane dyestuffs, wherein the metal-atom forms a lil-complex or l:2-complex, especially 1:2-chromium or l:2-cobalt complexes, which contain two identical, or two different, molecules of azo dyestuff bonded as a complex to a chromium atom or r helt ‘om. These d’rcstuffs can also contain, in the molecule, so-called fibre-reactive groupings which enter into a covalent bond with the fibre material to be dyed. Fibre-reactive dyestuffs of this type are particularly suitable.

The process according to the invention is suitable not only for actual dyeing but also for Optical brightening of textile materials since the residues of anionic optical brighteners can also be removed from the washing liquors.

The anionic optical brighteners can belong to any category of brightener. They are, in particular, stilbene compounds, pyrazolines, dibenzoxazolyl or dibenzimidazolyl 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.

I'he process according to the invention enables anionic 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 auxiliar44262 ies are described in more detail in the book TensideTextilhilfsmittel-Waschrohstoffe (Surface-active Agents - Textile Auxiliaries - Detergent Raw Materials) by Dr. Kurt Lindner (published by Wissenshaftlicher Verlagsgesellschaft Stuttgart, 1964). Anionic compounds of the alkylarylsulphonic acid type are of particular interest in practice.

According to the invention, cellulose-containing textile materials are preferably dyed with fibrereactive dyestuffs.

The cationic character of the modified cellulose materials which can be used according to the invention is due to the presence of basic substituents. The cellulose materials contain, as basic substituents of this type, for example amino groups,imino groups, quaternary ammonium groups, immonium groups, tertiary phosphine groups, quaternary phosphonium or sulphonlum groups and also thiuronium or guanidinium groups. It will be appreciated that the term cationically modified as used herein, is intended to cover not only cellulosic material containing cationic groups but also such material containing basic groups which can be quatemised.

Preferred basic substituents are amino groups, for example primary, secondary or, above all, tertiary amino groups, as well as quaternary ammonium groups. These contain, as N-substituents, aliphatic, cycloaliphatic or araliphatic 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, i.e. alkyl groups with 1 to 5 carbon atoms, which are optionally substituted by hydroxyl or cyano groups.

Suitable cationically modified cellulose materials which can be employed according to the invention are described, for example, in German Offenlegungsschriften 1,942,742 and 2,309,079· These materials, which are capable of adsorption, are cationically modified cellulose in which the hydroxyl groups have been at least partially replaced by quaternary ammonium groups of the formula (1) - CH2 - CH - CH2 - N (Alk)„ Θ a © An OH wherein each Alk denotes identical or different lower alkyl radicals and An O 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 preferably bonded to the cellulose part via a grouping of the formula (2) - 0 - CH2 - N in which the nitrogen belongs to an amide group of the 20 cationic radical and the oxygen is bonded to the cellulose part.

Advantageous cationically modified cellulose materials are characterised in that their cationic constituent is bonded to the cellulose part via the grouping of the formula (3) - CH0 - N - X 2 I R 44263 in which X denotes the divalent bridge - CO -, -C0-O-, -CS-,>C-NH, - P - (0) q'-l OR' or -SO^- 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.

In formula (3), X above all denotes the -CO- bridge.

R is preferably hydrogen or alkyl with 1 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 member of a nitrogen-containing hetero-ring, generally adjacent to the ring nitrogen, in which fhe groupings -CO-, -CS- and>C=NII can also be included, as in derivatives of 5-pyrazolane, 5-aminopyrazole, barbituric acid or cyanuric acid. R can also optionally represent a further grouping -0^-0-(11), which is optionally also bonded to the cellulose. Amongst these radicals, R is appropriately -CH^OiH) or preferably hydrogen, R' is preferably alkyl with 1 to 5 carbon atoms.

Depending on the nature of the starting components used to manufacture the cationically modified cellulose materials, the basic substituent can be bonded to the grouping of the formula (2) or (3) via any desired bridge members. Possible bridge members are, for example, divalent hydrocarbon radicals, 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-eyclohexylene group or lower alkenylene 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 modification of the cellulose materials can also be constituents of polymeric compounds, such as polycondensates, polymers or polyadducts.

Polymeric compounds of this type can correspond to the general formula 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 example 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, for example primary, secondary or tertiary amino groups, and/or onium groups, for example quaternary ammonium, sulphonium or phosphonium groups.

Cationic polymers containing methylol groups can be obtained, for example, by reacting basic, nibrogencontaining polymeric compounds which contain groupings which can be methylolated, for example carboxylic acid amide groups, sulphonic acid amide groups, phosphonic acid amide groups or aminotriazine groups, wiih form44262 aldehyde or formaldehyde donors, or also with glyoxal.

Suitable basic, nitrogen-containing, polymeric compounds in the abovementioned sense are, in principle, polymers which contain basic nitrogen atoms, which are capable of forming a salt, and amide groupings.

Suitable polymers are basic aminoplasts which are soluble in water or can be dispersed in water, for example formaldehyde-dicyandiamide condensate products. Appropriately, the reaction is carried out with condensation products of formaldehyde, dicyandiamide and one or more of the following components: urea, ammonium chloride and an alkylene-polyamide with, for example, a total of 2 to 1% and preferably with 2 to 8, carbon atoms and 2 to 5 amino groups.

The alkylenepolyamines are, for example, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, 1,2-propylenediamine, dipropylenetriamine, tripropylenetetramine, dihydroxydipropylenetriamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, dipentylenetriamine, tripentylenetetramine, tetrapentylenepentamine, dihexamethylenetriamine, trihexamethylenetetramine and tetrahexamethylenepentamine.

Particularly suitable basic aminoplasts are, above all, formaldehyde-dicyandiamide, formaldehyde-dicyandiamide-ethylene-dlamine or formaldehyde-urea-dicyandiamide condensation products. Preferred products are obtained, for example, by a condensation reaction of formaldehyde, dicyandiamide and ammonium chloride or of formaldehyde with the reaction product of dicyandiamide and ethylenediamine or the corresponding acid - 12 salt, such as the hydrochloride, or ammonium chloride, and are described, for example, in Swiss Patent Specification 456,475, German Offenlegungsschrift 2,321,627 and French Patent Specification 2,189,327. Further basic aminoplasts can be manufactured by a condensation reaction of urea, dicyandiamide and formaldehyde in the presence of an acid, such as hydrochloric acid, or by a condensation reaction of dicyandiamide with formaldehyde and the tetrahydrochloride of triethylenetetramine.

Reaction products, containing N-methylolamide groups, of halogonohyftins cr dnahy>lrIns with alkylene- or polyalkylene-polyamines or -imines, for example reaction products of epichlorohydrin with diethyl enetriamine, dipropylenetriamine or triethylenetetramine, or with polyethyleneimines, 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 precondensafces of aliphatic polyamines with polyepoxides, which are described, for example, in U.S. Patent Specification 3,346,519.

Basic, polyamides which are manufactured by a condensation reaction of dibasic carboxylic acids containing 2 to 10 carbon atoms, for example adipic acid or its functional derivatives, for example esters, amides or anhydrides, with polyamines, especially polyalkylenepolyamines, such as those polyamides described, for example, in U.S. Patent Specification 2,882,185, are also suitable as basic, nitrogencontaining polymers.

The polyamidepolyamines which are obtained by reacting polymerised, preferably dimerised to trimerised, fatty acids with polyamines, appropriately in a ratio such that the polyamide resin formed has an amine value in the range of approximately 200 to 650 mg of potassium hydroxide per gram of polyamidepolyamine, 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. 547,028 and it is possible to react these products with epoxide resins which are formed by reacting polyhydric phenols with polyfunctional halogenohydrins and/or glyceroldichlorohydrin and are described in U.S. Patent Specifications 2,585,115 and 2,559,245.

Further basic polyamide resins which can be methyl15 dated are, for example, the products obtained by reacting halogenohydrins, for example epichlorohydrin, with aminopolyamides obtained from polyalkyleneamines and aliphatic dicarboxylic acids with 2 to 10 carbon atoms, such as the products described, for example, in U.S.

Patent Specification 3,311,594· Suitable polyamide resins which can be used to manufacture 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 accordance with British Patent Specifications No. 878,985 and No.84I,544 ), monomeric fatty acids and lower poly30 alkylenepolyamines by condensation polymerisation at high temperatures can also be used for the manufacture of the cationically modified cellulose materials.

Further basic polymers are the polymers of an alkyieneimine with 2 to 4 carbon atoms which have an average molecular weight (MV/) 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 20°C of 500 to 20,000 centipoise (cp). Suitable alkyleneimines are, in particular, ethyleneimine, propyleneimine, 1,2-butyleneimine and 2,3-butyleneimine. Of all the alkyleneimines, ethyleneimine is preferably used. The methylolamide group can be introduced, for example, by reacting the polyalk.yleneimine with chloroacctamide ,.rd sub j-'qvently methylolating the reaction product.

Cationic polymers containing 2 - vinyl - 1 cycloamidinepropionamide groupings which have be.en methylolated or glycolated with glyoxal are also advantageous polymers which can be employed to modify the cellulose. Such polymers are described, for example, in U.S.,Patent Specification 3,772,259.

N-Methylolamide group-containing addition polymers and copolymers, for example optionally quaternised copolymers of base-substituted maleimides, acrylic acid esters and acrylamides as well as vinylpyridine and ethyleneically unsaturated comonomers are also suitable as basic polymers. Examples of suitable comonomers which may be mentioned are: alkyl acrylates or methacrylates with 1 to 12 carbon atoms in the alkyl radical, which can optionally also be further substituted, especially by hydroxyl groups, such as methyl acrylate or methacrylate, ethyl acrylate or methacrylate, phydroxyethyl acrylate or methacrylate, n-butyl acrylate or methacrylate and dodecyl acrylate or methacrylate; (meth)-acrylic acid, (meth)-acrylamide and (meth)-acrylonitrile; vinyl esters of aliphatic carboxylic acids con4436 - 15 taining 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 of carboxylic 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,w-dihalogenoalkanes or bis-chloromethyl-aromatic compounds with amino compounds, for example dialkylamines 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, monoimines or polyimines, or quaternary ammonium salts of these amines and imines, each of which contain at least one N-methylolamide group, are advantageously suitable for the cationic modification of the cellulose materials. The methylolamide group is capable of react ing with tile hydroxyl groups in the cellulose, .so that the basic compound is bonded to the cellulose part via the grouping of the formula (2) or (3).

Xt 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 Nmethylolcarboxamide group, which is optionally etherified by C^-C^-alkoxy. Amino compounds of this type can advantageously be derived from aliphatic monoamines or polyamines or from hydrogenated nitrogen-heterocyclic compounds, for example pyrrolidine, piperidine, pipecolines, morpholine or piperazines, but especially from a monoami.no compound which contains a single methylol35 amide group. 44^62 Monamino compounds containing an optionally etherified N-methylolcarboxamide group which are particularly suitable according to the invention are the compounds of the general formula (5) 1\ / N-Q-C0-N-CH2-0R'’ in which R denotes C^-C^-alkyl or, preferably, hydrogen, R^ and R2 independently of otie 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 Y or R^ and R2, together with the nitrogen atom which links them, denote a 5-membered or 6-membered heterocyclic radical, for example pyrrolidinyl, piperidine, morpholino or piperazinyl, Q denotes an alkylene- or alkyl-substituted alkylene chain with up to 8 carbon atoms, preferably C^-C^-alkylene, and Y denotes hydrogen, lower alkyl or -CHgOR. Methylol compounds of the formula (5) which contain only a single grouping of the formula (6) are particularly preferred. In these methylol compounds, R^ and R2 are appropriately both lower alkyl or lower alkoxy-lower alkyl or form, together with the nitrogen atom, a morpholino radical. R^ and R2 are, however, preferably lower alkyl, for example methyl or ethyl, Y is preferably hydrogen or -CHgOH, R is especially hydrogen and 0 is preferably ethylene.

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 formaldehyde or a formaldehyde donor, for example paraformaldehyde or trioxane. Suitable monoamines are, in particular, monoalkylamines or dialkylamines with 1 to 4 carbon atoms in each alkyl radical or optionally alkoxylated C^-C^-alkanolamines with 1 to 4 carbon atoms in any alkoxy radical which may be present and suitable amides are acrylamide, maleic acid diamide or chloracetamide. A specific amine is (h5c2^n- ch2ch2 - Cl.

Preferred cationically modified cellulose materials can be obtained when the modification is carried out with polyamino compounds which contain at least one N-methylolcarboxamide group and which are derived, for example, from alkylenepolyamines or hydrogenated diazines, especially from a N,N-dialkyl-ethylenediamine or a N,Ν-diaikyl-propylenediamine or piperazine. Polyamino compounds of the general formula (7) 3\ > R / in which Qj denotes an alkylene- or alkyl-substituted alkylene chain with up to 8 carbon atoms, preferably C2-C3-alkylene, R^, R^, and independently of one another denote hydrogen, lower alkyl which is optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula (6), - 18 or Rj and R^, together with the nitrogen atom which links them, denote a 5-memberea or 6-membered heterocyclic radical, for example of the type mentioned above for R^ and &£, or, if n is 1, R^ and R^, together with the grouping/>N-Q^-N<( which links them, also denote a divalent heterocyclic radical, especially a piperazino ring, and n denotes 1 to 1,000, preferably 1 to 4 and especially 1, and at least one of Rg, R^, R_ and Rg represents the group of the formula (6) and, if n denotes more than 1, each R^, independently of the others, can represent byrtrnrtu, 1 owei alkyl which 's optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula (6), or each R-, or individual R^s, toget15 her with the adjacent Rg and with the grouping>N-Q^-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 compounds given below, of the formula (8) R3 /Ν-β, -Ν-β-CO-N- CH-OR / 1 ί ί 2 r, r, r _ wherein R^, R^, R$, R, Q, and Y have the indicated meaning, are preferred.

Diamino compounds pf the formula (8) in which Rg and R^ both denote lower alkyl, especially methyl, and Rg denotes the group of the formula (6), or R^ and Rg, together with the grouping>N-Q1-N< which links them, denote a piperazino ring and R^ denotes the group of the formula (6), 2 denotes CpC^-alkylene, for example methylene or ethylene, 2* denotes ethylene or propylene, and especially 2 and 2^ denote ethylene, 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 (ll): (9) RrΊΘ \ _ 2 - CO - N - CH-OR'd An ® R/i I 2 Υχ Y (10) t/l 4 V- An Θ n + 1© n + 1 An ® wherein , V2 and V^ 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), Rj, R2 and Vp or R^, R^ and V2, together with the nitrogen atom which links them, denote a pyridine ring which is optionally substituted by lower alkyl and An® denotes 44202 the anion of an organic or inorganic acid, and R^, R2, Rg, R^, Rg, Rg, R, β, 2p y and n have the meaning indicated for formulae (7) and (8) and at least one of Rg, R^, Rg, Rg, Vg and Vg represents the group of the formula (6) and, if n denotes more than 1, each Rg or each Vg, 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 Rg, or individual RgS, together with the adjacent Rg and with the common grouping>N-2pN<, can also represent a divalent hetero -ycB.c radical, especially a piperazino ring. The compounds of the formula (ll) can also be only partially quaternised with Vg in the recurring units of the formula Amongst the quaternary ammonium compounds of the formulae (9)j (io) and (ll), the quaternary ammonium salts of the formula (12) in which R^, Rg, Rg, R, Vp 2j Sp Y, An and q have the indicated meaning, are preferred.

Ammonium salts of the formula (13) 1\ V, An N-2' - CO - NH - CH.OH or of the formula (14) N - 2' - CO - NH - CH20H wherein R ', R2'j Vl'’ R1'* anC* eac^ denote lower alkyl, in particular ' denotes methyl, or R^ ' and R2*, together with the nitrogen atom which links them, denote a morpholino ring, or R^’, R^' and ' together with the nitrogen atom which links them denotes a pyridine ring, R.j 1 denotes hydrogen or the group of the formula JO - 2« _ CO - NH - CH2OH 2' represents methylene, ethylene or propylene, ' represents ethylene or propylene, 2 denotes C^-C^alkylene and Αηθ has the indicated meaing, preferably a chloride ion, are particularly preferred. 2uaternised polymeric compounds of the formula (15) or block copolymers of the formula (l6) or 4426 2 (16) _ - 22 ~ / W1 Λ Q2 N “ /23-W2-CO-W3-A-W4-CO\ rZ1 n An θ 'Θ W1 ~ \22' ~ N / δ3 *-W2'“C°“w3'-A'-W4,-C0“ n An 0 which can also be only partially quaternised, can also be employed to modify the cellulose materials.

In the formulae (15) and (l6), 22, 23» 22' and 2g' 5 independently of one another denote an alkylene- or alkyl-substituted alkylene chain with 2 to 8 carbon atoms, and preferably with up to 4 carbon atoms, Vj, Ry, Vg’ and Ry' 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) - 2'-C0-N-CH2-0R, Y Q' denotes methylene or propylene, Wp Wp ' and W2' independently of one another each denote a direct bond, oxygen or thegroup)>N - Y; W , W,, W, ' and W ' 4 o 4 independently of one another each denote a direct bond or -NH-; -A- and -A'- each denote the radical derived by the removal of two carboxylic acid groups from a polybasic carboxylic acid, especially the radical of a saturated or unsaturated aliphatic dicarboxylic acid, or the radical of an aromatic dicarboxylic acid, such as of terephthalic acid or isophthalic acid or of naphthalene-2,6-dicarboxylic acid, r and p each denote - 23 44262 ίο to 10,000 and s denotes 1 to 10 and n, An ®, R and Y have the indicated meaning and at least one of V Ry, V^·, Ry’ and Y represents the group of the formula (6a) and, if n is more than 1, each Ry or Vand each Ry· 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 Ry and Ry· or individual RyS and Ry*s, together with an adjacent Ry or Ry* respectively and with the grouping>N - Q2 - NN-Q2’-N Amongst the quatemised polymeric compounds of the formula (15), those which correspond to the formula (17) -.

V, AlP (17) -NH - 2, NM-CO-A^-COch2-conh - ch2or· wherein and each denote C-^-C^-alkylene, Rn ’ denotes hydrogen or methyl, denotes lower alkyl and A^ denotes the radical of an aliphatic Cj-C^-dicarboxylic acid, especially C9-C.-alkylene, and r, a denotes 2 to 100 and An has the indicated meaning, are particularly preferred.

Addition polymers and copolymers for example 25 optionally quatemised polymers 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 42 6 2 - 24 molecule, for example, recurring units of the formulae (!·') and (19) (IS) Z, ZA \ I3 i4 CH - CH V C - C .Z, Z„d-lCO CO „ I I @/Ri R0CHo - N NH - Q, - N —Ro * I Ik* An (19) Ii -οΙ co Ύ@α An βχ - N 2-C0-N-CH.0R \ Y 2 In which one of Z and Z„ denotes hydrogen and the other j z denotes hydrogen, lower alkyl, phenyl, cyano, carboxyl or carbamoyl, Z^ and Z^ independently of one another denote hydrogen or lower alkyl and q denotes 1 or, preferably 2, and R1, Rg, R, Vp Q, 2p Y and An® have the indicated meaning.

Advantageous other polymers of ethylenically unsaturated monomers have recurring units of the formulae (20) and (21)· Z (20) -ch2 - C w5 - 2l -H S - co N - CH-0R ι 2 (21) and Ζ w_2 _n-2 - co - n - cnoR» 5 1 I I 2 wherein denotes oxygen, - COO - or CON Z' and Z and Z' each denote hydrogen or lower alkyl, for example methyl, and 2, βρ Rp R, Vp Y and An ® have the indicated meaning.

Tlie recurring uni ts of Lhe formula (20) and (21) can also be incorporated in copolymers with other copolymerisable vinyl compounds, for example the above-mentioned ethylenically unsaturated comonomers.

In the definition of the radicals of the compounds of the formulae (5) to (17)j which can be used to modify the cellulose materials, and of the recurring units of the formulae (18) to (21), lower alkyl and lower alkoxy represent those groups which contain 1 to 5, and especially 1 to 3, carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl or amyl, or methoxy, ethoxy or isopropoxy. Halogen, in connection with all of the above substituents, denotes, for example, fluorine, bromine or, preferably, chlorine.

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 - 26 value of 2 to 6, and heat-setting the treated cellulose materials, appropriately at temperatures of between 20 and 200°C, and preferably between 50 and 150°C, heatsetting 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 optionally be used for setting. Suitable catalysts are, for example, ammonium thiocyanate, ammonium chloride, ammonium hydrogen orthophosphate, magnesium chlor10 ide, zinc nitrate, maleic acid, tartaric acid or cleric 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, espec15 ially, methanol.

The cationically modified cellulose materials as a rule contain at least 0.4$ hy weight, and preferably 0.7 to 1.5$ by weight, of basic nitrogen. The total nitrogen content, which also includes the amide nitrogen, appropriately is at least 0.6$ by weight and preferably 0.3 to 3$ by weight.

Aminoplast precondensates which do not contain any basic groups, for example primary, secondary or tertiary amino groups or quaternary ammonium groups, can option25 ally also be used as reactants.

Aminoplast precondensates, as used herein, are addition products of formaldehyde and nitrogen compounds which can be methylolated, 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, - 27 4426 such as ethyleneurea, propyleneurea, dihydroxyethyleneurea, hydroxypropyleneurea and acetylenediurea, and also dicyandiamide, uroaea and hexahydropyrimidones.

Examples of 1,3,5-aminotriazines which may be mentioned are: melamine and N-substituted melamines, such as N-butylmelamine, N-trihalogenomethylmelamines, fcriazones, ammeline, guanamines, for example benzoguanamine, acetoguanamines and diguanamines, as well as K> guanidines which can be brought into a water-soluble form by conversion into corresponding ammonium salts.

Amitioplast precondensates which can be used are, preferably, the methylol compounds of the said ureas and 1,3,5-aminotriazines. Amongst these compounds, those to be singled out in particular are, above all, N-methylolureas and N-methylolmelamines. Partial ethers of such methylol compounds, 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 cationic modification may be bleached or unbleached pine sulphite cellulose, kraft sulphate cellulose, paper, cardboard products, waste paper, textile fibres made of cotton, rayon staple, jute, ramie, hemp, linen or viscose and also peat, mechanical wood pulp, sawdust, wood fibres, wood flour, cork flour, bark or cereal waste These cellulose materials 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, for example, 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, for example peat, kieselguhr or diatomaceous earth. In this case, the activated carbon is generally added to the adsorb5 ent materials in amounts of 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, and Which further illustrate the present invention, percentages are always percentages by weight Manufacturing instructions A. a) 115 g of an adduct obtained by an addition reaction of 2 mols of acrylamide with 1 mol of N,Ndimethylethylenediamine are dissolved in 93 ml of water and the solution is allowed to react, at a temperature of 0-10°C, with 85 ml of a 35·1$ strength solution of formaldehyde until the content of free formaldehyde is 0.7$, 293 g of a 50$ strength aqueous solution of the dimethylol compound of the formula (ιοί) (ch3)2n-ch2-ch2-n(ch2ch2-conh-ch2oh)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—110 C, and washed with water. The nitrogen content of this adsorbent is - 29 2.15%.

B. a) 43.2 g of an adduct obtained by an addition reaction of 1 mol of diethylamine with 1 mol of acrylamide are dissolved in 35-4 g of water and methylolated with 25.3 g of a 35% strength formaldehyde solution, with the addition of 0.1 g of sodium hydroxide, for 5 hours at 5O-6O°C. A 50% strength, yellowish solution of a methylol compound of the formula (102) (C?HS)2N - CH2CH2 - CONH - CH,0H is obtained.

This solution is then diluted with 417-5 g of water and the pH is adjusted to 3 with concentrated hydrochloric acid. b) 9-5 g of filter paper are so saturated with the acid solution prepared according to a) that 30.4 g of the acid solution are taken up by the paper. The impregnated paper is condensed for 10 minutes at 110°C 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 1$ g of paraformaldehyde and 0.2 g of sodium hydroxide in 80 ml of ethanol. The reaction mixture is then heated up to 50°C 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 -50°C using solid carbon dioxide. 29 g of a crystalline methylol compound of the formula 4262 (103) 0^_/Ν - CHgCHgCONH-CHgOH which has a melting point of 92-93°C are obtained. b) 9.3 g of filter paper are so saturated with a 10$ strength aqueous solution, of the methylol compound of the formula (103) which has been adjusted 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 a.. 110°C and washed with water. The nitrogen content of this adsorbent material is 1.6$. Ιθ D. a) 68.5 g of an adduct (melting point: 236-237°C) obtained by an addition reaction of 2 mols of acrylamide with 1 mol of piperazine are dissolved in 313 ml of water and methylolated with 51.3 g of a 35.1$ strength solution of formaldehyde, with the addition of 0.1 g of sodium hydroxide, for 5 hours at 5θ-6θ°Ο. A clear solution which has a formaldehyde content of 0.09$ forms. This solution is then completely evaporated and the residue is recrystailised from a mixture of ethanol and methanol (1:1). g of a methylol compound of the formula (104) CHg-CHg-CO-NH-CIIgOH which has a melting point of 151~153°C are obtained. b) 9.6 g of filter paper are so saturated with a 10# strength aqueous solution of the methylol compound of the formula (104), which has been adjusted to a pH of 3 with concentrated 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 110°C and washed with water. The nitrogen content of the resulting adsorbent material is 2.52%.

E a) 50 g of the product (melting point: 278-282°C with decomposition) obtained by reacting piperazine and chloracetamide are dissolved in 315 ml of water and methylolated with 42.8 g of a 35.i# 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 (105) CH9-C0-NH-CH„0H (.

CH2-C0-NH-CH20H 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 compound of the formula (105) that 33.7 g of this solution are taken up by the paper. The impregnated paper is condensed for 10 minutes at 120°C and washed with water. The nitrogen content of the adsorbent materials is 2.4%. 442θ 3 F. a) formula 22.6 g of the morpholinium eompound of the N-CH2-C0-NH2 Cl 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 50-55°C to give a methylol compound of the formula (106) Cl Θ 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 methylol15 compound of the formula (106) that 34-9 g of this solut ion are taken up by the paper. The impregnated paper is condensed at 140°C for 10 minutes and washed with water. The nitrogen content of the resulting adsorbent material is 0.8/2.

G. a) 27.2 g of the adduct obtained by an addition reaction of 2 mols of acrylamide with 1 mol of N,Ndiethylaminopropylamine are dissolved in 150 ml of ethanol and quaternised with 11 g of ethyl bromide for 5 hours at 60-70°C. The resulting solution is then evaporated at 50°C, after which 35.9 g of the partially - 33 quaternised ammonium compound are obtained in the form of a viscous oil. The ammonium compound is dissolved in 1?5 ml of water and methylolated with 10.4 g of a 36.5$ strength solution of formaldehyde, with the addition of 0.05 g of sodium hydroxide, for 5 hours at 5O-6O°C to give a methylol compound of the formula © (107) (C2H5)gN-CH2CH2CH2N(CH2CH2C0NHCH20H)2 Br© The resulting solution of the methylol compound is diluted with 182 ml of water and the pE is adjusted to 3 with concentrated 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 is condensed for 10 minutes at 130°C 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 hydrochloric acid are added to a solution of 34.9 g of 2-dimethylaminopropionamide 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 25°C. the conversion of formaldehyde is 98$ of theory. A 35$ strength aqueous solution of a methylol compound of the formula (iOS) (ch3)2n-ch2ch2-conh-ch2oh approximately 80$ of which is in the form of the hydrochloride, is obtained. 442θ3 - 34 The pH of 46 g of this solution is adjusted to 4 with l3% strength hydrochloric acid and the mixture is diluted with 30 ml of water. b) 7·7 g of filter paper are so saturated with 5 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 140°C and then washed with water. 8.3 g of an adsorbent are obtained. The nitrogen content of this adsorbent ina ter tai i.s 2.0,..

X. a) 69.7 g of an addition product of bis -(2ethoxyethyl) - 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 mi of water, .4 g of a 35-5% strength solution of formaldehyde, mi of water and 30 ml of a 2N sodium hydroxide solution are then added at 2S°C, whilst stirring.

After a reaction time of 14 days at 25°C, the conversion of formaldehyde is 96% of theory. 207 g of a 38% strength aqueous solution of the methylol compound of the formula (109) (C2Hs0CH2CH2)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% strenth solution. b) Using the acid solution prepared according to a), filter paper is so saturated, and condensed, as - 35 described in Instruction H. b), that 8.3 g of an adsorbent are obtained. After washing with water, the nitrogen content of this adsorbent material is 1.6$.

J. a) 144 g of 2-diethylaminopropionamide, 90 g of paraformaldehyde and 0.6 g of magnesium oxide are allowed to react for 40 minutes at 96-93°C, whilst stirring. The reaction product is then cooled to 40°C and water is then added. 430 g of a 47$ strength sol10 ution of the dimethylol compound of the formula (110) (CgHgJgN - CHgCHg - C0N(CH20H)2 are obtained. lhe pH of 33.4 g of this solution is adjusted to 4 with 5 N hydrochloric aci.d 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·θ 8 of an adsorbent are obtained. After washing with water, the nitrogen content of this adsorbent 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 added. The mixture is allowed to react for 10 hours at 45°C, whilst stirring. 91.4 g of a 36.9$ strength solution of hydrochloric acid and 92 g of methanol, are then added af 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 442θ3 - 36 (111) (C2H5)2N - CH2CH2 - CONH - CH2OCH3.HC1 are obtained. b) Using a 20% strength aqueous sdution of the compound 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 are added to a solution of 75-2 g of 2 - chloi'cpropinnamide in 750 ml of diojc.-ne at 50°C., whilst stirring. This mixture is stirred at a temperature of 100°C for 18 hours. The precipitate which has formed on cooling is filtered off and recrystallised from ethanol. 65 g of a compound of the formula 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 formaldehyde 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 IN sodium hydroxide solution. The conversion of formaldehyde is 60% of theory. 115 g of a 29% strength solution of the methylol compound of the formula are obtained. The pH of this solution is adjusted to 4 with hydrochloric acid and the mixture is diluted with water to give a LO# strength solution. b) Using tlie acid solution prepared according to 5 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 absorbent material is 1.9#.

M. a) 25 g of a 36# strength solution of formaldehyde xare added to a solution of 45.7 g of carbamoylcholine chloride in 150 ml of water. This mixture is stirred at a temperature of 25°C for 3 days and the pH value is kept at 8.5 hy adding a 0.1 N sodium hydroxide solution. This conversion of formaldehyde is 95# of theory. A 24# strength solution of a methylol compound of the formula. (113) [(ch )3n - ch2ch2-o-nh-ch2oh]Cl © is obtained. The pH of this solution is adjusted to 4 with hydrochloric acid and the mixture is diluted with water to give a 10# 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 condensed for 5 minutes, at 170°C and then washed with water. The nitrogen content of this adsorb25 ent material is 0.9#.

N. a) 20 g of a copolymer of the formula - 38 ,0 4 3 θ 3 - CH - CH2 CH - CH I I CO co CH2CH2CH2 - N(CH3)2 CH2 - C0NH2 Cr approximately 400 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 55°C 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 hou-s, the conversion of formaldehyde reaches 90% of theory. 113 g of a 20% strcngtn clear solution or uhe nevli...civ.: ι polymer of the formula (114) -CH- CH CH I co - CH I CO I © ch2ch2ch2 -n(ch3)2 Cl ch2 - corn -CH2eH agjraxinatBly 400 are 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 10% strength solution. b) Using the acid solution prepared, according to a) 7.7 g of filter paper are so saturated, and condensed, as described, in Instruction H. b), that 10.0 g of an absorbent are obtained. After washing with water, the nitrogen content of this absorbent material is 2.1%. - 39 0. ι) 25.5 g of a polymer of the formula CO - (CH2)4 - CONH ?H3 (ch2)3-n-(CH2)3nh 30 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-cc-chloracetamide are added to this solution at 70°Cj whilst stirring. The reaction mixture is stirred for a further 18 hours at 8O-85°C and is finally evaporated. The residue is dissolved in 147 nil of water. A 20% strength solution of a polymer of the formula CH.

Cl (115) CO - (CH2)4 - CONH (ch2)3- N -(CH2)3NH 30 CH2 -CONH~CH2OCH3 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 10% solution. b) Using the acid solution prepared according to a)) 7·7 g of filter paper are so saturated, and condensed, as described, 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 com25 pound of the formula (102), 4 parts of dimethylolmelamine and 76 parts of water/5 N-hydrochloric acid and 4 2 6 3 - 40 has been adjusted to a pH of 4 that 24.3 g of this solution are taken up by the paper. The impregnated paper is dried for 10 hours at 140°C and 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 100°C in 13 1 of an aqueous liquor which contains, relative to the fabric, 3% of the blue reactive dyesti'ff C.I No. 61,211 as well as 80 g/1 of sodium chloride and 2 g/l of sodium3-nitrobenzene-l-sulphonate. The temperature is lowered to 75°C in the course of 30 minutes and 20 g/l of sodium carbonate and 3 ml/l of a 40% strength solution of sodium hydroxide are added. Dyeing is then carried out for 60 minutes at 75°C 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 IN sulphuric acid, and the liquor is warmed to 55°C.

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 10 cm in diameter and contains 30 g of the adsorbent according to In'struction 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 IN sodium hydrox30 ide solution or 1 N sulphuric acid.

In respect of fastness bo rubbing (dry and wet) - 41 fastness to wet hot pressing, fastness to washing, fastness to Xenon (Trade Mark), light and shade, the dyeing finished in this way is equal to a dyeing finished in the conventional manner, that ς i.s 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.

IQ Example 2.

Using a liquor ratio of 1:20, 100 kg of cotton tricot are dyed, in a winch vat, for 45 minutes at 75°C with a dye liquor which contains 3 kg of a dye- and 70 g/1 of sodium chloride. The dyestuff is then fixed for one hour at 75-SO°C by adding 20 g/1 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 80°C and has a pH of 5-6 maintained by means of sulphuric acid this liquor being circulated through 6 kg of an adsorbent material, 44263 - 42 manufactured in accordance with Instruction K. b), which is in the form of chips (2mm x 13 mm) 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 coaxially.

The bath is circulated at a frequency of 14 per hour. After 4^ mint't' - the '-ishirg ’’nvor which ·-?? initially deeply coloured is virtually colourless.

With regard to the fastness properties, such as fastness bo washing, fastness to water, fastness to perspiration (alkaline or acid), fastness to rubbing (dry and wet) and fastness to 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 baths, but this dyeing appears to have a greater depth of colour and to be more brilliant.

Example 3. 325 g of a cotton tricot fabric are dyed, in a winch vat, for 10 minutes at 100°C in 13 1 of an aqueous liquor which contains, relative to the fabric, 3% of the blue reactive 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 75°C in the course of 30 minutes and 20 g/l of sodium carbonate and 3 ml/l of a 40# strength solution of sodium hydroxide are added. Dyeing is then carried out for 60 minutes at 75°C and the blue colouredresidual liquor is then run off. - 43 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 80°C.

The washing liquor is passed through an adsorption 5 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 of 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 fi sodium hydroxide solution or 1 N sulphuric acid. The liquor is virtually colourless after one hour.

In respect of fastness to rubbing (dry and wet), fastness to wet hot pressing, fastness to washing, fastness to Xenon light and shade, the dyeing finished i.n this way is equal to a dyeing 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 the 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 Examp: Adsorbent material prepared according .e to Instructions, or of the structure Amount (g) Form/dimension (mm) 4 A. b) 80 chips 2 x 13 5 C. b) 100 chips 2 x 13 6 D. b) 80 chips 2 x 13 7 E, b) 80 chips 1X0 8 F. b) 100 chips 1x6 9 6. b) 60 chips 2 x 13 10 H. b) 80 chips 2 x 13 11 I. b) 80 chips 2 x 13 12 J. b) 25 chips 2 x 13 13 K. b) 20 chips 2 x 13 14 K. b) 20 pulp 15 L. b) 40 chips 2 x 13 16 M. b) 80 chips 2 x 13 17 N. b) 80 chips 2 x 13 18 19 0. b) + Cell[0CH2CHCH2N(CH3)jCI-] OH 80 80 chips 2 x 13 chips 2 x 13 20 Cell[OC2H4N(C2H5)2] 80 Chips 2 x 13 - 45 Example 21. kg of non-mercerised cotton yarn are dyed in the customary manner, using a liquor ratio of 1:10, in a circulation apparatus with 40 g of a dyestuff of the formula OH The dye liquor is then run oft and the dyed goods ire rinsed with 20 1 of cold water. The dyestuff which has not been fixed is then removed in a bath at 8010 95°C and a pH value of 6 by continuously passing part of the liquor through a fixed bed arrangement (diameter 15 cm, packing density 0.2 g/cnr) in which there are 100 g of the adsorbent material prepared 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..

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.

When 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. kg of cotton tricot are dyed in the customary 442θ2 - 46 -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 dyeing is then finished in the next bath at 8090°C and a pH of 5-6 by continuously 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 4θ nm high pi-'foratpH sheet metal f yli nde-'-t 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 washed in the conventional manner.

Claims (5)

CLAMS 1. (1) 0 - CH„ - CH - CH, Jh N (Alk) 3 in which each Alk denotes identical or different lower alkyl radicals and An © is as defined in claim 23, is used. 35. Process according to any one of claims 1 to 34, wherein the cationic, modified cellulose material has been obtained with the additional 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 which R^ and R 2 both denote methyl or ethyl, Q denotes ethylene and Y and R denote hydrogen. 59 44262 37· Process according to claim 16, wherein the cationic constituent is derived from a compound of the formula (5) in which R^ and Rg both denote ethyl, Q denotes ethylene, Y denotes hydrogen and R denotes methyl. 5 38. Process according to claim 16, wherein the cationic constituent is derived from a compound of the formula (5), in which and Rg both denote ethyl, β denotes ethylene, Y denotes -CHgOil and R denotes hydrogen. 39· Process according to claim 17, wherein the 10 cationic constituent is derived from a compound of the formula (5) in which R. and Rg, together with Liie nitrogen atom which links them, denote morpholino, β denotes ethylene and Y and R denote hydrogen. 40. Process according to claim 22, wherein the cat15 ionic constituent is derived from a compound of the formula (8) in which Rg and R^ denote methyl, Rg denotes the group - β - CO - N - CH-OH, I 2 Y β and β^ each denote ethylene and Y denotes hydrogen. 20 41. Process according to claim 22, wherein the cationic constituent is derived from a compound of the formula (8) in which Rg denotes the group - β - CO - N - CH-OH, | 2 Y R^ and Rg, together with the grouping>Ν-β^-Ν·Οwhich 25 links them, denote piperazino, β denotes methylene or 443θ 3 - 60 ethylene and Υ denotes hydrogen. 1 T S 2 ί 1 ~ R, w W 2 -CO-W 3 -A-W 4 -COA . J ... Θ n An (16) V 'i f3 ra W l' [ fi 2 ~ R ~ Jig'-Wa'-CO-Wg'-.A'i.W^’-CO-j n An © Ry’/n in which 2 2 j 2 3 ’ 2 2 1 and 2/ independently of one another denote an alkylene- or alkyl-substituted alkylene chain with 2 to 8 carbon atom, Vj, Ry } V^' and Ry 1 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: 55 44262 (6a) - 2' - CO - N - CH 9 OR, Y 2 r denotes methylene or propylene, W^, W,,, 1 an d * independently of one another each denote a direct bond, oxygen or the group^>N-Y; W^, W^; 1 and W^ 1 independ5 ently of one another each denote a direct bond or -NH-; -A- and -A 1 - each independently denote the radical obtained by removal of two carboxylic groups from a polybasic carboxylic acid, r and p each independently denote 1 to 10,000 and s denotes 1 to 10 and n, AnO , R and Y 10 are as defined in claims 10 to 24 and f.l least -ne of V R?, 1 , R? 1 and Y represents the group of the formula: (6a) - Q’ - CO - N - CH„OR I 2 Y and, if n is more than 1, each R~ or V. and each R ' or 7 3 7 Vy ' independently of the others can represent hydrogen, 15 lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula (6a), or each R? and R?', or individual R?s and R?', together with an adjacent R? or Ry’ respectively and with the grouping 20 J>N-Q -N< and>N-Q„ '-N-^which link them, can represent a divalent heterocyclic radical. 27. Process according to claim 26, wherein the cationic constituent is derived from a polymeric compound of the formula (17) Γ -NH An 2 4-r NH - CO Θ ’ co CH 2 - CONH - CH 2 OR' 1\ / t R 11 V ' K 2 V 1 N - 2, ' - N - 2’ - CO - NH - CH„OH An In which R^ 1 , R 2 ', ', R^ and R 2 each denote lower alkyl, or R^ 1 and R 2 1 , together with the nitrogen atom 5 which links them, denote a morpholino ring, R^ 1 denotes hydrogen or the group of the formula - 2-CO-NH-CH 2 OH, 1 , | 2 R. Y in which Rg, Rp Rg, R, 2> Q and Y are as defined in 25 claim 19. 4 44» 63 - 52 22. Process according to Claim 21, wherein the cationic constituent of the modified cellulose material is derived from a diamino compound of the formula (8) in which Rg and R^ both denote lower alkyl and Rg 5 denotes the group of the formula (6), or R^ and Rg, together with the grouping>M-Q^-N< which links them, denote a piperazino ring and Rg denotes the group of the formula (6), Q denotes C^-Cg-alkylene, denotes ethylene or propylene and Y denotes hydrogen. 10 23· Process according to any one of claims 1 to 12, wherein the cationic constituent of the modified ceixulose material is derived from a quaternary ammonium compound of the formula (9) R i lx N R 2 V 1 CO N - CH-OR I 2 Y (10) (11) An© n + 1 © n + 1 An Θ in which Vp V 2 and Vg independently of one another denote hydrogen, lower alkyl which is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, benzyl or the group of the formula or - Q - CO - N - CH 9 0R, I z (6) 53 Rp R 2 and Vj, or Rp R^ and V^, together with the nitrogen atom which links them, denote a pyridine ring which is optionally substituted by lower alkyl and An θ denotes the anion of an organic or inorganic acid, and 5 Rp R 2 , Rp Rp Rp R ft , R, Q, β χ , Y and n are as defined in claims 16 to 21 and at least one of R., R., R. 3 7 4 5, Rp V 2 and represents the group of the formula (6) and, if n denotes more than 1, each or each independently of the others can represent hydrogen, lower alkyl which 10 is optionally substituted by halogen, cyano, hydroxyl or lower alkoxy, or benzyl or the group of the formula (6), or each Rp or individual. R,-s, together with the adjacent R^ and with the common grouping > N-QpN < , can also represent a divalent heterocyclic radical. 15 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

1. Process for dyeing (as hereinbefore defined) a textile material which comprises dyeing the material using an aqueous dye liquor containing a watersoluble anionic dyestuff (as hereinbefore defined), after dyeing is completed removing the residual liquor, washing the dyed material with water, continuously removing the resulting washing liquor containing dye and contacting said resulting washing liquor with a cationically modified (as hereinbefore defined)cellulose-containing material in order to remove the dye and recycling the purified washing liquor to the dyed materials for washing (he latte”. 2. ' denotes. methyl’ne or «ronvlene, Q...-’ denote: ethy' r·» x /‘V or propylene, 2 denotes C^-C^-alkylene and An is as defined in Claim 23. 10 26. Process according to any one of claims 1 to 12, wherein the cationic constituent is derived from a polymeric compound of the general formula v.,·. ι 4 ( 15) Vi, 4 2, - M -12, - w, - CO - W„- A-W.-CO 1 I 2 1 / 3 2 3 4 R 7 n An© or - w. - 2' 1 R 1 V 1 2 1 CO - NH ch 2 oh An (13) - 54 or of the formula (14) Ri ()2) N -/ Q, - 1 E /V V’-‘ Q _ CO - N - CH_0R I 2 γ In® in which Rp Rp R, R, Vj, Q, Qp Y and An - 7 are as 20 defined in claim 23 and q is 1 or 2. 25. Process according to Claim 23, wherein the cationic constituent of the modified cellulose material is derived from a quaternary ammonium compound of the formula R , ' 2 - N - 2 - CO- N - CHLOR 2 denotes C^-C^-alkylene and Y and R denote hydrogen. 18. Process according to Claim 15, wherein the cati.oni.c constituent is derived from an alkylene10 polyamine or hydro-.»nated r'iazir-· which - ,>ota i < at least one N-methylolcarboxamide group. 19. Process according to Claim 18, cationic constituent of the modified material is derived from a polyamino the general formula wherein the cellulose compound of (7) X N s n in which denotes an alkylene- or alkyl-substituted alkylene chain with up to 8 carbon atoms, R^, R^, R^ and Rg independently of one another denote hydrogen, lower alkyl which is optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cycloalkyl, benzyl or the group of the formula: (6) - 2 - CO - N.- CH 2 0R Y - 51 or Rg and R^, together with the nitrogen atom which links them, denote a 5-membered or 6- membered heterocyclic radical, or, if n is 1, R^ and Rg, together with the grouping >N-QpN< which links them, also denote a 5 divalent heterocyclic radical, and n denotes 1 to 1,000, and β, R and Y are as defined in claim 16 and at least one of Rg, R^, Rg and Rg represents the group of the formula (ό) and, if n denotes more than 1, each Rg independently of the others can represent hydrogen, lower 10 alkyl which is optionally substituted by hydroxyl, cyano, halogen or lower alkoxy, or cyaloalkyl, benzyl or the group of the formula (6), or each Rg, or individual R.s, together with the adjacent R. and with the grouping 3 3 > N - 2 χ - N< 15 which links them, can also represent a divalent heterocyclic radical, 20. Process according to claim 19 wherein the divalent heterocyclic radical is a piperazine ring and n denotes 1 to 4. 20 21. Process according to claim 19 or 20 wherein the cationic constituent of the modified cellulose material is derived from a diamino compound of the formula (8) R 3 \ (2) - 0 - CH 2 - N 15 in which the nitrogen atom forms part of an amide group of the cationic radical and the oxygen atom is bonded to the cellulose is used. 13. Process according to any one of claims 1 to 12, wherein the cationic constituent of the modified 20 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 any one of claims 1 to 12, wherein the cationic constituent of the modified 25 cellulose material is derived from an amino compound which contains at least one amino group and at least - 49 one N-methylolcarboxamide group which is etherified by Cj-C^-alkoxy. 15. Process according to claim 13, wherein the cationic constituent of the modified cellulose 5 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 any one of claims 13 to 10 15, wherein the cationic constituent of the modified cellulose material is derived from an optionally etherified methylol compound of the general formula: (5) Rj X N - Q - CO - N - CH„ - OR I in which R denotes hydrogen or C^-C^- alkyl, R^ 15 and Rg independently of one another denote hydrogen, lower (as hereinbefore defined) alkyl which is optionally substituted by halogen, hydroxyl, lower alkoxy or cyano, or cycloalkyl, benzyl or the group of the formula 20 (6) - Q - CO - N - CH„ - OR I 2 Y or R^ and R 2 , together with the nitrogen atom which links them, denote a 5-membered or 6-membered heterocyclic radical, 2 denotes an alkylene- or alkyl-substituted alkylene chain with up to 8 carbon atoms 25 and Y denotes hydrogen, lower alkyl or - CH 2 OR. - 50 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 and R 2 both denote lower alkyl or 5 lower alkoxy-lower alkyl, or R^ and R 2 , together with the nitrogen atom, denote a morpholino radical,

2. Process according to claim 1, wherein the temperature of the washing liquor is 30° to 100°C. 3. (3) -o-ch 2 -n-xin which X denotes the divalent bridge - CO -,CS 44362 - 53 >C=NH, OR' q'-l or -S0 2 ~ or a carbon atom which is a constituent of a nitrogen-containing heterocyclic ring and adjacent to the ring nitrogen, R and R' each independently denote hydrogen or an organic radical and q and q' in each case denote 1 or 2. 33. Process according to claim 32 wherein the cationic constituent is as defined in claim 30 or 31. 34. Process according to any one of claims 1 to 11, wherein a cationically modified cellulose in which the hydroxyl groups have been replaced by quaternary ammonium groups of the formula: (3) X 57 44262 in which X denotes the divalent bridge - CO - , -C0-0-, -CS-,>C = NH - , OR' or -SO,,- or a carbon atom which is a constituent of a 5 nitrogen-containing heterocyclic ring and adjacent to the ring nitrogen, R and R' each independently denote hydrogen or an organic radical and q and q> in each case denote 1 or 2. 30. Process according to claim 29, wherein the cation10 ic 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 CHjO-fH) optionally bonded to cellulose and R' denotes C^-Cg-alkyl. 31. Process according to claim 29 or 30, wherein the I 'ϊ cal ionic constituent of the modified cellulose material is bonded Go the cellulose part via the grouping of the formula (3) in whicli X denotes the -CO- group. 32. Process according to any one of claims 12 to l6 and 18 wherein the cationic constituent of the modified 20 cellulose material is bonded to the cellulose part via a radical of the formula:

3. Process according to claim 1 or 2, wherein the pH of the washing liquor is 3 to 9. 4.2. Process according to claim 25, wherein the cationic constituent is derived from a compound of the formula (13) in which r , R 2 1 and V^', together with 5 the nitrogen atom which links them, denote a pyridine ring, 2' denotes ethylene and An ©denotes a chlorine ion. 43. Process according to claim 25, wherein the cationic constituent is derived, from a compound of the 10 formula (13) ia whic, 1 and Rg ' > together wiuh the nitrogen atom which links them, denote morpholine, V^' denotes methyl, 2' denotes methylene and An© denotes a chloride ion. 44. Process according to claim 25, wherein the 15 cationic constituent is derived from a compound of the formula (14) in which R^ 1 ’, R 2 ' and ' each denote ethyl, R^' denotes the group - 2 '-CO-NH-CH^H, 2' and Q denote ethylene, 2j' denotes propylene and An© denotes a bromide Ion or chloride ion. 20 45- Process according to claim 29, wherein the cationic constituent is derived from a compound of the formula: © (CH 3 ) 3 NCH 2 CH 2 - 0 - CONH - CH 2 0H Cl© 46. Process according to claim 11, wherein the cationic 25 constituent is derived from a compound of the formula: (h 5 c 2 ) 2 n - ch 2 ch 2 - Cl. 44 262 47. Process according to claim 1 substantially as hereinbefore described. 48. A textile material whenever dyed by a process as claimed in any one of claims 1 to 47· 4 4 26 2 - 56 in which R' denotes hydrogen or methyl, Q and Q, each 4 5 denote C 2 -C^-alkylene, denotes the radical of an aliphatic C.-C.-dicarboxyllc acid and r, denotes 2 to 100 M 4 1 and An is as defined in claim 23. 25. Process according to any one of claims 1 to 12, wherein the cationic constituent is derived from a polymeric or copolymeric compound which contains, in the molecule, recurring units of the formulae An© (1-3) - 12, © Λ -N- r, (19) An N - Q-CO-N-CH.OR \ f in which one of and Zg denotes hydrogen and the other denotes hydrogen, lower alkyl, phenyl, cyano, carboxyl or carbamoyl, Z^ and Z^ independently of one another denote 15 hydrogen or lower alkyl and q denotes 1 or 2 and Rp R . R i Vp β, Qp Y and An^are as defined in claims l6 lo . 24. 29. Process according to any one of claims 12 to 28, wherein the cationic constituent of the modified cellulose 20 material is bonded to the cellulose part via a radical of the formula:

4. Process according to claim 3 wherein the pH of the washing liquor is 5 to 8. 5. Process according to any one of claims 1 to 4, wherein the washing liquor is circulated at least 5 times in one hour. 0. Process according to claim 5 wherein the washing liquor is circulated 10 to 20 times in one hour. 7. Process according to any one of claims 1 to 6, wherein the washing operation takes 0.3 to 3 hours. 8. Process according to any one of claims 1 to 7, wherein a brief preliminary rinsing with water is carried out prior to the continuous washing. 9. Process according to any one of claims 1 to 8 - 48 wherein the purification of the washing liquor is carried out by a fluidised bed or fixed bed process. 10. Process according to any one of claims 1 to 9, wherein cellulose-containing textile material is 5 dyed with i. fibre-reactive dyestuff. 11. Process according to any one of claims 1 to 10, wherein the modified cellulose material contains amino groups oi· quaternary ammonium groups as cationic subs 1 i.t'if'nti· XO 12. Process according to any one of claims 1 to 11, wherein a cationically modified, cellulose-containing material in which the cationic constituent is bonded to the cellulose via a bridge of the formula:

5. 49. A textile material whenever dyed by a process as claimed in any one of claims 1 to 16, 18, 32 and