EP0160872A2 - Process for treating cellulosic fibrous materials - Google Patents

Abstract

in der

• R, und R₂ unabhängig voneinander Wasserstoff oder einen C,-C4-Alkylrest und
• R einen C₁-C₁₈-Alkyl-, Cycloalkyl-, Aralkyl- oder Aryl- rest oder eine der Hydroxyalkylgruppen
  
  oder
  
  bedeuten mit der Maßgabe, daß die Menge an N-2-Hydroxyalkylaminen, in denen R für eine Hydroxyalkylgruppe steht, nicht mehr als (20) Gewichtsprozent der eingesetzten Hydroxyalkylamine beträgt,

gegebenenfalls durch Co-Kondensation mit Polyolen der Formel

in der

• A einen 2-, 3- oder 4-wertigen aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Rest bedeutet und
• n eine Zahl von 2 bis 4 ist,

und anschließende Quaternierung erhalten werden.The treatment of cellulosic fiber materials before or after dyeing or printing with substantive or reactive dyes is carried out with aqueous liquors which contain quaternized polyethers which are formed by condensation of N-2-hydroxyalkylamines of the formal

in the

• R, and R ₂ independently of one another hydrogen or a C, -C4-alkyl radical and
• R is a C ₁ -C ₁₈ alkyl, cycloalkyl, aralkyl or aryl radical or one of the hydroxyalkyl groups
  
  or
  
  with the proviso that the amount of N-2-hydroxyalkylamines in which R represents a hydroxyalkyl group is not more than (20) percent by weight of the hydroxyalkylamines used,

optionally by co-condensation with polyols of the formula

in the

• A represents a 2-, 3- or 4-valent aliphatic, cycloaliphatic, araliphatic or aromatic radical and
• n is a number from 2 to 4,

and subsequent quaternization can be obtained.

Description

in der

• R₁ und R₂ unabhängig voneinander Wasserstoff oder einen C₁-C₄-Alkylrest und
• R einen C₁-C₁₈-Alkyl-, Cycloalkyl-, Aralkyl- oder Arylrest oder eine der Hydroxyalkylgruppen
  
  oder
  
  mit der Maßgabe, daß die Menge an N-2-Hydroxyalkylaminen, in denen R für eine Hydroxyalkylgrugge steht, nicht mehr als 20 Gewichtsprozent der eingesetzten Hydroxyalkylamine beträgt,

gegebenenfalls durch Co-Kondensation mit Polyolen der Formel

in der

• A einen 2-, 3- oder 4-wertigen aliphatischen, cycloaliphatischen, araliphatischen oder aromatischen Rest bedeutet und
• n eine Zahl von 2 bis 4 ist,

und anschließende Quaternierung erhalten werden. Für R seien beispielsweise genannt:

• als C₁-C₁₈-Alkylreste der Methyl-, Ethyl-, Propyl-, n-Butyl-, sec.-Butyl-, 2-Ethylhexyl-, Decyl-, Dodecyl-oder Stearylrest;
• als Cycloalkylreste vor allem der Cyclohexylrest und durch C₁-C₄-Alkylgruppen substituierte Cyclohexylreste, wie der Methylcyclohexyl-, Ethylcyclohexyl-, Butylcyclohexyl-, Dimethylcyclohexyl- und der Diethylcyclohexylrest;
• als Aralkylreste insbesondere der gegebenenfalls durch C₁-C₄-Alkyl substituierte Benzylrest;
• als Arylreste vor allem der gegebenenfalls durch C₁-C₄-Alkyl substituierte Phenylrest wie der Kresyl-, Xylyl-, Ethylphenyl- und tert.-Butylphenylrest.

The invention relates to a process for the treatment of cellulosic fiber materials with aqueous liquors before or after dyeing or printing with noun or reactive dyes. The process is characterized in that the fiber materials are treated with aqueous liquors which contain quaternized polyethers by condensation of N-2-hydroxyalkylamines of the formula before or after dyeing or printing

in the

• R ₁ and R ₂ independently of one another hydrogen or a C ₁ -C ₄ alkyl radical and
• R is a C ₁ -C ₁₈ alkyl, cycloalkyl, aralkyl or aryl radical or one of the hydroxyalkyl groups
  
  or
  
  with the proviso that the amount of N-2-hydroxyalkylamines in which R represents a hydroxyalkylgrugge is not more than 20 percent by weight of the hydroxyalkylamines used,

optionally by co-condensation with polyols of the formula

in the

• A represents a 2-, 3- or 4-valent aliphatic, cycloaliphatic, araliphatic or aromatic radical and
• n is a number from 2 to 4,

and subsequent quaternization can be obtained. For R, for example:

• as C ₁ -C ₁₈ alkyl radicals the methyl, ethyl, propyl, n-butyl, sec-butyl, 2-ethylhexyl, decyl, dodecyl or stearyl radical;
• as cycloalkyl radicals, especially the cyclohexyl radical and cyclohexyl radicals substituted by C ₁ -C ₄ alkyl groups, such as the methylcyclohexyl, ethylcyclohexyl, butylcyclohexyl, dimethylcyclohexyl and the diethylcyclohexyl radical;
• as aralkyl radicals, in particular the benzyl radical optionally substituted by C ₁ -C ₄ alkyl;
• as aryl radicals, especially the phenyl radical optionally substituted by C ₁ -C ₄ alkyl, such as the cresyl, xylyl, ethylphenyl and tert-butylphenyl radical.

For R ₁ and R ₂ , the methyl, ethyl, n-propyl, iso-propyl, n-butyl and sec.-butyl radicals may be mentioned as C ₁ -C ₄ alkyl radicals.

In preferred compounds (I) R is C ₁ -C ₄ alkyl or cyclohexyl and R ₁ and R _{2 are} hydrogen or methyl.

worin

• _B für 0, S, CO oder C_yH_2y,
• x für 2 oder 3,
• y für 1 - 3 und
• z für 0 oder 1 stehen.

The aliphatic radicals A can be interrupted by heteroatoms and additionally by aromatic radicals. Particular mention should be made of C ₂ -C ₄ alkylene radicals or radicals of the formulas

wherein

• _B for 0, S, CO or C _y H _2y ,
• x for 2 or 3,
• y for 1 - 3 and
• z stands for 0 or 1.

• Aliphatische Polyole, z.B. Diole, wie Ethylenglykol, Propylenglykol, Butylenglykol, Diethylenglykol, Triethylenglykol, Tetraethylenglykol; Triole wie Glycerin, Trimethylolethan, Trimethylolpropan; Tetraole wie Pentaerythrit; 1,4-Di-ß-hydroxy-ethoxy-benzol, 4,4'-Di-ßhydroxyethoxydiphenylether, 4,4'-Di-B-hydroxyethoxydiphenylsulfid, 4,4'-Di-ß-hydroxybenzophenon, 2,2-Bis-(4-β-hydroxyethoxyphenyl)-propan; cycloaliphatische Diole, wie 1,4-Bis-methylolbenzol.

Preferred cycloaliphatic, araliphatic and aromatic radicals A are derived from cyclohexylene, xylylene and phenylene. The following may be mentioned as polyols:

• Aliphatic polyols, for example diols, such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol; Triols such as glycerin, trimethylolethane, trimethylolpropane; Tetraols such as pentaerythritol; 1,4-di-ß-hydroxy-ethoxy-benzene, 4,4'-di-ß-hydroxyethoxydiphenyl ether, 4,4'-di-B-hydroxyethoxydiphenyl sulfide, 4,4'-di-ß-hydroxybenzophenone, 2,2-bis - (4-β-hydroxyethoxyphenyl) propane; cycloaliphatic diols such as 1,4-bis-methylolbenzene.

It has proven expedient to choose the amount of polyols condensed in not higher than 25 percent by weight, based on the weight of the polyether.

The average molecular weight of the polyethers to be used according to the invention should be between 500 and 20,000, preferably 1,000 to 15,000.

The polyethers to be used according to the invention are linear or slightly branched polyethers. The linear polyethers can be prepared by known methods by condensing N-2-hydroxyalkylamines of the formula I in the presence of acidic catalysts, for example H ₃ PO ₃ high temperatures, for example 150 - 280 ° C can be obtained. In order to obtain branched polyethers, the diols containing tertiary amino groups are condensed together with triols containing tertiary amino groups, ie N-2-hydroxyalkylamines of the formula I in which R represents one of the stated B-hydroxyalkyl groups. In order to avoid crosslinking, however, the amount of triols in the condensation mixture should not be more than 20 percent by weight, preferably 2-15 percent by weight.

The polyethers to be used according to the invention are known, for example, from GB-A-1 107 818 and DE-A-2 060 572.

B-Hydroxyalkylamines of the formula (I) which may be mentioned are, for example, the N-di- (2-hydroxyalkyl) amines as used in the addition of ethylene, propylene and butylene oxide or mixtures of these alkylene oxides to primary aliphatic, cycloaliphatic, araliphatic and aromatic amines are formed.

• N,N-Bis-(2-hydroxyethyl)-N-methylamin, N,N-Bis-/2-hydroxypropyl-(117-methylamin, N,N-Bis-L2-hydroxy-butyl-(1)]-methylamin, N,N-Bis-(2-hydroxyethyl)-N-isopropylamin, N,N-Bis-(2-hydroxyethyl)-N-n-butylamin, N,N-Bis-(2-hydroxyethyl)-cyclohexylamin, N,N-Bis-(2-hydroxyethyl)-N-benzylamin, N,N-Bis-(2-hydroxyethyl)-N-(4-methylbenzyl)-amin, N,N-Bis-(2-hydroxyethyl)-anilin, N,N-Bis-[2-hydroxypropyl-(1)]-anilin, N,N-Bis-(2-hydroxyethyl)-3-methylanilin, N,N-Bis-(2-hydroxyethyl)-4-tert.-butylanilin.

Representatives of these N-di- (2-hydroxyalkyl) amines (I) are, for example:

• N, N-bis (2-hydroxyethyl) -N-methylamine, N, N-bis- / 2-hydroxypropyl- (117-methylamine, N, N-bis-L2-hydroxybutyl- (1)] methylamine , N, N-bis (2-hydroxyethyl) -N-isopropylamine, N, N-bis (2-hydroxyethyl) -Nn-butylamine, N, N-bis (2-hydroxyethyl) cyclohexylamine, N, N -Bis- (2-hydroxyethyl) -N-benzylamine, N, N-bis- (2-hydroxyethyl) -N- (4- methylbenzyl) amine, N, N-bis (2-hydroxyethyl) aniline, N, N-bis [2-hydroxypropyl- (1)] aniline, N, N-bis (2-hydroxyethyl) -3 -methylaniline, N, N-bis (2-hydroxyethyl) -4-tert-butylaniline.

Triethanolamine, triisopropanolamine and tributanolamine may be mentioned in particular as representatives of the triols used to prepare the branched polyethers.

The quaternization is carried out in a manner known per se by reacting the polyethers which are optionally dissolved or suspended in alcohol / water mixtures with known alkylating agents, such as dimethyl sulfate or diethyl sulfate; p-toluenesulfonic acid alkyl esters, e.g. p-toluenesulfonic acid methyl ester; Alkyl halides, e.g. Methyl iodide or ethyl bromide; Chloroacetamide, halocarboxylic acid salts, halocarboxylic acid esters, alkane sultones, benzyl chloride, methanephosphonic acid dimethyl ester, trimethyl phosphate or alkylene oxide such as ethylene oxide and propylene oxide in the presence of acids.

It is not necessary to completely quaternize the basic polyether, but effective compounds can be obtained if only a part of the basic nitrogen atoms of the polyether is quaternized.

The amounts in which the quaternized polyethers to be used according to the invention are added to the aqueous liquors can fluctuate within wide limits. In general, an addition of 0.1-2%, preferably 0.2-1%, based on the weight of the fiber materials, has proven useful.

The quaternized polyethers can be applied in a pretreatment process to the untreated fiber material to be dyed or printed in order to improve the color yield by impregnating or printing with aqueous liquors which contain the quaternized polyethers. The fiber material treated in this way is e.g. squeezed to a liquor intake of 60-100%, dried and, if necessary after heat treatment, e.g. by brief steaming at 102 - 120 °, colored or printed in the usual way.

The aftertreatment of the dyed or printed fiber material to improve the wet fastness is carried out either in the exhaust process, e.g. for 20-30 minutes into an aqueous liquor which contains the quaternized polyethers to be used according to the invention and has a pH of e.g. 4-8, preferably 5.5-6.5, and a temperature of 20-40 ° C, or the liquor used for after-treatment continuously, e.g. by means of a foulard onto which colored or printed material is applied.

Suitable dyes for producing the dyeings and prints are, for example, in the Color Index, 3rd edition (1971), Vol. 2 listed on pages 2005-2478 as direct dyes and on pages 1001-1562 as acid dyes. Suitable reactive dyes are described, for example, in Venkataraman, The Chemistry of Synthetic Dyes, Volume VI, Reactive Dyes (Academic Press, New York, London 1972).

Fiber materials suitable according to the invention are, above all, those made from natural or regenerated cellulose; Cotton, hemp, jute, linen, as well as viscose and cellulose acetate fibers and blended fabrics containing cellulose fibers are mentioned.

The fiber material can be in various processing states and e.g. exist as loose material, yarn, woven or knitted fabric.

With the aid of the method according to the invention, the color yield and the fastness properties of dyeings and prints, in particular the fastness to perspiration, water and washing, are considerably improved.

Compared to the condensation products of ammonium salts, cyanamide derivatives and formaldehyde that are often used to improve wet fastness properties, e.g. described in American Patent 3,290,310 or in Rev. Prog. Coloring Vol. 12 (1982), pp. 76-77, the compounds according to the invention offer the advantage of being completely free from formaldehyde.

Another advantage of the claimed compounds is the slight impairment in the grip of the treated ones Fiber materials and the lightfastness of the dyeings. Furthermore, they do not cause color changes in the colorings.

Preparation of the polyethers used in the examples:

Polyether A

1500 Teile Di-ß-hydroxyethylcyclohexylamin wurden in Gegenwart von 15 Teilen H₃P0₃ 3 Stunden unter Stickstoff bei 220 - 230°C kondensiert. Anschließend wurde die Reaktionsmischung zum Entfernen der flüchtigen Bestandteile 1 Stunde unter vermindertem Druck (12 mmHg) auf 220°C erhitzt. Der als Rückstand anfallende Polyether stellt einen gelben wasserunlöslichen Sirup dar (mittleres Molekulargewicht: 4460, OH-Zahl: 25).

1500 parts of di-ß-hydroxyethylcyclohexylamine were condensed in the presence of 15 parts of H ₃ PO _{3 for} 3 hours under nitrogen at 220-230 ° C. The reaction mixture was then heated to 220 ° C. for 1 hour under reduced pressure (12 mmHg) to remove the volatile constituents. The resulting polyether is a yellow water-insoluble syrup (average molecular weight: 4460, OH number: 25).

The solution of 150 parts of this polyether in 200 parts by volume of methanol was mixed with 82 parts of dimethyl sulfate (0.75 mol of dimethyl sulfate per mole of basic amino group) at the boiling point. The reaction mixture was refluxed for 3 hours. The solvent was then distilled off in vacuo. The quaternization product remains as a yellow water-soluble syrup.

polyether B

Polyether B was produced analogously to polyether A, except that instead of the 82 parts of dimethyl sulfate, only 54 parts of dimethyl sulfate (0.5 mol of dimethyl sulfate per mole of basic amino group) were used for the quaternization. The _Q remains uaternierungsprodukt back as a yellow water-soluble syrup.

Polyether C

Polyether C was prepared analogously to polyether A, except that 108 parts of dimethyl sulfate (1.0 mol of dimethyl sulfate per mol of basic amino group) were used instead of the 82 parts of dimethyl sulfate for the quaternization. The quaternization product remains as a yellow water-soluble syrup.

Polyether D

• Zunächst wurden 500 Teile N,N-Di-(ß-hydroxyethyl)-N-cyclohexylamin in Gegenwart von 7,5 Teilen H₃PO₃ analog zur Herstellung des Polyethers A zu einem Polyether mit einer OH-Zahl 8,6 entsprechend einem mittleren Molekulargewicht 13.000 kondensiert. Der Polyether läßt sich durch die Formel
  

beschreiben.Starting product:

• First, 500 parts of N, N-di- (β-hydroxyethyl) -N-cyclohexylamine in the presence of 7.5 parts of H ₃ PO _{3 were} analogous to the preparation of polyether A to give a polyether with an OH number 8.6 corresponding to an average Molecular weight condensed 13,000. The polyether can be represented by the formula
  

describe.

85 parts of this polyether were suspended in 80 parts by volume of methanol, and 19 parts of dimethyl sulfate (0.3 mol of dimethyl sulfate per mole of basic amino group) were added at the boiling point. After heating at the reflux temperature for two hours, the solvent was distilled off. The quaternized polyether was obtained in the form of a yellow water-soluble syrup.

Polyether E.

1900 Teile N,N-Di-(-ß-hydroxyethyl)-N-butylamin wurden in Gegenwart von 19 Teilen H₃PO₃ unter Stickstoff 9 Stunden bei 200°C kondensiert. Anschließend wurde die Reaktionsmischung zum Entfernen der flüchtigen Bestandteile 2 Stunden unter vermindertem Druck (12 mmHg) auf 200°C erhitzt. Der als Rückstand anfallende Polyether stellt ein wasserunlösliches, leicht rötlich gefärbtes viskoses öl dar (mittleres Molekulargewicht: 5000; OH-Zahl: 22).

1900 parts of N, N-di - (- ß-hydroxyethyl) -N-butylamine were condensed in the presence of 19 parts of H ₃ PO ₃ under nitrogen at 200 ° C. for 9 hours. The reaction mixture was then heated to 200 ° C. for 2 hours under reduced pressure (12 mmHg) to remove the volatile constituents. The resulting polyether is a water-insoluble, slightly reddish viscous oil (average molecular weight: 5000; OH number: 22).

190 parts of the polyether obtained were dissolved in 150 parts of isopropanol, and 166 parts of dimethyl sulfate (1.0 mol of dimethyl sulfate per mol of basic amino group) were added at 60-70 ° C. After heating at the reflux temperature for two hours, the solvent was distilled off. The quaternized polyether was obtained in the form of a highly viscous water-soluble syrup.

Polyether F

700 Teile N,N-Di-(B-hydroxypropyl)-N-methylamin wurden in Gegenwart von 10,5 Teilen H₃PO₃ unter Stickstoff bei 220°C kondensiert. Anschließend wurde die Reaktionsmischung zum Entfernen der flüchtigen Bestandteile 1 Stunde unter vermindertem Druck (12 mmHg) auf 220°C erhitzt. Der als Rückstand anfallende Polyether stellt ein schwach rötlich gefärbtes wasserlösliches öl dar (mittleres Molekulargewicht: 1340; OH-Zahl: 84).

700 parts of N, N-di- (B-hydroxypropyl) -N-methylamine were condensed in the presence of 10.5 parts of H ₃ PO ₃ under nitrogen at 220 ° C. The reaction mixture was then heated to 220 ° C. for 1 hour under reduced pressure (12 mmHg) to remove the volatile constituents. The resulting polyether is a slightly reddish colored water-soluble oil (average molecular weight: 1340; OH number: 84).

150 parts of the polyether obtained were dissolved in 100 parts of isopropanol, and 144 parts of dimethyl sulfate (1.0 mol of dimethyl sulfate per mol of basic amino group) were added at 60-70.degree. After heating at the reflux temperature for two hours, the solvent was distilled off. The quaternized polyether was obtained in the form of a highly viscous water-soluble syrup.

Polyether G.

• Zunächst wurden 500 Teile N,N-Di-(ß-hydroxyethyl)-N-cyclohexylamin in Gegenwart von 7,5 Teilen H₃PO₃ analog zur Herstellung des Polyethers A zu einem Polyether mit einer OH-Zahl 14 entsprechend einem mittleren Molekulargewicht 8000 kondensiert. Der Polyether läßt sich durch die Formel
  
  beschreiben.

Starting product:

• First, 500 parts of N, N-di- (β-hydroxyethyl) -N-cyclohexylamine in the presence of 7.5 parts of H ₃ PO ₃ ana log condensed to produce polyether A into a polyether with an OH number 14 corresponding to an average molecular weight of 8000. The polyether can be represented by the formula
  
  describe.

The solution of 338 parts of this polyether in 400 parts by volume of methanol was mixed with 173 parts of methyl chloroacetate at the boiling point (0.8 mol of chloroacetic acid ester per mol of basic amino group). After heating at the reflux temperature for 3 hours, the solvent was distilled off in vacuo. The quaternization product was obtained in the form of a water-soluble yellowish oil.

Polyether H

• 1800 Teile N,N-Di-(B-hydroxyethyl)-N-cyclohexylamin, 200 Teile 2,2-Di-[B-hydroxyethoxy)-phenyl]-propan wurden in Gegenwart von 20 Teilen H₃PO₃ 5 Stunden unter Stickstoff bei 220 - 230°C kondensiert. Anschließend wurde die Reaktionsmischung zum Entfernen der flüchtigen Bestandteile 1 Stunde unter vermindertem Druck (12 mmHg) auf 220°C erhitzt. Der als Rückstand anfallende Polyether stellt einen gelben Sirup dar (mittleres Molekulargewicht: 8000, OH-Zahl: 14; Gehalt an basischen Aminogruppen: 5,16 Äquivalente/kg Polyether).

Starting product:

• 1800 parts of N, N-di- (B-hydroxyethyl) -N-cyclohexylamine, 200 parts of 2,2-di- [B-hydroxyethoxy) phenyl] propane were in the presence of 20 parts of H ₃ PO _{3 for} 5 hours under nitrogen condensed at 220 - 230 ° C. Subsequently the reaction mixture was heated at 220 ° C for 1 hour under reduced pressure (12 mmHg) to remove the volatiles. The resulting polyether is a yellow syrup (average molecular weight: 8000, OH number: 14; content of basic amino groups: 5.16 equivalents / kg polyether).

The solution of 300 parts of the polyether in 300 parts by volume of methanol was added dropwise at the boiling point with 158 parts of dimethyl sulfate (0.8 mol of dimethyl sulfate per mole of basic amino group). The reaction mixture was heated to reflux temperature for 2 hours. The solvent was then distilled off in vacuo. The quaternization product remains as a slightly yellowish water-soluble syrup.

Polyether I

• 1385 Teile N,N-Di-(ß-hydroxypropyl)-N-methylamin wurden in Gegenwart von 62 Teilen H₃P0₃ 5 Stunden unter Stickstoff bei 210 - 220°C kondensiert. Anschließend wurde die Reaktionsmischung zum Entfernen der flüchtigen Bestandteile 1 Stunde unter vermindertem Druck (12 mmHg) auf 210°C erhitzt. Der als Rückstand anfallende Polyether stellt eine schwach rötliches viskoses wasserlösliches öl dar (mittleres Molekulargewicht: 1280; OH-Zahl: 86; Gehalt an basischen Aminogruppen: 7 Äquivalente/kg Polyether).

Starting product No. 1:

• 1385 parts of N, N-di- (β-hydroxypropyl) -N-methylamine were condensed in the presence of 62 parts of H ₃ P0 _{3 for} 5 hours under nitrogen at 210-220 ° C. The reaction mixture was then heated to 210 ° C. for 1 hour under reduced pressure (12 mmHg) to remove the volatile constituents. The resulting polyether is a slightly reddish viscous water-soluble oil (average molecular weight: 1280; OH number: 86; content of basic amino groups: 7 equivalents / kg polyether).

beschreiben.The polyether can be represented by the formula

describe.

• 710 Teile dieses Polyethers und 710 Teile N,N-Di-(ß- hydroxyethyl)-N-cyclohexylamin wurden in Gegenwart von 15 Teilen H₃PO₃ 10 Stunden unter Stickstoff bei 220°C kondensiert. Anschließend wurde die Reaktionsmischung zum Entfernen der flüchtigen Bestandteile 3 Stunden unter vermindertem Druck (12 mmHg) auf 220°C erhitzt. Der als Rückstand anfallende Mischpolyether stellt einen wasserunlöslichen, orangefarbenen Sirup dar (mittleres Molekulargewicht: 6150; OH-Zahl: 18; Gehalt an basischen Aminogruppen: 6,8 Äquivalente/kg Polyether).

Starting product 2:

• 710 parts of this polyether and 710 parts of N, N-di- (β-hydroxyethyl) -N-cyclohexylamine were condensed in the presence of 15 parts of H ₃ PO ₃ under nitrogen at 220 ° C. for 10 hours. The reaction mixture was then heated to 220 ° C. for 3 hours under reduced pressure (12 mmHg) to remove the volatile constituents. The resulting mixed polyether is a water-insoluble, orange syrup (average molecular weight: 6150; OH number: 18; content of basic amino groups: 6.8 equivalents / kg polyether).

The solution of 500 parts of the mixed polyether in 500 parts by volume of methanol was added dropwise at the boiling point with 128 parts of dimethyl sulfate (0.3 mol of dimethyl sulfate per mole of amino group). The reaction mixture was heated to reflux temperature for 6 hours. The solvent was then distilled off in vacuo. The quaternization product remains as a water-soluble yellow syrup.

Polyether K

• 360 Teile N,N-Di-(ß-hydroxyethyl)-N-cyclohexylamin und 40 Teile Triethanolamin wurden in Gegenwart von 1,5 Teilen H₃PO_J 5 Stunden unter Stickstoff bei 220°C kondensiert. Anschließend wurde die Reaktionsmischung zum Entfernen der flüchtigen Bestandteile 1 Stunde unter vermindertem Druck (12 mmHg) auf 170°C erhitzt. Der als Rückstand anfallende verzweigte Mischpolyether stellt einen schwach gelblich gefärbten wasserunlöslichen Sirup dar (OH-Zahl: 108; Gehalt an basischen Aminogruppen: 6,3 Äquivalente/kg Polyether).

Starting product:

• 360 parts of N, N-di- (β-hydroxyethyl) -N-cyclohexylamine and 40 parts of triethanolamine were condensed in the presence of 1.5 parts of H ₃ PO _{J for} 5 hours at 220 ° C. under nitrogen. The reaction mixture was then heated to 170 ° C. for 1 hour under reduced pressure (12 mmHg) to remove the volatile constituents. The branched mixed polyether obtained as residue is a slightly yellowish, water-insoluble syrup (OH number: 108; content of basic amino groups: 6.3 equivalents / kg polyether).

200 parts of the polyether were suspended in 300 parts by volume of methanol and 79 parts of dimethyl sulfate were added at the boiling point (0.5 mol of dimethyl sulfate per mole of amino group). After heating at the reflux temperature for 3 hours, the solvent was distilled off in vacuo. The quaternized polyether was obtained in the form of a water-soluble syrup.

Example 1:

A cotton fabric is at an _H aspelkufe treated with a dyeing liquor at a liquor ratio of 1:20 at 40 ° C, per liter, 1 g of the dye Direct Red contains 79 (CI 29065). The dyebath is heated to 98 ° C. in the course of 30 minutes and then 10 g / 1 of sodium sulfate are added. and stains for one hour at the same temperature. After the dye bath has cooled to 80 ° C., the dyeing is rinsed in cold water. The coloring is then in a fresh bath, which is in liters

0.5 g of polyether A

0.2 g 60% acetic acid

contains, treated at 30 ° C for 30 min. and then rinsed with cold water and dried. The authenticity tests which are carried out with this aftertreated dyeing show that the wet fastness level was significantly improved by the aftertreatment.

Example 2:

A cotton fabric is dyed, rinsed and dried as described in Example 1.

The dyeing is then done on a foulard with a liquor in liters

15 g of polyether C

0.5 g 60% acetic acid

contains padded and dried at room temperature and a liquor absorption of 100%.

As a result of this aftertreatment, the wet fastness level is substantially improved, as in Example 1.

Example 3:

A cotton fabric is treated on a reel runner in a liquor ratio of 1:20 at 25 ° C. with a dyeing liquor which contains 2 g of the red dye of DE-A 2 264 698, Example 3 in liters. The dyebath is heated to 40 ° C. in the course of 30 minutes and then 50 g / 1 of sodium sulfate and, after a further 10 minutes, 20 g / 1 of sodium carbonate are added, and the mixture is colored at 40 ° C. for 1 hour. Then it is rinsed cold, hot and boiling. The dyeing is then treated with the polyether A in a fresh bath as described in Example 1.

The authenticity tests which are carried out with this aftertreated dyeing show that the wet fastness level was significantly improved by the aftertreatment.

Example 4:

A cotton fabric is dyed, rinsed, soaped and dried as described in Example 3.

The dyeing is then treated as in Example 2. As a result of the aftertreatment, the wet fastness level is significantly improved, as in Example 3.

Example 5:

A cotton fabric is printed with an aqueous preparation, which is in liters

60 g of the polyether D and

500 g of the 4% aqueous solution of a nonionic thickener

contains and then dried.

The material pretreated in this way is then dyed and rinsed as described in Example 1. The printed areas show a significantly deeper staining than the unprinted areas.

Claims (7)

1. A process for the treatment of cellulosic fiber material before or after dyeing or printing with substantive or reactive dyes, characterized in that the aqueous liquors contain quaternized polyethers which are condensed by N-2-hydroxyalkylamines of the formula

in the R ₁ and R ₂ independently of one another hydrogen or a C ₁ -C ₄ alkyl radical and R is a C ₁ -C ₁₈ alkyl, cycloalkyl, aralkyl or aryl radical or one of the hydroxyalkyl groups -CH ₂ -CH-OH ^R ₁ or

mean, with the proviso that the amount of N-2-hydroxyalkylamines in which R represents a hydroxyalkyl group is not more than 20 percent by weight of the hydroxyalkylamines used,
optionally by co-condensation with polyols of the formula

in the A represents a 2-, 3- or 4-valent aliphatic, cycloaliphatic, araliphatic or aromatic radical and n is a number from 2 to 4,
and subsequent quaternization can be obtained. A method according to claim 1, characterized in that the polyethers have a molecular weight of 500-20,000. Process according to Claim 1, characterized in that the polyethers are prepared from N-2-hydroxyalkylamines of the formula of Claim 1, in which R is C ₁ -C ₄ alkyl or cyclohexyl and R ₁ and R _{2 are} hydrogen or methyl. 4. The method according to claim 1, characterized in that the liquors contain 0.1 - 2 wt .-% of the polyether. 5. The method according to claim 1, characterized in that the fiber materials are treated with the aqueous liquors after dyeing or printing after the exhaust process. 6. The method according to claim 1, characterized in that the fiber materials are treated after dyeing or printing by a continuous process with the aqueous liquors. 7. The method according to claim 1, characterized in that the untreated fiber materials are treated with the aqueous liquors before dyeing or printing.