EP1236793B1 - Washing agent and laundry treatment agent comprising one or more dye transfer inhibiting dye fixatives - Google Patents

Abstract

Washing agents contain transfer-inhibiting dye fixing agents. Washing agents contain transfer-inhibiting dye fixing agents obtained by reaction of: (i) polyamines with cyanamides and amidosulfuric acid; (ii) cyanamides with aldehydes and ammonium salts; or (iii) amines with epichlorhydrin.

Description

Out US 6,008,316 Detergents are known which contain reaction products of polyamines and dicyandiamide as color transfer inhibiting substances, but these reaction products contain no ionic groups, for example by co-reaction of amidosulfuric acid.

The invention relates to detergents and laundry treatment compositions containing at least 0.1% dye-transfer inhibiting dye fixing agents, these dye fixing agents being obtained by reacting polyamines with cyanamides and amidosulfuric acid.

The term polyamines in this case comprises e.g. Diamines, triamines, tetraamines, etc. Examples of these are ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine and higher polyamines. Particularly preferred is diethylenetriamine.

The cyanamides may be cyanamide or dicyandiamide.

These color fixing agents are added to the detergents according to the invention to improve the wash fastness of textile dyes by reducing their bleeding.

At the same time, these color fixing agents also have the effect of inhibiting dye transfer by binding residual amounts of bleeding dye in the wash liquor in the case of very poor wash fastnesses of the dyed textiles, thus preventing deposition on washed-on white or other-colored fabric.

The detergent formulations in which the dye transfer inhibiting dye fixing agents described can be used are powder, granular, paste, gel or liquid. Examples of these are heavy duty detergents, mild detergents, color detergents, wool detergents, curtain detergents, modular detergents, washing tablets, bar soaps, detergent formulations packaged in water-soluble films and stain salts. Laundry treatment agents are e.g. Laundry starches and stiffeners as well as ironing aids.

In addition, the color transfer-inhibiting dye fixing agents mentioned can be used in laundry pre- or laundry after-treatment agents which can be used before or after the actual wash cycle and which are used exclusively for laundry care and laundry conditioning, but not for cleaning the laundry.

The detergents according to the invention contain at least 0.1%, preferably between 0.1 and 10% and particularly preferably 0.5 to 5% of the dye transfer inhibiting dye fixing agents described.

Formulations used as laundry pre- and / or post-whitening agents may contain between 1 and 99% of the color fixing agents. Depending on their intended use, the formulations should be adapted in their composition to the type of textiles to be washed.

They contain conventional detergents and cleaners ingredients, as they correspond to the prior art. Representative examples of such detergent ingredients will be described below.

The total concentration of surfactants in the final detergent formulation may be from 1 to 99%, and preferably from 5 to 80% (all wt%). The surfactants used may be anionic, nonionic, amphoteric and cationic. It is also possible to use mixtures of the surfactants mentioned. Preferred detergent formulations contain anionic and / or nonionic surfactants and mixtures thereof with other surfactants.

Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof. Suitable cations here are alkali metals, e.g. Sodium or potassium or alkaline earth metals, e.g. Calcium or magnesium and ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures thereof. The following types of anionic surfactants are particularly preferred: alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates, alkanesulfonates and soaps, as described below.

Alkyl ester sulfonates include linear esters of C ₈ -C ₂₀ carboxylic acids (ie, fatty acids) which are sulfonated by means of gaseous SO ₃ as described in U.S. Pat. The Journal of the American Oil Chemists Society "52 (1975), pp. 323-329 is described. Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but may also be synthetic in nature.

worin R¹ einen C₈-C₂₀-Kohlenwasserstoflrest, bevorzugt Alkyl, und R einen C₁-C₆ Kohlenwasserstoffrest, bevorzugt Alkyl, darstellt. M steht für ein Kation, das ein wasserlösliches Salz mit dem Alkylestersulfonat bildet. Geeignete Kationen sind Natrium, Kalium, Lithium oder Ammoniumkationen, wie Monoethanolamin, Diethanolamin und Triethanolamin. Bevorzugt bedeuten R¹ C₁₀-C₁₆-Alkyl und R Methyl, Ethyl oder Isopropyl. Besonders bevorzugt sind Methylestersulfonate, in denen R¹ C₁₀-C₁₆-Alkyl bedeutet.Preferred alkyl ester sulfonates, especially for detergent applications, are compounds of the formula

wherein R ^{1 is} a C ₈ -C ₂₀ hydrocarbon radical, preferably alkyl, and R is a C ₁ -C ₆ hydrocarbon radical, preferably alkyl. M stands for a cation, the one forming water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R ^{1 is} C ₁₀ -C ₁₆ -alkyl and R is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates in which R ^{1 is} C ₁₀ -C ₁₆ alkyl.

Alkyl sulfates are here water-soluble salts or acids of the formula ROSO ₃ M, wherein R is a C ₁₀ -C ₂₄ hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with C ₁₀ -C ₂₀ -Alkgkomponente, more preferably a C ₁₂ -C ₁₈ alkyl or Hydroxyalkyl radical. M is hydrogen or a cation, for example an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium, eg methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine , Diethylamine, triethylamine and mixtures thereof. Alkyl chains with C ₁₂ -C ₁₆ are preferred for low wash temperatures (eg below about 50 ° C) and alkyl chains with C ₁₆ -C ₁₈ for higher wash temperatures (eg above about 50 ° C).

Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, where R is an unsubstituted C ₁₀ -C ₂₄ -alkyl or hydroxyalkyl radical, preferably a C ₁₂ -C ₂₀ -alkyl or hydroxyalkyl radical, more preferably C ₁₂ -C _{18 represents} alkyl or hydroxyalkyl. A is an ethoxy or propoxy moiety, m is a number greater than 0, preferably between about 0.5 and about 6, more preferably between about 0.5 and about 3 and M is a hydrogen atom or a cation such as Sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples include C ₁₂ - to C ₁₈ called fatty alcohol ether sulfates wherein the content of EO is 1, 2, 2.5, 3, or 4 moles per mole of fatty alcohol ether sulfate, and in which M is sodium or potassium.

In secondary alkanesulfonates, the alkyl group may be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group. The sulfo group can be at any position of the C chain, with the primary methyl groups at the beginning and end of the chain having no sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably about 10 to about 20 carbon atoms, and more preferably about 13 to 17 carbon atoms. The cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium, and mixtures thereof. Sodium as a cation is preferred.

In addition to secondary alkanesulfonates, it is also possible to use primary alkanesulfonates in the detergents according to the invention.

The preferred alkyl chains and cations are the same as those of the secondary alkanesulfonates.
The preparation of primary alkanesulfonic acid, from which the corresponding surfactant sulfonates are obtained, is for example in EP 854 136-A1 described.

Other suitable anionic surfactants are alkenyl or alkylbenzenesulfonates. The alkenyl or alkyl group may be branched or linear and optionally substituted with a hydroxyl group. The preferred alkylbenzenesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation being sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof.
For mild surfactant systems, magnesium is preferred as a cation, whereas sodium is preferred for standard washing applications. The same applies to alkenylbenzenesulfonates.

The term anionic surfactants also includes olefin sulfonates obtained by sulfonation of C ₈ -C ₂₄ , preferably C ₁₄ -C _16, α-olefins with sulfur trioxide and subsequent neutralization. Due to the manufacturing process, these Olefinsulfonate smaller amounts of Hydroxyalkansulfonaten and Alkandisulfonaten included. Specific mixtures of α-olefin sulfonates are in US 3,332,880 described.

Other preferred anionic surfactants are carboxylates, e.g. Fatty acid soaps and comparable surfactants. The soaps may be saturated or unsaturated and may contain various substituents such as hydroxyl groups or α-sulfonate groups. Preferred are linear saturated or unsaturated hydrocarbon radicals as hydrophobic moiety with about 6 to about 30, preferably about 10 to about 18 carbon atoms.

Also suitable as anionic surfactants are salts of acylaminocarboxylic acids which are acylsarcosinates formed by reaction of fatty acid chlorides with sodium sarcosinate in an alkaline medium; Fatty acid-protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; Salts of alkylsulfamidocarboxylic acids; Salts of alkyl and alkylaryl ether carboxylic acids; sulfonated polycarboxylic acids prepared by sulfonation of the pyrolysis products of alkaline earth metal citrates, as described, for example, in US Pat GB 1,082,179 ; Alkyl and alkenyl glycerol sulfates such as oleyl glycerol sulfates, alkyl phenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N-acyl taurides, alkyl succinates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxycarboxylates such as those of the formula RO (CH ₂ CH ₂ ) _k CH ₂ COO ^- M ⁺ , wherein RC ₈ bis C ₂₂ alkyl, k is a number from 0 to 10 and M is a cation.
Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch).

Suitable nonionic surfactants are, for example, the following compounds: condensation products of aliphatic alcohols with from about 1 to about 25 mol of ethylene oxide.

The alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of C ₁₀ - to C ₂₀ -alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol. The alkyl chain can be saturated or unsaturated. The alcohol ethoxylates may have a narrow range ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("Broad Range Ethoxylates"). Examples of commercially available nonionic surfactants of this type are Tergitol ^® 15-S-9 (the condensation product of a linear secondary C ₁₁ -C ₁₅ alcohol with 9 moles ethylene oxide), Tergitol ^® 24-L-NMW (the condensation product of a linear primary C ₁₂ -C _14- alcohol with 6 moles of ethylene oxide with a narrow molecular weight distribution). Also included in this product class are Genapol ^® brands from Clariant GmbH.

Condensation products of ethylene oxide having a hydrophobic base formed by condensation of propylene oxide with propylene glycol.

The hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800. The addition of ethylene oxide to this hydrophobic part leads to an improvement in water solubility. The product is liquid up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation with up to about 40 moles of ethylene oxide. Commercially available examples of this product class are the Pluronic ^® brands from BASF and the ^® Genapol PF brands from Clariant GmbH.

Condensation products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.

The hydrophobic moiety of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of about 2500 to 3000. Ethylene oxide is added to this hydrophobic unit to a content of about 40 to about 80 wt .-% polyoxyethylene and a molecular weight of about 5000 to 11000. Commercially available Examples of this class of compounds are the ^® Tetronic brands of BASF and the ^® Genapol PN brands of Clariant GmbH.

Semipolar nonionic surfactants

R ist hierbei eine Alkyl-, Hydroxyalkyl- oder Alkylphenolgruppe mit einer Kettenlänge von ca. 8 bis ca. 22 Kohlenstoffatomen, R² ist eine Alkylen- oder Hydroxyalkylengruppe mit ca. 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon, jeder Rest R¹ ist eine Alkyl- oder Hydroxyalkylgruppe mit ca. 1 bis ca. 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit ca. 1 bis ca. 3 Ethylenoxideinheiten und x bedeutet eine Zahl von 0 bis etwa 10. Die R¹-Gruppen können miteinander über ein Sauerstoff- oder Stickstoffatom verbunden sein und somit einen Ring bilden. Aminoxide dieser Art sind besonders C₁₀-C₁₈-Alkyldimethylaminoxide und C₈-C₁₂-Alkoxiethyl-Dihydroxyethylaminoxide.This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides, and water-soluble sulfoxides each having an alkyl group of about 10 to about 18 carbon atoms. Semi-polar nonionic surfactants are also amine oxides of the formula

R here is an alkyl, hydroxyalkyl or alkylphenol group having a chain length of about 8 to about 22 carbon atoms, R ² is an alkylene or hydroxyalkylene group having about 2 to 3 carbon atoms or mixtures thereof, each R ¹ is an alkyl or hydroxyalkyl group having from about 1 to about 3 carbon atoms or a polyethylene oxide group having from about 1 to about 3 ethylene oxide units, and x represents a number from 0 to about 10. The R ¹ groups may be linked together via an oxygen or nitrogen atom and thus form a ring. Amine oxides of this type are especially C ₁₀ -C ₁₈ -alkyldimethylamine oxides and C ₈ -C ₁₂ -alkoxyethyl-dihydroxyethylamine oxides.

fatty acid amides Fatty acid amides have the formula

worin R eine Alkylgruppe mit ca. 7 bis ca. 21, bevorzugt ca. 9 bis ca. 17 Kohlenstoffatomen ist und jeder Rest R¹ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Hydroxyalkyl oder (C₂H₄O)_xH bedeutet, wobei x von ca. 1 bis ca. 3 variiert. Bevorzugt sind C₈-C₂₀-Amide, -monoethanolamide, -diethanolamide und -isopropanolamide.

wherein R is an alkyl group having from about 7 to about 21, preferably from about 9 to about 17 carbon atoms, and each R ^{1 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl or (C ₂ H ₄ O) _x H, where x varies from about 1 to about 3. C ₈ -C ₂₀ -amides, -monoethanolamides, -diethanolamides and -isopropanolamides are preferred.

Further suitable nonionic surfactants are alkyl and Alkenyloligoglycoside and Fettsäurepolyglykolester or Fettaminpolyglykolester having in each case 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, mixed ethers or Mischformale, Alkyloligoglycoside, Alkenyloligoglycoside, fatty acid N-alkylglucamide, phosphine oxides, dialkyl sulfoxides and protein hydrolysates.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.

These compounds include the condensation products of alkylphenols having a C ₆ to C ₂₀ alkyl group, which may be either linear or branched, with alkene oxides. Preference is given to compounds having about 5 to 25 mol of alkene oxide per mole of alkylphenol. Commercially available surfactants of this type include Igepal ^® CO-630, Triton ^® X-45, X-114, X-100 and X102, and the Arkopal N ^® brands from Clariant GmbH. These surfactants are referred to as Alkylphenolalkoxilate, eg Alkylphenolethoxilate.

worin R¹ C₈-C₂₂-Alkyl- oder -Alkenyl, R² Wasserstoff oder CH₂CO₂M, R³ CH₂CH₂OH oder CH₂CH₂OCH₂CH₂CO₂M, R⁴ Wasserstoff, CH₂CH₂OH oder CH₂CH₂COOM, Z CO₂M oder CH₂CO₂M, n 2 oder 3, bevorzugt 2, M Wasserstoff oder ein Kation wie Alkalimetall, Erdalkalimetall, Ammonium oder Alkanolammonium bedeutet.Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amide betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium compounds of the formula

wherein R ^{1 is} C ₈ -C ₂₂ alkyl or alkenyl, R ^{2 is} hydrogen or CH ₂ CO ₂ M, R ^{3 is} CH ₂ CH ₂ OH or CH ₂ CH ₂ OCH ₂ CH ₂ CO ₂ M, R ^{4 is} hydrogen, CH ₂ CH ₂ OH or CH ₂ CH ₂ COOM, Z CO ₂ M or CH ₂ CO ₂ M, n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonium or alkanolammonium.

Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples of these are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate) and cocoamphoacetate.

Further preferred amphoteric surfactants are alkyldimethylbetaines and alkyldipolyethoxybetaines having an alkyl group of about 8 to about 22 carbon atoms, which may be linear or branched, preferably having 8 to 18 carbon atoms and more preferably having about 12 to about 18 carbon atoms. These compounds are marketed, for example, by Clariant GmbH under the trade name ^® Genagen LAB.

Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R ¹ N (CH ₃ ) ₃ ^⊕ X ^⊖ , R ¹ R ² N (CH ₃ ) ₂ ^⊕ X ^⊖ , R ¹ R ² R ³ N (CH ₃ ) ^⊕ X ^⊖ or R ¹ R ² R ³ R ⁴ N ^⊕ X ^⊖ . The radicals R ¹ , R ² , R ³ and R ⁴ may preferably independently of one another unsubstituted alkyl having a chain length between 8 and 24 carbon atoms, in particular between 10 and 18 carbon atoms, hydroxyalkyl having from about 1 to about 4 C Atoms, phenyl, C ₂ - to C ₁₈ -alkenyl, C ₇ - to C ₂₄ -aralkyl, (C ₂ H ₄ O) _x H, where x is from about 1 to about 3, one or more ester groups-containing alkyl radicals or cyclic quaternary ammonium salts. X is a suitable anion.

Other detergent ingredients that may be included in the present invention include inorganic and / or organic builders to reduce the degree of hardness of the water.

These builders can be included at levels of from about 5% to about 80% by weight in the detergent compositions. Inorganic builders include, for example, alkali, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.

Examples of silicate builders are the alkali metal silicates, in particular those having a SiO ₂ : Na ₂ O ratio of between 1.6: 1 and 3.2: 1, and phyllosilicates, for example sodium layer silicates, as described in US Pat US 4,664,839 , available from Clariant GmbH under the trademark ^SKS® . SKS- ^6® is a particularly preferred phyllosilicate builder.

Aluminosilicate builders are particularly preferred for the present invention. These are, in particular, zeolites of the formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] .xH ₂ O, where z and y are integers of at least 6, the ratio of z to y is between 1.0 is about 0.5, and x is an integer of about 15 to about 264.

Suitable aluminosilicate-based ion exchangers are commercially available. These aluminosilicates may be of crystalline or amorphous structure, and may be naturally occurring or synthetically produced. Methods for the preparation of aluminosilicate-based ion exchangers are described in US Pat US 3,985,669 and US 4,605,509 , Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the designation zeolite A, zeolite P (B) (including those described in US Pat EP-A-0 384 070 aluminosilicate having a particle diameter between 0.1 and 10 μm.

Suitable organic builders (co-builders) include polycarboxylic compounds such as, for example, ether polycarboxylates and oxydisuccinates, such as, for example, in US Pat US 3,128,287 and US 3,635,830 described. Likewise on "TMS / TDS" equipment from US 4,663,071 to get expelled.

Other suitable builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1 , 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.
Important organic builders are also polycarboxylates based on acrylic acid and maleic acid, such as the Sokalan CP brands from BASF.

Citrate-based builders, e.g. Citric acid and its soluble salts, in particular the sodium salt, are preferred polycarboxylic acid builders which can also be used in granulated formulations, in particular together with zeolites and / or sheet silicates.

Other suitable builders are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Pat US 4,566,984 are disclosed.

If phosphorus based builders can be used, and especially if hand soap bars are to be formulated by hand, various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate can be used. Also, phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates such as those described in U.S. Pat US 3,159,581 . US 3,213,030 . US 3,422,021 . US 3,400,148 and US 3,422,137 are disclosed.

The detergents and laundry treatment compositions of the present invention may contain conventional adjuvants or other materials which enhance detergency, serve to treat or care for the fabric being washed, or alter the performance properties of the detergent composition.

Suitable adjuvants include those in US 3,936,537 substances, for example enzymes, in particular proteases, lipases, cellulases and amylases, mannanases, enzyme stabilizers, foam boosters, foam brakes, Anti-tarnish and / or corrosion inhibitors, suspending agents, dyes, fillers, optical brighteners, disinfectants, alkalis, hydrotropes, antioxidants, perfumes, solvents, solubilizers, anti-redeposition agents, dispersants, processing aids, plasticizers, antistatic agents and soil release polymers such as the TexCare brands / Fa. Clariant, the Repel-O-Tex brands / Fa. Rhodia or Sokalan SR-100 / Fa. BASF.

The detergents and cleaners according to the invention containing dye-transfer-inhibiting dye-fixing agents may additionally contain the known and commercially available dye transfer inhibitors.
Examples of these color transfer inhibitors are polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), eg Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, eg Sokalan HP 50 / Fa. BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.
A significant disadvantage of the hitherto commercially available dye transfer inhibitors is that they not only bind the dye removed from the textiles and contained in the wash liquor, but additionally can also remove dyes from the textiles and thus promote a fading of the washed dye fabrics.
By combining with the dye transfer inhibiting color fixing agents not only the color transfer inhibiting effect of the known dye transfer inhibitors can be improved, but it can additionally be counteracted by the fading of the color fabrics promoted by these products.

The detergent compositions of the present invention may optionally contain one or more conventional bleaching agents, as well as bleach activators, bleach catalysts and suitable stabilizers. In general, it must be ensured that the bleaching agents used are compatible with the detergent ingredients. Conventional test methods, such as the determination of the bleach activity of the final formulated detergent as a function of storage time, can be used for this purpose.

The peroxyacid may be either a free peroxyacid or a combination of an inorganic persalt, for example, sodium perborate or sodium percarbonate and an organic peroxyacid precursor, which is converted to a peroxyacid when the combination of the persalt and the peroxyacid precursor is dissolved in water. The organic peroxyacid precursors are often referred to in the art as bleach activators. Examples of suitable organic peroxyacids are disclosed in US 4,374,035 . US 4,681,592 . US 4,634,551 . US 4,686,063 . US 4,606,838 and US 4,671,891 ,

Examples of compositions which are suitable for bleaching laundry and which contain perborate bleaches and activators are described in US Pat US 4,412,934 . US 4,536,314 . US 4,681,695 and US 4,539,130 ,
Examples of peroxyacids preferred for use in this invention include peroxydodecanedioic acid (DPDA), nonylamide of peroxysuccinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) and decyldiperoxysuccinic acid (DDPSA).

Bleach systems based on a persalt such as perborates or pecarbonates with the bleach activator tetraacetylethylenediamine (TAED) are particularly preferably used in the detergents and laundry treatment compositions according to the invention.

It is known that many of the aforementioned bleaching agents, the purpose of which is the oxidative destruction of colored stains, also cause damage to the textile dyes of colored textiles.
By using the dye transfer inhibiting dye fixing agents, the harmful influence of the bleaching agents on the textile dyes can be reduced.

The described color fixing agents can also be used in commercial laundry conditioners for domestic use. These contain essentially plasticizing components, co-plasticizers, Emulsifiers, perfumes, dyes and electrolytes, and are adjusted to an acidic pH of below 7, preferably between 3 and 5, adjusted.

eingesetzt, worin

R¹ =

C₈-C₂₄ n- bzw. iso-Alkyl, bevorzugt C₁₀-C₁₈ n-Alkyl

R² =

C₁-C₄-Alkyl, bevorzugt Methyl

R³ =

R¹ oder R²

R⁴ =

R² oder Hydroxyethyl oder Hydroxypropyl oder deren Oligomere

X^- =

Bromid, Chlorid, Jodid, Methosulfat, Acetat, Propionat, Lactat sind.

As softening components are quaternary ammonium salts of the type

used in which

R ¹ =

C ₈ -C ₂₄ n- or iso-alkyl, preferably C ₁₀ -C ₁₈ n-alkyl

R ² =

C ₁ -C ₄ -alkyl, preferably methyl

R ³ =

R ¹ or R ²

R ⁴ =

R ² or hydroxyethyl or hydroxypropyl or their oligomers

X ^- =

Bromide, chloride, iodide, methosulfate, acetate, propionate, lactate.

Examples of these are distearyldimethylammonium chloride, ditallowalkyldimethylammonium chloride, ditallowalkylmethylhydroxypropylammonium chloride, cetyltrimethylammonium chloride or the corresponding benzyl derivatives such as dodecyldimethylbenzylammonium chloride. Cyclic quaternary ammonium salts such as alkyl morpholine derivatives can also be used.

worin

R =

C₈-C₂₄ n- bzw. iso-Alkyl, bevorzugt C₁₀-C₁₈ n-Alkyl

X =

Bromid, Chlorid, Jodid, Methosulfat

A =

-NH-CO-, -CO-NH-, -O-CO-, -CO-O-

ist.In addition, besides the quaternary ammonium compounds, imidazolinium compounds (1) and imidazoline derivatives (2) can be used.

wherein

R =

C ₈ -C ₂₄ n- or iso-alkyl, preferably C ₁₀ -C ₁₈ n-alkyl

X =

Bromide, chloride, iodide, methosulfate

A =

-NH-CO-, -CO-NH-, -O-CO-, -CO-O-

is.

mit

R¹ =

C₁-C₃ Hydroxyalkyl, bevorzugt Hydroxyethyl und

R², R³ =

R¹ oder C₁-C₃ Alkyl, bevorzugt Methyl.

A particularly preferred class of compounds are the so-called ester quats. These are reaction products of alkanolamines and fatty acids, which are then quaternized with conventional alkylating or hydroxyalkylating agents.
Preferred alkanolamines are compounds according to the formula

With

R ¹ =

C ₁ -C ₃ hydroxyalkyl, preferably hydroxyethyl and

R ² , R ³ =

R ¹ or C ₁ -C ₃ alkyl, preferably methyl.

Particularly preferred are triethanolamine and methyldiethanolamine.

Further particularly preferred starting materials for esterquats are aminoglycerol derivatives, such as, for example, dimethylaminopropanediol.

Alkylating or hydroxyalkylating agents are alkyl halides, preferably methyl chloride, dimethyl sulfate, ethylene oxide and propylene oxide.

wobei R-C-O abgeleitet ist von C₈-C₂₄-Fettsäuren, die gesättigt oder ungesättigt sein können. Beispiele hierfür sind Capronsäure, Caprylsäure, hydrierte oder nicht oder nur teilweise hydrierte Talgfettsäuren, Stearinsäure, Ölsäure, Linolensäure, Behensäure, Palminstearinsäure, Myristinsäure und Elaidinsäure. n liegt im Bereich von 0 bis 10, vorzugsweise 0 bis 3, besonders bevorzugt 0 bis 1.Examples of esterquats are compounds of the formulas:

wherein RCO is derived from C ₈ -C ₂₄ fatty acids, which may be saturated or unsaturated. Examples of these are caproic acid, caprylic acid, hydrogenated or not or only partially hydrogenated tallow fatty acids, stearic acid, oleic acid, linolenic acid, behenic acid, palminstearic acid, myristic acid and elaidic acid. n is in the range of 0 to 10, preferably 0 to 3, particularly preferably 0 to 1.

worin

R¹ und R²

unabhängig voneinander C₈-C₂₄ n- bzw. iso-Alkyl, bevorzugt C₁₀-C₁₈ n-Alkyl,

A

-CO-NH- oder -NH-CO-,

n

1 - 3, bevorzugt 2,

m

1 - 5, bevorzugt 2 - 4

bedeuten.Further preferred fabric softener raw materials with which the color fixing agents can be combined are, for example, amido-amines Dialkyltriamines and long-chain fatty acids, and their oxethylates or quaternized variants. These compounds have the following structure:

wherein

R ¹ and R ²

independently of one another C ₈ -C ₂₄ n- or iso-alkyl, preferably C ₁₀ -C ₁₈ n-alkyl,

A

-CO-NH- or -NH-CO-,

n

1-3, preferably 2,

m

1-5, preferably 2-4

mean.

By quaternization of the tertiary amino group may additionally be a radical R ³ , which may be C ₁ -C ₄ alkyl, preferably methyl, and a counterion X, which may be chloride, bromide, iodide or methyl sulfate, are introduced. Amidoaminooxethylates or their quaternized secondary products are available under the trade names ^® Varisoft 510, ^® Varisoft 512, ^® Rewopal V 3340 and ^® Rewoquat W 222 LM.

The preferred use levels of the color fixing agents in the fabric softener formulations are the same as those called for detergent formulations.

Examples

Examples of the color transfer-inhibiting dye fixing agents used in the detergents according to the invention are:

Example 1 Reaction product of diethylenetriamine with dicyandiamide and amidosulfuric acid.

The dye transfer-inhibiting dye fixing agents were tested for their color-retaining effect in combination with standard detergents on various dye fabrics. At the same time, the test was for a color transfer inhibiting effect.

For this purpose, to a wash liquor containing 6 g / l of a phosphate-free or a phosphate-containing test washing powder, without bleach additive (composition see Tables 1 and 3) and with a bleach additive (composition see Tables 2 and 4), respectively 300 ppm of the color fixative and colored Cotton fabric washed together with white cotton fabric.
Further, a washing test was carried out with a liquid detergent.

The fabrics were then rinsed with clear water, dried and the dL, da, db values were determined to give the color differences delta E. For comparison, the fabrics were washed with the test detergents without the addition of dye fixatives. The washing conditions are given in Table 3. A total of five wash cycles were performed.

The values obtained on the white fabric after the first wash serve to quantify the dye transfer inhibiting effect.
The values measured on the colored fabric quantify the obtained color retention. To compare the color-retaining effect of the color fixing agents, the average dE value obtained on five different color fabrics was calculated. Table 1: Phosphate-free standard test washing powder IEC-A. Linear alkyl benzene sulfonate (C _average = 11.5) 11.0% C _12-18 -alcohol * EO ₇ 5.90% Soap (65% C _12-18 , 35% C _20-22 ) 4.10% Zeolite A 36.80% sodium 13.40% Na-salt of an acrylic and maleic acid copolymer (Sokalan CP5 ^®) 5.90% Sodium silicate (SiO ₂ : NaO ₂ = 3.32: 1) 3.80% carboxymethylcellulose 1.50% Phosphonate ((Dequest 2066 ^®) 3.50% stilbene 0.30% Foam inhibitor (Dow Corning ^® DC2-4248S) 5.00% sodium sulphate 8.40% Protease (Savinase ^® 8.0) 0.40% Linear alkyl benzene sulfonate (C _average = 11.5) 8.80% C _12-18 -alcohol * EO ₇ 4.72% Soap (65% C _12-18 , 35% C _20-22 ) 3.28% Zeolite A 29.44% sodium 10.72% Na-salt of an acrylic and maleic acid copolymer (Sokalan CP5 ^®) 4.72% Sodium silicate (SiO ₂ : NaO ₂ = 3.32: 1) 3.04% carboxymethylcellulose 1.20% Phosphonate ((Dequest 2066 ^®) 2.80% stilbene 0.24% Foam inhibitor (Dow Corning ^® DC2-4248S). 4.00% sodium sulphate 6.72% Protease (Savinase ^® 8.0) 0.32% TAED (Peractive P ^®) 5.00% sodium 15.00% Linear alkyl benzene sulfonate (C _average = 11.5) 8.00% C _12-18 alcohol * EO ₁₄ 2.90% Soap (13-25% C _12-16 , 74-87% C _18-22 ) 3.50% sodium tripolyphosphate 43.70% Sodium silicate (SiO ₂ NaO ₂ = 3.3: 1) 7.50% magnesium silicate 1.90% carboxymethylcellulose 1.25% EDTA 0.25% stilbene 0.25% sodium sulphate 21.00% water 9.75% Linear alkyl benzene sulfonate (C _average = 11.5) 6.40% C _12-18 alcohol * EO ₁₄ 2.30% Soap (13-25% C _12-16 , 74-87% C _18-22 ) 2.80% sodium tripolyphosphate 35.00% Sodium silicate (SiO ₂ : NaO ₂ = 3.3: 1) 6.00% magnesium silicate 1.50% carboxymethylcellulose 1.00% EDTA 0.20% stilbene 0.20% sodium sulphate 16.80% water 7.80% TAED (Peractive P ^®) 5.00% sodium 15.00% C ₁₄ / C ₁₅ -Oxoalkohopolyglykolether with 8 EO (Genapol OA-080 ^®) 12.0% Fatty acid mixture (Prifac 7976 ^®) 14.0% Potassium hydroxide (85%) 2.6% triethanolamine 2.0% 1,2-propylene glycol 5.0% water 35.4% Tri-sodium citrate-2 hydrate 5.0% Secondary Alkansufonat (Hostapur SAS 60 ^®) 17.0% Phosphonate (Dequest 2066 ^®) 4.0% ethanol 3.0% Washing machine: Linitest Detergent concentration: 6 g / l Additive concentration: 300 ppm Water hardness: 15 ° dH Liquor ratio: 1:40 Washing temperature: 60 ° C Washing time: 30 min. Tables 7 to 11 show average delta E values obtained on red, blue, green, violet and black colored fabrics. The lower these values are, the better is the color retention achieved with the dye fixing agents in the detergents according to the invention. Detergent / additive ∅delta E-values Color differences to unwashed fabric after five washes IEC-A without additive 7.6 + Ex. 1 5.3 Detergent / additive ∅delta E-values Color differences to unwashed fabric after five washes IEC-A without additive 7.4 + Ex. 1 6.4 Detergent / additive ∅delta E-values Color differences to unwashed fabric after five washes IEC-B without additive 6.1 + Ex. 1 4.9 Detergent / additive ∅delta E-values Color differences to unwashed fabric after five washes IEC-B without additive 6.6 + Ex. 1 5.6 Detergent / additive ∅delta E-values Color differences to unwashed fabric after five washes Liquid detergent without additive 3.9 + Ex. 1 2.9

In the following examples, the color transfer inhibiting effect of the inventive detergents comprising the dye transfer inhibiting dye fixing agents on the white fabrics washed together with the dye fabrics is shown.
The lower the measured dE values of the white tissue, the lower its staining by the bled-out dye. Table 12: Color transfer inhibiting effect in combination with the phosphate-free test washing powder IEC-A on violet test fabric. Detergent / additive delta E values of the white test fabric washed together with violet color fabric after a wash IEC-A without additive 36.9 + Ex. 1 12.7 Detergent / additive delta E values of the white test fabric washed together with blue color fabric after a wash IEC-A without additive 32.6 + Ex. 1 8.7 Detergent / additive Delta E values of the white test fabric washed along with other color fabrics after a wash. black green red IEC-A without additive 35.1 22.0 37.5 + Ex. 1 15.1 10.9 28.3

Claims (7)

1. A laundry detergent comprising at least 0.1 % of dye-transfer-inhibiting dye fixatives, where these dye-transfer-inhibiting dye fixatives are obtained by reacting polyamines with cyanamides and amidosulfuric acid.
2. The laundry detergent as claimed in claim 1, comprising anionic surfactants, nonionic surfactants and inorganic or organic builders.
3. The laundry detergent as claimed in claim 1, comprising dye transfer inhibitors.
4. The laundry detergent as claimed in claim 1, comprising cationic surfactants.
5. The laundry detergent as claimed in claim 1, comprising soil release polymers.
6. The laundry detergent as claimed in claim 1, comprising cellulases.
7. The laundry detergent as claimed in claim 1, comprising bleaches.