United States Patent (19) 11 Patent Number: 6,165,969 Böckh Et Al

USOO6165969A United States Patent (19) 11 Patent Number: 6,165,969 Böckh et al. (45) Date of Patent: Dec. 26, 2000

54 USE OF QUATERNIZED POLYMERIZATES 5,710,118 1/1998 Busch et al...... 510/360 CONTAINING UNITS OF WINYL MIDAZOL 5,710,119 1/1998 Busch et al...... 510/360 ASA COLOR FIXING AND COLOR 5,773,545 3/1996 Schade et al...... 526/262

TRANSFER INHIBITING ADDITIVE TO 5,804,543 9/1998 Wertz et al. ------510/303 DETERGENT POST TREATMENTAGENTS 5,846,924 12/1998 Detering et al...... 510/475 AND DETERGENTS FOREIGN PATENT DOCUMENTS 75 Inventors: Dieter Böckh, Limburgerhof, 2232 353 1/1973 Germany. Hans-Ulrich Jäger, Neustadt; Jirgen 2.... yE. EReIIllally ...... C11D 17/08 SENNERSSt. 4235798 4/1994 Germany ...... C11D 3/37 Limburgerhof,s Christian; Jurg Schade,9, 1348 212 3/1974 United Kingdom. Ludwigshafen, all of Germany Primary Examiner Yogendra Gupta Assistant Examiner-Christine Ingersoll 73 Assignee: BASF Aktiengesellschaft, Attorney, Agent, or Firm-Oblon, Spivak, McClelland, Ludwigshafen, Germany Maier & Neustadt, P.C. 21 Appl. No.: 09/284.967 57 ABSTRACT 22 PCT Filed: Oct. 28, 1997 The use of polymers which comprise at least 5 mol % of 86 PCT No.: PCT/EP97/05939 quaternized 1-vinylimidazole units of the formula S371 Date: May 5, 1999 (I) S 102(e) Date: May 5, 1999 R1 87 PCT Pub. No.: WO98/21301 -CH-CH-N1. N-R X, PCT Pub. Date: May 22, 1998 , GE 30 Foreign Application Priority Data R2 R3 Nov. 11, 1996 DEI Germany ...... 19646437 (51) Int. Cl...... C11D 10/00 where 52 U.S. Cl...... 510/475; 510/303 R is C-C-alkyl, Cs-Co-cycloalkyl or benzyl 58 Field of Search ...... 510/475,303 R.R.R are identical or different and are H, CH and C2H5, and 56) References Cited X is an anion, U.S. PATENT DOCUMENTS as color-fixing and color transfer-inhibiting additive to laun dry aftertreatment aids and to detergents.

5,500,153 3/1996 Figueroa et al...... 252/548 5,622,926 4/1997 Schade et al...... 510/340 5,627,151 5/1997 Detering et al...... 510/475 11 Claims, No Drawings 6,165,969 1 2 USE OF QUATERNIZED POLYMERIZATES as color-fixing and color transfer-inhibiting additive to laun CONTAINING UNITS OF WINYL MIDAZOL dry aftertreatment aids and to detergents. ASA COLOR FIXING AND COLOR The polymers to be used according to the invention TRANSFER INHIBITING ADDITIVE TO usually comprise at least 10 mol % of quaternized DETERGENT POST TREATMENT AGENTS 1-vinylimidazole units of the formula I and have a molecular weight of from 5000 to 1 million. The polymers preferably AND DETERGENTS employed comprise from 20 to 100 mol % of quaternized 1-vinylimidazole units of the formula I and have a molecular The invention relates to the use of polymers which weight of from 10000 to 500000 (determined by light comprise at least 5 mol % of quaternized, unsubstituted or Scattering). Substituted Vinylimidazole units, as color-fixing and color The polymers to be employed according to the invention transfer-inhibiting additive to laundry aftertreatment aids can be obtained by free-radical polymerization of quaternary and to detergents. 1-vinylimidazoles of the formula II When colored textiles are washed, the dye is partly removed from the colored textiles and transferred from the (II) wash liquor to other fabrics. If, for example, white laundry 15 is washed together with colored textiles, the white laundry R1 is Stained. Color detergents which comprise polymeric color transfer inhibitors were developed to prevent transfer of the HC=CH-N SN-R xe, removed textile dye from the wash liquor to the laundry. These inhibitors are, for example, homo- and copolymers of vinylpyrrolidone and vinylimidazole, cf. DE-B-22 32 353 and DE-A-28 14 287. WO-A-94/10281 discloses the use of copolymers of where (a) 1-vinylpyrrolidone and/or 1-vinylimidazole and R is C-C2s-alkyl, Cs-Co-cycloalkyl or benzyl, R',R, (b) nitrogenous, basic ethylenically unsaturated mono 25 Rare identical or different and are H, CH and CHs, mers in the form of the free bases, of the salts or in and quaternized form X is an anion, preferably Cl-, Br-, -, CHOSO as additive to detergents to inhibit dye transfer during the or CHOSO Washing process. in the presence or absence of other monoethylenically Polymers of alkyl-1-vinylimidazoles and processes for unsaturated monomers. preparing them by free-radical polymerization of alkyl-1- Examples of Such monomers are Vinylimidazoles, in the presence or absence of other 1-vinyl-2-methyl-3-benzylimidazolium chloride, monomers, in water or C-C-alcohols are disclosed in 1-vinyl-2,4-dimethyl-3-benzylimidazolium chloride, WO-A-95/15345. The polymers obtainable in this way are 35 1-vinyl-2,4,5-trimethyl-3-benzylimidazolium bromide, used as additive to detergents to inhibit dye transfer during 1-vinyl-2,4,5-trimethyl-3-ethylimidazolium chloride, the Washing process. 1-vinyl-2-ethyl-3-benzylimidazolium chloride, EP-A-0462 806 discloses the use of cationic dye fixatives 1-vinyl-4,5-diethyl-3-methylimidazolium chloride and in laundry aftertreatment baths together with fabric soften 1-vinyl-2,4,5-triethyl-3-benzylimidazolium chloride. ers. The aftertreatment of the laundry takes place in the Washing machines normally used in the household at below 40 The polymers to be used according to the invention can 40 C. The dye fixatives can, according to the Statements in also be obtained by quaternizing polymers which comprise the application, also be employed in nonionic detergents. 1-vinylimidazole units of the formula The cationic fixatives retard removal of the dye from the colored textiles during the treatment process. (III) It is an object of the present invention to provide other 45 compositions for Suppressing dye removal and dye transfer to other textiles during washing and during the aftertreat ment of colored textiles. We have found that this object is achieved by the use of polymers which comprise at least 5 mol % of quaternized 50 1-vinylimidazole units of the formula where R', R, R are identical or different and are H, CH, (I) and CHs, with C-C-alkylating agents. Polymers of this R1 55 type are described, for example, in WO-A-94/10281 and WO-A-94/14861. -CH-CH-N1. N-R X, Examples of Suitable quaternizing agents are alkyl halides GE Such as the preferably used C-C-s-alkyl chlorides or alkyl bromides, Cs-Co-cycloalkyl halides or benzyl chloride or R2 R3 60 benzyl bromide. Examples of Suitable alkylating agents are methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, propyl chloride, n-propyl bromide, isopropyl where chloride, butyl chloride, hexylchloride, cyclohexylchloride, R is C-C-alkyl, Cs-Co-cycloalkyl or benzyl octyl chloride, dodecyl chloride and Stearyl chloride. R,R,R are identical or different and are H, CH, and 65 C-C-Alkyl chlorides or alkyl bromides, and benzyl chlo C2H5, and ride or benzyl bromide, are preferably used as quaternizing X is an anion, agents. 6,165,969 3 4 Further Suitable alkylating agents are dialkyl Sulfates and mula I to be used according to the invention are preferably alkyl Sulfonates. Examples of Suitable dialkyl Sulfates are employed in detergents containing no anionic Surfactants. dimethyl sulfate and diethyl sulfate. Examples of suitable Detergent formulations of these types comprise, for alkyl sulfonates are methyl methylsulfonate and methyl example, toluenesulfonate. Dimethyl sulfate and diethyl sulfate are (i) 1 to 50% by weight of at least one nonionic surfactant, preferred alkylating agents. (ii) 0 to 4.0% by weight, preferably up to 2.5%, of an Examples of quaternized 1-vinylimidazoles of the for anionic Surfactant and mula II are 3-methyl-1-vinylimidazolium chloride, (iii) 0.05 to 2.5% by weight of at least one polymer which 3-benzyl-1-vinylimidazolium chloride, 3-ethyl-1- comprises at least 5 mol % of quaternized vinylimidazolium sulfate, 3-n-dodecyl-1-vinylimidazolium 1-vinylimidazole units of the formula I. bromide and 3-n-octadecyl-1-vinylimidazolium chloride. Examples of Suitable nonionic Surfactants (I) are alkoxy The polymers which are preferably employed comprise lated C-C2-alcohols. The alkoxylation can be carried out units of the formula I where R', R, R-H and R is methyl, with ethylene oxide, propylene oxide and/or butylene oxide. ethyl or benzyl. They comprise, for example, The Surfactants which can be employed in this connection (a) 25 to 100 mol % of quaternary vinylimidazoles of the 15 are all alkoxylated alcohols which comprise at least two formula II, molecules of an abovementioned alkylene oxide in the (b) 0 to 75 mol % of 1-vinylpyrrollidone, adduct. Said alkylene oxide adducts can be block copoly Vinyloxazolidone, N-Vinylcaprolactam, N-Vinylamides mers of ethylene oxide, propylene oxide and/or butylene of C-C-carboxylic acids, acrylonitrile, Vinyl esters of oxide or adducts which contain Said alkylene oxides in C1-Co-carboxylic acids, acrylic esters and meth random distribution. The nonionic Surfactants comprise, per acrylic esters of C1-Co-alcohols or mixtures of Said mole of alcohol, for example 2 to 50, preferably 3 to 20 mol monomers and of at least one alkylene oxide in the adduct. Ethylene oxide (c) 0 to 30 mol% of other monoethylenically unsaturated is preferably employed as alkylene oxide. The alcohols are OOCS preferably derived from compounds having 10 to 18 carbon as copolymerized units. 25 atoms. These can be natural or Synthetic alcohols. Particularly preferred copolymers are those which com Another class of nonionic Surfactants comprises alkyl prise polyglucosides having 8 to 22, preferably 10 to 18, carbon (a) 40 to 100 mol % of quaternary vinylimidazoles of the atoms in the alkyl chain. These compounds comprise, for formula II and example, 1 to 20, preferably 1.1 to 5, glucoside units. (b) 0 to 60 mol % of 1-vinylpyrrollidone, Another class of nonionic Surfactants comprises N-Vinylformamide, N-Vinylcaprolactam, Vinyl acetate, N-alkylglucamides of the structure I or II vinyl propionate, methyl acrylate or mixtures of Said monomers as copolymerized units. If the monomers of (I) A-C-N-C component (b) are present in the polymers, their con 35 tent is preferably 20 to 50 mol%. O B (c) Examples of Suitable monomers (c) are monoethyl (II) enically unsaturated carboxylic acids Such as acrylic A-N-C-C acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride. 40 B O Other Suitable comonomers are hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, where A is C-C2-alkyl, B is H or C-C-alkyl and C is a hydroxypropyl methacrylate, hydroxybutyl acrylate, polyhydroxyalkyl radical having 5 to 12 carbon atoms and hydroxybutyl methacrylate, phenoxyethyl acrylate, at least 3 hydroxyl groups. It is preferred for A to be dimethylaminoethyl acrylate, dimethylaminoethyl 45 Co-C-alkyl, B to be CH and C to be a Cs or C radical. methacrylate, diethylaminoethyl (meth)acrylate, meth Compounds of this type are obtained, for example, by the oxyethyl acrylate. acylation of reductively aminated Sugars with chlorides of Further Suitable monomers are: (meth) acrylamide, Co-C-carboxylic acids. The detergent formulations con N-methylol (meth) acrylamide, N-substituted (meth) tain Co-C-alcohols preferably ethoxylated with 3-12 mol acrylamides such as N-methyl(meth) acrylamide, N-t- 50 of ethylene oxide, particularly preferably ethoxylated fatty butylacrylamide, diallyldimethylammonium chloride, dial alcohols, as nonionic Surfactants. ly 1 diethylam monium chloride, Further suitable and preferred surfactants are the dime thy la mino propyl me thacrylamide, endgroup-capped fatty amide alkoxylates, disclosed in diethylamino propyl methacrylamide, Styrene, WO-A-95/11225, of the formula methylstyrene, Vinyl alkyl etherS Such as vinyl methyl ether, 55 Vinyl ethyl ether, Vinyl propyl ether, StyreneSulfonate, R"-CO-NH-(CH), O-(AO)-R (III), Vinylsulfonate, 2-Sulfoethyl methacrylate and 2-acrylamido where 2-methylpropanesulfonic acid. The polymers comprising quaternized vinylimidazole R" is C5-C1-alkyl or -alkenyl, units of the formula I are employed, for example, in amounts 60 R’ is C-C-alkyl, of from 0.05 to 2.5, preferably 0.1 to 1.5, 9% by weight in A is C-C-alkylene, detergents which comprise less than 4% by weight of an n is 2 or 3, and anionic Surfactant. The polymers preferably used in deter X has a value from 1 to 6. gent formulations containing anionic Surfactants comprise Examples of Such compounds are the products of the units of the formula I where R', R, R=H and R is 65 reaction of n-butyltriglycolamine of the formula HN C-C2-alkyl or benzyl and X is an anion. The polymers (CH-CH-O)-CH with methyl dodecanoate or the comprising quaternized 1-vinylimidazole units of the for products of the reaction of ethyltetraglycolamine of the 6,165,969 S 6 formula HN-(CH-CH-O)-CHs with a commer weight of at least one of the quaternized polymers described cial mixture of Saturated C-C-fatty acid methyl esters. above having at least 5 mol % of units of the formula I. The powder or granular detergents may additionally con The quaternized polymers to be used according to the tain one or more builders. Examples of Suitable inorganic invention not only have a color transfer-inhibiting effect builder Substances are all the conventional inorganic build when colored textiles are washed together with uncolored erS Such as aluminosilicates, Silicates, carbonates and phos textiles but, Surprisingly, also have a color-fixing effect. This phates. means that the removal of dyes from colored textiles during Examples of Suitable inorganic builders are aluminosili the Washing proceSS is not as great as on use of other color cates with ion-exchanging properties Such as Zeolites. Vari transfer inhibitors such as polymers of N-vinylpyrrolidone. ous types of Zeolites are Suitable, in particular Zeolites A, X, Polymers comprising at least 5 mol % of quaternized B, P, MAP and HS in their Na form or in forms in which Na 1-vinylimidazole units of the formula I have a pronounced is partly replaced by other cations Such as Li, K, Ca, Mg or color-fixing effect and, moreover, act as color transfer ammonium. Suitable Zeolites are described, for example, in inhibitors in laundry aftertreatment and care aids. The poly EP-A-0 038591, EP-A-0021 491, EP-A-0087 035, U.S. mers comprising quaternized vinylimidazole units of the Pat. No. 4,604,224, GB-A-2 013 259, EP-A-0 522 726, 15 formula I are therefore advantageously employed in after EP-A-O 384 O70 and WO-A-94/24251. wash treatment compositions. Laundry aftertreatment aids Examples of other Suitable inorganic builders are amor comprise, for example, phous or crystalline Silicates Such as amorphous disilicates, (i) 1 to 50% by weight of a fabric softener for laundry, crystalline disilicates such as the sheet silicate SKS-6 (ii) 1 to 50% by weight of a nonionic surfactant and (manufactured by Hoechst AG). The silicates can be (iii) 0.1 to 2.5% by weight of polymer comprising at least employed in the form of their alkali metal, alkaline earth one quaternized 1-vinylimidazole unit of the formula I metal or ammonium Salts. Na, Li and Mg Silicates are in an amount of at least 5 mol%. preferably employed. The laundry aftertreatment aids preferably comprise as Further Suitable inorganic builder Substances are carbon component (i) 2.5 to 30% by weight of a fabric softener for ates and bicarbonates. These can be employed in the form of 25 laundry. Examples of Suitable fabric Softeners are quaternary their alkali metal, alkaline earth metal or ammonium Salts. ammonium compounds, polysiloxanes and nonionic cellu Na, Li and Mg carbonates and bicarbonates, in particular lose ethers, cf., for example, EP-A-0239910, EP-A-0 150 Sodium carbonate and/or Sodium bicarbonate, are preferably 867 and EP-A-0 213 730. Examples of fabric softeners for employed. laundry are dialkyldimethylammonium chlorides and alky The inorganic builders can be present in the detergents in limidazolium methylsulfates. amounts of from 0 to 60% by weight, together with organic The laundry aftertreatment aids comprise as component cobuilders to be used where appropriate. The inorganic (ii) for example 1 to 50, preferably 2 to 20, 9% by weight of builders can be incorporated either alone or in any combi a nonionic Surfactant. Nonionic Surfactants have been nation with one another into the detergent. described above as component (i) in the composition of the Powder or granular or other Solid detergent formulations 35 detergents. The compounds mentioned there can likewise be comprise organic cobuilders in amounts of from 0 to 20% by employed in laundry aftertreatment aids. The laundry after weight, preferably in amounts of from 1 to 15% by weight, treatment aids comprise as component (iii) 0.1 to 2.5, together with inorganic builders. Powder or granular heavy preferably 0.2 to 2.0, % by weight of a quaternary polymer duty detergents may additionally contain other conventional as color-fixing and color transfer-inhibiting additive. ingredients Such as bleaching Systems consisting of at least 40 The polymers to be used according to the invention one bleach, where appropriate combined with a bleach achieve a maximum effect, for example in a formulation activator and/or a bleach catalyst, and other conventional containing no anionic Surfactants, at a concentration as low ingredients Such as Soil release polymers, antiredeposition as from 20 to 100 ppm in the wash liquor or the liquor of the agents, enzymes, inorganic fillerS Such as Sodium Sulfate, laundry aftertreatment aid. A further increase in the amount complexing agents, optical brighteners, dyes, perfume oils, 45 of the polymers used normally results in only a Small further foam Suppressants, corrosion inhibitors, phosphates and/or increase in the effectiveness. phosphonates in the usual amounts. Unless otherwise evident from the context, the percentage The detergents preferably contain no anionic Surfactants data in the examples are 96 by weight. The K values were but may comprise them as component (ii) in amounts of up determined by the method of H. Fikentscher, Cellulose to 4% by weight, preferably up to 2.5% by weight. Examples 50 Chemie, 13 (1932) 58–65 and 71-74 at 25° C. and with a of Suitable anionic Surfactants are Sulfates of fatty alcohols polymer concentration of 1% by weight in 0.5 molar aque having 8 to 22 carbon atoms, Sulfated, ethoxylated C-C- ous NaCl Solution. alcohols and their water-Soluble alkali metal and ammonium The following quaternary polymers were used: Salts. Further Suitable anionic Surfactants are alkylsulfonates Polymer 1 Such as C-C2-alkaneSulfonates, Soaps Such as the alkali 55 Copolymer of 1-vinylimidazole and 1-vinylpyrrolidone in metal Salts of C-C - carboxylic acids, and the molar ratio 55:45 which was quaternized by reaction N-acylsarcosinates with Cs-C-acyl radicals. Also Suitable with dimethyl sulfate to give a terpolymer with units of as an ionic Surfactants are linear Co-Co 1-vinylimidazole, 1-vinyl-3-methylimidazolinium metho alkylbenzenesulfonates (LAS). The anionic Surfactants may sulfate and 1-vinylpyrrollidone in the molar ratio 45:10:45. also be employed, for example, in the form of the 60 The quaternary polymer had a K value of 34.7. hydroxyethylammonium, di(hydroxyethyl)ammonium and Polymer 2 tri(hydroxyethyl)ammonium salts. Preferably employed if Copolymer of 1-vinylimidazole and 1-vinylpyrrolidone in the detergents according to the invention comprise anionic the molar ratio 60:40, which was quaternized by reaction Surfactants are Soaps, acylsarcosinates or Sulfated ethoxy with dimethyl Sulfate to give a terpolymer which comprised lated C-C2-alcohols. 65 units of 1-vinylimidazole, 1-vinyl-3-methylimidazolium The detergents contain according to the invention as methoSulfate and 1-vinylpyrrolidone in the molar ratio component (iii) 0.05 to 2.5, preferably 0.1 to 1.5, 9% by 40:20:40. The quaternized polymer had a K value of 34.8. 6,165,969 7 8 Polymer 3 Washing temperature: 40 C. Copolymer of 1-vinylimidazole and 1-vinylpyrrolidone in Water hardness: 14.5 German hardness the molar ratio 55:45, which was quaternized by reaction with dimethylsulfate and benzyl chloride to give a polymer Ca/Mg ratio: 4.0:1.0 which comprised units of 1-vinylimidazole, 1-vinyl-3- Washing time: 30 min. methylimidazolium chloride, 1-vinyl-3-benzylimidazolium chloride and 1-vinylpyrrolidone in the molar ratio 45:5:5:45. TABLE 1. The polymer had a K value of 83.3. Results of tests on the color transfer inhibition and the Polymer 4 reduction in the loss of color with Direct Red 212 on cotton Homopolymer of 1-vinylimidazole with a K value of 23, which was converted by reaction with benzyl chloride in the Amount in Softlan molar ratio 1:1 into poly-(N-benzyl)vinylimidazolium chlo fabric Loss of Color transfer ride. softener color inhibition Polymer 5 Polymer % % % Copolymer of 1-vinylimidazole and 1-vinylpyrrolidone in 15 the molar ratio 1:1 with a K value of 17, which was Ex. quaternized by reaction in aqueous Solution with 1 mol of 1. Polymer 1 2 18.3 85.2 benzyl chloride per mole of 1-vinylimidazole to give a 2 Polymer 2 2 18.4 86.9 co polymer which comprised units of 3 Polymer 3 2 16.8 85.6 N-benzylvinylimidazolium chloride and 1-vinylpyrrolidone Comparative Example in the molar ratio 1:1. 1. Ole 25.1 O 2 PVP1) 2 25.1 48.5 EXAMPLES 3 VI/VP2) 2 26.3 76.O copolymer Use in a fabric Softener: To test the color removal-reducing and color transfer 25 PVP = Poly-N-vinylpyrrolidone inhibiting effect, the polymers to be used according to the 2VI/VP = 1-Vinylimidazole?1-vinylpyrrolidone invention were added to a commercial laundry fabric Soft The results with the polymers to be used according to the ener. The colored fabric was prerinsed with an aqueous solution of the fabric softener at 25 C., rinsed again with tap invention show that the polymerS Show, on addition to a water, dried and ironed. Subsequently, the pretreated colored commercial fabric Softener, a better color transfer-inhibiting fabrics were washed together with white test fabrics using a effect than on addition of polyvinylpyrrolidone with a commercial detergent. The color Strength of the white test molecular weight of 40000 or VI/VP copolymer with a fabrics compared with the previously measured color molecular weight of 10000. In addition, the removal of color strength was determined by the method of A. Kud, Seifen, from the colored fabrics is distinctly reduced, and thus there 35 is a distinct decrease in the fading of colored textiles on Ole, Fette, Wachse 119 (1993)590–594. The color strengths Washing. of each of the stains on the white fabric were determined, To test the polymers according to the invention in deter and the color transfer-inhibiting effect of the polymers was gent formulations, the color transfer-inhibiting and color determined therefrom. To test the loss of color from the removal-reducing effect was tested in various heavy-duty colored test fabric, the treatment with fabric Softener, Sub 40 detergents and color detergents (Tables 2 and 3). In the Sequent washing and drying was repeated 5 times with the formulation examples, the polymers according to the inven same colored fabric. The loss of color was determined from tion Show a distinct reduction in the color transfer and the color strength of the colored fabric before the first wash and the color Strength after the 5th wash using the following distinctly leSS color removal than on use of commercial formula: color transfer inhibitors such as PVP, VI/VP copolymers or 45 poly-4-vinylpyridine N-oxide.

Loss of color 9% = TABLE 2

Color strengthere wash - Color strength after wash) : 100. I II III IV V VI VII Color strength before wash) 50 Polymer 1 1.5 1.O O.S O6 O.3 Polymer 2 1.O Test conditions: Polymer 3 1.O AA/MA (70000) 7.5 5.0 5.0 Apparatus: Launder-O-meter AAMAWAc 5.0 terpolymer (40000) Colored fabric: 1.0 g of cotton fabric colored with 0.8% 55 Na perborate 15 15 15 7.5 Direct Blue 71 monohydrate White fabric: 2.5g of cotton fabric Na percarbonate 18 15 18 Pretreatment: TAED 4.0 3.8 5.0 5.0 2.9 4.2 2.0 Na lauryl sulfate 1.O Fabric softener: Softlance (manufactured by Colgate linear Na alkyl benzenesulfonate Palmolive) Concentration of the polymers used in the 60 fabric Softener: 2.0% Amount of fabric Softener used: Sulfated fatty alcohol 1.5 ethoxylate 1.75 g/l Temperature (rinsing): 30° C. Rinsing time: 10 Commercial oleyl 3.1 2.O min sarcosinate in the Washing: acid form Soap 0.4 2.5 1.5 2.4 Detergent: Ajax(R) (manufactured by Colgate-Palmolive) 65 3.0 Amount: 5.0 g/l alcohol.3 EO Amount of liquor: 250 g 6,165,969 9

TABLE 2-continued TABLE 3-continued

I II III IV V VI. VII VII VIII IX X XI XII C13/C1s OXO 7.5 4.7 18.5 8.0 6.5 Sodium citrate 2.0 9.O 2.5 alcohol:7 EO Protease 0.5 1.O C13/C1s OXO 3.0 Cellulase 1.O 1.O O.8 1.O alcohol.10 EO Water tO tO tO tO tO tO C2/C14 fatty 1.O.O 1OO 100 1 OO 100 100 100 alcohol:7 EO Lauryl alcohol 13 EO 5.0 For abbreviations, see legend to Table 2 Zeolite A 25 25 15 3O 15 35 Zeolite P 40 The effect of polymerS4 and 5 in a detergent composition SKS-6 14 15 with a low anionic Surfactant content is illustrated in the Na disilicate 2.5 3.9 0.5 4.5 1.5 Mg silicate 1.O O.8 1.O. 10 O-6 following examples. The test conditions chosen for this were Sodium sulfate 2.O 2.5 15.2 2.0 1.5 5.5 3.4 15 as follows: Sodium bicarbonate 9.O 6.5 Apparatus: Launder-O-meter Sodium carbonate 120 13.6 1O.O 8.0 9.8 Soil-release polymer 0.4 0.5 Colored fabric: 1.0 g of cotton fabric colored with 0.8% Polyethylene 1.O O.S. O.8 1.O Direct Blue 71 terephthalate? Oxyethylene White fabric: 2.5 g of cotton fabric terephthalate Detergent composition in % (detergent A) Carboxymethyl- O.6 13 O-6 1.0 0.6 0.6 0.5 Cs oxo alcohol *7 EO 15.0 cellulose Zeolite A 50.0 Dequest (R) 2046 0.5 (phosphonate) Sodium carbonate 10.0 Citric acid 6.8 5.0 2.5 3.8 Sodium citrate 9.0 Lipase 1.O 25 Protease 1.O 1.O 0.5 O6 Sulfated C fatty alcohol ethoxylate *3 EO 1.0 Cellulase O6 Commercial oleylsarcosinate in the acid form 2.0 Water to tO tO tO tO tO tO 1OO 100 100 1 OO 100 1 OO 100 Polymer of 70% acrylic acid and 30% maleic acid, Na salt, molecular weight 70000 4.0 Abbreviations: carboxymethylcellulose 0.5 TAED Tetraacetylethylenediamine SKS-6 Sheet silicate Nasalt (manufactured by Hoechst) Water to 100 EO Ethylene oxide Washing: AA/MA (70000) = Acrylic acid/maleic acid copolymer in the ratio 70:30 by weight, molecular weight Mw = 70,000 Detergent: detergent A AA/MA/VAc (40000) = Acrylic acid/maleic acid/vinyl acetate terpolymer 35 Amount: 5.0 g/l in the molar ratio 4.0:10:50 with molecular weight Mw = 40,000 Soil-release polymer commercial graft copolymer of vinyl acetate on poly Amount of liquor: 250 g ethylene glycol Water temperature: 60° C. Water hardness: 14.50 German hardness Table 4 indicates the composition of color detergents Ca/Mg ratio: 4.0:1.0 which contain the cationic condensates to be used according 40 to the invention. Washing time: 30 min TABLE 4 TABLE 3 Results of tests on color transfer inhibition and reduction in VII VIII IX X XI XII 45 the loss of color with Direct Blue 71 on cotton Polymer 1 1.0 1.0 0.5 1.O O.S. O.3 Amount in Loss of Color transfer AA/MA (70000) 6.O 4.O 3.5 2.O 2.5 8.5 detergent A color inhibition Na lauryl sulfate 1.O Linear Na alkylbenzene- 0.5 Polymer % % % Sulfonate Ex. Sulfated fatty alcohol 1.5 50 ethoxylate 4 Polymer 4 1. 16.2 99.6 Commercial oleylsarcosinate 2.O 5 Polymer 5 1. 12.7 98.2 in the acid form Comparative Example Soap 2.5 1.O 15 1.5 C/Cs oxo alcohol.3 EO 1O.O 1.5 4 Ole 9.6 O C/Cs oxo alcohol 7 EO 6.7 16.O 13.5 14.O 7.5 55 5 VI/VP1) 1. 20.9 99.3 C/Cs oxo alcohol 10 EO 6.3 copolymer Lauryl alcohol 13 EO 2.0 9.O Zeolite A 28 55 35 37 18 VI/VP = 1-Vinylimidazole/1-vinylpyrrolidone Zeolite P 36 SKS-6 12 Na disilicate 4.5 O.S 4.5 The results with polymers 4 and 5 to be used according to Mg silicate 1.O 1.O 1.O 1.O 60 the invention show that the polymers have, with detergent A Sodium sulfate 24 5.8 11.5 8.O 45 10.O with a low anionic Surfactant content, a very good color Sodium bicarbonate 6.5 6.5 transfer-inhibiting effect and, furthermore, have distinctly Sodium carbonate 12.O 6.0 1O.O. 9.0 less of a color-removing effect than the non-quaternized Carboxymethylcellulose 0.6 0.5 0.6 1.O. O.6 0.6 Sokalan (E) HP 22 1.O 0.5 VI/VP copolymer with a molecular weight of 10000. Polyethylene terephthalate/ 1.O O.S 0.5 65 We claim: Oxyethylene terephthalate 1. A process for inhibiting dye removal and color transfer from colored textiles during the aftertreatment of and/or 6,165,969 11 12 Washing process for these textiles, which comprises adding to laundry aftertreatment aids and/or to detergents a polymer (II) which consists of: R1 (a) 5 to 100 mol % of quaternized 1-vinylimidazole units represented by formula (I): HC=CH-N SN-R xe, (I)

1O wherein R is C-C-alkyl, Cs-Co-cycloalkyl or benzyl, R,R,R are identical or different and are H, CH, and CH5, and 15 X is an anion, wherein (b) 0 to 75 mol % of 1-vinylpyrrollidone, R is C-C-alkyl, Cs-Co-cycloalkyl or benzyl, Vinyloxazolidone, N-Vinylcaprolactam, N-Vinylamides R", R, R are identical or different and are H, CH, or of C-C-carboxylic acids, Vinyl esters of C1-Co CH5, and carboxylic acids, acrylic esters and methacrylic esters X is an anion, of C1-Co-alcohols or mixtures of Said monomers, and (b) 0 to 75 mol % of 1-vinylpyrrollidone, (c) 0 to 30 mol% of other monoethylenically unsaturated Vinyloxazolidone, N-Vinylcaprolactam, N-Vinylamides monomerS Selected from the group consisting of acrylic of C-C-carboxylic acids, Vinyl esters of C1-Co acid, methacrylic acid, fumaric acid, maleic acid, 25 maleic anhydride, itaconic acid, itaconic anhydride, carboxylic, acids, acrylic esters and methacrylic esters hydroxyethyl acrylate, hydroxyethyl methacrylate, of C1-Co-alcohols or mixtures of Said monomers as hydroxypropyl acrylate, hydroxypropyl methacrylate, copolymerized units, and hydroxybutyl acrylate, hydroxybutyl methacrylate, (c) 0 to 30 mol% of other monoethylenically unsaturated phenoxyethyl acrylate, and methoxyethyl acrylate, monomerS Selected from the group consisting of acrylic or by quaternization of polymers which consist of acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (a) 5 to 100 mol%. 1-vinylimidazole units represented by hydroxyethyl acrylate, hydroxyethyl methacrylate, formula (III): hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, (III) phenoxyethyl acrylate, and methoxyethyl acrylate as 35 R1 copolymerized units. 2. A process as claimed in claim 1, wherein the polymer consists of at least 10 mol % of quaternized 1, 1-vinylimidazole units represented by formula I and have molecular weights of from 5000 to 1 million. 40 3. A process as claimed in claim 1, wherein the polymer consists of from 20 to 100 mol % of quaternized 1-vinylimidazole units represented by formula I and have wherein R, R, R are identical or different and are H, molecular weights of from 10000 to 500000. CH and CH5, with C-C-alkylating agents, and 4. A process as claimed in claim 1, wherein the polymer 45 (b) 0 to 75 mol % of 1-vinylpyrrollidone, consists of units represented by formula I wherein R', R, Vinyloxazolidone, N-Vinylcaprolactam, N-Vinylamides R=H and R is methyl, ethyl or benzyl. of C-C-carboxylic acids, Vinyl esters of C1-Co 5. A process as claimed in claim 1, wherein the polymer carboxylic acids, acrylic esters and methacrylic esters consists of quaternized vinylimidazole units represented by of C1-Co-alcohols or mixtures of Said monomers, and formula I in amounts of from 0.05 to 2.5% by weight in 50 (c) 0 to 30 mol% of other monoethylenically unsaturated detergents which comprise less than 4% by weight of an monomerS Selected from the group consisting of acrylic anionic Surfactant. acid, methacrylic acid, fumaric acid, maleic acid, 6. A process as claimed in claim 1, wherein the polymer maleic anhydride, itaconic acid, itaconic anhydride, consists of quaternized vinylimidazole units represented by hydroxyethyl acrylate, hydroxyethyl methacrylate, formula I in detergents containing no anionic Surfactants. 55 hydroxypropyl acrylate, hydroxypropyl methacrylate, 7. A process as claimed in claim 1, wherein the polymer hydroxybutyl acrylate, hydroxybutyl methacrylate, consists of units of the formula I where R', R, R=H and R phenoxyethyl acrylate, and methoxyethyl acrylate as is C-C-alkyl or benzyl and X is an anion. copolymerized units. 8. A process as claimed in claim 1, wherein the polymer 10. A process as claimed in claim 1, wherein the polymer consists of units of the formula I where R', R, R-H and R 60 is a quaternized homopolymer of 1-vinyl imidazole. is C-C-alkyl or benzyl and X is an anion. 11. A process as claimed in claim 1, wherein the polymer 9. A process as claimed in claim 1, wherein the polymer is a quaternized copolymer of 1-vinylimidazole and is obtained by free-radical polymerization of 1-vinylpyrrolidone. (a) 5 to 100 mol % quaternary 1-vinylimidazoles repre sented by formula (II):