WO2015024880A1

WO2015024880A1 - Detergents and cleaning products having improved performance

Info

Publication number: WO2015024880A1
Application number: PCT/EP2014/067498
Authority: WO
Inventors: Inga Kerstin Vockenroth; Eva-Maria Wikker; Sylvia Aust
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2013-08-23
Filing date: 2014-08-15
Publication date: 2015-02-26
Also published as: EP3036315B1; EP3036315A1; DE102013216776A1

Abstract

The present invention relates to the use of a combination of polyalkoxylated polyamine and polyacrylate in detergents or cleaning products to improve the washing or cleaning performance with respect to bleachable stains and with respect to protein-containing stains.

Description

Detergents and cleaning agents with improved performance

The present invention relates to the use of polyalkoxylated polyamines in detergents and cleaners to improve the washing or cleaning performance.

While the formulation of powdered, bleach-containing detergents and cleaners today no longer causes any problems, the formulation of stable liquid, bleach-containing detergents and cleaners is still a problem dar. Due to the usual lack of bleaching agents in liquid detergents and cleaning agents such Stains, which are usually removed in particular due to the bleach contained, often removed only inadequate. A similar problem also exists for bleach-free color detergents in which the bleaching agent is omitted in order to protect the dyes in the textile and to prevent their bleaching. In the absence of bleaching agents, it is aggravating that instead of removing the so-called bleachable soils which are normally at least partially removed by the peroxygen-based bleaching agent, on the contrary, intensification and / or worsening of the removability of the soiling is often brought about by the washing process may be due to initiated chemical reactions, which may for example in the polymerization of certain dyes contained in the stains.

Such problems occur especially with stains containing polymerizable substances. The polymerisable substances are, above all, polyphenolic dyes, preferably flavonoids, in particular from the class of anthocyanidins or anthocyanins. The stains may have been caused in particular by food products or beverages containing corresponding dyes. The stains can be, in particular, stains of fruits or vegetables or even red wine stains, which in particular contain polyphenolic dyes, especially those from the class of anthocyanidins or anthocyanins.

From the international patent application WO 2008/141858 A2, the washing power-enhancing effect of reaction products of certain cyclic carbonates or ureas with polyalkylene leniminen against oil and / or greasy stains known.

Alkoxylated polyamines and their use in detergents and cleaners are known, for example, from International Patent Applications WO 95/32272 A1 and WO 2006/108857 A1. From the patent application DE 10 201 1 082 917 A1, the suitability of polyalkoxylated polyamines in detergents or cleaners to improve the washing or cleaning performance against bleachable stains is known.

Surprisingly, it has been found that by using a combination of polyalkoxylated polyamine and polyacrylate, the washing or cleaning performance of the washing or cleaning agent on the one hand can be significantly improved once again with regard to bleachable soiling and, on the other hand, also an improvement with respect to proteolytic removable stains is achieved.

A first object of the present invention is therefore the use of a combination of polyalkoxylated polyamine and polyacrylate in detergents or cleaners to improve the washing or cleaning performance against bleachable soils and proteinaceous soils. The invention thus leads to an overall improved washing and cleaning result, if at the same time bleachable stains and protein-containing soils are to be removed in a washing or cleaning process.

The term "bleachable stains" is to be understood as meaning those which on exposure to oxidizing agents such as H 2 O 2, alkali metal perborate or alkali perborate show at least partial lightening, even if they are not always completely removed from the textile in conventional washing processes using a bleach-containing detergent Bleachable soils usually contain polymerizable substances, in particular polymerizable dyes, wherein the polymerizable dyes are preferably polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds Besides the removal of stains in the colors green , yellow, red or blue also comes from stains in intermediate colors, especially violet, purple, brown, purple or pink, and also from stains, which include a green, yellow, red, purple, purple, brown, pu purple, pink or blue tint without essentially being itself entirely of this color. The colors mentioned can also be light or dark in each case. These are preferably stains, in particular stains of grass, fruits or vegetables, in particular soiling by food products, such as spices, sauces, chutneys, curries, purees and jams, or drinks, such as coffee, tea, wines and Juices containing the corresponding green, yellow, red, purple, purple, brown, purple, pink and / or blue dyes.

The term "proteinaceous soils" is to be understood here as meaning those which, on exposure to protease, if appropriate in cooperation with lipase, amylase, mannanase and / or pectinase, show at least partial removal or whitening, even if they are washing process using an enzyme-containing detergent is not always completely removed from the textile.

The stains to be removed according to the invention can be caused in particular by cherry, morelle, grape, apple, pomegranate, aronia, plum, sea buckthorn, agai, kiwi, mango, grass, or berries, especially by red or black currants, elderberries, blackberries, raspberries , Blueberries, cranberries, cranberries, strawberries or blueberries, by coffee, tea, red cabbage, blood orange, eggplant, tomato, carrot, beetroot, spinach, paprika, red meat or potato, red onion, milk, egg, chocolate, cocoa, blood , Grass, salad dressing and mixtures of the above, such as those found in foods such as chocolate milk, jams or pudding.

The polyalkoxylated polyamine is a polymer having an N-atom containing backbone bearing polyalkoxy groups on the N atoms. The polyamine has primary amino functions at the ends and preferably both secondary and tertiary amino functions in the interior; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine. The ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1. The ratio of primary to tertiary amino groups in the polyamine is preferably in the range from 1: 0.2 to 1: 1, in particular in the range from 1: 0.5 to 1: 0.8. Preferably, the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 2000 g / mol. The average molecular weights indicated here and later, if appropriate, for other polymers are weight-average molar masses M _w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard. The N atoms in the polyamine are preferably separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1, 2-propylene groups, 1, 3-propylene groups, and mixtures thereof. The primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function must be alkoxy group-substituted. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 5 to 100, in particular 10 to 80. The alkoxy groups in the polyalkoxylated polyamine are preferably ethoxy, propoxy or butoxy groups or mixtures thereof, in particular ethoxy groups ; Particularly preferably according to the invention, the alkoxy groups consist exclusively of ethoxy groups. The polyalkoxylated polyamines are accessible by reacting the polyamines with the epoxides corresponding to the alkoxy groups. If desired, the terminal OH function can at least some of the polyalkoxy substituted by an alkyl ether function having 1 to 10, in particular 1 to 3 carbon atoms, be replaced.

The polyacrylate is an alkali metal or ammonium salt of a polymer obtainable by radical polymerization of acrylic acid and / or methacrylic acid. In this case, sodium, potassium, ammonium, mono-, di-, tri- and tetraalkylammonium salts and mixtures of these are preferred, wherein each of the N-atom of the ammonium unit alkyl groups also carry an OH substituent may, and preferably has 1 to 3 carbon atoms. The polyacrylate preferably has an average molar mass in the range from 1000 g / mol to 20 000 g / mol, in particular from 1500 g / mol to 15000 g / mol. If desired, in addition to the proportions derived from acrylic acid and / or methacrylic acid, the polymer may also contain minor proportions, in particular not more than 30 mol%, of moieties derived from other ethylenically unsaturated monomers. Such other monomers are preferably selected from maleic acid, fumaric acid, maleic anhydride, crotonic acid, itaconic acid, dimethylacrylic acid, vinylacetic acid, glutaconic acid, carboxyethylacrylic acid, acrylic acid esters and methacrylic acid esters of the formula

wherein R is H or Chta and R ^{2 is} a linear or branched Ci to C20, in particular C3 to Ci2 alkyl radical, alpha-olefins of the formula

wherein R is H or CH3 and R ^{2 is} a linear or branched alkyl radical of C1 to C20, preferably C3 to C12, and mixtures thereof; the said acid group-containing monomers may also be present in the form of their salts, in particular their alkali metal salts.

The use according to the invention of the combination of polyalkoxylated polyamine and polyacrylate is preferably carried out in detergents or cleaning agents by adding them in an amount of 0.1% by weight to 5% by weight, in particular in an amount of 1% by weight. In this case and in the following, the statements of "% by weight" in each case relate to the weight of the total washing or cleaning agent Weight ratio in the range of 3: 1 to 1: 3, in particular 2: 1 to 1: 2 before.

The washing or cleaning agent may be present in any of the prior art and / or any convenient dosage form. These include, for example, solid, powdered, liquid, gel or pasty dosage forms, optionally also consisting of several phases; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions.

The use according to the invention in this case takes place in a preferred embodiment in a washing and cleaning agent which contains no bleaching agents. By this is meant that the agent does not contain any bleaching agents in the narrower sense, ie hypochlorites, hydrogen peroxide or water. containing substance peroxide, contains; preferably, it also has no bleach activators and / or bleach catalysts.

The detergent is in a particularly preferred embodiment, a liquid laundry detergent.

In another particularly preferred embodiment, the detergent is a powdered or liquid color detergent, ie a textile detergent for colored textiles.

The detergents and cleaning agents may moreover comprise customary other constituents of detergents or cleaners, in particular laundry detergents, in particular selected from the group of builders, surfactants, polymers, disintegration aids, fragrances and perfume carriers.

The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, if there are no ecological prejudices against their use, also the phosphates.

The finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or zeolite P. Zeolite P is, for example, zeolite ^MAP® (commercial product from Crosfield). Also suitable, however, are zeolite X and mixtures of zeolite A, X and / or P. Commercially available and usable in the context of the present invention is, for example, also a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), ^■ the 1-n) K ₂ 0 ^■ ^■ AI2O3 (2 n by the formula Na ₂ 0 (- 2.5) S1O2 ^■ (3,5 - 5.5), H2O can be described. The zeolite can be used both as a builder in a granular compound and as a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, whereby usually both ways of incorporating the zeolite into the premix are used have mean particle size of less than 10 μΐη (volume distribution, measuring method: Coulter Counter) and preferably contain 18 wt .-% to 22 wt .-%, in particular 20 wt .-% to 22 wt .-% of bound water.

It may also be crystalline layered silicates of general formula NaMSix02x + i ^■ y H2O are used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, particularly preferred values for x 2, 3 or 4, and y for a number from 0 to 33, preferably from 0 to 20 stands. The crystalline layered silicates of the formula NaMSix02x + i ^■ y H2O, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂ 2045 ^■ x H2O, kenyaite), Na-SKS-2 _(Na2 Sii40 ₂ 9 ^■ x H2O, magadiite), Na-SKS-3 (Na ₂ Si ₈ 0i7 ^■ x H2O) or Na-SKS-4 (Na ₂ Si ₄ 09 ^■ x H2O, makatite).

Crystalline layer silicates of the formula NaMSix02x + i ^■ H2O y, in which x is 2 are preferred. In particular, both .beta.- and δ-sodium Na2Si20s ^■ y H2O and further especially Na-SKS-5 (a-Na ₂ Si ₂ 05), Na-SKS-7 _(.beta.-Na2 _Si2 05, natrosilite) Na-SKS-9 (NaHSi ₂ 0 ₅ ^■ H2O), Na-SKS-10 (NaHSi ₂ 0 ₅ 3 ^■ H2O, kanemite), Na-SKS-1 1 (t-Na ₂ Si ₂ 05) and Na-SKS -13 (NaHSi ₂ 0 ₅ ), but especially Na-SKS-6 (5-Na ₂ Si ₂ O) is preferred. Detergents or cleaning agents preferably contain a proportion by weight of the crystalline layered silicate of the formula

NaMSix0 ₂ x i ₊ y ^■ H2O of 0.1 wt .-% to 20 wt .-%, preferably 0.2 wt .-% to 15 wt .-% and especially 0.4 wt .-% to 10 wt .-%.

It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and secondary wash properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. The term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most cause one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle.

Alternatively or in combination with the abovementioned amorphous sodium silicates, it is possible to use X-ray amorphous silicates whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

These silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali silicates, are, if present, in detergents or cleaners in amounts of from 3% by weight to 60% by weight, preferably 8% by weight % to 50 wt .-% and in particular from 20 wt .-% to 40 wt .-%. It is also possible to use the generally known phosphates as builders, if such use is not to be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Alkalimetallphosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HP03) n and orthophosphoric acid H3PO4 in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance. Technically important phosphates are the pentasodium triphosphate, NasPsO-io (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K5P3O10 (potassium tripolyphosphate). Preference is also given to using the sodium potassium tripolyphosphates. If phosphates are used in detergents or cleaners, preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5% by weight. % to 80 wt%, preferably from 15 wt% to 75 wt%, and more preferably from 20 wt% to 70 wt%.

Further usable are alkali carriers. Examples of alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali metal silicates, alkali metal silicates mentioned, and mixtures of the abovementioned substances, preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesqui carbonate. Particularly preferred may be a builder system containing a mixture of tripolyphosphate and sodium carbonate. Because of their low chemical compatibility with the other ingredients of detergents or cleaners in comparison with other builders, the alkali metal hydroxides are usually only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt. -% and in particular below 2 wt .-%, used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides. Preference is given to the use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of 2% by weight to 50% by weight, preferably 5% by weight. % to 40 wt .-% and in particular from 7.5 wt .-% to 30 wt .-%.

Particularly suitable organic builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and also phosphonates. Useful are, for example, the polycarboxylic acid which can be used in the form of the free acid and / or its sodium salts. acids, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids and / or their salts.

Another class of substances with builder properties are the phosphonates. These are the salts of, in particular, hydroxyalkane or aminoalkanephosphonic acids. Among the hydroxyalkanephosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance. It is used in particular as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline. Particularly suitable aminoalkanephosphonic acids are ethylenediamine tetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs. They are used in particular in the form of the neutral-reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. Mixtures of the mentioned phosphonates can also be used as organic builders. In particular, the aminoalkanephosphonates also have a pronounced heavy metal binding capacity.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 g / mol to 500000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and also so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 g / mol to 30,000 g / mol. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. Ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably used in form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. If desired, suitable amounts are in particular in zeolite-containing and / or silicate-containing formulations at 3 wt .-% to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

Detergents and cleaners may contain nonionic, anionic, cationic and / or amphoteric surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Detergents or cleaning agents with particular preference contain nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably methyl-branched in the 2-position may be or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example Ci2-i4-alcohols with 3 EO or 4 EO, C9-n-alcohol with 7 EO, Ci3-is alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ₂ -i8 Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-i4-alcohol with 3 EO and Ci2-is-alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). Alternatively or in addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be used. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

R1

I

RC ON- [Z] in the R for an aliphatic acyl radical having 6 to 22 carbon atoms, R for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein Ci-4-alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In cleaning agents are nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO / AO / EO-nonionic surfactants, or the PO / AO / PO nonionic surfactants, especially the PO / EO / PO nonionic surfactants are particularly preferred. Such PO / EO / PO nonionic surfactants are characterized by good foam control.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Preferred surfactants of the sulfonate type are C9-i3-alkylbenzenesulfonates, olefinsulfonates, i. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from Ci2-i8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration. Also suitable are alkanesulfonates, which are obtained from C12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (tert-sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerines are to be understood as meaning the mono-, di- and triesters and mixtures thereof, such as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut oil fatty alcohol, tallow fatty alcohol, lauryl alcohol, ristyl, cetyl or stearyl alcohol or the Cio-C2o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From a washing-technical point of view, preference is given to the C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 1 -C -alkyl sulfates. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the sulfuric acid monoesters of straight-chain or branched C7-2i alcohols ethoxylated with from 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-n alcohols having on average 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 up to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1% by weight to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs -is-fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants. As cationic active substances, for example, cationic compounds of the following formulas can be used:

Ri

-N- (CH ₂ ) _n -T-R2

(CH ₂ ) _n -T-R2

wherein each R is independently selected from C 1-6 alkyl, alkenyl, or hydroxyalkyl groups; each R ^{2 group is} independently selected from Cs-28 alkyl or alkenyl groups; R ³ = R or (CH ₂₎ NTR ^2; R ⁴ = R or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer feel and reduced electrostatic charge (increased wearing comfort) .The active ingredients of these formulations are quaternary ammonium compounds having two hydrophobic radicals, such as the disteria. ryldimethylammonium chloride, which, however, due to its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.

Such "esterquats" with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents. Further suitable as a finish is dimethylolethyleneurea.

Proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, as well as their mixtures, are particularly suitable for the enzymes which may optionally be used in detergents or cleaners. These enzymes are in principle natural leap; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Washing or cleaning composition preferably contain enzymes in total amounts of 1 x 10 ^{^"6} wt .-% to 5 wt .-% on active protein. The protein concentration can be determined using known methods, for example the BCA method and the biuret method become.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of usable amylases are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae, as well as improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

It is possible to use lipases or cutinases because of their triglyceride-splitting activity. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed therefrom, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases and / or cutinases whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases

(= Pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases.

If desired, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect. Advantageously, it is additionally preferable to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or different redox potentials between the oxidizing enzymes and the soiling to ensure the flow of electrons (mediators).

The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers. Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating. Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

Preference is given to one or more enzymes and / or enzyme preparations, preferably protease preparations and / or amylase preparations, in amounts of 0.1 to 5% by weight, preferably 0.2% by weight. to 4.5 wt .-% and in particular from 0.4 wt .-% to 4 wt .-%, used.

As perfume oils or fragrances, individual perfume compounds, for example synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. Thus, most fragrances have molecular weights up to about 200 g / mol, while molar masses of 300 g / mol and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "body note" ) and "base note" (end note or dry out). Since the smell perception is based to a large extent also on the smell intensity, the top note consists of a Perfumes or fragrance not only from volatile compounds, while the base note for the most part consists of less volatile, ie adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

When choosing the colorant that may be present, it must be taken into account that the colorants can have a high storage stability and insensitivity to light as well as not too high an affinity for textile surfaces and, in particular, for synthetic fibers. At the same time it should also be considered that colorants may have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 wt% to 10 ^-3 wt% are typically selected. On the other hand, in the case of the pigment dyes which are particularly preferred but less readily water-soluble because of their brilliance, the suitable concentration of the colorant in detergents or cleaners is typically about 10 ^-3 % by weight to 10 ^-4 % by weight. Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.

In addition to the components mentioned so far, the detergents or cleaning agents may contain further ingredients which further improve the performance and / or aesthetic properties of these agents. Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Repellents and impregnating agents, swelling and sliding agents and UV absorbers.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCb in the detergents or cleaners is preferred. In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation.

As foam inhibitors, soaps, oils, fats, paraffins or silicone oils come into consideration, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. In the context of the present application preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R2SiO) x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1000 g / mol and 150000 g / mol and viscosities between 10 mPa.s and 1000000 mPa.s.

As soil repellents are known from the prior art polymers of phthalic acid and / or terephthalic acid and derivatives thereof, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate or anionic and / or nonionic modified derivatives of these, into consideration. Particularly preferred are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Optical brighteners may in particular be added to the detergents in order to eliminate graying and yellowing of the treated textiles. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure with the yellowness of the grayed or yellowed wash White results. Suitable compounds for example, originate from the substance classes of the 4,4 ^{^{'diamino-2,2-stilbenedisulfonic}} acids (flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems, and the heterocyclic-substituted pyrene derivatives.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Continue to leave Use soluble starch preparations, eg degraded starch, aldehyde starches, etc. Also, polyvinylpyrrolidone is useful. Also usable as graying inhibitors are cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and crushing transversely to the fiber direction, synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability. Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents may also be included. The antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. A further field of application of repellents and impregnating agents is the water-repellent finishing of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing). The Hydrophobie used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable hydrophobizing agents are e.g. Paraffins, waxes, metal soaps etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organotin compounds and glutaric dialdehyde and perfluorinated compounds. The hydrophobicized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening. Thus, e.g. Silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.

Antimicrobial agents can be used to combat microorganisms. Here you differentiate depending on the antimicrobial spectrum and mechanism of action Bacteriostats and bactericides, fungistatics and fungicides, etc. Substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenolic mer- curetate, although these compounds can also be dispensed with entirely.

To prevent undesirable changes to the detergents and cleaners and / or the treated fabrics caused by atmospheric oxygenation and other oxidative processes, the compositions may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased comfort may result from the additional use of antistatic agents. Antistatic agents increase the surface conductivity and thus enable an improved outflow of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional softening effect being achieved.

In order to improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, silicone derivatives can be used in textile detergents. These additionally improve the rinsing out of detergents or cleaning agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which have, for example, polyethylene glycols, and the polyalkylene oxide-modified dimethylpolysiloxanes.

Finally, it is also possible to use UV absorbers which are applied to the treated textiles and improve the light resistance of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid. Protein hydrolyzates are due to their fiber-care effect other suitable active substances. Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). Protein hydrolysates of both vegetable and animal origin can be used. Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be in the form of salts. Preference is given to the use of protein hydrolysates of plant origin, for example soybean, almond, rice, pea, potato and wheat protein hydrolysates. Although the use of the protein hydrolyzates is preferred as such, other amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.

Examples

Example 1: Cleaning performance

Washing tests were carried out at 20 ° C. as a six-fold determination on standardized soiling on cotton given in Table 2 using a Miele W 1514 Novotronic® household washing machine (70 minutes main wash program, 3.5 kg of clean accompanying laundry), 75 ml of the inventive detergent M1 and for comparison of detergents V0 to V2 having the compositions shown in Table 1. After hanging drying and mangling the cotton rag, their whiteness was determined spectrophotometrically (Minolta® CR400-1). Table 2 shows the differences of the remission values of the detergents M1, V1 and V2 to the detergent V0.

Table 1: Composition [% by weight]

VO V1 V2 M1

Na-C9-i3-alkylbenzenesulfonate 4 4 4 4

Ci2-i4 fatty alcohol ether sulfate 2-EO 5 5 5 5

Ci2-i8 fatty alcohol 7-EO 4 4 4 4

Ci2-18 fatty acid 2.2 2.2 2.2 2.2

Citric acid 1, 5 1, 5 1, 5 1, 5

NaOH 2 2 2 2

Boric acid 1 1 1 1

Enzymes (protease, amylase, man

1 1 1 1

nanase, cellulase)

Glycerine 2 2 2 2

Ethanol 1 1 1 1

NaCl 0.2-0.2 0.2 0.2

diethylenetriamine

0.2 0.2 0.2 0.2

phosphonic acid, hepta sodium salt

Optical brightener 0.05 0.05 0.05 0.05

Perfume 0.5 0.5 0.5 0.5

Ethoxylated polyamine ^a) 0 3 0 1, 5

Polyacrylate ^b) 0 0 3 1, 5

Water at 100 a): Polyethyleneimine with molecular weight 1300, average degree of ethoxylation 43 b): Sokalan® PA 15

Table 2: Remission differences

The whiteness increments with the addition of the combination of polymers were significantly greater in the same active content of the mixture compared to the single substance than those resulting from the use of only one of the two polymers in the liquid detergent, which corresponds to improved stain removal. This means that the two polymers interact synergistically.

Claims

claims

1. Use of a combination of polyalkoxylated polyamine and polyacrylate in detergents or cleaners to improve the washing or cleaning performance against bleachable stains and proteinaceous stains.

2. Use according to claim 1, characterized in that the soils polymerizable sizable substances selected from polyphenolic dyes, in particular from flavonoids, especially from dyes of the class of anthocyanidins or anthocyanins or oligomers of these compounds, and proteins.

3. Use according to claim 1 or 2, characterized in that the soils are selected from soiling by cherry, morelle, grape, apple, pomegranate, a ronia, plum, sea buckthorn, agai, kiwi, mango, grass, or berries, in particular by red or black currants, elderberries, blackberries, raspberries, blueberries, cranberries, cranberries, strawberries or blueberries, coffee, tea, red cabbage, blood orange, aubergine, tomato, carrot, beetroot, spinach, paprika, red-fleshed or blue-legged Potato, red onion, milk, egg, chocolate, cocoa, blood, grass, salad dressing and mixtures of these.

4. Use according to one of claims 1 to 3, characterized in that the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular of

550 g / mol to 2000 g / mol.

5. Use according to one of claims 1 to 4, characterized in that the N atoms in the polyamine are separated by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups have the same C Must have atomic number.

6. Use according to one of claims 1 to 5, characterized in that the average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is 5 to 100, in particular 10 to 80.

7. Use according to any one of claims 1 to 6, characterized in that the alkoxy groups in the polyalkoxylated polyamine are ethoxy, propoxy or butoxy groups or mixtures thereof, in particular ethoxy groups.

8. Use according to one of claims 1 to 7, characterized in that the polyacrylate has an average molecular weight in the range of 1000 g / mol to 20,000 g / mol, in particular from 1500 g / mol to 15000 g / mol.

9. Use according to one of claims 1 to 8, characterized in that in the combination polyalkoxylated polyamine and polyacrylate in a weight ratio in the range of 3: 1 to 1: 3, in particular 2: 1 to 1: 2 is present.

10. Use according to one of claims 1 to 9, characterized in that the combination of polyalkoxylated polyamine and polyacrylate in detergents or cleaners in an amount of 0.1 wt .-% to 5 wt .-%, in particular in an amount from 1% by weight to

3 wt .-%, used.