Color-stable liquid detergent

Abstract

The invention relates to a liquid detergent containing, based on the total weight thereof, a) 22 to 50 wt.% anionic surfactant; b) 0.1 to 8 wt.% gluconic acid salt; c) 0 to 2 wt.% antioxidant; d) 5 to 25 wt.% organic solvent; e) 0.1 to 15 wt.% water; f) less than 0.1 wt.% organic phosphonate, and g) 0.01 to 5 wt.% perfume composition.

Description

[0001] Henkel AG & Co. KGaA

[0002] Color-stable liquid detergent

[0003] The present invention relates to color-stable liquid detergents. In particular, the invention relates to color-stable liquid detergents containing gluconic acid salts.

[0004] The packaging and presentation of detergents and washing products are subject to constantly changing requirements. For some time now, a major focus has been on convenient dosing by the consumer and simplifying the steps required for washing or cleaning. Pre-portioned detergents or washing products offer a solution, for example, foil pouches with one or more compartments for solid or liquid detergents or washing products. From a technical perspective, a key focus is on developing and manufacturing liquid detergents suitable for packaging in water-soluble foil pouches.

[0005] The commercial success of a detergent portion unit is largely determined by its ability to provide a product that meets consumer interests.

[0006] An important means of communicating the product quality and promises of a liquid detergent is its appearance, for example, the color of the detergent itself or the shape and color of the portion unit it contains. This is especially true for water-soluble foil pouches, whose soluble films are usually transparent, allowing a view of the solid or liquid detergent inside. Colored, i.e., non-white, liquid detergents can generally be produced easily by adding appropriate dyes. The long-term stability of the resulting color is influenced, among other factors, primarily by the ingredients of the liquid detergent.

[0007] From EP 3 257 927 A1 it is known that certain perfume raw materials and alkanolamines lead to a color change in a detergent composition. To minimize the color change of the composition, perfume raw materials that react with alkanolamines are replaced.

[0008] Another crucial aspect of successfully marketing a liquid detergent is its ecological footprint. This footprint is determined not only by the amount of energy and water used in its production, but also by the biodegradability of the ingredients and packaging materials. Providing high-performance liquid detergents with a continuously decreasing ecological footprint is a further objective in the development of detergents and cleaning agents. In summary, the application aimed to provide a visually appealing liquid detergent characterized by high color stability. The liquid detergent should have a high concentration of active ingredients, be suitable for packaging in water-soluble foil pouches, and contain a high proportion of readily biodegradable ingredients.

[0009] A first subject matter of the application is a liquid detergent containing, based on its total weight, a) 22 to 50 wt.% anionic surfactant, b) 0.1 to 8 wt.% gluconic acid salt, c) 0 to 2 wt.% antioxidant, d) 5 to 25 wt.% organic solvent, e) 0.1 to 15 wt.% water, f) less than 0.1 wt.% organic phosphonate and g) 0.01 to 5 wt.% perfume composition.

[0010] These liquid detergents exhibit surprising color stability even under demanding storage conditions. This applies to both dye-free and dye-containing detergents, which retain their original color, acquired during manufacturing, even under challenging storage conditions.

[0011] The detergent is liquid under standard conditions (20°C, 1013 mbar). Preferred detergents have a viscosity (21°C, Brookfield viscometer type DV-II. Pro, spindle no. 2, 20 rpm) above 400 mPas, preferably above 1000 mPas.

[0012] A first essential component of the liquid detergent is 22 to 50 wt.% anionic surfactant, wherein preferred liquid detergents contain 27 to 45 wt.%, preferably 32 to 40 wt.% anionic surfactant, based on their total weight.

[0013] The anionic surfactant is preferably selected from the group comprising C9-C13 alkylbenzenesulfonates, olefin sulfonates, Ci2-Ci8 alkanesulfonates, ester sulfonates, alk(en)yl sulfates, fatty alcohol ether sulfates, C12-18 fatty acid salts, and mixtures thereof. Compositions comprising Cg-C alkylbenzenesulfonates and fatty alcohol ether sulfates as the anionic surfactant exhibit particularly good dispersing properties. Suitable sulfonate-type surfactants include preferably Cg-C alkylbenzenesulfonates, olefin sulfonates (i.e., mixtures of alkene and hydroxyalkanesulfonates), and disulfonates, such as those obtained, for example, from Ci2-Ci8 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.Also suitable are Ci2-Ci8-alkanesulfonates and the esters of α-sulfofaticial acids (estersulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

[0014] It is particularly preferred if the composition contains at least one anionic surfactant of formula (I),

[0015] <0 in the

[0016] R' and R" are independent of H or alkyl and together contain 8 to 18, preferably 9 to 15 and particularly 9 to 13 C atoms and Y + a monovalent cation or the nth part of an n-valent cation (especially monoethanolamine).

[0017] The group of alkyl ether sulfates includes fatty alcohol ether sulfates, for example, the sulfuric acid monoesters of straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C12-18 fatty alcohols with 1 to 4 EO. Alkyl ether sulfates with formula (II) are preferred.

[0018] R 1 -O-(AO) n -SO3- X- (II)

[0019] In this formula (II) R 1 for a linear or branched, substituted or unsubstituted alkyl group, preferably for a linear, unsubstituted alkyl group, particularly preferably for a fatty alcohol group. Preferred groups R 1The residues of formula (II) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups and mixtures thereof, with the representatives having an even number of carbon atoms being preferred. Particularly preferred residues R 1 of formula (II) are derived from fatty alcohols with 12 to 18 C atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 20 C atoms.

[0020] In formula (II), AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The subscript n in formula (I) is an integer from 1 to 50, preferably from 1 to 20, and particularly from 2 to 10. n 2, 3, 4, 5, 6, 7, or 8 is especially preferred. X is a monovalent cation or the nth part of an n-valent cation, preferably the alkali metal ions, including Na. + or K+ , where Na + is highly preferred. Further cations X+ can be selected from NHY, 14 Zn 2+ 0.14 mg 2+ ,14 Ca 2+ ,14 Mn 2+ , and mixtures thereof, as well as primary and secondary amines, in particular monoethanolamine. Particularly preferred compositions contain an alkyl ether sulfate selected from fatty alcohol ether sulfates of formula (III) with k = 11 to 19, n = 2, 3, 4, 5, 6, 7, or 8. Particularly preferred representatives are Na fatty alcohol ether sulfates with 12 to 18 carbon atoms and 2 EOs (k = 11 to 13, n = 2 in Formula III). The stated degree of ethoxylation represents a statistical average, which may be a whole number or a fraction for a specific product. The stated degrees of alkoxylation represent statistical averages, which may be a whole number or a fraction for a specific product. Preferred alkoxylates / ethoxylates exhibit a narrow range of homologs (narrow range ethoxylates, NRE).

[0021] In summary, preferred liquid detergents contain an anionic surfactant selected from the group consisting of Cs-is alkylbenzenesulfonates, Cs-is olefin sulfonates, Ci2-18 alkanesulfonates, Cs-is ester sulfonates, Cs-is alkyl sulfates, Cs-rs alkenyl sulfates, fatty alcohol ether sulfates and C12-18 fatty acid salts, preferably from the group consisting of Cs-is alkylbenzenesulfonates, Cs-is alkyl sulfates, fatty alcohol ether sulfates and C12-18 fatty acid salts and in particular from the group consisting of Cs-is alkylbenzenesulfonates and C12-18 fatty acid salts.

[0022] The use of anionic surfactants from the group of alkanolamine-Cs-is-alkylbenzenesulfonates has proven to be particularly advantageous for the storage stability of liquid detergents.

[0023] In preferred liquid detergents, the anionic surfactant is selected from the group of alkanolamine-Cs-is-alkylbenzenesulfonates with alkanolamine from the group monoethanolamine, monoisopropanolamine, diisopropanolamine, preferably from the group monoethanolamine.

[0024] Other preferably used anionic surfactants belong to the group of C12-18 fatty acid salts. Particularly preferred C12-18 fatty acid salts are selected from the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and mixtures thereof.

[0025] In preferred liquid detergents, the anionic surfactant is selected from the group of alkanolamine-Ci2-18 fatty acid salts with alkanolamine from the group monoethanolamine, monoisopropanolamine, diisopropanolamine, preferably from the group monoethanolamine.

[0026] The C12-18 fatty acid salts are classified within the scope of this application as anionic surfactants. Both storage stability and washing and cleaning performance can be further improved by the composition of the surfactant system. In preferred detergents, the weight ratio of Cs-is alkylbenzenesulfonate to C12-18 fatty acid salts is 8:1 to 2:1, preferably 7:1 to 5:2, and particularly 6:1 to 3:1. Detergents in which the weight ratio of alkanolamine Cs-is alkylbenzenesulfonate to alkanolamine Ci2-is fatty acid salt is 8:1 to 2:1, preferably 7:1 to 5:2, and particularly 6:1 to 3:1 are especially preferred.

[0027] The detergents contain a nonionic surfactant as a preferred, optional component. Its weight fraction in the total weight of the detergent is preferably 12 to 36 wt.%, particularly preferably 15 to 33 wt.%, and especially 18 to 30 wt.%.

[0028] The use of non-ionic surfactants from the group of alkyl ethoxylates is particularly preferred, wherein preferred alkyl ethoxylates are selected from the group of ethoxylated primary Cs-is alcohols, preferably the ethoxylated primary Cs-is alcohols with a degree of alkoxylation of 4 to 10, particularly preferably the Ci2-14 alcohols with 4 EO or 7 EO, the Cg-n alcohols with 7 EO, the C13-15 alcohols with 5 EO, 7 EO or 8 EO, the Ci3-15 oxo alcohols with 7 EO, the Ci2-18 alcohols with 5 EO or 7 EO, in particular the Ci2-18 fatty alcohols with 7 EO or the Ci3-15 oxo alcohols with 7 EO.

[0029] In summary, preferred detergents contain, based on their total weight, 12 to 36 wt.%, particularly preferably 15 to 33 wt.% and particularly 18 to 30 wt.% non-ionic surfactant from the group of ethoxylated primary Cs-is alcohols, preferably the ethoxylated primary Cs-is alcohols with a degree of alkoxylation of 4 to 10, particularly preferably the C12-14 alcohols with 4 EO or 7 EO, the Cg-n alcohols with 7 EO, the C-is alcohols with 5 EO, 7 EO or 8 EO, the Ci3-is oxo alcohols with 7 EO, the Ci2-is alcohols with 5 EO or 7 EO, in particular the Ci2-is fatty alcohols with 7 EO or the Ci3-is oxo alcohols with 7 EO.

[0030] With regard to the rheological properties of the detergents, their processability and cleaning effect, it has proven advantageous to use non-ionic surfactant and anionic surfactant in a weight ratio of 3:1 to 1:3, preferably from 2:1 to 1:2 and particularly from 3:2 to 2:3.

[0031] As a further optional component, preferred detergents contain 1 to 10 wt.%, preferably 1.2 to 7 wt.% and in particular 1.5 to 4 wt.% polyalkoxylated amine with a weight-average molecular weight M to increase washing or cleaning performance. w in the range of 600 g / mol to 10000 g / mol, obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines having a molecular weight below 200 g / mol with alkylene oxides. Preferred polyalkoxylated amines have a weight-average molecular weight M w in the range of 1300 g / mol to 6000 g / mol, particularly from 1400 g / mol to 4500 g / mol. (The mean molecular weights given here and later, where applicable, for other polymers are weight-average molecular weights M.) w, which can generally be determined by gel permeation chromatography using an RL detector, whereby the measurement is expediently carried out against an external standard.) For their preparation, one can start in a known manner from ammonia, a monoalkylamine, a monoalkyl monoalkanolamine or a monoalkyl dialkanolamine or a mono-, di- or trialkanolamine, for example triethanolamine, methyl-, ethyl-, propyl- and isopropyl-diethanolamine, methyl-, ethyl-, propyl- and isopropyl-diisopropanolamine, tripropanolamine, triisopropanolamine, N,N-di-(2-hydroxyethyl)cyclohexylamine, N,N-di-(2-hydroxypropyl)cyclohexylamine, n-butylamine, n-hexylamine, n-octylamine, isopropylamine, sec-butylamine, tert-butylamine, cyclohexylamine, 2-ethylhexylamine, 2-phenylethylamine and mixtures thereof, which is combined with an alkylene oxide, in particular selected from the group consisting of ethylene oxide, propylene oxide, Butylene oxide and mixtures thereof, is reacted, in particular with a mixture containing propylene oxide and preferably ethylene oxide, especially preferably with propylene oxide.The polyalkoxylated amines obtained in this way can have block or random structures. A polyalkoxylated amine obtainable by propoxylation of triethanolamine, preferably with a length of 15 propylene oxide units for each of the three side arms, is particularly preferred. A polyalkoxylated amine obtainable by propoxylation of triisopropanolamine, preferably with a length of 15 propylene oxide units for each of the three side arms, is also preferred. Polyalkoxylated monoalkylamines with a linear, branched, or cyclic alkyl group are also suitable, wherein alkoxylation is performed with an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, preferably with a mixture containing propylene oxide, and particularly preferably with propylene oxide.A polyalkoxylated amine obtainable by propoxylation of tert-butylamine is also preferred, preferably with a length of the two side arms of 12 propylene oxide units each.

[0032] Preferred polyalkoxylated amines satisfy the general formula (IV), in the R for a linear, optionally branched or optionally cyclic alkyl group with

[0033] 1 to 12 C atoms or a group -(CH2CHR'O) n “-(CH2CHR“O)m"-H stands,

[0034] R' and R" independently represent H, CH3 or CH2CH3, n, n' and n" independently represent numbers from 0 to 30, preferably from 0 to 10 and particularly from 0 to 5, and m, m' and m" independently represent numbers from 0 to 30, preferably from 5 to 20 and particularly from 12 to 16, provided that the sum n + n' + n" + m + m' + m" is at least 14, preferably in the range of 18 to 100 and particularly in the range of 20 to 70. Preferably, in the compounds of formula I, at least one of the residues R' and R" is a CHs group.

[0035] Polyalkoxylated amines, particularly preferred due to their purification performance, are obtained by reacting triethanolamine with alkylene oxides, preferably by reacting triethanolamine with ethylene oxide and propylene oxide. Polyalkoxylated amines obtained by reacting triethanolamine with ethylene oxide followed by reaction with propylene oxide are especially preferred.

[0036] A second essential component of the detergent is a gluconic acid salt. The weight fraction of the gluconic acid salt in the total weight of the detergent is preferably 0.2 to 6 wt.% and particularly 0.4 to 4 wt.%. The addition of the gluconic acid salt has proven particularly advantageous for stabilizing the dye in the liquid detergent. Due to its availability and ease of processing, the use of sodium gluconate is especially preferred.

[0037] The color of liquid detergent can be further stabilized by using antioxidants. An antioxidant is a molecule that can slow down or prevent the oxidation of other molecules. Oxidation reactions can produce free radicals, which in turn can trigger further degradation chain reactions. Antioxidants stop these chain reactions by removing the intermediate products of free radicals and inhibiting other oxidations, while themselves being oxidized. Therefore, antioxidants are often reducing agents.The antioxidant is preferably selected from the group consisting of butylhydroxyltoluene (BHT), butylhydroxylanisole (BHA), trimethoxybenzoic acid (TMBA), α-, β-, A- and β-tocopherol (vitamin E acetate), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox), 1,2, benzisothiazolinone (Proxel GLX), tannic acid, galic acid, Tinoguard AO-6, Tinoguard TS, ascorbic acid, alkylated phenol, ethoxyquin 2,2,4-trimethyl, 1,2-dihydroquinoline, lignosulfonic acid and its salts, benzofuran, benzopyran, tocopherol sorbate, butylhydroxylbenzoic acid and its salts, galic acid and its alkyl esters, uric acid, its salts and alkyl esters, sorbic acid and its Salts, dihydroxyfumaric acid and its salts and mixtures thereof.

[0038] Particularly preferred antioxidants are selected from the group of sulfites, hydrogen sulfites and disulfites, preferably from the group of sodium sulfite, sodium hydrogen sulfite and sodium disulfite, in particular from the group containing sodium sulfite and sodium disulfite.

[0039] The use of antioxidants from the disulfite group, preferably from the sodium disulfite group, has proven to be particularly effective. The weight fraction of the antioxidant in the total weight of the detergent is preferably 0.02 to 1 wt.% and particularly 0.05 to 0.5 wt.%.

[0040] As a further essential component, the liquid detergent contains 5 to 25 wt.% organic solvent. The weight fraction of the organic solvent in the total weight of the detergent is preferably 7 to 20 wt.% and particularly 10 to 18 wt.%.

[0041] Preferred organic solvents are selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, and propylene glycol ethyl ether.

[0042] Propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol tert-butyl ether, di-n-octyl ether, and mixtures thereof, preferably from the group consisting of propanediol, glycerol, and mixtures thereof. Any alkanolamine used to neutralize the anionic surfactant is not classified as an organic solvent.

[0043] The liquid detergent contains water. Detergents containing 5 to 15%, preferably 8 to 15% by weight, of water are preferred.

[0044] The weight fraction of organic phosphonate in the total weight of the detergent is less than 0.1 wt.%.

[0045] Phosphonates are used as complexing agents and stabilizers in most detergents. They primarily bind heavy metal ions and prevent laundry from becoming gray. However, they are difficult to biodegrade.

[0046] Preferred liquid detergents contain no organic phosphonates, in particular no phosphonates at all. Examples of phosphonate compounds that are preferably not contained in the detergent are phosphonates from the group of hydroxyalkane and / or aminoalkane phosphonates, in particular from the group consisting of 1-hydroxyethane-1,1-diphosphonate (HEDP), ethylenediaminetetramethylenephosphonate (EDTMP), and diethylenetriaminepentamethylenephosphonate (DTPMP).

[0047] The liquid detergent also contains a perfume composition in amounts of 0.01 to 5% by weight. Perfume compositions are typically complex mixtures of perfume raw materials with various functional groups, such as alcohols, esters, ketones, aldehydes, etc.

[0048] However, some perfume raw materials can cause stability problems in liquid detergents. For example, perfume ketones or perfume aldehydes can react with amine-containing components of the liquid detergent, such as alkanolamines, which are used as neutralizing agents in liquid detergents, leading to undesirable changes in color and / or odor.

[0049] This adverse effect is more pronounced with reduced amounts of organic phosphonate. Surprisingly, it was found that the presence of gluconic acid salts significantly reduces these interactions and, in particular, the discoloration. This allows the use of perfume compositions with perfume ketones and / or perfume aldehydes.

[0050] Accordingly, a preferred liquid detergent comprises a perfume composition containing at least 0.01 wt% of a perfume raw material selected from perfume ketones, perfume aldehydes and mixtures thereof.

[0051] A particularly preferred liquid detergent comprises a perfume composition containing at least 0.01% by weight of a perfume raw material selected from the group consisting of Adoxal (2,6,10-Trimethyl-9-undecenal), Anisaldehyde (4-Methoxybenzaldehyde), Cymal or Cyclamenaldehyde (3-(4-isopropylphenyl)-2-methylpropanal), Nympheal (3-(4-isobutyl-2-methylphenylpropanal), Ethylvanillin, Florhydral (3-(3-isopropylphenyl)butanal), Trifernal (3-phenylbutyraldehyde), Helional (3-(3,4-Methylenedioxyphenyl)-2-methylpropanal), Heliotropin, Hydroxycitronellal, Lauraldehyde, Lyral (3- and 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde), Methylnonylacetaldehyde, Lilial (3-(4-tert-butylphenyl)-2-methylpropanal), phenylacetaldehyde, undecylenaldehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), triplal (2,4-Dimethyl-3-cyclohexene-1-carboxaldehyde), 4-methoxybenzaldehyde, benzaldehyde, 3-(4-tert-butylphenyl)-propanal,2-Methyl-3- (para-methoxyphenyl)propanal, 2-Methyl-4-(2,6,6-timethyl-2(1 )-cyclohexen-1-yl)butanal, 3-Phenyl- 2-propenal, cis- / trans-3,7-Dimethyl-2,6-octadien-1-al, 3,7-Dimethyl-6-octen-1-al, [(3,7-Dimethyl-6- octenyl)oxy]acetaldehyd, 4-lsopropylbenzylaldehyd, 1 ,2,3,4,5,6,7,8-Octahydro-8,8-dimethyl-2- naphthaldehyd, 4-(4-Methylpent-3-enyl)cyclohex-3-en-1-carbaldehyd, 1-Methyl-4-(4- methylpentyl)cyclohex-3-en-1-carbaldehyd, 8,8-Dimethyl-6,7-dihydro-5H-naphthalen-2- carbaldehyd, 2,4-Dimethyl-3-cyclohexen-1-carboxaldehyd, 2-Methyl-3-(isopropylphenyl)propanal, 1 -Decanal, 2,6-Dimethyl-5-heptenal, 4-(Tricyclo[5.2.1.0(2,6)]-decyliden-8)-butanal, Octahydro-4,7- methan-1H-indencarboxaldehyd, 3-Ethoxy-4-hydroxybenzaldehyd, para-Ethyl-alpha,alpha- dimethylhydrozimtaldehyd, alpha-Methyl-3,4-(methylendioxy)-hydrozimtaldehyd, 3,4- Methylendioxybenzaldehyd, alpha-n-Hexylzimtaldehyd, m-Cymen-7-carboxaldehyd, alpha- Methylphenylacetaldehyd, Tetrahydrocitral (3,7-Dimethyloctanal), Citral, Undecenal,2,4,6- Trimethyl-3-cyclohexen-1-carboxaldehyd, 4-(3)(4-Methyl-3-pentenyl)-3-cyclohexencarboxaldehyd,

[0052] 1 -Dodecanal, 2,4-Dimethylcyclohexen-3-carboxaldehyd, 4-(4-Hydroxy-4-methylpentyl)-3- cylohexen-1-carboxaldehyd, 7-Methoxy-3,7-dimethyloctan-1-al, 2-Methyldecanal, 1-Nonanal, 1- Octanal, 2,6,10-Trimethyl-5,9-undecadienal, 2-Methyl-3-(4-tert-butyl)propanal, Dihydrozimtaldehyd,

[0053] 1-Methyl-4-(4-methyl-3-pentenyl)-3-cyclohexen-1-carboxaldehyd, 5- oder 6-Methoxyhexahydro-4,7- methanindan-1- oder -2-carboxaldehyd, 3,7-Dimethyloctan-1-al, 1-Undecanal, 10-Undecen-1-al, 4- Hydroxy-3-methoxybenzaldehyd, 1-Methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyd, 7- Hydroxy-3,7-dimethyl-octanal, trans-4-Decenal, 2,6-Nonadienal, para-Tolylacetaldehyd, 4- Methylphenylacetaldehyd, 2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, ortho- Methoxyzimtaldehyd, Citronellyloxyacetaldehyd, 3,5,6-Trimethyl-3-cyclohexencarboxaldehyd, 3,7- Dimethyl-2-methylen-6-octenal, Phenoxyacetaldehyd, 3-(4-propan-2-ylphenyl)propanal, 5,9- Dimethyl-4,8-decadienal, Päonienaldehyd (6,10-Dimethyl-3-oxa-5,9-undecadien-1-al), Hexahydro- 4,7-methanindan-1-carboxaldehyd, 3-(4-tert-Butylphenyl)propanal, 3-(3-Propan-2-ylphenyl)butanal,

[0054] 2-Methyloctanal, alpha-Methyl-4-(1-methylethyl)benzolacetaldehyd, 6,6-Dimethyl-2-norpinen-2- propionaldehyd, para-Methylphenoxyacetaldehyd, 2-Methyl-3-phenyl-2-propen-1-al, 3,5,5- Trimethylhexanal, Hexahydro-8,8-dimethyl-2-naphthaldehyd, 3-Propylbicyclo[2.2.1]-hept-5-en-2- carbaldehyd, 9-Decenal, 3-Methyl-5-phenyl-1-pentanal, Floral (4,8-Dimethyl-4,9-decadienal), Aldehyd C12MNA (2-Methylundecanal), Liminal (beta-4-Dimethylcyclohex-3-ene-1-propan-1-al), 3- (1 ,3-Benzodioxol-5-yl)-2-methylpropanal, 2-(4-Methylphenyl)methylenheptenal, 3-(4-methyl-1- cyclohex-3-enyl)butanal, Methylnonylacetaldehyd, Hexanal, trans-2-Hexenal, Methyl-beta- naphthylketon, Moschusindanon (1 ,2,3,5,6,7-Hexahydro-1 , 1 ,2,3,3-pentamethyl-4H-inden-4-on), Calone (Methylbenzodioxepinon), Tonalid (6-Acetyl-1 ,1,2,4,4,7-hexamethyltetralin), alpha- Damascone, beta-Damascone, delta-Damascone, iso-Damascone, Damascenone, Methyldihydrojasmonat (Hedion), Menthon, Carvon, Kampfer, Koavon (3,4,5,6,6-Pentamethylhept-

[0055] 3-en-2-on), Fenchon, alpha-lonon, beta-lonon, Dihydro-beta-lonon, gamma-Methyl-lonon, Fleuramon (2-Heptylcyclopentanon), Frambinonmethylether (4-(4-Methoxyphenyl)butan-2-on), Dihydrojasmon, cis-Jasmon, 1-(1 ,2,3,4,5,6,7,8-Octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)- ethan-1-on und Isomere davon, Methylcedrenylketon, Acetophenon, Methylacetophenon, para- Methoxyacetophenon, Methyl-beta-naphtylketon, Benzylaceton, Benzophenon, para- Hydroxyphenylbutanon, Sellerie-Keton(3-Methyl-5-propyl-2-cyclohexenon), 6-lsopropyldeca-hydro-

[0056] 2-naphton, Dimethyloctenon, Frescomenthe (2-Butan-2-ylcyclohexan-1-on), 4-(1-Ethoxyvinyl)- 3,3,5,5-tetramethylcyclohexanon, 5-Methylhept-2-en-4-on, 6-Methylhept-5-en-2-on, 2-(2-(4-Methyl-

[0057] 3-cyclohexen-1-yl)propyl)cyclopentanon, 1-(p-Menthen-6(2)yl)-1-propanon, 4-(4-Hydroxy-3- methoxyphenyl)-2-butanon, 2-Acetyl-3,3-dimethylnorbornan, 6,7-Dihydro-1 ,1 ,2,3,3-pentamethyl- 4(5H)in-danon, 4-Damascol, Dulcinyl (4-(1,3-Benzodioxol-5-yl)butan-2-on), Hexalon (1-(2,6,6- Trimethyl-2-cyclohexen-1-yl)-1 ,6-heptadien-3-on), Isocyclemon E (2-Acetonaphthon-1 ,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), Methylnonylketon, Methylcyclocitron, Methyllavendelketon, Orivon (4-tert-Amylcyclohexanon), 4-tert-Butylcyclohexanon, Delphon (2- Pentylcyclopentanon), Muscon (CAS 541 -91 -3), Neobutenon (1-(5,5-dimethyl-1-cyclo- hexenyl)pent-4-en-1-on), Plicaton (CAS 41724-19-0), Velouton (2,2,5-trimethyl-5-pentylcyclopentan- 1-on), 2,4,4,7-Tetramethyl-oct-6-en-3-on, 2-[2-(4-Methyl-1-cyclohex-3-enyl)propyl]cyclopentan-1- on, Tetrameran (6,10-dimethylundecen-2-on) und Mischungen daraus enthält.

[0058] In addition to improved product aesthetics due to significantly less discoloration, the increased use of perfume ketones and / or perfume aldehydes leads to improved olfactory performance, as perfume ketones and / or perfume aldehydes are an essential component of perfume compositions in detergents.

[0059] As mentioned at the beginning, the detergents exhibit surprisingly high color stability even under demanding storage conditions. This applies to both dye-free and dye-containing detergents.

[0060] Preferred detergents contain a dye as an optional component. The dye is preferably selected from the group of water-soluble dyes, in particular from the group of water-soluble acid dyes, water-soluble direct dyes, and water-soluble polymer dyes, especially water-soluble polymer dyes.

[0061] Geeignete Farbstoffe sind Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1 , Acid Yellow 3 (CI 47005), Acid Yellow 11 , Acid Yellow 23 (CI 19140), Acid Yellow 3, Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5:2 (CI 42051 :2), Food Red 7(01 16255), Food Yellow 13 (CI 47005), Food Yellow 3 (CI 15985), Food Yellow 4 (CI 19140), Reactive Green 12, Solvent Green 7 (CI 59040).

[0062] Preferred dyes are also water-soluble acid dyes, for example Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet48, Acid Blue 80(01 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570) or Acid Green 81.

[0063] Water-soluble direct dyes, such as Direct Yellow 28 (CI 19555), Direct Blue 199 (CI 74190) and water-soluble reactive dyes, such as Reactive Green 12, as well as the dyes Food Yellow 3 (CI 15985) or Acid Yellow 184, can also be used.

[0064] In particularly preferred embodiments, water-soluble polymer dyes, for example Liquitint, Liquitint Blue HP (CAS No. 162874-54-6), Liquitint Blue MC, Liquitint Blue 65, Liquitint Cyan 15 (CAS No. 888888-03-0), Liquitint Patent Blue (CAS No. 162874-57-9), Liquitint Violet 129 (CAS No. 888888-06-7), Liquitint Royal Blue (CAS No. 162874-58-0), Liquitint Red ET (CAS No. 888888-02-9), Liquitint Experimental Yellow 8949-43, Liquitint Green HMC, Liquitint Yellow LP, Liquitint Yellow II), Liquitint Aquamarine, (CAS No. 888888-04-4), Liquitint Blue (CAS No. 888888-02-6), Liquitint Bright Yellow Dye (CAS No. 888888-03-7), Liquitint Brilliant Orange Dye (GAS No. 888888-03-6), Liquitint Green (CAS No. 888888-05-5), Liquitint Orange (GAS No. 888888- 03-5), Liquitint Purple (GAS No. 888888-02-7), Liquitint Red (GAS No. 888888-02-9), Liquitint Sky Blue Dye (GAS No. 888888-03-8), Liquitint Violet (GAS No. 888888-06-7) and mixtures thereof.

[0065] Water-soluble polymer dyes from the group Liquitint Cyan 15 (CAS No. 888888-03-0), Liquitint Blue HP (CAS No. 162874-54-6), Liquitint Violet 129 (CAS No. 888888-06-7) and Liquitint Red ET (CAS No. 888888-02-9) are particularly preferred.

[0066] The weight fraction of the dye in the total weight of dye-containing detergents is preferably 0.001 to 0.5 wt.%, preferably 0.002 to 0.3 wt.% and particularly 0.005 to 0.2 wt.%.

[0067] In summary, particularly preferred liquid detergents contain, based on their total weight, a) 22 to 50 wt.% anionic surfactant from the group of alkanolamine-Cs-is-alkylbenzenesulfonates and alkanolamine-Ci2-18 fatty acid salts; b) 0.1 to 8 wt.% gluconic acid salt; c) 0.01 to 2 wt.% antioxidant from the group of sodium sulfite and sodium disulfite; d) 5 to 25 wt.% organic solvent; e) 0.1 to 15 wt.% water; f) no organic phosphonate; g) 0.01 to 5 wt.% a perfume composition; and h) 0.001 to 0.5 wt.% water-soluble polymer dye.

[0068] In an alternative embodiment, the detergents do not contain any dye.

[0069] Corresponding particularly preferred liquid detergents contain, based on their total weight, a) 22 to 50 wt.% anionic surfactant from the group of alkanolamine-Cs-is-alkylbenzenesulfonates and alkanolamine-Ci2-18 fatty acid salts; b) 0.1 to 8 wt.% gluconic acid salt; c) 0.01 to 2 wt.% antioxidant from the group of sodium sulfite and sodium disulfite; d) 5 to 25 wt.% organic solvent; e) 0.1 to 15 wt.% water; f) no organic phosphonate; g) 0.01 to 5 wt.% a perfume composition; and h) no dye. Preferred detergents contain detergent- or cleaning-active polymers. Particularly preferred detergent- or cleaning-active polymers are selected from the group of soil release polymers, color transfer inhibitors, graying inhibitors, and antireposition agents.

[0070] Soil release agents are components that positively influence the washability of oil and grease from textiles. This effect is particularly noticeable when a textile becomes soiled after having been repeatedly washed with a product containing this oil- and grease-dissolving component. Preferred soil release agents include, for example, non-ionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxyl group content of 15 to 30 wt.% and a hydroxypropoxyl group content of 1 to 15 wt.%, based on the non-ionic cellulose ether, as well as polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, with monomeric and / or polymeric diols, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.Anionic or nonionic polyesters of polypropylene terephthalates are still preferred. Such polyesters are commercially available, for example, under the trade name Texcare®. In summary, detergents are preferred which contain a washing- or cleaning-active polymer from the group consisting of phthalic acid and / or terephthalic acid or their derivatives with monomeric and / or polymeric diols, preferably from the group consisting of polymers of ethylene terephthalates and / or polyethylene glycol terephthalates and / or polypropylene terephthalates or anionically and / or nonionically modified derivatives thereof, and particularly preferably from the group consisting of anionic or nonionic polyesters of polypropylene terephthalates.

[0071] It is preferred that the color transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. Polymers suitable as color transfer inhibitors include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine N-oxide, poly-N-carboxymethyl-4-vinyl ipyridium chloride, polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, and mixtures thereof. Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) are particularly preferred as color transfer inhibitors. The polyvinylpyrrolidones (PVP) used preferably have a mean molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53.The vinylpyrrolidone and vinylimidazole (PVP / PVI) copolymers used preferably have a molecular weight in the range of 5,000 to 100,000 g / mol. A PVP / PVI copolymer is commercially available, for example, from BASF under the name Sokalan® HP 56. Anti-graying agents serve to keep the dirt detached from the textile fibers suspended in the cleaning solution. Water-soluble colloids, mostly of organic origin, are suitable for this purpose, such as starch, glue, gelatin, salts of ethercarboxylic or ethersulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, starch derivatives other than those mentioned above can be used, for example, aldehyde starches.Preferably, cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof can be used.

[0072] Anti-reposition agents can be used in particular on (co)polymers based on polyethyleneimine, polyvinyl acetate and polyethylene glycol, preferably in mixtures with anti-reposition agents.

[0073] Particularly preferred is the use of ethoxylated polyethyleneimine with ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine, wherein the weight fraction of this ethoxylated polyethyleneimine in the total weight of the detergent is preferably 1 to 10 wt. %, preferably 1.2 to 7 wt. %, and particularly 1.5 to 4 wt. %,.

[0074] The ethoxylated polyalkylenemine is a polymer with a polyalkylenemine backbone bearing polyalkoxy groups at the nitrogen atoms. The ethoxylated polyethyleneimine preferably has a polyethyleneimine backbone with a weight-average molecular weight in the range of 100 g / mol to 2000 g / mol, particularly from 400 g / mol to 800 g / mol. The weight-average molecular weight of the ethoxylated polyethyleneimine is preferably from 5000 g / mol to 20000 g / mol, particularly from 8000 g / mol to 14000 g / mol.

[0075] The polyalkylenemine has primary amino groups at its ends and preferably both secondary and tertiary amino groups in its interior; optionally, it may also have only secondary amino groups in its interior, resulting in a linear rather than a branched-chain polyalkylenemine. The ratio of primary to secondary amino groups in the polyalkylenemine is preferably in the range of 1:0.5 to 1:1.5, particularly in the range of 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkylenemine is preferably in the range of 1:0.2 to 1:1, particularly in the range of 1:0.5 to 1:0.8. The nitrogen atoms in the polyalkylenemine are separated from one another by alkylene groups with 2 to 12 carbon atoms, particularly 2 to 6 carbon atoms, whereby not all alkylene groups need to have the same number of carbon atoms. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof.The primary amino groups in the polyalkylenemine can bear one or two polyalkoxy groups, and the secondary amino groups one polyalkoxy group, although not every amino group needs to be alkoxy substituted. The average number of alkoxy groups per primary and secondary amino group in the ethoxylated polyalkylenemine is preferably 5 to 100, and more particularly 10 to 50. The ethoxylated polyalkylenemines are accessible by reacting the polyalkylenemines with ethylene oxide.

[0076] In summary, particularly preferred detergents contain washing or cleaning active polymers from the group of carboxymethyl celluloses, nonionic cellulose ethers, polyalkoxylated polyethyleneimines and (co)polymers of phthalic or terephthalic acid.

[0077] To further increase cleaning performance, preferred detergents contain, based on their total weight, 0.5 to 7 wt.%, preferably 1.0 to 6 wt.% enzyme preparations.

[0078] An enzyme preparation comprises, in addition to the actual enzyme protein, other components such as enzyme stabilizers, carrier materials, or fillers. The enzyme protein typically constitutes only a fraction of the total weight of the enzyme preparation. Preferably, enzyme preparations contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, more preferably between 0.4 and 20 wt.%, and most preferably between 0.8 and 10 wt.% of the enzyme protein. In such compositions, an enzyme stabilizer may be present in an amount of 0.05 to 35 wt.%, preferably between 0.05 and 10 wt.%, based on the total weight in the enzyme composition.

[0079] Protein concentration can be determined using established methods, such as the BCA method (bicinchoninic acid; 2,2'-bicinolyl-4,4'-dicarboxylic acid) or the biuret method. The determination of the active protein concentration is carried out by titrating the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonylfluoride (PMSF)) and determining the residual activity.

[0080] The detergents preferably contain at least one enzyme preparation, particularly preferably at least three enzyme preparations of enzymes from the group consisting of lipase, mannanase, amylase, protease, cellulase, hexosaminidase, preparations of a pectinolytic enzyme and endoglucanase.

[0081] With regard to their cleaning performance, preferred detergents contain, based on their total weight, 0.1 to 0.4 wt.% and in particular 0.2 to 0.3 wt.% hexosaminidase preparation, especially preferably β-hexosaminidase preparation.

[0082] The term "hexosaminidase" refers to a polypeptide with hexosaminidase activity (hexosaminidases) and includes enzymes that catalyze the hydrolysis of N-acetyl-D-hexosamine or N-acetyl-glucosamine polymers.

[0083] Polypeptides with hexosaminidase activity include dispersins such as dispersin B (DspB), which are β-N-acetylglucosamininidases belonging to the glycoside hydrolase 20 family. Dispersins are produced by the periodontal pathogen Aggregatibacter actinomycetemcomitans, a Gram-negative oral bacterium. Dispersin B is a β-hexosaminidase that specifically hydrolyzes β-1,6-glycosidic bonds of acetylglucosamine polymers. The use of hexosaminidases from the β-hexosaminidase group is preferred.

[0084] It is preferred if the detergent contains at least one lipase preparation. According to the invention, preferred lipases are selected from at least one enzyme of the group consisting of triacylglycerol lipase (EC 3.1.1.3), lipoprotein lipase (EC 3.1.1.34) and monoglyceride lipase (EC 3.1.1.23).

[0085] Preferred lipase preparations are the commercial products marketed by Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE®, and Lipase F® (also Lipase JV®). Lipase F®, for example, occurs naturally in Rhizopus oryzae. Lipase M-AP10®, for example, occurs naturally in Mucor javanicus.

[0086] A highly preferred lipase is commercially available under the trade name Lipex® from the company Novozymes (Denmark) and can be advantageously used in the detergents according to the invention. The lipase Lipex® 100 L is particularly preferred.

[0087] Preferred detergents are characterized by the fact that they contain 0.01 to 1 wt.%, in particular 0.05 to 0.3 wt.%, of lipase preparation based on their total weight.

[0088] The detergents preferably contain at least one amylase, in particular an α-amylase. α-Amylases (EC 3.2.1.1) act as enzymes to hydrolyze internal α-1,4-glycosidic bonds of starch and starch-like polymers. Examples include α-amylases from Bacillus licheniformis, B. amyloliquefaciens, and B. stearothermophilus, as well as their improved formulations for use in detergents or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the trade name Termamyl® and from Genencor under the trade name Purastar®ST. Further developments of these α-amylases are available from Novozymes under the trade names Duramyl® and Termamyl®ultra, from Genencor under the name Purastar®OxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The α-amylase of B.Amyloliquefaciens is marketed by Novozymes under the name BAN®, and derivatives of the α-amylase from B. stearothermophilus are marketed under the names BSG® and Novamyl®, also by Novozymes. Examples of α-amylases from other organisms are the further developments of α-amylase from Aspergillus niger and A. oryzae, available from Novozymes under the trade names Fungamyl®. The weight fraction of the amylase preparation, in particular the α-amylase preparation, in the total weight of the detergents is preferably 0.1 to 2% by weight, and more specifically 0.2 to 1% by weight.

[0089] It is preferred if the detergent contains at least one protease as an enzyme. A protease is an enzyme that cleaves peptide bonds by hydrolysis. According to the invention, each of the enzymes from class EC 3.4 falls under this category (comprising each of the thirteen subclasses included therein). “Protease activity” is present if the enzyme possesses proteolytic activity (EC 3.4). Various types of protease activity are known: The three main types are: trypsin-like, wherein cleavage of the amide substrate occurs along the amino acids Arg or Lys at P1; chymotrypsin-like, wherein cleavage occurs along one of the hydrophobic amino acids at P1; and elastase-like, wherein cleavage of the amide substrate occurs along the Ala at P1.

[0090] Surprisingly, it was found that a protease of the alkaline protease type from Bacillus lentus DSM 5483, or a sufficiently similar protease (with respect to sequence identity) exhibiting several of these modifications in combination, is particularly suitable for use in the detergents according to the invention and is advantageously stabilized therein. The advantages of using this protease thus arise particularly with regard to washing performance and / or stability.

[0091] Most preferably, the detergent contains a protease of the alkaline protease type from Bacillus lentus DSM 5483 or a sufficiently similar protease (with respect to sequence identity) that exhibits several of these modifications in combination.

[0092] The weight fraction of the protease preparation in the total weight of the detergents is preferably 0.2 to 4 wt.% and particularly 0.4 to 3 wt.%.

[0093] Preferred detergents contain, as an optional component, based on their total weight, 0.05 to 2 wt.%, preferably 0.1 to 0.4 wt.%, of a preparation of a pectinolytic enzyme.

[0094] Within the scope of the present invention, the pectinolytic enzymes include enzymes designated as pectinase, pectate lyase, pectin esterase, pectin demethoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectin pectyl hydrolase, pectin depolymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin polygalacturonase, endo-polygalacturonase, poly-α-1,4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1,4-α-galacturonidase, exopolygalacturonase, poly(galacturonate) hydrolase, exo-D-galacturonanase, and exo-D-galacturonanase. Exopoly-D-galacturonase, exo-poly-α-galacturonosidase, exopolygalacturonosidase, or 25-exopolygalacturanosidase. The use of pectate lyases is particularly preferred.

[0095] Within the EC classification of enzymes, the numerical classification system for enzymes, pectinolytic enzymes belong specifically to the enzyme classes (Enzyme Commission numbers) EC 3.1.1.11, EC 3.2.1.15, EC 3.2.1.67, and EC 3.2.1.82. Consequently, they are part of the third of the six main enzyme classes, the 10 hydrolases (EC 3.1.1.1), specifically the glycosylases (EC 3.2.1.1.1), and within these, the glycosidases (EC 3.2.1.1.1), i.e., enzymes that hydrolyze O- and / or S-glycosyl compounds. Pectinolytic enzymes are therefore particularly effective against residues on dishes containing pectic acid and / or other galacturonans, and catalyze their hydrolysis.

[0096] Pectate lyases within the meaning of the invention are enzymes which catalyze the non-hydrolytic cleavage of pectate via an endo-mechanism.

[0097] Examples of suitable pectinolytic enzymes are the enzymes and enzyme preparations available under the trade names Gamanase®, Pectinex AR®, X-Pect® or Pectaway® from Novozymes, under the trade names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, 30 Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes and under the trade name Pyrolase® from Diversa Corp., San Diego, CA, USA.

[0098] The detergent preferably contains 0.01 to 1 wt.%, preferably 0.02 to 0.3 wt.% of a mannanase preparation.

[0099] A mannanase catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannan, and galactoglucomannan. These mannanases are classified as EC 3.2.1.78 according to enzyme nomenclature.

[0100] As a further preferred ingredient, the detergents contain a cellulase preparation. Synonymous terms can be used for cellulases, in particular endoglucanase, endo-1,4-beta-glucanase, carboxymethylcellulase, endo-1,4-beta-D-glucanase, beta-1,4-glucanase, beta-1,4-endoglucan hydrolase, celludextrinase, or avicelase. The decisive factor in determining whether an enzyme is a cellulase within the meaning of the invention is its ability to hydrolyze 1,4-β-D-glucosidic bonds in cellulose.

[0101] Suitable cellulases (endoglucanases, EG) include, for example, fungal endoglucanase (EG)-rich compounds offered by Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kDa EG and 43 kDa EG from Humicola insolens DSM 1800, respectively. Other usable products from this company are Cellusoft®, Renozyme®, and Celluclean®. Also suitable are cellulases available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, which are at least partially based on the 20 kDa EG from Melanocarpus. Other cellulases from AB Enzymes include Econase® and Ecopulp®. Further suitable cellulases are derived from Bacillus sp. CBS 670.93 and CBS 669.93, the latter being Bacillus sp. CBS 670.93, which is available from Danisco / Genencor under the trade name Puradax®.Other usable commercial products from the company Danisco / Genencor are “Genencor detergent cellulase L” and IndiAge®Neutra.

[0102] The weight fraction of the cellulase preparation in the total weight of the detergent is preferably 0.01 to 1 wt.%, preferably 0.05 to 0.3 wt.%.

[0103] EXAMPLES

[0104] The composition of some preferred detergents can be found in the following tables (the values ​​are given in wt% based on the total weight of the preparation unless otherwise stated. The symbol indicates "free from"). The detergents are packaged in the form of detergent portion units, in which the detergent preparation is completely enclosed by a water-soluble film. * with at least 0.01% by weight of a perfume raw material selected from perfume ketones, perfume aldehydes and mixtures thereof

[0105] * with at least 0.01% by weight of a perfume raw material selected from perfume ketones, perfume aldehydes and mixtures thereof

[0106] The detergent according to the invention is characterized by high color stability and is therefore particularly suitable for packaging in transparent containers. Preferred detergents are packaged in transparent containers. The transparent container allows the detergent inside to be seen. Examples of such transparent packaging include transparent plastic bottles or transparent water-soluble film pouches.

[0107] The terms "transparent" or "transparency" mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40%, and particularly greater than 50%. Thus, as soon as a wavelength of the visible spectrum of light exhibits a transmittance greater than 20%, it is to be considered transparent within the meaning of the invention.

[0108] Another preferred subject matter of this application is a detergent portion unit comprising i) a detergent according to the invention; ii) a transparent water-soluble film which completely encloses the detergent.

[0109] The water-soluble film enclosing the detergent can comprise one or more structurally different water-soluble polymers. Particularly suitable water-soluble polymers include those from the group of (optionally acetalized) polyvinyl alcohols (PVALs) and their copolymers.

[0110] Water-soluble films are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer with a molecular weight in the range of 10,000 to 1,000,000 gmol. 1 , preferably from 20,000 to 500,000 gmol' 1 , especially preferred from 30,000 to 100,000 gmok 1 and especially from 40,000 to 80,000 gmol 1 lies.

[0111] The production of polyvinyl alcohols and polyvinyl alcohol copolymers generally involves the hydrolysis of intermediate polyvinyl acetates. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.

[0112] Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylene-unsaturated carboxylic acid, its salt, or its ester. Particularly preferred are such polyvinyl alcohol copolymers containing, besides vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof; among the esters, Ci-4 alkyl esters or hydroxyalkyl esters are preferred. Further suitable monomers include ethylene-unsaturated dicarboxylic acids, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof.

[0113] Suitable water-soluble films for use are distributed by companies such as MonoSol LLC under the designations M8630, M8720, M8310, C8400, or M8900. Films such as Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL from Aicello Chemical Europe GmbH, or the VF-HP films from Kuraray, are also suitable.

[0114] The water-soluble films may contain additional active ingredients or fillers, as well as plasticizers and / or solvents, especially water.

[0115] Other active ingredients include, for example, materials that protect the ingredients of the preparation, enclosed by the film material, from degradation or deactivation by light exposure. Antioxidants, UV absorbers, and fluorescent dyes have proven particularly suitable for this purpose.

[0116] Suitable plasticizers include, for example, glycerin, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1,3-propanediol, sorbitol, or mixtures thereof. To reduce its coefficient of friction, the surface of the water-soluble film of the detergent dispenser can optionally be dusted with a fine powder. Sodium aluminosilicate, silicon dioxide, talc, and amylose are examples of suitable powders.

[0117] Preferred water-soluble films are suitable for processing in a thermoforming apparatus.

[0118] The volume of the detergent portion unit is preferably from 10 to 30 ml, in particular from 12 to 25 ml.

[0119] Preferred detergent portion units have one to four receiving chambers, preferably three or four. In detergent portion units with two or more receiving chambers, preferably at least one, and preferably the majority, of the receiving chambers is transparent. Preferred detergent portion units have three or four receiving chambers, and at least two of the chambers contain a detergent according to the invention.

[0120] The following further embodiments are particularly preferred:

[0121] Detergent portion unit comprising at least two receiving chambers surrounded by a water-soluble film, wherein one receiving chamber is filled with the detergent according to the invention and the further receiving chamber is filled with a second detergent different from the detergent according to the invention; detergent portion unit comprising at least three receiving chambers surrounded by a water-soluble film, wherein two receiving chambers are filled with the detergent according to the invention and the further receiving chamber is filled with a second detergent different from the detergent according to the invention;

[0122] Detergent portion unit comprising at least four receiving chambers surrounded by a water-soluble film, wherein three receiving chambers are filled with the detergent according to the invention and the further receiving chamber is filled with a detergent different from the detergent according to the invention.

[0123] As stated at the outset, the detergent is particularly suitable for cleaning textiles in machine textile cleaning. A further subject matter of this application is therefore a method for textile cleaning in which a detergent or a detergent portion unit according to the invention is introduced into the washing liquor of a textile washing machine.

[0124] The machine-based textile cleaning process preferably takes place at temperatures of 20°C to 60°C, preferably from 30°C to 45°C. This application provides, among other things, the following items:

[0125] 1. Liquid detergent containing, based on its total weight, a) 22 to 50 wt.% anionic surfactant; b) 0.1 to 8 wt.% gluconic acid salt; c) 0 to 2 wt.% antioxidant; d) 5 to 25 wt.% organic solvent; e) 0.1 to 15 wt.% water; f) less than 0.1 wt.% organic phosphonate; g) 0.01 to 5 wt.% of a perfume composition.

[0126] 2. Detergent according to point 1, wherein the anionic surfactant is selected from the group consisting of CB-IS alkylbenzenesulfonates, Cs-is olefin sulfonates, Ci2-18 alkanesulfonates, Cs-is ester sulfonates, CB-IS alkyl sulfates, Cs-is alkenyl sulfates, fatty alcohol ether sulfates and fatty acid salts, preferably from the group consisting of Cs-is alkylbenzenesulfonates, Cs-is alkyl sulfates, fatty alcohol ether sulfates and C12-18 fatty acid salts and in particular from the group consisting of Cs-is alkylbenzenesulfonates and C12-18 fatty acid salts.

[0127] 3. Detergent according to one of the previous points, wherein the anionic surfactant is selected from the group of alkanolamine-Cs-is alkylbenzenesulfonates and alkanolamine-Ci2-is fatty acid salts.

[0128] 4. Detergent according to one of the previous points, wherein the anionic surfactant is selected from the group of alkanolamine-Cs-is-alkylbenzenesulfonates.

[0129] 5. Detergent according to one of points 3 or 4, wherein the anionic surfactant is selected from the group of alkanolamine-Cs-is-alkylbenzenesulfonates with alkanolamine from the group monoethanolamine, monoisopropanolamine, diisopropanolamine, preferably from the group monoethanolamine.

[0130] 6. Detergent according to any of the preceding points, wherein the detergent contains, based on its total weight, 27 to 45 wt.%, preferably 32 to 40 wt.% anionic surfactant.

[0131] 7. Detergent according to any of the preceding points, wherein the detergent contains Cs-is-alkylbenzenesulfonate and C12-18 fatty acid salt and the weight ratio of Cs-is-alkylbenzenesulfonate to C12-18 fatty acid salt is 8:1 to 2:1, preferably 7:1 to 5:2 and particularly 6:1 to 3:1.

[0132] 8. Detergent according to any of the preceding points, wherein the detergent contains alkanolamine-Cs-is-alkylbenzenesulfonate and alkanolamine-Ci2-18 fatty acid salt and the weight ratio of alkanolamine-Cs-is-alkylbenzenesulfonate to alkanolamine-Ci2-18 fatty acid salt is 8:1 to 2:1, preferably 7:1 to 5:2 and particularly 6:1 to 3:1.

[0133] 9. Detergent according to any of the preceding points, wherein the detergent further contains, based on its total weight, 12 to 36 wt.%, preferably 15 to 33 wt.% and particularly 18 to 30 wt.% non-ionic surfactant.

[0134] 10. Detergent according to point 9, wherein the non-ionic surfactant is selected from the group of ethoxylated primary Cs-is alcohols, preferably the ethoxylated primary Cs-is alcohols with a degree of alkoxylation of 4 to 10, particularly preferably the Ci2-14 alcohols with 4 EO or 7 EO, the Cg-n alcohols with 7 EO, the Ci3-15 alcohols with 5 EO, 7 EO or 8 EO, the C13-15 oxo alcohols with 7 EO, the Ci2-is alcohols with 5 EO or 7 EO, in particular the Ci2-is fatty alcohols with 7 EO or the Ci3-is oxo alcohols with 7 EO.

[0135] 11. Detergent according to any of the preceding points, wherein the detergent, based on its total weight, contains 1 to 10 wt.%, preferably 1.2 to 7 wt.% and particularly 1.5 to 4 wt.% polyalkoxylated amine with a weight-average molecular weight M win the range of 600 g / mol to 10000 g / mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines having a molecular weight below 200 g / mol with alkylene oxides.

[0136] 12. Detergent according to point 11, wherein the polyalkoxylated amine is obtained by reacting triethanolamine with alkylene oxides, preferably by reacting triethanolamine with ethylene oxide and propylene oxide.

[0137] 13. Detergent according to one of points 11 or 12, wherein the polyalkoxylated amine has a weight-average molecular weight M w in the range of 1300 g / mol to 6000 g / mol, in particular from 1400 g / mol to 4500 g / mol.

[0138] 14. Detergent according to any of the preceding points, wherein the detergent contains, based on its total weight, 0.2 to 6 wt.% and in particular 0.4 to 4 wt.% gluconic acid salt, preferably sodium gluconate.

[0139] 15. Detergent according to any of the preceding points, wherein the detergent contains antioxidants from the group consisting of sulfites, hydrogen sulfites and disulfites, preferably from the group consisting of sodium sulfite, sodium hydrogen sulfite and sodium disulfite, and in particular from the group consisting of sodium sulfite and sodium disulfite.

[0140] 16. Detergent according to any of the preceding clauses, wherein the detergent contains an antioxidant from the disulfite group, preferably from the sodium disulfite group. 17. Detergent according to any of the preceding clauses, wherein the detergent contains, based on its total weight, 0.02 to 1 wt.% and in particular 0.05 to 0.5 wt.% antioxidant.

[0141] 18. Detergent according to any of the preceding items, wherein the detergent is an organic solvent from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycyl, propyldiglycol, butyldiglycyl, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol-t-butyl ether, Di-n-octyl ether and mixtures thereof, preferably from the group consisting of propanediol, glycerol and mixtures thereof.

[0142] 19. Detergent according to any of the preceding points, wherein the detergent contains, based on its total weight, 7 to 20 wt.%, preferably 10 to 18 wt.% organic solvent.

[0143] 20. Detergent according to any of the preceding points, wherein the detergent contains 5 to 15, preferably 8 to 15 wt.% water based on its total weight.

[0144] 21. Detergent according to any of the previous points, wherein the detergent does not contain organic phosphonate.

[0145] 22. Detergent according to any of the preceding points, wherein the detergent is a dye from the group of water-soluble dyes, in particular from the group of water-soluble acid dyes, water-soluble direct dyes and water-soluble polymer dyes, in particular water-soluble polymer dyes.

[0146] 23. Detergent according to one of the previous points, where the detergent dye is from the group Liquitint Blue HP (GAS No. 162874-54-6), Liquitint Cyan 15 (CAS No. 888888-03-0), Liquitint Patent Blue (CAS No. 162874-57-9), Liquitint Violet 129 (CAS No. 888888-06-7), Liquitint Royal Blue (CAS No. 162874-58-0), Liquitint Red ET (CAS No. 888888-02-9), Liquitint Aquamarine, (CAS No. 888888-04-4), Liquitint Blue (CAS No. 888888-02-6), Liquitint Bright Yellow Dye (CAS No. 888888- 03-7), Liquitint Brilliant Orange Dye (CAS No. 888888-03-6), Liquitint Green (CAS No. 888888-05-5), Liquitint Orange (CAS No. 888888-03-5), Liquitint Purple (CAS No. 888888-02-7), Liquitint Red (CAS No. 888888-02-9), Liquitint Sky Blue Dye (CAS No. 888888-03-8), Liquitint Violet (CAS No. 888888-06-7) and mixtures thereof. 23. Detergent according to any of the preceding items, wherein the detergent contains, based on its total weight, 0.001 to 0.5 wt.%, preferably 0.002 to 0.3 wt.%.-% and in particular contains 0.005 to 0.2 wt% dye.

[0147] 24. Detergent according to one of the previous points, wherein the detergent does not contain dye.

[0148] 25. Detergent according to any of the preceding items, wherein the detergent contains a washing or cleaning active polymer from the group consisting of soil release polymers, color transfer inhibitors, graying inhibitors and anti-reposition agents.

[0149] 26. Detergent according to any of the preceding items, wherein the detergent contains a washing or cleaning active polymer from the group consisting of carboxymethyl celluloses, nonionic cellulose ethers, polyalkoxylated polyethyleneimines and (co)polymers of phthalic or terephthalic acid.

[0150] 27. Detergent according to any of the preceding points, wherein the detergent contains, based on its total weight, 1 to 10 wt.%, preferably 1.2 to 7 wt.%, and in particular 1.5 to 4 wt.% ethoxylated polyethyleneimine with ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine.

[0151] 28. Detergent according to point 27, wherein the ethoxylated polyethyleneimine has a polyethyleneimine backbone with a weight-average molecular weight in the range of 100 g / mol to 2000 g / mol, in particular from 400 g / mol to 800 g / mol.

[0152] 29. Detergents according to one of points 27 or 28, wherein the ethoxylated polyethyleneimine has a weight-average molecular weight in the range of 5000 g / mol to 20000 g / mol, in particular from 8000 g / mol to 14000 g / mol.

[0153] 30. Detergent according to any of the preceding points, wherein the detergent contains a washing or cleaning active polymer from the group consisting of phthalic acid and / or terephthalic acid or their derivatives with monomeric and / or polymeric diols, preferably from the group consisting of polymers consisting of ethylene terephthalates and / or polyethylene glycol terephthalates and / or polypropylene terephthalates or anionically and / or nonionically modified derivatives thereof, particularly preferably from the group consisting of anionic or nonionic polyesters of polypropylene terephthalates.

[0154] 31. Detergent according to any of the preceding clauses, wherein the detergent contains, based on its total weight, 0.5 to 7 wt.%, preferably 1.0 to 6 wt.% enzyme preparations. 32. Detergent according to clause 31, wherein the enzyme preparations have, based on their total weight, a weight fraction of active protein of 0.1 to 40 wt.%, preferably 0.2 to 30 wt.%.

[0155] 33. Detergents according to any of the preceding points, wherein the detergent contains at least one enzyme preparation, preferably at least three enzyme preparations of enzymes from the group consisting of lipase, mannanase, amylase, protease, cellulase, hexosaminidase, preparations of a pectinolytic enzyme and endoglucanase.

[0156] 34. Detergent according to any of the preceding points, wherein the detergent contains, based on its total weight, 0.1 to 0.4 wt.% and in particular 0.2 to 0.3 wt.% hexosaminidase preparation, particularly preferably β-hexosaminidase preparation.

[0157] 35. Detergent according to any of the preceding points, wherein the detergent contains, based on its total weight, 0.1 to 2 wt.%, preferably 0.2 to 1 wt.% of an amylase preparation.

[0158] 36. Detergent according to any of the preceding points, wherein the detergent contains, based on its total weight, 0.2 to 4 wt.%, preferably 0.4 to 3 wt.% of a protease preparation.

[0159] 37. Detergent according to any of the preceding points, wherein the detergent contains, based on its total weight, 0.01 to 1 wt.%, preferably 0.02 to 0.3 wt.% of a mannanase preparation.

[0160] 38. Detergent according to any of the preceding points, wherein the detergent contains, based on its total weight, 0.01 to 1 wt.%, preferably 0.05 to 0.3 wt.% of a cellulase preparation.

[0161] 39. Detergent according to one of the previous points, wherein the detergent is packaged in a transparent container.

[0162] 40. Detergents according to any of the preceding items, wherein the detergent contains a perfume composition containing at least 0.01% by weight of a perfume raw material selected from perfume ketones, perfume aldehydes and mixtures thereof.

[0163] 41. Detergent according to any of the preceding items, wherein the detergent comprises a perfume composition containing at least 0.01% by weight of a perfume raw material selected from the group consisting of Adoxal (2,6,10-Trimethyl-9-undecenal), Anisaldehyde (4-Methoxybenzaldehyde), Cymal or Cyclamenaldehyde (3-(4-isopropylphenyl)-2-methylpropanal), Nympheal (3-(4-isobutyl-2-methylphenyl)propanal), Ethylvanillin, Florhydral (3-(3-Isopropylphenyl)butanal), Trifernal (3-Phenylbutyraldehyde), Helional (3-(3,4-Methylenedioxyphenyl)-2-methylpropanal), Heliotropin, Hydroxycitronellal, Lauraldehyde, Lyral (3- and 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde). Methylnonylacetaldehyde, Lilial (3-(4-tert-butylphenyl)-2-methylpropanal), Phenylacetaldehyde, Undecylenaldehyde, Vanillin, 2,6,10-Trimethyl-9-undecenal, 3-Dodecen-1-al, alpha-n-Amylcinnamaldehyde, Melonal (2,6-Dimethyl-5-heptenal), Triplal (2,4-dimethyl-3-cyclohexene-1-carboxaldehyde), 4-methoxybenzaldehyde, benzaldehyde,3-(4-tert- Butylphenyl)-propanal, 2-Methyl-3-(para-methoxyphenyl)propanal, 2-Methyl-4-(2,6,6-timethyl-2(1)- cyclohexen-1-yl)butanal, 3-Phenyl-2-propenal, cis- / trans-3,7-Dimethyl-2,6-octadien-1-al, 3,7- Dimethyl-6-octen-1-al, [(3,7-Dimethyl-6-octenyl)oxy]acetaldehyd, 4-lsopropylbenzylaldehyd, 1 ,2,3,4,5,6,7,8-Octahydro-8,8-dimethyl-2-naphthaldehyd, 4-(4-Methylpent-3-enyl)cyclohex-3-en-1- carbaldehyd, 1-Methyl-4-(4-methylpentyl)cyclohex-3-en-1-carbaldehyd, 8,8-Dimethyl-6,7-dihydro- 5H-naphthalen-2-carbaldehyd, 2,4-Dimethyl-3-cyclohexen-1-carboxaldehyd, 2-Methyl-3- (isopropylphenyl)propanal, 1 -Decanal, 2,6-Dimethyl-5-heptenal, 4-(Tricyclo[5.2.1.0(2,6)]-decyliden- 8)-butanal, Octahydro-4,7-methan-1H-indencarboxaldehyd, 3-Ethoxy-4-hydroxybenzaldehyd, para- Ethyl-alpha,alpha-dimethylhydrozimtaldehyd, alpha-Methyl-3,4-(methylendioxy)-hydrozimtaldehyd, 3,4-Methylendioxybenzaldehyd, alpha-n-Hexylzimtaldehyd, m-Cymen-7-carboxaldehyd, alpha- Methylphenylacetaldehyd, Tetrahydrocitral (3,7-Dimethyloctanal), Citral, Undecenal, 2,4,6- Trimethyl-3-cyclohexen-1-carboxaldehyd, 4-(3)(4-Methyl-3-pentenyl)-3-cyclohexencarboxaldehyd, 1 -Dodecanal, 2,4-Dimethylcyclohexen-3-carboxaldehyd, 4-(4-Hydroxy-4-methylpentyl)-3- cylohexen-1-carboxaldehyd, 7-Methoxy-3,7-dimethyloctan-1-al, 2-Methyldecanal, 1-Nonanal, 1- Octanal, 2,6,10-Trimethyl-5,9-undecadienal, 2-Methyl-3-(4-tert-butyl)propanal, Dihydrozimtaldehyd,

[0164] 1-Methyl-4-(4-methyl-3-pentenyl)-3-cyclohexen-1-carboxaldehyd, 5- oder 6-Methoxyhexahydro-4,7- methanindan-1- oder -2-carboxaldehyd, 3,7-Dimethyloctan-1-al, 1-Undecanal, 10-Undecen-1-al, 4- Hydroxy-3-methoxybenzaldehyd, 1-Methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyd, 7- Hydroxy-3,7-dimethyl-octanal, trans-4-Decenal, 2,6-Nonadienal, para-Tolylacetaldehyd, 4- Methylphenylacetaldehyd, 2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, ortho- Methoxyzimtaldehyd, Citronellyloxyacetaldehyd, 3,5,6-Trimethyl-3-cyclohexencarboxaldehyd, 3,7- Dimethyl-2-methylen-6-octenal, Phenoxyacetaldehyd, 3-(4-propan-2-ylphenyl)propanal, 5,9- Dimethyl-4,8-decadienal, Päonienaldehyd (6,10-Dimethyl-3-oxa-5,9-undecadien-1-al), Hexahydro- 4,7-methanindan-1-carboxaldehyd, 3-(4-tert-Butylphenyl)propanal, 3-(3-Propan-2-ylphenyl)butanal,

[0165] 2-Methyloctanal, alpha-Methyl-4-(1-methylethyl)benzolacetaldehyd, 6,6-Dimethyl-2-norpinen-2- propionaldehyd, para-Methylphenoxyacetaldehyd, 2-Methyl-3-phenyl-2-propen-1-al, 3,5,5- Trimethylhexanal, Hexahydro-8,8-dimethyl-2-naphthaldehyd, 3-Propylbicyclo[2.2.1]-hept-5-en-2- carbaldehyd, 9-Decenal, 3-Methyl-5-phenyl-1-pentanal, Floral (4,8-Dimethyl-4,9-decadienal), Aldehyd C12MNA (2-Methylundecanal), Liminal (beta-4-Dimethylcyclohex-3-ene-1-propan-1-al), 3- (1 ,3-Benzodioxol-5-yl)-2-methylpropanal, 2-(4-Methylphenyl)methylenheptenal, 3-(4-methyl-1- cyclohex-3-enyl)butanal, Methylnonylacetaldehyd, Hexanal, trans-2-Hexenal, Methyl-beta- naphthylketon, Moschusindanon (1 ,2,3,5,6,7-Hexahydro-1 , 1 ,2,3,3-pentamethyl-4H-inden-4-on), Calone (Methylbenzodioxepinon), Tonalid (6-Acetyl-1 ,1,2,4,4,7-hexamethyltetralin), alpha- Damascene, beta-Damascone, delta-Damascone, iso-Damascone, Damascenone, Methyldihydrojasmonat (Hedion), Menthon, Carvon, Kampfer, Koavon (3,4,5,6,6-Pentamethylhept- 3-en-2-on), Fenchon, alpha-lonon, beta-lonon, Dihydro-beta-lonon, gamma-Methyl-lonon, Fleuramon (2-Heptylcyclopentanon), Frambinonmethylether (4-(4-Methoxyphenyl)butan-2-on), Dihydrojasmon, cis-Jasmon, 1-(1 ,2,3,4,5,6,7,8-Octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)- ethan-1-on und Isomere davon, Methylcedrenylketon, Acetophenon, Methylacetophenon, para- Methoxyacetophenon, Methyl-beta-naphtylketon, Benzylaceton, Benzophenon, para-,

[0166] Hydroxyphenylbutanon, Sellerie-Keton(3-Methyl-5-propyl-2-cyclohexenon), 6-lsopropyldeca-hydro-

[0167] 2-naphton, Dimethyloctenon, Frescomenthe (2-Butan-2-ylcyclohexan-1-on), 4-(1-Ethoxyvinyl)- 3,3,5,5-tetramethylcyclohexanon, 5-Methylhept-2-en-4-on, 6-Methylhept-5-en-2-on, 2-(2-(4-Methyl-

[0168] 3-cyclohexen-1-yl)propyl)cyclopentanon, 1-(p-Menthen-6(2)yl)-1-propanon, 4-(4-Hydroxy-3- methoxyphenyl)-2-butanon, 2-Acetyl-3,3-dimethylnorbornan, 6,7-Dihydro-1 ,1 ,2,3,3-pentamethyl- 4(5H)in-danon, 4-Damascol, Dulcinyl (4-(1,3-Benzodioxol-5-yl)butan-2-on), Hexalon (1-(2,6,6- Trimethyl-2-cyclohexen-1-yl)-1 ,6-heptadien-3-on), Isocyclemon E (2-Acetonaphthon-1 ,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), Methylnonylketon, Methylcyclocitron, Methyllavendelketon, Orivon (4-tert-Amylcyclohexanon), 4-tert-Butylcyclohexanon, Delphon (2- Pentylcyclopentanon), Muscon (CAS 541 -91 -3), Neobutenon (1-(5,5-dimethyl-1-cyclo- hexenyl)pent-4-en-1-on), Plicaton (CAS 41724-19-0), Velouton (2,2,5-trimethyl-5-pentylcyclopentan- 1 -on), 2,4,4,7-Tetramethyl-oct-6-en-3-on, 2-[2-(4-Methyl-1-cyclohex-3-enyl)propyl]cyclopentan-1- on, Tetrameran (6,10-dimethylundecen-2-on) und Mischungen daraus, enthält

[0169] 42. Detergent portion unit comprising i) a detergent according to any of points 1 to 41 ii) a transparent water-soluble film which completely encloses the detergent.

[0170] 43. Detergent portion unit according to point 42 wherein the detergent portion unit has a volume of 10 to 30 ml, preferably 12 to 25 ml.

[0171] 44. Detergent portioning unit according to one of points 42 or 43, wherein the detergent portioning unit has one to four receiving chambers, preferably three or four receiving chambers.

[0172] 45. Detergent portion unit according to one of points 42, 43 or 44, wherein the detergent portion unit has three or four receiving chambers and at least two of the chambers contain a detergent according to one of points 1 to 38.

[0173] 46. ​​A method for textile cleaning in which a detergent according to one of points 1 to 41 or a detergent portion unit according to one of points 42 to 45 is introduced into the washing liquor of a textile washing machine. Examples

[0174] Example 1

[0175] The following three liquid detergents were produced by mixing their ingredients.

[0176] Table 1a: Laundry detergent base formulations (wt%)

[0177] 1) Texcare SRN 170

[0178] 2) Ethoxylated polyethyleneimine with ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine

[0179] 3) This results in a turquoise coloration of the base formulations.

[0180] The following perfume compositions were incorporated into the base formulations shown above:

[0181] A: 3% w / w Perfume P01

[0182] B: 0.1% w / w perfume P02

[0183] C: 3% w / w Perfume P01 + 0.1% w / w P02

[0184] Perfume P01 is a perfume composition that does not contain perfume ketones and / or perfume aldehydes.

[0185] Perfume P02 is a perfume composition that contains only perfume ketones and / or perfume aldehydes.

[0186] The various liquid detergents were stored for 4 or 8 weeks under different climatic conditions after their production. The L*, a*, and b* values ​​of the liquid detergents were determined immediately after production and again after 4 and / or 8 weeks. To determine the L*, a*, and b* values ​​according to the CIE L*a*b* system, 3 ml of the undiluted samples were placed in disposable cuvettes and measured using a colorimeter (Dr. Lange Lico 3000 spectral colorimeter).

[0187] Table 1b: b* (measured value) with 3 wt% perfume P01

[0188] * “Summer” simulation: Storage with oscillating temperatures between 24 and 40 °C

[0189] ** Simulation “Autumn”: Storage with oscillating temperatures between X and Y °C

[0190] Table 1c: b* (measured value) with 0.1 wt% perfume P02

[0191] Table 1d: b* (measured value) with 3 wt% perfume P01 and 0.1 wt% perfume P02

[0192] The samples show an increase in the b* value during storage, especially at higher temperatures, and thus a shift from blue to yellow. Adding gluconate (E1) or, in particular, gluconate and sulfite (E2) to phosphonate-free formulas can stabilize them and reduce the color shift.

Claims

Patent claims:

1. Liquid detergent containing, based on its total weight, a) 22 to 50 wt.% anionic surfactant; b) 0.1 to 8 wt.% gluconic acid salt; c) 0 to 2 wt.% antioxidant; d) 5 to 25 wt.% organic solvent; e) 0.1 to 15 wt.% water; f) less than 0.1 wt.% organic phosphonate and g) 0.01 to 5 wt.% of a perfume composition.

2. Detergent according to claim 1, wherein the anionic surfactant is selected from the group consisting of alkanolamine-Cs-is alkylbenzenesulfonates and alkanolamine-Ci2-is fatty acid salts.

3. Detergent according to any of the preceding claims, wherein the detergent contains, based on its total weight, 0.2 to 6 wt.% and in particular 0.4 to 4 wt.% gluconic acid salt.

4. Detergent according to any of the preceding claims, wherein the detergent contains antioxidants from the group consisting of sulfites, hydrogen sulfites and disulfites, preferably from the group consisting of sodium sulfite, sodium hydrogen sulfite and sodium disulfite, in particular from the group consisting of sodium sulfite and sodium disulfite.

5. Detergent according to any of the preceding claims, wherein the detergent contains antioxidants from the group of disulfites, preferably from the group of sodium disulfites.

6. Detergent according to any of the preceding claims, wherein the detergent contains, based on its total weight, 0.02 to 1 wt.% and in particular 0.05 to 0.5 wt.% antioxidant.

7. Detergent according to any of the preceding claims, wherein the detergent does not contain any organic phosphonate.

8. Detergent according to one of the preceding claims, wherein the detergent contains a dye from the group of water-soluble dyes, in particular from the group of water-soluble acid dyes, water-soluble direct dyes and water-soluble polymer dyes, in particular water-soluble polymer dyes.

9. Detergent according to any of the preceding claims, wherein the detergent comprises a perfume composition comprising at least 0.01 wt% of a perfume raw material selected from the group consisting of Adoxal (2,6,10-Trimethyl-9-undecenal), Anisaldehyde (4-Methoxybenzaldehyde), Cymal or Cyclamenaldehyde (3-(4-isopropylphenyl)-2-methylpropanal), Nympheal (3-(4-lsobutyl-2-methylphenyl)propanal), Ethylvanillin, Florhydral (3-(3- Isopropylpheny l)butanal]), Trifernal (3-Phenylbutyraldehyd), Helional (3-(3,4-Methylendioxyphenyl)- 2-methylpropanal), Heliotropin, Hydroxycitronellal, Lauraldehyd, Lyral (3- und 4-(4-Hydroxy-4- methylpentyl)-3-cyclohexen-1-carboxaldehyd), Methylnonylacetaldehyd, Lilial (3-(4-tert- Butylphenyl)-2-methylpropanal), Phenylacetaldehyd, Undecylenaldehyd, Vanillin, 2,6,10-Trimethyl- 9-undecenal, 3-Dodecen-1-al, alpha-n-Amylzimtaldehyd, Melonal (2,6-Dimethyl-5-heptenal), Triplal (2,4-Dimethyl-3-cyclohexen-1-carboxaldehyd), 4-Methoxybenzaldehyd, Benzaldehyd, 3-(4-tert- Butylphenyl)-propanal, 2-Methyl-3-(para-methoxyphenyl)propanal, 2-Methyl-4-(2,6,6-timethyl-2(1)- cyclohexen-1-yl)butanal, 3-Phenyl-2-propenal, cis- / trans-3,7-Dimethyl-2,6-octadien-1-al, 3,7- Dimethyl-6-octen-1-al, [(3,7-Dimethyl-6-octenyl)oxy]acetaldehyd, 4-lsopropylbenzylaldehyd, 1 ,2,3,4,5,6,7,8-Octahydro-8,8-dimethyl-2-naphthaldehyd,4-(4-Methylpent-3-enyl)cyclohex-3-en-1- carbaldehyd, 1-Methyl-4-(4-methylpentyl)cyclohex-3-en-1-carbaldehyd, 8,8-Dimethyl-6,7-dihydro- 5H-naphthalen-2-carbaldehyd, 2,4-Dimethyl-3-cyclohexen-1-carboxaldehyd, 2-Methyl-3- (isopropylphenyl)propanal, 1 -Decanal, 2,6-Dimethyl-5-heptenal, 4-(Tricyclo[5.2.1.0(2,6)]-decyliden- 8)-butanal, Octahydro-4,7-methan-1H-indencarboxaldehyd, 3-Ethoxy-4-hydroxybenzaldehyd, para- Ethyl-alpha,alpha-dimethylhydrozimtaldehyd, alpha-Methyl-3,4-(methylendioxy)-hydrozimtaldehyd, 3,4-Methylendioxybenzaldehyd, alpha-n-Hexylzimtaldehyd, m-Cymen-7-carboxaldehyd, alpha- Methylphenylacetaldehyd, Tetrahydrocitral (3,7-Dimethyloctanal), Citral, Undecenal, 2,4,6- Trimethyl-3-cyclohexen-1-carboxaldehyd, 4-(3)(4-Methyl-3-pentenyl)-3-cyclohexencarboxaldehyd, 1 -Dodecanal, 2,4-Dimethylcyclohexen-3-carboxaldehyd, 4-(4-Hydroxy-4-methylpentyl)-3- cylohexen-1-carboxaldehyd, 7-Methoxy-3,7-dimethyloctan-1-al, 2-Methyldecanal, 1-Nonanal, 1- Octanal, 2,6,10-Trimethyl-5,9-undecadienal, 2-Methyl-3-(4-tert-butyl)propanal, Dihydrozimtaldehyd, 1-Methyl-4-(4-methyl-3-pentenyl)-3-cyclohexen-1-carboxaldehyd, 5- oder 6-Methoxyhexahydro-4,7- methanindan-1- oder -2-carboxaldehyd, 3,7-Dimethyloctan-1-al, 1-Undecanal, 10-Undecen-1-al, 4- Hydroxy-3-methoxybenzaldehyd, 1-Methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyd, 7- Hydroxy-3,7-dimethyl-octanal, trans-4-Decenal, 2,6-Nonadienal, para-Tolylacetaldehyd, 4- Methylphenylacetaldehyd, 2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, ortho- Methoxyzimtaldehyd, Citronellyloxyacetaldehyd, 3,5,6-Trimethyl-3-cyclohexencarboxaldehyd, 3,7- Dimethyl-2-methylen-6-octenal, Phenoxyacetaldehyd, 3-(4-propan-2-ylphenyl)propanal, 5,9- Dimethyl-4,8-decadienal, Päonienaldehyd (6,10-Dimethyl-3-oxa-5,9-undecadien-1-al), Hexahydro- 4,7-methanindan-1-carboxaldehyd, 3-(4-tert-Butylphenyl)propanal, 3-(3-Propan-2-ylphenyl)butanal, 2-Methyloctanal, alpha-Methyl-4-(1-methylethyl)benzolacetaldehyd, 6,6-Dimethyl-2-norpinen-2- propionaldehyd, para-Methylphenoxyacetaldehyd, 2-Methyl-3-phenyl-2-propen-1-al, 3,5,5- Trimethylhexanal, Hexahydro-8,8-dimethyl-2-naphthaldehyd, 3-Propylbicyclo[2.2.1]-hept-5-en-2- carbaldehyd, 9-Decenal, 3-Methyl-5-phenyl-1-pentanal, Floral (4,8-Dimethyl-4,9-decadienal), Aldehyd C12MNA (2-Methylundecanal), Liminal (beta-4-Dimethylcyclohex-3-ene-1-propan-1-al), 3- (1 ,3-Benzodioxol-5-yl)-2-methylpropanal, 2-(4-Methylphenyl)methylenheptenal, 3-(4-methyl-1- cyclohex-3-enyl)butanal, Methylnonylacetaldehyd, Hexanal, trans-2-Hexenal, Methyl-beta- naphthylketon, Moschusindanon (1 ,2,3,5,6,7-Hexahydro-1 , 1 ,2,3,3-pentamethyl-4H-inden-4-on), Calone (Methylbenzodioxepinon), Tonalid (6-Acetyl-1 ,1,2,4,4,7-hexamethyltetralin), alpha- Damascene, beta-Damascone, delta-Damascone, iso-Damascone, Damascenone, Methyldihydrojasmonat (Hedion), Menthon, Carvon, Kampfer, Koavon (3,4,5,6,6-Pentamethylhept- 3-en-2-on), Fenchon, alpha-lonon, beta-lonon, Dihydro-beta-lonon, gamma-Methyl-lonon, Fleuramon (2-Heptylcyclopentanon), Frambinonmethylether (4-(4-Methoxyphenyl)butan-2-on), Dihydrojasmon, cis-Jasmon, 1-(1 ,2,3,4,5,6,7,8-Octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)- ethan-1-on und Isomere davon, Methylcedrenylketon, Acetophenon, Methylacetophenon, para- Methoxyacetophenon, Methyl-beta-naphtylketon, Benzylaceton, Benzophenon, para- Hydroxyphenylbutanon, Sellerie-Keton(3-Methyl-5-propyl-2-cyclohexenon), 6-lsopropyldeca-hydro- 2-naphton, Dimethyloctenon, Frescomenthe (2-Butan-2-ylcyclohexan-1-on), 4-(1-Ethoxyvinyl)- 3,3,5,5-tetramethylcyclohexanon, 5-Methylhept-2-en-4-on, 6-Methylhept-5-en-2-on, 2-(2-(4-Methyl- 3-cyclohexen-1-yl)propyl)cyclopentanon, 1-(p-Menthen-6(2)yl)-1-propanon, 4-(4-Hydroxy-3- methoxyphenyl)-2-butanon, 2-Acetyl-3,3-dimethylnorbornan, 6,7-Dihydro-1 ,1 ,2,3,3-pentamethyl- 4(5H)in-danon, 4-Damascol, Dulcinyl (4-(1,3-Benzodioxol-5-yl)butan-2-on), Hexalon (1-(2,6,6- Trimethyl-2-cyclohexen-1-yl)-1 ,6-heptadien-3-on), Isocyclemon E (2-Acetonaphthon-1 ,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), Methylnonylketon, Methylcyclocitron, Methyllavendelketon, Orivon (4-tert-Amylcyclohexanon), 4-tert-Butylcyclohexanon, Delphon (2- Pentylcyclopentanon), Muscon (CAS 541 -91 -3), Neobutenon (1-(5,5-dimethyl-1-cyclo- hexenyl)pent-4-en-1-on), Plicaton (CAS 41724-19-0), Velouton (2,2,5-trimethyl-5-pentylcyclopentan- 1 -on), 2,4,4,7-Tetramethyl-oct-6-en-3-on, 2-[2-(4-Methyl-1-cyclohex-3-enyl)propyl]cyclopentan-1- on, Tetrameran (6,10-dimethylundecen-2-on) und Mischungen daraus, enthält.

10. Detergent according to any of the preceding claims, wherein the detergent is packaged in a transparent container.

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